CN108178816A - The manufacturing method of water-absorbing resins with high rate of liquid aspiration - Google Patents
The manufacturing method of water-absorbing resins with high rate of liquid aspiration Download PDFInfo
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- CN108178816A CN108178816A CN201711407444.7A CN201711407444A CN108178816A CN 108178816 A CN108178816 A CN 108178816A CN 201711407444 A CN201711407444 A CN 201711407444A CN 108178816 A CN108178816 A CN 108178816A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- 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
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- C08J3/12—Powdering or granulating
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- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
A kind of manufacturing method of the water-absorbing resins with high rate of liquid aspiration, includes the following steps：It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution；Unsaturated acrylic monomer will be contained and cross-linking agent aqueous solution monomer polymerize, obtain aqueous gel shape cross-linked polymer；Aqueous gel shape cross-linked polymer is ground into gel particle, and be dried, crush and sieve through high shear and/or the granulation of squeezing action power in the course of the polymerization process or after polymerization.Advantage is：One kind is provided without using additives such as foaming agent, surfactants, can efficiently produce the method for the water-absorbing resins with high speed rate of liquid aspiration, and obtain a kind of water-absorbing resins with high speed rate of liquid aspiration.
Description
Technical field
The present invention relates to a kind of water-absorbing resins and its manufacturing method with high rate of liquid aspiration.It is particularly applicable to absorbabilities
Article, such as：Paper nappy (disposable diaper), sanitary napkin, incontinence pad, mattress, pet pads, Wound care material, construction material,
In the products such as soil water-retaining material.
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、
CN1668343A、CN1296981A、CN101050244A、CN101143913A、CN101423588A、CN104448155A、
CN102311557A、CN104448102A、CN103214616A、CN103476811A、CN103857714A、
CN105377921A、CN102317329A、CN102010560A)；(2) agglomerated particle type water-absorbing resin is prepared using micro mist granulation
(such as EP0591168A)；(3) logical fluidity enhancer (such as special crosslinking agent) is added in water-absorbing resin and promotes water-absorbing resin
Logical fluidity, further improve its rate of liquid aspiration (such as WO2001089591A)；(4) surface conditioning agent (such as clay, nothing are added
Machine material etc.) increase the rate of liquid aspiration of water-absorbing resin (such as US20050239942A, WO2005120221A).Wherein, it studies
More and more effective method is foamed polymer strategy.
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 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, need using even
Nitrogen compound, carbonate compound, peroxide etc. can generate the chemical substance of gas as additive or need toward single
Gas is persistently blasted in liquid solution, brings the problem of the production cost increases.In addition, foaming effect preferably absorbs water tree in order to obtain
Fat often needs to add in surfactant in polymerization system, and to stablize Air Bubble Size, this can cause water-absorbing resin using process
The reduction of middle surface tension inhibits the imbibition characteristic of product.Surfactant is added in polymerization system can influence the table of resin
Face tension, and then influence the absorbent of product.
Therefore, it is necessary to provide a kind of method for the rate of liquid aspiration that water-absorbing resin is effectively promoted without using additive.
Invention content
The method of the water-absorbing resins with high speed rate of liquid aspiration can be efficiently produced, and obtained a kind of with suction at a high speed
The water-absorbing resins of liquid speed rate.
In order to solve described problem, the present invention makees the shear stress of gel and extruding by increasing in granulation process
Firmly, the original surface texture of gel is destroyed, gel surface is made to form rough rough surface, after crushed and sieved,
The rough surface of water-absorbing resin provides higher specific surface area for it, and then effectively promotes its rate of liquid aspiration.
To achieve the above object, the present invention provides a kind of manufacturing method of the water-absorbing resins with high rate of liquid aspiration,
Include the following steps：
It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
Unsaturated acrylic monomer will be contained and cross-linking agent aqueous solution monomer polymerize, obtain the crosslinking of aqueous gel shape
The step of polymer,
Aqueous gel shape cross-linked polymer is granulated in the course of the polymerization process or after polymerization through high shear and/or squeezing action power
The step of being ground into gel particle,
The aqueous gel shaped polymer water content is 20~60wt%,
The high shear forces power and/or squeezing action power are twisted by increasing the resistance to flow output of Minced Steak machine baffle and/or being promoted
Meat machine screw speed and length and/or repeatedly granulation provide,
Gel particle and clear gel granular mass ratio after the granulation with micro-roughened surface are 1:1~
1000:1,
The step of being thermally dried to the gel particle after crushing,
The step of grain refined is carried out to dry post-crosslinking polymer and is sieved.
The invention discloses a kind of water-absorbing resins and its manufacturing method with high rate of liquid aspiration, can be without using gas
Manufacture the water-absorbing resins with high rate of liquid aspiration to body and additive and stability and high efficiency.
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] polyacrylic has the manufacturing method of the water-absorbing resins of high rate of liquid aspiration
The polyacrylic acid water-absorbent resin of the present invention is manufactured by following steps.
It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
Unsaturated acrylic monomer will be contained and cross-linking agent aqueous solution monomer polymerize, obtain the crosslinking of aqueous gel shape
The step of polymer,
Aqueous gel shape cross-linked polymer is granulated in the course of the polymerization process or after polymerization through high shear and/or squeezing action power
The step of being ground into gel particle,
The aqueous gel shaped polymer water content is 20~60wt%,
The high shear forces power and/or squeezing action power are twisted by increasing the resistance to flow output of Minced Steak machine baffle and/or being promoted
Meat machine screw speed and length and/or repeatedly granulation provide,
Gel particle and clear gel granular mass ratio after the granulation with micro-roughened surface are 1:1~
1000:1,
The step of being thermally dried to the gel particle after crushing,
The step of grain refined is carried out to dry post-crosslinking polymer 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 25~100 moles of %, particularly preferably reaches at least 40~95 moles of %, more preferably up to 50~90 rub
You are %.The neutralization of monomer of the unsaturation containing acid groups can carry out before or after the polymerization.Alkali metal hydrogen-oxygen can be used
Compound, alkaline earth metal hydroxide, ammonia and carbonate and bicarbonate are neutralized.It is in addition it is possible to use any other
The alkali of water soluble salt can be formed with the acid.It can also be neutralized using a variety of alkali.It is preferable to use ammonia or alkali metal hydroxides
Object 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 60 moles of more than %, preferably 75 moles of more than %, preferably 90 moles of more than %, into one
Step is preferably 95 moles of more than %.
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 25 weight %, production
Ability can reduce, therefore not good enough.When monomer concentration is higher than in the case of 60 weight %, crushing load increases, and leads to production stability
It is 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
0.001~5 mole of %, more preferably 0.005~2 mole of %, further preferably 0.01~1 mole of %.If internal crosslinker
Usage amount is less than 0.001 mole of %, and the water soluble apparent extract of gained water-absorbing resins increases, and can not substantially ensure under pressurization
Water absorption.If the usage amount of internal crosslinking agent is more than 5 moles of %, chemical crosslinking density is too high, the water imbibition tree of gained
The water absorption at cosmetics end is insufficient.In addition, internal crosslinking agent can be once added in reaction system, can also be added batch-wise to anti-
It answers in system.
1.2 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, polymerization start temperature be 20~120 DEG C, preferably 40~110 DEG C, further preferably 60~
100℃.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
It may also reduce.If polymerizeing start temperature higher than 120 DEG C, the worry that the physical property for having water-absorbing resins reduces.For polymerization
Time is not particularly limited, and is suitably determined, but in terms of production capacity according to the type of monomer and polymerization initiator, polymerization temperature etc.
For, the shorter polymerization time the better.
1.3 granulation 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.Preferably 0.5~10 millimeter of gel particle size after crushing, if gel particle is too small, wind that level of residual monomers can be brought higher
Danger if water-setting gum polymers are not crushed or gel particle is too big, cannot obtain final granular product, especially
In subsequent heat drying steps, it is difficult to evaporate the moisture in hydrogel.
In order to obtain effect of the present invention, by increasing to the shear stress of gel and squeezing action power, it is original to destroy gel
Surface texture, gel surface is made to form rough rough surface, after crushed and sieved, the rough surface of water-absorbing resin
Higher specific surface area is provided for it, and then effectively promotes its rate of liquid aspiration.High shear forces power and/or squeezing action power pass through
Change meat grinder outlet damper aperture, gel strength, the dosage and temperature for being granulated water, screw speed and length or multiple be granulated to carry
For being specifically not particularly limited.Gel passes through high shear forces power and/or squeezing action power, and original surface topography destroys ratio and is
50~100%.Gel particle surface after granulation forms coarse surface, and solidifying with micro-roughened surface after the granulation
Glue particle is 1 with clear gel granular mass ratio:1~1000:1, preferably 2:1~1000:1, further preferably 5:1~
1000:1。
1.4 heat-drying step
Heat-drying step is that the aqueous gel shape cross-linked polymer is subject to drying, forms polymer.It is dry usual
It is carried out at a temperature of 60~300 DEG C as heating medium temperature, preferably 100~250 DEG C, more preferable 120~220 DEG C.It is dry
The dry time depends on surface area and the water content of polymer and drier type, is selected to obtain target water content (aqueous
Amount is by 105 DEG C of dry 3 hours weightless measurements).
Water content for water-absorbing resin of the present invention is not particularly limited, more preferable 0.2~30 weight % of water content, into one
Walk preferably 0.3~15 weight %, particularly preferred 0.5~10 weight %.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.
1.5 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 dry post-crosslinking polymer 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 is 0~8 weight
Measure %, preferably 0~5 weight %, more preferable 0~2 weight %.In addition, the fewer diameter the better higher than 850 microns of particle fraction,
It controls as 0~8 weight %, preferably 0~5 weight %, more preferable 0~2 weight %.It is in the present invention, it is preferred to micro- 150~850
The ratio of the particle of rice carries out surface-crosslinked under conditions of being more than 95 weight %, more preferably more than 98 weight %.Granularity point
The logstandard deviation (σ ζ) of cloth is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20~
0.36。
The recycling of 1.6 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.
It is 1.7 surface-crosslinked
In the manufacturing method of the present invention, it further includes using surface crosslinking agent to the water-absorbing resins surface after Sieving and casing
Nearby carry out the step of surface treatment forms covalent bond.By carrying out surface-crosslinked step to the water-absorbing resins after Sieving and casing
Suddenly, the water absorbent rate and permeability for liquids under resin pressurization can effectively be promoted.But for the present invention water-absorbing resin from
Heart water holding capacity (CRC), compared to having and reducing to a certain degree before crosslinking, is original centrifuge retention capacity after surface-crosslinked
50~95%, it is further reduced to 60~90%.The reduction degree of centrifuge retention capacity can by the type and dosage of crosslinking agent,
Reaction temperature and time adjustment.
The surface-crosslinked processing of the present invention means to increase the operation of crosslink density near particle surface.More specifically
It says, it is that by being added in molecule in particle surface there are at least two compounds of functional group that can be reacted with carboxyl to be formed
New crosslinked operation, the compound can be by forming key with the carboxyl included in particulate water-absorbing resin or its reactant salt
It closes.The surface crosslinking agent that this step uses is preferably able to form covalent bond or ionic bond with water-absorbing resins surface functional group
Surface crosslinking agent.
As the surface crosslinking agent that can be used in this step, preferably for example：It is polyol compound, epoxide, more
Amine compounds or with the condensation product, oxazoline compounds of its halogenated epoxy compound, (mono-, di- or poly-) oxazoles pyridine ketone compound,
Carbonic acid alkane diester compound.It specifically includes：Polyalcohol such as polyethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, a contracting dipropyl two
Alcohol, 2,3,4- trimethyl -1,3- pentanediols, polypropylene glycol, glycerine, polyglycereol, 2- butylene-1,4-diols, 1,4- butanediols, 1,
3- butanediols, 1,5- pentanediols, 1,6-HD, 1,2- cyclohexanedimethanols etc.；Epoxide such as ethylene glycol two shrinks sweet
Oily ether, Polyethylene Glycol Bisglycidyl Ether, glycidol etc.；Multivalence amine compounds such as ethylenediamine, diethylenetriamines, triethylene
Tetramine, tetren, penten, polyethyleneimine etc.；Halogenated epoxide such as epoxychloropropane, epoxy bromine
Propane, Alpha-Methyl epoxychloropropane etc.；The condensation product of multivalence amine compounds and halogenated epoxide；Oxazolidinone compounds example
Such as 2- oxazolidones；Ring urea；Alkylene carbonate compound is such as ethylene carbonate.They can be used alone or a variety of
It is used in combination.To give full play to the effect of the present invention, it is preferable to use polyol compound and epoxide combination.As polynary
Alcohol, the preferably polyalcohol with 2~10 carbon atoms, the further preferably polyalcohol with 3~8 carbon atoms.
The dosage of surface crosslinking agent depends on using type of crosslinking agent and a combination thereof, is preferably based on water-absorbing resin 0.01
~10 weight %, more preferable 0.05~5 weight %.
In the present invention is surface-crosslinked, use of water is preferred for the solvent of surface crosslinking agent.The dosage of water depends on surface-crosslinked
The water content of agent effective ingredient consumption and water-absorbing resin, is preferably based on water-absorbing resin 0.2~20 weight %, more preferable 0.3~
15 weight %, further preferred 0.5~10 weight %.In addition, hydrophilic organic solvent can be used to be used in mixed way with water, when using
During hydrophilic organic solvent, preferable organic solvent dosage is based on water-absorbing resin 0~10 weight %, more preferable 0~8 weight %, into
One step preferably 0~5 weight %.
It is preferred that surface crosslinking agent is pre-mixed in water and/or hydrophilic organic solvent, then to by treatment fluid spraying or
It is added dropwise to water-absorbing resin, more preferable spray method.The mean droplet size of the spraying is preferably 0.1~500 micron, more preferably
0.1~200 micron.
After surface crosslinking agent is added to water-absorbing resin, preferably it is heat-treated.It is 100~220 to be surface-treated temperature
DEG C, preferably 130~210 DEG C, further preferred 160~200 DEG C, heating time is preferably 1 minute~2 hours.
1.8 chelating agent
By adding in chelating agent, the time course point derived from component in urine with the water absorbing agent of Fe ionic reactions can inhibit
Solution, equally can inhibit the dissolving of water absorbing agent, reduces the absorptivity of water absorbing agent, reduce the permeability for liquids of water absorbing agent.Chelating agent exists
Following one or more times add in：(1) during polymerization；(2) after polymerisation with it is surface-crosslinked before；(3) on surface
During crosslinking；(4) during agglomeration.
Chelating agent for water absorbing agent of the present invention is preferably to have high sealing ability or sequestering power to Fe or Cu ions
Chelating agent, preferably amino polyvalent carboxylic acid and its salt particularly preferably have the amino carboxylic acid and its salt of no less than 3 carboxyls.
It is 0.00001~10wt%, preferably 0.0001~1wt% that the dosage of amino polyvalent carboxylic acid, which is based on water-absorbing resin,.
1.9 inorganic powder
By adding in inorganic powder, the permeability for liquids of water-absorbing resin can be effectively promoted, preferably inorganic powder is average grain
SiO 2 powder of the diameter below 100 nanometers.The inorganic powder additive amount in terms of water-absorbing resins, be 0.001~
10wt%, preferably 0.005~1wt%, further preferred 0.01~0.5wt%.
1.10 other additives
Other auxiliary agents can be added in water-absorbing resins as needed, including：Oxidant, antioxidant, reducing agent, face
The water-insolubles such as colouring stabilizer, water, polyvalent metal compounds, metallic soap are inorganic or organic dust, deodorant, antiseptic, paper pulp
Or thermoplastic fibre etc..
[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 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) to the sodium-chloride water solution of 0.9 weight % is preferably 10~60g/g, more preferably
20~55g/g, further preferably 25~50g/g, especially preferably 25~45g/g.For absorbability.CRC gets over Gao Yue
It is good, but need to be balanced with other physical property as the case may be in actual use.
2.2 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 10~
50sec/g.Water absorbing agent of the infiltration rate more than 60sec/g may not achieve the effect that enough.
2.3 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
~8 weight %, preferably 0~5 weight %, more preferable 0~2 weight %.In addition, diameter is fewer higher than 850 microns of particle fraction
It is better, it controls as 0~8 weight %, preferably 0~5 weight %, more preferable 0~2 weight %.In the present invention, it is preferred to 150~
The ratio of 850 microns of particle carries out surface-crosslinked under conditions of being more than 95 weight %, more preferably more than 98 weight %.Grain
The logstandard deviation (σ ζ) of degree distribution is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20
~0.36.
2.4 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 1~10 weight %, more preferable 2~10 weight %.
[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 30~100 weight %, preferably 40~100 weight %, more preferably 50~100 weight %, further preferably 60~
100 weight %.
[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 0.90 weight %'s
Sodium-chloride water solution.
4.1 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) is represented under no pressurization to 0.90 weight % sodium-chloride water solutions (also referred to as physiology food
Brine) water absorbent rate that is centrifuged after water suction 30 minutes.
0.20 gram of water-absorbing resins is weighed, record weight is W0(g), it is uniformly 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 W of bag is measured after the similar operations of water absorbing agent1(g).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
4.2 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.
4.3 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.
Large face plate and each empty sieve (being accurate to 0.1 gram) weight, and record.In the correct order (850 microns, 600
Micron, 300 microns, 150 microns, 45 microns) sieve is placed to (fine the bottom of, coarse upper) on the oscillator.Claim
It takes in 100 grams of (being accurate to 0.1 gram) samples to beaker to be tested, m1.Load weighted sample is poured into uppermost sieve.It presses
Sifter cap on the indicating cover of manufacturer.Oscillator is sieved by following parameter setting：Oscillation intensity 70 ± 2% is (according to Retsch VE
The setting of 1000 oscillators), 1.0 millimeters of amplitude, duration of oscillation 10 minutes.Open vibrator, after ten minutes by each sieve and
Pallet is carefully removed and is weighed respectively, is accurate to 0.01 gram, m2.The percentage (w) for calculating every section of sample 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 is respectively the grain size of R=84.1% weight and R=15.9% weight
4.4 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.
Weigh about 1 gram of water-absorbing resin (weight W7[g]) it is placed in measuring cup (weight W6[g]) in 105 DEG C of calm drying
3 hours are stood in machine, is subject to drying.Measure total weight (W of dried measuring cup and particulate water-absorbing resin8[g]), root
It is calculated according to the following formula.
Water content [weight %]={ (W8-W6-W7)/W7}×100。
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.In addition, by delivery pump by the sodium persulfate aqueous solution (flow 60kg/h) of a concentration of 4wt%
It is delivered in monomer by monomer solution pipeline branch mouth, initiated polymerization.Reaction solution is sprayed onto reaction bed, obtains aqueous gel shape
Polymer.
Embodiment 1
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (6 millis is in orifice plate aperture
Rice) it repeats to be crushed the fine grained gel for twice, obtaining that there is rough surface, the fine grained gel proportions with rough surface
More than 90%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is obtained
To cross-linked structure polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtains grain
The water imbibition that diameter is 300~425 microns, moisture 3.2wt%, CRC 41.3g/g, swirl method infiltration rate are 39sec/g
Resin.
Embodiment 2
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (6 millis is in orifice plate aperture
Rice) it repeats to be crushed the fine grained gel for three times, obtaining that there is rough surface, the fine grained gel proportions with rough surface
More than 90%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is obtained
To cross-linked structure polymer (100~200 microns of aperture).Particulate is carried out to dry post-crosslinking polymer using broken cooking machine
Change, and sieved, acquisition grain size is 300~425 microns, moisture 3.1wt%, CRC 40.3g/g, swirl method absorb
Speed is the water-absorbing resins of 35sec/g.
Embodiment 3
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (6 millis is in orifice plate aperture
Rice) it repeats to be crushed four times, the fine grained gel with rough surface is obtained, the fine grained gel proportions with rough surface
More than 95%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is obtained
To cross-linked structure polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtains grain
The water imbibition that diameter is 300~425 microns, moisture 3.0wt%, CRC 41.1g/g, swirl method infiltration rate are 33sec/g
Resin.
Embodiment 4
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (4 millis is in orifice plate aperture
Rice) it is crushed once, the fine grained gel with rough surface is obtained, the fine grained gel proportions with rough surface are more than
80%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is handed over
Join structural polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.6wt%, CRC 42.5g/g, swirl method infiltration rate be 41sec/g water imbibition tree
Fat.
Embodiment 5
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (4 millis is in orifice plate aperture
Rice) the fine grained gel for three times, obtaining that there is rough surface is crushed, the fine grained gel proportions with rough surface are more than
90%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is handed over
Join structural polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.0wt%, CRC 41.5g/g, swirl method infiltration rate be 33sec/g water imbibition tree
Fat.
Embodiment 6
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (8 millis is in orifice plate aperture
Rice) it is crushed four times, the fine grained gel with rough surface is obtained, the fine grained gel proportions with rough surface are more than
90%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is handed over
Join structural polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.1wt%, CRC 42.6g/g, swirl method infiltration rate be 37sec/g water imbibition tree
Fat.
Comparative example 1
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (8 millis is in orifice plate aperture
Rice) it is crushed once, the fine grained gel with rough surface is obtained, the fine grained gel proportions with rough surface are less than
10%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is handed over
Join structural polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtaining grain size is
300~425 microns, moisture 4.5wt%, CRC 44.6g/g, swirl method infiltration rate be 52sec/g water imbibition tree
Fat.
Comparative example 2
Aqueous gel shaped polymer in Production Example 1 (water content~50wt%) is taken, using meat grinder, (8 millis is in orifice plate aperture
Rice) the fine grained gel for twice, obtaining that there is rough surface is crushed, the fine grained gel proportions with rough surface are less than
15%.And gel particle is spread over and is dried on woven wire, drying temperature is 190 DEG C, and the time is 40 minutes, is handed over
Join structural polymer.Grain refined is carried out, and sieved to dry post-crosslinking polymer using broken cooking machine, obtaining grain size is
300~425 microns, moisture 3.9wt%, CRC 42.5g/g, swirl method infiltration rate be 45sec/g water imbibition tree
Fat.
By Examples 1 to 6 and comparative example 1,2 it is found that can have to the shear strength of gel by controlling in granulation process
The degree of roughness of effect control gel surface, and then the rate of liquid aspiration of end article is influenced, water-absorbing resins can be substantially improved
Infiltration rate is to 33sec/g.
Therefore, the suction with high speed rate of liquid aspiration can efficiently be produced without using additive the present invention provides one kind
The method of water-base resin, and obtain a kind of water-absorbing resins with high speed rate of liquid aspiration.
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 (9)
1. a kind of manufacturing method of the water-absorbing resins with high rate of liquid aspiration, which is characterized in that it includes the following steps：
(a) it obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,
(b) unsaturated acrylic monomer will be contained and cross-linking agent aqueous solution monomer polymerize, and obtain the crosslinking of aqueous gel shape
The step of polymer,
(c) aqueous gel shape cross-linked polymer is granulated in the course of the polymerization process or after polymerization through high shear and/or squeezing action power
The step of being ground into gel particle,
(c1) the aqueous gel shaped polymer water content is 20~60wt%,
(c2) the high shear forces power and/or squeezing action power are twisted by increasing the resistance to flow output of Minced Steak machine baffle and/or being promoted
Meat machine screw speed and length and/or repeatedly granulation provide,
(c3) gel particle after the granulation with micro-roughened surface and clear gel granular mass ratio are 1:1~
1000:1,
(d) the step of being thermally dried to the gel particle after crushing,
(e) the step of grain refined being carried out to dry post-crosslinking polymer and being sieved.
2. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that described
The aqueous solution of unsaturated acrylic monomer and crosslinking agent is the water soluble salt of acrylic acid and/or acrylic acid as the mixed of principal component
Close solution.
3. the manufacturing method of the water-absorbing resins according to claim 1 or 2 with high rate of liquid aspiration, which is characterized in that
The unsaturation acrylic monomer and cross-linking agent aqueous solution a concentration of 20~60wt%, preferably 30~55wt%, it is further excellent
Select 35~50wt%.
4. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that described
Crosslinking agent is selected from intramolecular contains the compound of multiple vinyl, intramolecular contains at least one vinyl compound and at least one
It is a can have with the compound for the functional group that carboxyl reacts on the unsaturated monomer, intramolecular it is multiple can with it is described unsaturated single
It is one or more in the compound for the functional group that carboxyl reacts on body.
5. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that described
In the step of monomer solution is polymerize, polymerization start temperature is 20~120 DEG C.
6. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that described
High shear forces power and/or squeezing action power by change meat grinder outlet damper aperture, gel strength, the dosage for being granulated water and
Temperature, screw speed and length are repeatedly granulated offer.
7. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that gel
By high shear forces power and/or squeezing action power, it is 50~100% that original surface topography, which destroys ratio,.
8. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that be granulated
Gel particle surface afterwards forms coarse surface.
9. the manufacturing method of the water-absorbing resins according to claim 1 with high rate of liquid aspiration, which is characterized in that described
Gel particle and clear gel granular mass ratio after granulation with micro-roughened surface are 1:1~1000:1, preferably 2:1
~1000:1, further preferably 5:1~1000:1.
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Cited By (4)
| 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 |
| CN112011007A (en) * | 2020-07-28 | 2020-12-01 | 浙江卫星新材料科技有限公司 | High water absorption resin capable of multiple absorption and preparation method thereof |
| CN113544166A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles, method for producing same, absorbent body, and absorbent article |
| CN113543877A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles, absorbent body, absorbent article, method for measuring liquid flow retention rate of water-absorbent resin particles, and method for producing water-absorbent resin particles |
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2017
- 2017-12-22 CN CN201711407444.7A patent/CN108178816A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113544166A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles, method for producing same, absorbent body, and absorbent article |
| CN113543877A (en) * | 2019-03-08 | 2021-10-22 | 住友精化株式会社 | Water-absorbent resin particles, absorbent body, absorbent article, method for measuring liquid flow retention rate of water-absorbent resin particles, and method for producing water-absorbent resin particles |
| 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 |
| CN112011007A (en) * | 2020-07-28 | 2020-12-01 | 浙江卫星新材料科技有限公司 | High water absorption resin capable of multiple absorption and preparation method thereof |
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Application publication date: 20180619 |
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