CN106279494A - A kind of acrylic absorbent resin of high rate of liquid aspiration and its production and use - Google Patents
A kind of acrylic absorbent resin of high rate of liquid aspiration and its production and use Download PDFInfo
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- CN106279494A CN106279494A CN201510237299.7A CN201510237299A CN106279494A CN 106279494 A CN106279494 A CN 106279494A CN 201510237299 A CN201510237299 A CN 201510237299A CN 106279494 A CN106279494 A CN 106279494A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- 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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- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The invention provides acrylic absorbent resin of a kind of high rate of liquid aspiration and its production and use.Wherein, the raw material preparing described acrylic absorbent resin includes: mass ratio is (25 45): (7 22): the acrylic acid of (33 68), alkali and water, and based on acrylic acid quality meter, cross-linking agent: 0.001 1wt%；High temperature resistant foaming agent: 0.01 2wt%；Comonomer: 0 10wt%；Reducing agent: 30 500ppm；Initiator: 0.001 1wt%.The rate of liquid aspiration of described acrylic absorbent resin is 15 40s.Described water-absorbing resin can be used in the aspects such as health industry diaper, baby diapers and sanitary towel as imbibition material, it is also possible to for industries such as control of desert, Water in Water Shutoff in Oil Field and agricultural water conservations as water suction and water-storage material.
Description
Technical field
The present invention relates to chemical field, it is more particularly related to the water suction tree of a kind of high rate of liquid aspiration
Fat and its production and use.
Background technology
High hydrophilous resin is a kind of cross-linked network macromolecule containing a large amount of highly polar groups, the earliest by Fanta etc.
Starch-grafted polyacrylonitrile is used to prepare through saponification again.From the sixties in last century so far, High hydrophilous resin is
It is able to general development in the whole world, two big classes can be divided into by raw material: the first kind is natural polymer, as formed sediment
Powder, cellulose；Equations of The Second Kind is synthesis macromolecule, such as polyacrylic acid, polyoxyethylene, polyvinyl alcohol, wherein
The High hydrophilous resin of current more than 80% is to be formed by polymerizable acrylic monomer.Owing to crosslinked acrylic acid is inhaled
Water-resin has network structure, so it can absorb the pure water of sole mass hundreds times even thousand times, and pins
Moisture does not oozes out.Therefore, acrylic absorbent resin is widely used in the health row such as baby diapers, diaper
Industry, also has certain applications in the industries such as agricultural water conservation, control of desert, Water in Water Shutoff in Oil Field simultaneously.
Health industry has the highest requirement to acrylic absorbent resin performance, and one of them is exactly rate of liquid aspiration,
Require that diaper sponges baby or adult's urine at short notice, and only possess the propylene of high rate of liquid aspiration
Acid water-absorbing resin could meet this requirement.In order to improve rate of liquid aspiration, general principle is to increase water-absorbing resin
Specific surface area, concrete grammar is: (1) add porogen, can decompose in course of reaction and discharge gas,
Such as sodium bicarbonate, azodiisobutyronitrile etc.；(2) low-boiling point liquid is added, easily by steam in course of reaction
Change, such as ethanol, normal propyl alcohol etc..But owing to acroleic acid polymerization heat release makes system temperature higher, in this condition
Bubble produced by lower first method is difficult to stable existence, easy coalescence under high temperature, ruptures；The second side
The pore that method is formed is limited, because moisture volatilizees in a large number in polymerization process, also can stay big in gel
Pore, rather than tiny micropore.Therefore, it is difficult to significantly improve acrylic acid by both the above method merely inhale
The rate of liquid aspiration of water-resin.
Recently, it is thus proposed that prepared by the initiation method or polymerization changing acroleic acid polymerization and there is height
The acrylic absorbent resin of rate of liquid aspiration.China's publication CN103360555A proposes to use electron beam spoke
The method penetrating crosslinking prepares polymer gel, is then passed through extraction and freezes and obtain High hydrophilous resin with lyophilization.In
State's publication CN103408689A proposes the synthetic method of a kind of wink suction type High hydrophilous resin, the method
It is by acrylic monomers aqueous dispersion uses in oil phase inverse emulsion polymerization prepare water-absorbing resin.This
A little methods or because technical sophistication and energy consumption are big and be difficult to industrialization, or do not meet because of inadequate environmental protection
Industry future developing trend, so being all difficult to the rate of liquid aspiration of effective raising acrylic absorbent resin,
Meet the market demand.
Summary of the invention
An object of the present invention is to provide a kind of acrylic absorbent resin possessing high rate of liquid aspiration, uses
The mixture of conventional surfactants and animal and vegetable protein surfactant compound as high temperature resistant foaming agent, this
Plant foaming agent not only foamability strong, and high temperature bubble is stable, thus overcome conventional hole forming technology institute
The bubble produced is difficult to the drawback of stable existence under the hot environment of thermal-initiated polymerization, so can be effectively improved
The specific surface area of acrylic absorbent resin.Owing to this water absorbing resin particle surface does not contain only a large amount of hydrophilic group,
And possibly together with a large amount of small pores inside it, therefore, its rate of liquid aspiration is significantly better than suction in the market
Water-resin product, is suitable in health product, meets the market demand.
For achieving the above object, technical scheme provided by the present invention is as follows:
The acrylic absorbent resin of a kind of high rate of liquid aspiration, wherein, the raw material preparing it includes: mass ratio is
(25-45): (7-22): the acrylic acid of (33-68), alkali and water, also include: based on acrylic acid quality meter,
Cross-linking agent: 0.001-1wt%, preferably 0.005-0.8wt%, more preferably 0.01-0.5wt%；
High temperature resistant foaming agent: 0.01-2wt%, preferably 0.05-1.8wt%, more preferably 0.1-1.6wt%；
Comonomer: 0-10wt%, preferably 0.01-9wt%, more preferably 0.1-8wt%；
Reducing agent: 30-500ppm, preferably 40-400ppm, more preferably 50-300ppm；
Initiator: 0.001-1wt%, preferably 0.005-0.8wt%, more preferably 0.01-0.5wt%；
In one embodiment of the invention, the rate of liquid aspiration of the acrylic absorbent resin of above-mentioned high rate of liquid aspiration
For 15-40s, preferably 18-35s, more preferably 20-32s.
In one embodiment of the invention, described alkali is sodium hydroxide.
In one embodiment of the invention, described cross-linking agent is ethylene glycol, propylene glycol, glycerol, poly-second two
Alcohol, Ethylene glycol diglycidyl ether, ethoxylated glycerol triacrylate, N,N methylene bis acrylamide,
One in polyethyleneglycol diglycidylether, pentaerythritol triacrylate and pentaerythritol triallyl ether
Or two or more, preferably pentaerythritol triacrylate.
In one embodiment of the invention, described high temperature resistant foaming agent is to comprise conventional surfactants and move
The compounding foaming agent of vegetable protein surfactant, conventional surfactants and animal and vegetable protein surfactant
Mass ratio be 6～9:1～4.
In one embodiment of the invention, described conventional surfactants be sodium lauryl sulphate, 12
Sodium alkyl sulfonate, polyoxyethylenated alcohol sodium sulfate, dodecylbenzene sodium sulfonate, span (Span) and
One or two or more in tween (Tween), preferably sodium dodecyl sulfate；Described animal and vegetable protein
Surfactant is the one in sodium abietate, tea saponin, saponin, hydrolysis of animal hoof tips and hydrolysis blood glue
Or two or more, preferably saponin.
In one embodiment of the invention, described comonomer is the cationic ethylene base with charged group
One or more in monomer and anionic vinyl monomer, preferably sodium allylsulfonate, metering system sulphur
Acid sodium, 2-acrylamide-2-methyl propane sulfonic, acrylyl oxy-ethyl-trimethyl salmiac, methacryloxypropyl
One or two or more in ethyl-trimethyl salmiac and dimethyl diallyl ammonium chloride, more preferably
Sodium allylsulfonate.
In one embodiment of the invention, described reducing agent is sodium sulfite, sodium sulfite, secondary phosphorous
One or two or more in acid sodium and ascorbic acid, preferably sodium sulfite；Described initiator is persulfuric acid
One or two or more in ammonium, sodium peroxydisulfate, potassium peroxydisulfate and hydrogen peroxide, initiator system of ammonium persulfate.
In one embodiment of the invention, in one embodiment of the invention, prepare acrylic water-absorbent tree
The raw material of fat also includes surface crosslinking agent；Alternatively, water soluble polymer is also included.
Wherein, described surface crosslinking agent is by water, polyhydric alcohol, glycidyl ether, ethylene carbonate, carbonic acid third
One or two or more composition in alkene ester and polyvalent metal compounds；Wherein, described polyhydric alcohol include but
Be not limited to ethylene glycol, propylene glycol or glycerol, described polyvalent metal compounds include but not limited to aluminum chloride,
Magnesium chloride, aluminum sulfate or calcium chloride；Described water soluble polymer is Polyethylene Glycol, polyvinyl alcohol, polypropylene
One or two or more in amide and polyvinylpyrrolidone, preferably polyethylene alcohol.
In one embodiment of the invention, described water is preferably deionized water.Wherein, a part of water is used as
Acrylic acid solvent, another part water is used as the solvent of sodium hydroxide.
Another object of the present invention is to provide the preparation side of the acrylic absorbent resin of above-mentioned high rate of liquid aspiration
Method.
The method preparing aforesaid propylene acid water-absorbing resin comprises the steps:
A) acrylic acid is dissolved in water and forms acrylic acid aqueous solution, with alkali liquor, acrylic acid aqueous solution is neutralized,
To containing acrylic acid incomplete neutralizer；
B) in the neutralizer of step a) gained, add cross-linking agent, high temperature resistant foaming agent and reducing agent, optionally add
Enter comonomer, add initiator after mix homogeneously, carry out aqueous solution polymerization, obtain hydrogel；
C) hydrogel of step b) gained is shredded, after drying, broken, screening, obtain primary acrylic water-absorbent
Resin；
D) surface crosslinking agent is used to carry out surface-crosslinked, then by the primary acrylic absorbent resin of step c) gained
Optionally spray water soluble polymer aqueous solution at particle surface, obtain acrylic absorbent resin.
Wherein in an embodiment, alkali liquor used in the step a) of preparation method of the present invention is hydroxide
Sodium water solution, concentration of lye is 30-50wt%；The quality of acrylic acid, sodium hydroxide and water three in step a)
Than for (25-45): (7-22): (33-68), in step a), acrylic acid degree of neutralization is 50-90%.
It was found by the inventors of the present invention that in described neutralizer, the concentration of acrylic acid aqueous solution is the lowest will cause step
Rapid polyreaction b) is slow, and the hydrogel water content obtained is high, certainly will extend drying time, energy consumption
Increase；When excessive concentration then can cause step a) to neutralize, sodium acrylate separates out, and polyreaction is violent,
Heat is difficult to distribute, and has the danger that implode occurs.
Wherein in an embodiment, the step b) of preparation method of the present invention can add or without altogether
Poly-monomer, described comonomer is cationic vinyl monomer and the anionic vinyl list with charged group
One or two or more in body, preferably sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide
-2-methyl propane sulfonic acid, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride
With the one or two or more in dimethyl diallyl ammonium chloride, more preferably sodium allylsulfonate.This
When class comonomer is aggregated in acrylic absorbent resin network, polymeric electrostatic effect can be produced, promote solidifying
Glue expands water absorption course.
Wherein, comonomer addition is the 0-10% relative to acrylic monomers quality；Preferably 0.01-9wt%,
More preferably 0.1-8wt%.
Wherein in an embodiment, the cross-linking agent described in the step b) of preparation method of the present invention is second two
Alcohol, propylene glycol, glycerol, Polyethylene Glycol, Ethylene glycol diglycidyl ether, ethoxylated glycerol three acrylic acid
Ester, N,N methylene bis acrylamide, polyethyleneglycol diglycidylether, pentaerythritol triacrylate and
One or two or more in pentaerythritol triallyl ether, preferably pentaerythritol triacrylate.Crosslinking
The addition of agent is the 0.001-1% relative to acrylic monomers quality；Preferably 0.005-0.8wt%, more preferably
0.01-0.5wt%.
Wherein in an embodiment, the initiator described in the step b) of preparation method of the present invention is over cure
One or two or more in acid ammonium, sodium peroxydisulfate, potassium peroxydisulfate and hydrogen peroxide, initiator system of ammonium persulfate.
The addition of initiator is the 0.001-1% relative to acrylic monomers quality；Preferably 0.005-0.8wt%, more
Preferably 0.01-0.5wt%.
Wherein in an embodiment, the high temperature resistant foaming agent described in the step b) of preparation method of the present invention
It is the compounding foaming agent comprising conventional surfactants and animal and vegetable protein surfactant, both mass ratioes
It is 6～9:1～4.The addition of high temperature resistant foaming agent is the 0.01-2% compared to acrylic acid quality；Preferably
0.05-1.8wt%, more preferably 0.1-1.6wt%.
Described conventional surfactants is including but not limited to sodium lauryl sulphate, dodecyl sodium sulfate, fat
In fat polyoxyethylenated alcohol sodium sulfate, dodecylbenzene sodium sulfonate, Span and Tween one or both or
Multiple, preferably sodium dodecyl sulfate.
Described animal and vegetable protein surfactant is including but not limited to sodium abietate, tea saponin, saponin, water
Solve the one or two or more in animal hoof and foot and hydrolysis blood glue, preferably saponin.
The high temperature resistant foaming agent that the present invention uses, in addition to comprising the surfactant of routine, also introduces dynamic
Vegetable protein surfactant, under stirring, not only foamability is strong, and high temperature bubble can be grown
Time stable existence, so still can produce a large amount of Minute pores, greatly in gel under the hot environment of polymerization
Improve greatly the specific surface area of acrylic absorbent resin granule.
Wherein in an embodiment, the reducing agent described in the step b) of preparation method of the present invention is sulfurous
One or two or more in acid sodium, sodium sulfite, sodium hypophosphite and ascorbic acid, preferably sulfurous
Acid sodium.The addition of reducing agent is the 30-500ppm relative to acrylic acid quality；Preferably 40-400ppm, more
Preferably 50-300ppm.
By regulating the consumption of reducing agent, the gel cream time that can reach to control reactant liquor is 5-100s,
It is preferably 6-50s, more preferably 8-30s.
In preparation method of the present invention, the consumption of reducing agent is the most small, much smaller than in conventional oxidation reduction system
The required consumption using reducing agent, it simply promotes that a small amount of initiator produces free radical, shortens thermal-initiated polymerization
Induction period, therefore this had both been different from traditional redox initiation system, also different from thermal initiation purely
System, but between.
Wherein in an embodiment, the polymerization temperature of the step b) of preparation method of the present invention is 40-90 DEG C,
Polymerization time is 3-30min.
Wherein in an embodiment, the hydrogel described in the step c) of preparation method of the present invention is chopped into
After size be 4-14mm；Baking temperature is 100-200 DEG C；Drying time is 40-200min, preferably
80-180min。
Wherein in an embodiment, in the step c) of preparation method of the present invention, the primary acrylic acid of gained is inhaled
Water-resin particle size range is 100-800 μm.
Wherein in an embodiment, with primary acrylic water-absorbent tree in the step d) of preparation method of the present invention
It is water, polyhydric alcohol, glycidyl ether, ethylene carbonate, carbonic acid that fat carries out surface-crosslinked surface crosslinking agent
One or two or more in propylene and polyvalent metal compounds.The consumption of surface crosslinking agent be relative to
The 2-8% of the primary acrylic absorbent resin quality of step c).Described surface-crosslinked reaction temperature is
100-200 DEG C, the response time is 10-100min.
Wherein, described polyhydric alcohol includes but not limited to ethylene glycol, propylene glycol or glycerol, polyvalent metal chemical combination
Thing includes but not limited to aluminum chloride, magnesium chloride, aluminum sulfate or calcium chloride.
Wherein in an embodiment, in the step d) of preparation method of the present invention, can add or without
Water soluble polymer, described water soluble polymer is Polyethylene Glycol, polyvinyl alcohol, polyacrylamide and gathers
One or two or more in vinylpyrrolidone, preferably polyethylene alcohol.This type of water soluble polymer all contains
There is substantial amounts of hydrophilic polar group, be coated to after acrylic absorbent resin surface carries out hydrophilic strengthening, energy
Greatly speed up the wet processes before acrylic absorbent resin particulate water absorbent.The addition of described water soluble polymer
0-10% for the primary acrylic absorbent resin powder quality relative to step c).
Wherein in an embodiment, the acrylic water-absorbent tree obtained in the step d) of preparation method of the present invention
Fat granule footpath is 100-800 μm, preferably 300-500 μm.Wherein, the rate of liquid aspiration of acrylic absorbent resin is
15-40s, preferably 18-35s, more preferably 20-32s.
It is also another object of the present invention to provide a kind of acrylic absorbent resin for health industry diaper, baby
The aspects such as youngster's diaper and sanitary towel are as imbibition material, and protect for control of desert, Water in Water Shutoff in Oil Field and agricultural
The industries such as water are as water suction and the purposes of water-storage material.
According to technique scheme, the present invention compared with prior art has the advantage that
(1) a kind of novel high temperature resistant foaming agent is incorporated in the preparation process of acrylic absorbent resin, this
Plant foaming agent not only foamability strong, and high temperature bubble is stable, thus overcome conventional hole forming technology institute
The bubble produced is difficult to the drawback of stable existence under the hot environment of thermal-initiated polymerization, so can be effectively improved
The specific surface area of acrylic absorbent resin.
(2) on the basis of thermal initiation, use the reducing agent of denier (only relative to acrylic acid quality
30-500ppm), the gel cream time of regulation reactant liquor, be conducive to controlling process and the gel of polyreaction
In air vent content.
(3) add charged cation or anionic vinyl comonomer the most alternatively, increase
Permeable pressure head inside and outside gel network when the electrostatic effect of strong acrylic absorbent resin and water suction, promotes that gel is inhaled
Water expansion process.
(4) after surface-crosslinked, alternatively water soluble polymer is coated to the table of acrylic absorbent resin
Face, carries out hydrophilic strengthening, helps lend some impetus to the wet processes before particulate water absorbent.
Due to above technological merit, the wet processes before acrylic absorbent resin water suction is accelerated, suction during water suction
Water process is also accelerated, so the acrylic absorbent resin using the method to prepare possesses high rate of liquid aspiration, energy
Meet the strict demand to product rate of liquid aspiration of the health product industry market very well.
Detailed description of the invention
In order to be better understood from the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but this
The content of invention is not limited solely to the following examples.
Embodiment 1
A) in the reactor with high-speed stirring apparatus, 1250g acrylic acid and 3020g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 730g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, add 3.125g pentaerythritol triacrylate, 0.125g foaming
Agent and 0.0375g sodium sulfite, foaming agent is 9:1 by dodecyl sodium sulfate and sodium abietate in mass ratio
Formulated, after being uniformly mixed, reactant liquor is added rapidly in polymerization tank, and is simultaneously introduced 25g
The 10wt% ammonium persulfate aqueous solution prepared, obtains hydrogel after polyreaction 20min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 8-14mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent consumption and step c)
The proportioning at end is 5:100 (mass ratio, lower same).In high speed rotating blender, want according to aforementioned proportion
Ask the surface that surface crosslinking agent is uniformly sprayed onto primary acrylic absorbent resin powder, after stirring mixing 5min,
Acrylic absorbent resin powder is put into 180 DEG C of baking ovens, takes out, after screened machine classification after heating 60min
I.e. obtaining acrylic absorbent resin product, size is 400-700 μm.
Embodiment 2
A) in the reactor with high-speed stirring apparatus, 2250g acrylic acid and 460g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 2290g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, 1.125g N,N methylene bis acrylamide, 45g foaming agent are added
With 1.125g sodium sulfite, it is formulated that foaming agent is pressed 6:4 by sodium lauryl sulphate and saponin, stirring
After mix homogeneously, reactant liquor is added rapidly in polymerization tank, and be simultaneously introduced that 67.5g has prepared 10%
Ammonium persulfate aqueous solution, obtains hydrogel after polyreaction 5min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 6-12mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 7:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out, i.e. obtain acrylic water-absorbent tree after screened machine classification after heating 60min
Fat prod, size is 300-500 μm.
Embodiment 3
A) in the reactor with high-speed stirring apparatus, 1500g acrylic acid and 2200g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1300g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained add 4.5g polyethyleneglycol diglycidylether, 6g foaming agent and
0.12g sodium sulfite, it is formulated that foaming agent is pressed 7:3 by dodecylbenzene sodium sulfonate and tea saponin, stirs
After mixing mix homogeneously, reactant liquor is added rapidly in polymerization tank, and be simultaneously introduced that 48g has prepared 10%
Ammonium persulfate aqueous solution, obtains hydrogel after polyreaction 8min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 4-10mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 4:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out after heating 60min, are used by the Aqueous Solutions of Polyethylene Glycol that concentration is 10% while hot
Aerosol apparatus sprays to toner surface, carries out hydrophilic strengthening, Aqueous Solutions of Polyethylene Glycol and toner
Proportioning is 4:100, and last screened machine classification i.e. obtains acrylic absorbent resin product, and size is
100-600μm。
Embodiment 4
A) in the reactor with high-speed stirring apparatus, 1700g acrylic acid and 1920g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1380g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, 25.5g methylpropene sodium sulfonate comonomer, 3.4g ethoxy are added
Nitro triacrylate, 3.4g foaming agent and 0.085g sodium hypophosphite, foaming agent is by fatty alcohol polyoxy
It is formulated that vinyl Ether sodium sulfate and hydrolysis of animal hoof foot press 6:4, after being uniformly mixed, reactant liquor is quick
Join in polymerization tank, and be simultaneously introduced 10% ammonium persulfate aqueous solution that 51g has prepared, polyreaction
Hydrogel is obtained after 18min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 6-12mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 6:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out, i.e. obtain acrylic water-absorbent tree after screened machine classification after heating 60min
Fat prod, size is 300-800 μm.
Embodiment 5
A) in the reactor with high-speed stirring apparatus, 1900g acrylic acid and 1670g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1430g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained add 19g 2-acrylamide-2-methyl propane sulfonic comonomer,
2.85g pentaerythritol triallyl ether, 5.7g foaming agent and 0.19g ascorbic acid, foaming agent is by dodecyl
It is formulated that 8:2 pressed by sodium sulfate and hydrolysis blood glue, after being uniformly mixed, is added rapidly to gather by reactant liquor
In conjunction groove, and it is simultaneously introduced 10% ammonium persulfate aqueous solution that 47.5g has prepared, polyreaction 12min
After obtain hydrogel.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 5-10mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 7:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out after heating 60min, are the polyacrylamide solution of 10% by concentration while hot
Spray to toner surface with aerosol apparatus, carry out hydrophilic strengthening, poly-polyacrylamide solution and resin
The proportioning of powder is 3:100, and last screened machine classification i.e. obtains acrylic absorbent resin product, and particle diameter is big
Little for 200-600 μm.
Embodiment 6
A) in the reactor with high-speed stirring apparatus, 2000g acrylic acid and 1300g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1700g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, 24g sodium allylsulfonate comonomer, 2.4g tetramethylolmethane are added
Triacrylate, 6g foaming agent and 0.18g sodium sulfite, foaming agent is by sodium lauryl sulphate and hydrolysis blood
It is formulated that glue and saponin press 7:1:2, after being uniformly mixed, is added rapidly to gather by reactant liquor
In conjunction groove, and it is simultaneously introduced 10% ammonium persulfate aqueous solution that 70g has prepared, after polyreaction 15min
Obtain hydrogel.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 6-12mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 5:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out after heating 60min, are used by the polyvinyl alcohol water solution that concentration is 10% while hot
Aerosol apparatus sprays to toner surface, carries out hydrophilic strengthening, polyvinyl alcohol water solution and toner
Proportioning is 6:100, and last screened machine classification i.e. obtains acrylic absorbent resin product, and size is
200-500μm。
Comparative example 1
A) in the reactor with high-speed stirring apparatus, 1750g acrylic acid and 1830g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1420g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, add 2.1g pentaerythritol triacrylate, be uniformly mixed
After, reactant liquor is added rapidly in polymerization tank, and is simultaneously introduced 10% Ammonium persulfate. that 52.5g has prepared
Aqueous solution, obtains hydrogel after polyreaction 10min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 4-14mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 5:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out, i.e. obtain acrylic water-absorbent tree after screened machine classification after heating 60min
Fat prod, size is 300-500 μm.
Comparative example 2
A) in the reactor with high-speed stirring apparatus, 2000g acrylic acid and 1300g deionized water are added, so
Being slowly added into the sodium hydrate aqueous solution of 1700g 48% in backward reactor, controlling neutralizer temperature is 60 DEG C.
B) in the neutralizer of step a) gained, 24g sodium allylsulfonate comonomer, 2.4g tetramethylolmethane are added
Triacrylate, after being uniformly mixed, is added rapidly to reactant liquor in polymerization tank, and is simultaneously introduced 60g
10% ammonium persulfate aqueous solution prepared, obtains hydrogel after polyreaction 10min.
C) by the hydrogel Screw Extrusion crusher machine of step b) gained, obtaining size is the solidifying of 4-14mm
Glue granule, after then dry 120min in the baking oven of 180 DEG C, more size-reduced crusher machine and screening machine classification,
Obtain primary acrylic absorbent resin powder.
D) with water, glycerol, Ethylene glycol diglycidyl ether, aluminum chloride according to 300:140:80:110's
The primary acrylic absorbent resin powder obtained in proportions surface crosslinking agent, surface crosslinking agent and step c)
Proportioning is 5:100.In high speed rotating blender, require uniformly to spray surface crosslinking agent according to aforementioned proportion
It is spread across the surface of primary acrylic absorbent resin powder, after stirring mixing 5min, by acrylic absorbent resin powder
180 DEG C of baking ovens are put at end, take out, i.e. obtain acrylic water-absorbent tree after screened machine classification after heating 60min
Fat prod, size is 300-500 μm.
The acrylic absorbent resin product that above example and comparative example are obtained carry out rate of liquid aspiration test (see
Table 1), method of testing uses swirl method, specifically comprises the following steps that
(1) weigh 50g normal saline, pour in the beaker that capacity is 100ml；
(2) being placed in constant temperature blender with magnetic force by beaker, controlling normal saline temperature is 25 DEG C, puts into diameter
The iron core tetrafluoro stirrer of 25mm, starts stirring；
(3), after observing that in beaker, solution whirlpool occurs and stablizes, add 2g acrylic absorbent resin, and open
Beginning timing, the time until whirlpool disappears is the rate of liquid aspiration of product.
Table 1 acrylic absorbent resin rate of liquid aspiration table
| Rate of liquid aspiration (s) | |
| Embodiment 1 | 32 |
| Embodiment 2 | 23 |
| Embodiment 3 | 24 |
| Embodiment 4 | 26 |
| Embodiment 5 | 21 |
| Embodiment 6 | 20 |
| Comparative example 1 | 51 |
| Comparative example 2 | 48 |
From table 1, the rate of liquid aspiration of the acrylic absorbent resin of the present invention is far above prepared by comparative example 1-2 third
Olefin(e) acid water-absorbing resin.
Claims (28)
1. the acrylic absorbent resin of a high rate of liquid aspiration, it is characterised in that the raw material preparing it includes:
Mass ratio is (25-45): (7-22): the acrylic acid of (33-68), alkali and water, also includes: based on acrylic acid
Quality meter,
Cross-linking agent: 0.001-1wt%, preferably 0.005-0.8wt%, more preferably 0.01-0.5wt%；
High temperature resistant foaming agent: 0.01-2wt%, preferably 0.05-1.8wt%, more preferably 0.1-1.6wt%；
Comonomer: 0-10wt%, preferably 0.01-9wt%, more preferably 0.1-8wt%；
Reducing agent: 30-500ppm, preferably 40-400ppm, more preferably 50-300ppm；
Initiator: 0.001-1wt%, preferably 0.005-0.8wt%, more preferably 0.01-0.5wt%.
Acrylic absorbent resin the most according to claim 1, it is characterised in that described acrylic water-absorbent
The rate of liquid aspiration of resin is 15-40s, preferably 18-35s, more preferably 20-32s.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described alkali is hydrogen
Sodium oxide.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described cross-linking agent
For ethylene glycol, propylene glycol, glycerol, Polyethylene Glycol, Ethylene glycol diglycidyl ether, ethoxylated glycerol three
Acrylate, N,N methylene bis acrylamide, polyethyleneglycol diglycidylether, tetramethylolmethane three propylene
One or two or more in acid esters and pentaerythritol triallyl ether, preferably pentaerythritol triacrylate.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described high temperature resistant
Foaming agent is the compounding foaming agent comprising conventional surfactants and animal and vegetable protein surfactant；Conventional table
The mass ratio of face activating agent and animal and vegetable protein surfactant is 6～9:1～4.
Acrylic absorbent resin the most according to claim 5, it is characterised in that described conventional surface is lived
Property agent is sodium lauryl sulphate, dodecyl sodium sulfate, polyoxyethylenated alcohol sodium sulfate, dodecane
One or two or more in base benzene sulfonic acid sodium salt, span and tween, preferably sodium dodecyl sulfate；Described
Animal and vegetable protein surfactant is sodium abietate, tea saponin, saponin, hydrolysis of animal hoof tips and hydrolysis blood
One or two or more in glue, preferably saponin.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described reducing agent
For the one or two or more in sodium sulfite, sodium sulfite, sodium hypophosphite and ascorbic acid, excellent
Select sodium sulfite.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described initiator
For the one or two or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate and hydrogen peroxide, preferably over cure
Acid ammonium.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described copolymerization list
Body is to have one or more in the cationic vinyl monomer of charged group and anionic vinyl monomer,
It is preferably sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic, acryloyl-oxy
Ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride
In one or two or more, more preferably sodium allylsulfonate.
Acrylic absorbent resin the most according to claim 1 and 2, it is characterised in that described water is
Deionized water.
The method of 11. 1 kinds of acrylic absorbent resins prepared as according to any one of claim 1-10, bag
Include following steps:
A) acrylic acid is dissolved in water and forms acrylic acid aqueous solution, with alkali liquor, acrylic acid aqueous solution is neutralized,
To containing acrylic acid incomplete neutralizer；
B) in the neutralizer of step a) gained, add cross-linking agent, high temperature resistant foaming agent and reducing agent, optionally add
Enter comonomer, add initiator after mix homogeneously, carry out aqueous solution polymerization, obtain hydrogel；
C) hydrogel of step b) gained is shredded, after drying, broken, screening, obtain primary acrylic water-absorbent
Resin；
D) surface crosslinking agent is used to carry out surface-crosslinked, then by the primary acrylic absorbent resin of step c) gained
Optionally spray water soluble polymer aqueous solution at particle surface, obtain acrylic absorbent resin.
12. methods according to claim 11, it is characterised in that alkali liquor used in step a) is
Sodium hydrate aqueous solution, the concentration of alkali liquor is 30-50wt%.
13. methods according to claim 12, it is characterised in that acrylic acid, hydrogen-oxygen in step a)
The mass ratio changing sodium and water three is (25-45): (7-22): (33-68).
14. methods according to claim 11, it is characterised in that described in step b) high temperature resistant
Infusion is to comprise conventional surfactants and the mixture of animal and vegetable protein surfactant compound, both matter
Amount ratio is 6～9:1～4；The addition of described high temperature resistant foaming agent is the 0.01-2% relative to acrylic acid quality,
Preferably 0.05-1.8wt%, more preferably 0.1-1.6wt%.
15. methods according to claim 14, it is characterised in that described conventional surfactants is selected
From sodium lauryl sulphate, dodecyl sodium sulfate, polyoxyethylenated alcohol sodium sulfate, detergent alkylate
One or two or more in sodium sulfonate, span and tween, preferably sodium dodecyl sulfate；Described moving is planted
Thing protein surface activating agent is selected from sodium abietate, tea saponin, saponin, hydrolysis of animal hoof tips and hydrolysis blood glue
In one or two or more, preferably saponin.
16. methods according to claim 11, it is characterised in that the copolymerization list described in step b)
Body is to have one or more in the cationic vinyl monomer of charged group and anionic vinyl monomer,
It is preferably sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic, acryloyl-oxy
Ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and dimethyl diallyl ammonium chloride
In one or two or more, more preferably sodium allylsulfonate；Described comonomer addition is relative
In the 0-10% of acrylic acid quality, preferably 0.01-9wt%, more preferably 0.1-8wt%.
17. methods according to claim 11, it is characterised in that the cross-linking agent described in step b)
For ethylene glycol, propylene glycol, glycerol, Polyethylene Glycol, Ethylene glycol diglycidyl ether, ethoxylated glycerol three
Acrylate, N,N methylene bis acrylamide, polyethyleneglycol diglycidylether, tetramethylolmethane three propylene
One or two or more in acid esters and pentaerythritol triallyl ether, preferably pentaerythritol triacrylate；
The addition of cross-linking agent is the 0.001-1% relative to acrylic monomers quality, preferably 0.005-0.8wt%, more
Preferably 0.01-0.5wt%.
18. methods according to claim 11, it is characterised in that the initiator described in step b)
For the one or two or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate and hydrogen peroxide, preferably over cure
Acid ammonium；The addition of initiator is the 0.001-1% relative to acrylic monomers quality, preferably 0.005-0.8wt%,
More preferably 0.01-0.5wt%.
19. methods according to claim 11, it is characterised in that described in step b), reducing agent is
One or two or more in sodium sulfite, sodium sulfite, sodium hypophosphite and ascorbic acid, preferably
Sodium sulfite；The addition of reducing agent is the 30-500ppm relative to acrylic acid quality.
20. according to the method described in any one of claim 11-19, it is characterised in that the polymerization of step b)
Temperature is 40-90 DEG C, and polymerization time is 3-30min.
21. methods according to claim 11, it is characterised in that the hydrogel described in step c)
Size after being chopped into is 4-14mm；Baking temperature is 100-200 DEG C, and drying time is 40-200min,
Preferably 80-180min.
22. methods according to claim 21, it is characterised in that the primary third of gained in step c)
Olefin(e) acid water-absorbing resin particle size range is 100-800 μm.
23. methods according to claim 11, it is characterised in that with primary acrylic acid in step d)
Water-absorbing resin carry out surface-crosslinked surface crosslinking agent be water, polyhydric alcohol, glycidyl ether, ethylene carbonate,
One or two or more in Allyl carbonate and polyvalent metal compounds；The consumption of surface crosslinking agent is phase
2-8% for the primary acrylic absorbent resin quality of step c).
24. methods according to claim 23, it is characterised in that described polyhydric alcohol include ethylene glycol,
Propylene glycol or glycerol；Described polyvalent metal compounds includes aluminum chloride, magnesium chloride, aluminum sulfate or calcium chloride.
25. according to the method described in claim 23 or 24, it is characterised in that described surface-crosslinked anti-
Answering temperature to be 100-200 DEG C, the response time is 10-100min.
26. methods according to claim 11, it is characterised in that the water solublity described in step d)
Macromolecule is one or both in Polyethylene Glycol, polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone
Or multiple, preferably polyethylene alcohol；The addition of described water soluble polymer is the primary third relative to step c)
The 0-10% of olefin(e) acid water-absorbing resin quality.
27. methods according to claim 11, it is characterised in that the acrylic acid obtained in step d)
The rate of liquid aspiration of water-absorbing resin is 15-40s, preferably 18-35s, more preferably 20-32s.
Acrylic absorbent resin or arbitrary by claim 11-27 described in 28. any one of claim 1-0
Acrylic absorbent resin prepared by the described method of item is made for health industry diaper, baby diapers and sanitary towel
For imbibition material, and control of desert, Water in Water Shutoff in Oil Field and agricultural water conservation industry aspect are as water suction and water-retention material
The purposes of material.
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| CN113372611A (en) * | 2021-06-07 | 2021-09-10 | 万华化学集团股份有限公司 | Super-absorbent polymer capable of improving absorption speed and preparation method and application thereof |
| CN113372611B (en) * | 2021-06-07 | 2023-12-29 | 万华化学集团股份有限公司 | Super-absorbent polymer capable of improving absorption speed and preparation method and application 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 |
| CN116036349A (en) * | 2023-01-10 | 2023-05-02 | 露乐健康科技股份有限公司 | Flexible and thin daily absorbent core with red buttock prevention function and extremely rapid absorption capacity and application thereof |
| CN116036349B (en) * | 2023-01-10 | 2023-09-01 | 露乐健康科技股份有限公司 | Flexible and thin daily absorbent core with red buttock prevention function and extremely rapid absorption capacity and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106279494B (en) | 2018-06-12 |
| WO2016179842A1 (en) | 2016-11-17 |
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