CN106832134A - A kind of one-way lock water-resin material preparation method and the unidirectional water lock material for obtaining - Google Patents
A kind of one-way lock water-resin material preparation method and the unidirectional water lock material for obtaining Download PDFInfo
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- CN106832134A CN106832134A CN201710097457.2A CN201710097457A CN106832134A CN 106832134 A CN106832134 A CN 106832134A CN 201710097457 A CN201710097457 A CN 201710097457A CN 106832134 A CN106832134 A CN 106832134A
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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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
Abstract
The present invention proposes a kind of preparation method of one-way lock water-resin material, including：Sodium Polyacrylate water suction core is formed by PAA polymerization-filling, then unidirectional osmosis putamina is formed by adding hydroxy-acid group epoxy cross-linking catalysts the carboxyl contained by Sodium Polyacrylate core surfaces is carried out cross-linking reaction with the epoxy contained by oil phase.The putamina possesses locking moisture content, sun-proof water and anti-aging function after unidirectional osmosis moisture, water suction, so as to be obviously improved water lock stability, yellowing resistance and the weatherability of product.The invention also discloses a kind of with superelevation water absorption capacity, ultra-long time water lock ability, ageing-resistant one-way lock water-resin material, it uses the preparation method of the one-way lock water-resin material to prepare.
Description
Technical field
The present invention relates to chemical materials preparation field, a kind of preparation side of one-way lock water-resin micro-sphere material is particularly related to
Method, the present invention also designs the unidirectional water lock material prepared by the method.
Background technology
High hydroscopic resin (Superabsorbent polymer, SAP) is a kind of typical functional high molecule material, and general
Logical water suction or hygroscopic material, such as sponge, fiber are compared, big with uptake, the features such as absorption speed is fast, water holding capacity is strong,
But common high hydroscopic resin seeps water due to being easy to aging after water suction, water lock ability just disappears for 2~3 hours under sunlight irradiation
Lose, because the water lock time is short, it is impossible to adapt to desert water conservation greening purposes, also reverse osmosis etc. easily occur no for hygiene article sector
Good phenomenon.
The content of the invention
The first object of the present invention is to overcome that common high hydroscopic resin is easily aging after absorbing water to cause water lock anergy etc.
Problem, a kind of one-way lock water-resin micro-sphere material is prepared by inverse suspension polymerization, by introducing carboxylic acid-ring in polymerization system
Oxygen catalysts make microsphere surface form shell membrane, on the one hand solve dispersant residue problem, the lock of another aspect reinforcing material
Aqueous energy and anti-yellowing property.
The technical proposal of the invention is realized in this way：
A kind of preparation method of one-way lock water-resin micro-sphere material, including：Poly- third is formed by PAA polymerization-filling
Olefin(e) acid sodium water suction core, then make the carboxyl contained by Sodium Polyacrylate core surfaces by adding acid-epoxy cross-linking catalysts
Cross-linking reaction is carried out with the epoxy contained in oil phase form putamina.After the putamina possesses hydrophobicity, unidirectional osmosis moisture, water suction
Locking moisture content, chemical defence water and anti-aging function, so as to lift many-sided effect of the product for obtaining.
Further, the preparation method of the one-way lock water-resin micro-sphere material, mainly includes the following steps that：
(1) water is mutually prepared：Appropriate acrylic acid and/or methacrylic acid are taken, is neutralized to NaOH/potassium solution or ammoniacal liquor
Degree of neutralization is 65~85 ﹪, adds acrylamide and/or polyvinyl alcohol.Initiator, crosslinking agent are subsequently adding, it is well mixed to obtain
Water phase；
(2) prepared by oil phase：Addition dispersant obtains oil phase in organic solvent, wherein, the dispersant is white carbon, silicon
One kind or mixture in diatomaceous earth, ultra-fine alchlor, consumption are the 1-3% of organic solvent quality；Then epoxy radicals is added
Compound, consumption is the 2-6% of organic solvent quality, and 15~30min, stirring are disperseed under the rotating speed of 1000~1600r/min
Uniformly obtain oil phase.
(3) polymerisation：Oil phase is warming up to 65~95 DEG C, oil phase stir speed (S.S.) is 50~100r/min；To prepare
Water be mutually slowly dropped into oil phase, rate of addition is 5-15mL/min, drip continuation react 0.5h after carboxy-epoxy is crosslinked
Catalyst enters in oil phase, and oil phase temperature rises to 80~105 DEG C, terminates after continuing to react 20-40 minutes
(4) solid-liquid separation step：Reactant is filtered, washed and dried the described unidirectional of prepared uniform particle diameter from oil phase
Water lock resin microsphere material product.
More specifically, wherein, (1) water mutually prepare including：By acrylic acid and/or methacrylic acid under cold bath, with hydrogen
It is 65~85% that sodium oxide molybdena/potassium solution (wt%=25~35 ﹪) and ammoniacal liquor (wt%=20~25 ﹪) are neutralized to degree of neutralization, plus
Enter acrylamide and/or polyvinyl alcohol (alcoholysis degree=87~89 ﹪), be subsequently adding initiator, reducing agent, crosslinking agent and mix
Uniformly, it is cooled to room temperature.
Further to lift effect, also to the following restriction that carries out of reactant, the acrylamide consumption is inventor
The 5~20% of acrylic acid (and/or methacrylic acid) quality.
Further, (methyl) acrylic acid alkali lye is neutralized in water phase includes NaOH/potassium hydroxide solution and ammoniacal liquor,
Monomer is first neutralized to degree of neutralization for 45~55% with NaOH/potassium hydroxide solution, then with mass fraction be 20~
It is 65~85% that 25% ammoniacal liquor continues to be neutralized to degree of neutralization.
Further, the initiator is divided into an initiator and secondary initiator, and adds at twice, described once to trigger
Agent is directly added into water phase, and the secondary initiator is added after initiator completion of dropping reaction 0.5h.
Further, the initiator for being used in reaction is redox system initiator, and including once triggering
Agent and secondary initiator, wherein oxidant for initiator is potassium peroxydisulfate/ammonium, reducing agent be frerrous chloride, ferrous sulfate,
One or more in sodium sulfite.The oxidant of secondary initiator is in hydrogen peroxide, carbamide peroxide, SODIUM PERCARBONATE
Plant or several, reducing agent is one or more in frerrous chloride, sulphite, sodium thiosulfate, L-AA.Oxidant
Consumption is the 0.01~2% of monomer mass, and reducing agent consumption is the 0.01~1% of monomer mass.Two kinds have been selected to decompose activation
The different initiation system of energy, initial reaction stage, acrylic acid concentration is high, the low initiation system of selection decomposition activation energy, effectively prevents quick-fried
It is poly-.Reaction middle and later periods, low polymer is more, and system is triggered from low decomposition activation energy, makes low-molecular weight polymer quick
High molecular weight product is aggregated into an orderly manner.
Further, the crosslinking agent is the mono bis glycidol ether of polyalcohol and/or mono bis/3 third of polyalcohol
One or more in olefin(e) acid ester, consumption is the 0.01~1% of monomer mass.
Further, in the preparation of (2) oil phase, it is R that the epoxy compounds use molecular structure1- COOCH2-
CHm1(CH2OH)n1Or R2- CHm2(CH2OH)n2, wherein R1And R2It is alkyl, carbon number is respectively 4~18 and 12~18, m1
With the integer that m2 is 2~0, n1 and n2 corresponds to 1~3 integer, more preferably glycerin monostearate.
It is lifting reaction effect, wherein, the organic solvent is toluene, dimethylbenzene, hexamethylene, phenyl silicone oil, castor oil
With the one of which in atoleine, preferably phenyl silicone oil and atoleine, more preferably phenyl silicone oil, oil-water ratio is preferably
5~10, more preferably 7~9.The epoxide is oxirane, expoxy propane, epoxidized soybean oil, epoxy resin, epoxy
One kind or combination in chloropropane, consumption are the 1~4% of organic solvent quality.
In step (3) polymerisation, including：Oil phase is warming up to 65~75 DEG C, oil phase stir speed (S.S.) is 50~100r/
min；The water that will be prepared mutually is slowly dropped into oil phase, and rate of addition is 5-15mL/min, and dripping will after 0.5h is reacted in continuation
The carboxy-epoxy crosslinking catalyst and secondary initiator are added in oil phase, and oil phase temperature rises to 85~105 DEG C, continue to react
Terminate after 20-40 minutes.
Further, the carboxy-epoxy crosslinking catalyst is the one kind or several in phosphoric acid, hydrochloride and sulfate
Kind, preferably hydrochloride, more preferably iron chloride and copper chloride, relative to the quality of the epoxide, its consumption is 2~
4%.
After polymerization terminates, in (4) solid-liquid separation step, through filtering, washing, being dried to obtain bead-shaped water absorbing microballoon.
Used as another object of the present invention, disclosing a kind of has superelevation water absorption capacity, ultra-long time water lock ability, resistance to
Aging unidirectional water lock material, it uses the preparation method of the one-way lock water-resin micro-sphere material to prepare.
Preparation method of the invention and resulting product have the following advantages that and beneficial effect：
The molten boiling point of organic solvent selected by the present invention is high, oxidation resistance is strong, can be recycled for a long time.
The present invention by add in reaction system appropriate carboxy-epoxy crosslinking catalyst (selected from phosphoric acid, hydrochloride and
Sulfate), (molecular structure is R to make epoxide1- COOCH2- CHm1(CH2OH)n1Or R2- CHm2(CH2OH)n2) grafting
In microsphere surface, so as to cover a layer function shell membrane in microsphere surface, color inhibition, the water of resistance to change and the water lock energy of material are greatly improved
Power.
The present invention has selected the different initiation system of two kinds of decomposition activation energies, and initial reaction stage, acrylic acid concentration is high, selection point
The low initiation system of solution activation energy, effectively prevents implode.Reaction middle and later periods, low polymer is more, and activation is decomposed from low
System can be triggered, low-molecular weight polymer is rapidly and orderly aggregated into high molecular weight product.
Metal ion in currently preferred carboxy-epoxy crosslinking catalyst such as hydrochloride and sulfate can also and carboxylic
Base is complexed, and plays a part of surface crosslinking agent, so that resin outer layer crosslink density increases, improves water lock ability.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
Other accompanying drawings are obtained with according to these accompanying drawings.
Fig. 1 is the described unidirectional water lock material profile figure that embodiment 1 is prepared；
Fig. 2 is the described unidirectional water lock material profile figure that embodiment 2 is prepared；
Fig. 3 is the described unidirectional water lock material profile figure that embodiment 3 is prepared；
Fig. 4 is the described unidirectional water lock material profile figure that embodiment 4 is prepared；
Fig. 5 is the described unidirectional water lock material profile figure that embodiment 5 is prepared；
Fig. 6 is the described unidirectional water lock material profile figure that embodiment 6 is prepared；
Fig. 7 is the described unidirectional water lock material profile figure that embodiment 7 is prepared；
Fig. 8 is the described unidirectional water lock material profile figure that embodiment 8 is prepared.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 66.66g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 70%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.36g crosslinkings
Agent PEG400 double methacrylate, 0.036g potassium peroxydisulfates, (potassium peroxydisulfate and sodium sulfite can be first for 0.072g sodium sulfites
It is formulated as solution), it is placed in after stirring standby in cold bath.
(2) 440g phenyl silicone oils are weighed, 4.4g glycerin monostearates are added, is disperseed with the rotating speed of 1600r/min
10min, then heats to 70 DEG C, and rotating speed is 100r/min.
(3) by the way that by acrylic acid neutralizer instillation oil phase, completion of dropping continues to add 0.088g chlorinations after reacting 0.5h
Iron, 0.036g hydrogen peroxide, 0.072g sodium sulfites, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, while hot mistake
Filter, with ethanol washed product three times, is dried to obtain the particle diameter about bead-like resin of 1.2mm, as the one-way lock water tree lipid microspheres
Material, outline drawing is as shown in Figure 1.
Embodiment 2：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 66.66g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 70%, sequentially adds 48g acrylamides.It is subsequently added into 0.36g crosslinking agents PEG400 double
Acrylate, 0.036g potassium peroxydisulfates, 0.072g sodium sulfites (potassium peroxydisulfate and sodium sulfite can first be formulated as solution), stirring
It is placed in after uniform standby in cold bath
(2) 440g phenyl silicone oils are weighed, 4.4g glycerin monostearates are added, is disperseed with the rotating speed of 1600r/min
10min, then heats to 70 DEG C, and rotating speed is 100r/min.
(3) 0.088g iron chloride, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium sulfites, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, washed with ethanol
Wash product three times, be dried to obtain the particle diameter about bead-like resin of 0.9mm, outline drawing is as shown in Figure 2.
Embodiment 3：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 66.66g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 70%, sequentially adds 36g acrylamides.It is subsequently added into 0.36g crosslinking agents PEG400 two
Glycidol ether, 0.036g ammonium persulfates, 0.072g potassium sulfites (potassium peroxydisulfate and sodium sulfite can first be formulated as solution) are stirred
It is placed in after mixing uniformly standby in cold bath
(2) 440g phenyl silicone oils are weighed, 4.4 glycerin monostearates are added, 10min are disperseed with the rotating speed of 1600r/min,
70 DEG C are then heated to, rotating speed is 100r/min.
(3) 0.088g iron chloride, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium sulfites, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, washed with ethanol
Wash product three times, be dried to obtain the bead-like resin that particle diameter is about 800 μm, outline drawing is as shown in Figure 3.
Embodiment 4：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 66.66g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 70%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.18g crosslinkings
Agent PEG400 double methacrylate and 0.18g PEG400 diglycidyl ethers, 0.036g potassium peroxydisulfates, 0.072g are sub-
Sodium sulphate (potassium peroxydisulfate and sodium sulfite can first be formulated as solution), is placed in standby in cold bath after stirring
(2) 440g phenyl silicone oils are weighed, 4.4g glycerin monostearates are added, is disperseed with the rotating speed of 1600r/min
10min, then heats to 70 DEG C, and rotating speed is 100r/min.
(3) 0.088g iron chloride, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium sulfites, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, washed with ethanol
Wash product three times, be dried to obtain the bead-like resin that particle diameter is about 600 μm, outline drawing is as shown in Figure 4.
Embodiment 5：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 66.66g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 70%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.36g crosslinkings
Agent PEG400 double methacrylate, 0.036g potassium peroxydisulfates, (potassium peroxydisulfate and sodium sulfite can be first for 0.072g sodium sulfites
It is formulated as solution), it is placed in after stirring standby in cold bath.
(2) 440g atoleines are weighed, 4.4g glycerin monostearates are added, is disperseed with the rotating speed of 1600r/min
10min, then heats to 70 DEG C, and rotating speed is 100r/min.
(3) 0.088g copper chlorides, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium sulfites, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, use acetic acid second
Ester washed product three times, is dried to obtain the bead-like resin that particle diameter is about 500 μm, and outline drawing is as shown in Figure 5.
Embodiment 6：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 93.33g mass fractions are 30%
Potassium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 75%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.36g crosslinkings
Agent PEG400 double methacrylate, 0.036g potassium peroxydisulfates, (potassium peroxydisulfate and sodium sulfite can be first for 0.072g sodium sulfites
It is formulated as solution), it is placed in after stirring standby in cold bath.
(2) 440g atoleines are weighed, 4.4g glycerin monostearates are added, is disperseed with the rotating speed of 1600r/min
10min, then heats to 70 DEG C, and rotating speed is 100r/min.
(3) 0.088g copper chlorides, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium thiosulfate, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, use acetic acid
Ethyl ester washed product three times, is dried to obtain the bead-like resin that particle diameter is about 400 μm, and outline drawing is as shown in Figure 6.
Embodiment 7：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 73.33g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 75%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.36g crosslinkings
Agent pentaerythritol triacrylate, 0.036g potassium peroxydisulfates, (potassium peroxydisulfate and sodium sulfite can be prepared first 0.072g sodium sulfites
It is solution), it is placed in after stirring standby in cold bath
(2) 440g atoleines are weighed, 4.4 glycerin monostearates are added, 10min are disperseed with the rotating speed of 1600r/min,
70 DEG C are then heated to, rotating speed is 100r/min.
(3) 0.088g copper chlorides, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g sodium thiosulfate, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, use acetic acid
Ethyl ester washed product three times, is dried to obtain the bead-like resin that particle diameter is about 300 μm, and outline drawing is as shown in Figure 7.
Embodiment 8：
(1) weigh 72g acrylic acid and 36g deionized waters are well mixed, take the hydroxide that 73.33g mass fractions are 30%
Sodium solution is neutralized under cold bath.Liquid to be neutralized is cooled to room temperature, takes the ammoniacal liquor that 28.04g mass fractions are 25% and continues to neutralize,
Final acrylic acid degree of neutralization is 75%, sequentially adds 36g acrylamides, 0.36g polyvinyl alcohol.It is subsequently added into 0.12g crosslinkings
Agent pentaerythritol triacrylate, 0.12g PEG400s diacrylate, 0.12g PEG400 diglycidyl ethers.
0.036g potassium peroxydisulfates, 0.072g sodium sulfites (potassium peroxydisulfate and sodium sulfite can first be formulated as solution), stir rearmounted
It is standby in cold bath
(2) 440g atoleines are weighed, 4.4 glycerin monostearates are added, 10min are disperseed with the rotating speed of 1600r/min,
70 DEG C are then heated to, rotating speed is 100r/min.
(3) 0.088g copper chlorides, 0.036g are added by acrylic acid neutralizer instillation oil phase by dropper after 0.5h
Hydrogen peroxide, 0.072g frerrous chlorides, mixing speed is upgraded to 200r/min.Terminate reaction after 0.5h, filter while hot, use acetic acid second
Ester washed product three times, is dried to obtain the bead-like resin that particle diameter is about 200 μm, and outline drawing is as shown in Figure 8.
The performance evaluation of embodiment 1-8
Inventor carries out distilled water multiplying power, water lock performance, yellowing resistance and light shine to the product that embodiment 1-8 is obtained
The many-side such as aqueous is measured analysis, as a result as follows：
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of one-way lock water-resin micro-sphere material, it is characterised in that including：By PAA polymerization-filling
Sodium Polyacrylate water suction core is formed, then makes Sodium Polyacrylate core surfaces institute by adding acid-epoxy cross-linking catalysts
The epoxy contained in the carboxyl and oil phase that contain carries out cross-linking reaction and forms putamina.
2. the preparation method of one-way lock water-resin micro-sphere material as described in the appended claim 1, it is characterised in that：Including (1) water phase
Preparation, the preparation of (2) oil phase, (3) polymerisation and (4) solid-liquid separation step.
3. the preparation method of one-way lock water-resin micro-sphere material as stated in claim 2, it is characterised in that：Wherein, water is mutually made
It is standby to include：By acrylic acid and/or methacrylic acid under cold bath, being neutralized to degree of neutralization with NaOH/potassium solution and ammoniacal liquor is
65~85%, acrylamide and/or polyvinyl alcohol are added, it is subsequently adding initiator, reducing agent, crosslinking agent and is well mixed, it is cold
But to room temperature.
4. the preparation method of one-way lock water-resin micro-sphere material as stated in claim 2, it is characterised in that：Wherein, oil phase system
It is standby to include：Bonus point powder in organic solvent, add epoxy compounds disperse 15 under the rotating speed of 1000~1600r/min~
30min obtains oil phase..
5. the preparation method of one-way lock water-resin micro-sphere material as stated in claim 2, it is characterised in that：Wherein, it is polymerized anti-
Should include：After continuing to react 0.5~1h during water to communicate the oil phase for slowly dropping to 65~95 DEG C, after completion of dropping, then
Add secondary initiator and carboxy-epoxy crosslinking catalyst, and reaction 20 after oil phase temperature is increased into 80~105 DEG C~
Terminate to obtain disperseing the solid polymer for being suspended in oil phase after 40min.
6. the preparation method of one-way lock water-resin micro-sphere material as claimed in claim 5, it is characterised in that：Polymerization is passed through after terminating
Filter, wash, being dried to obtain one-way lock water-resin micro-sphere material described in pearl.
7. the preparation method of one-way lock water-resin micro-sphere material as claimed in claim 3, it is characterised in that：Initiator is divided into one
Secondary initiator and secondary initiator, and add at twice, one time initiator is directly added into water phase, and secondary initiator is once dripping
Added after adding Bi Fanying 0.5h.
8. the preparation method of one-way lock water-resin micro-sphere material as claimed in claim 3, it is characterised in that：Water mutually neutralizes propylene
The alkali lye of acid and/or methacrylic acid includes NaOH/potassium hydroxide solution and ammoniacal liquor, first with NaOH/potassium hydroxide
It is 45~55% that monomer is neutralized to degree of neutralization by solution, then with mass fraction for 20~25% ammoniacal liquor continue to be neutralized to degree of neutralization
It is 65~85%.
9. a kind of unidirectional water lock material, it is characterised in that：Prepared using any methods described in claim 1-9.
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| CN109435385A (en) * | 2018-12-26 | 2019-03-08 | 苏州净雅无尘科技有限公司 | A kind of two plane type high-hydroscopicity dust-free cloth manufacturing process |
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| CN1733815A (en) * | 2005-04-28 | 2006-02-15 | 华南师范大学 | Preparation method of high-intensity water absorbent material |
| CN102936348A (en) * | 2012-11-01 | 2013-02-20 | 烟台万华聚氨酯股份有限公司 | Crylic acid water-absorbent resin with excellent water-retaining property and yellowing resistance and preparation method thereof |
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