CN107501580A - A kind of sucking blood with Sodium Polyacrylate high exhaustion and preparation method thereof with gradual change type hierarchical structure - Google Patents
A kind of sucking blood with Sodium Polyacrylate high exhaustion and preparation method thereof with gradual change type hierarchical structure Download PDFInfo
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- CN107501580A CN107501580A CN201710757755.XA CN201710757755A CN107501580A CN 107501580 A CN107501580 A CN 107501580A CN 201710757755 A CN201710757755 A CN 201710757755A CN 107501580 A CN107501580 A CN 107501580A
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- high exhaustion
- sodium polyacrylate
- resin
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 title claims abstract description 28
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 239000008280 blood Substances 0.000 title claims abstract description 24
- 210000004369 blood Anatomy 0.000 title claims abstract description 24
- 230000008859 change Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 229920001155 polypropylene Polymers 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002924 oxiranes Chemical group 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000012530 fluid Substances 0.000 description 33
- 208000016253 exhaustion Diseases 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 239000002250 absorbent Substances 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002118 epoxides Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Hematology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
A kind of preparation method sucked blood with Sodium Polyacrylate high exhaustion with gradual change type hierarchical structure, comprises the following steps：(1) Metal aluminum salt is configured to water solution A；(2) compound containing epoxide group is configured to solution B；(3) 80 95 DEG C of water solution A is sprayed onto after Sodium Polyacrylate high exhaustion and be incubated at 50 60 DEG C, then sprayed 60 75 DEG C of solution B, be incubated at 40 60 DEG C；(4) resin obtained by step (3) is subjected to cross-linking reaction, the surface modification for obtaining having gradual change type hierarchical structure is sucked blood with Sodium Polyacrylate high exhaustion.Present invention obtains the high exhaustion with gradual change type hierarchical structure, has extremely strong performance of sucking blood, while also has rate of liquid aspiration, liquid absorption and the gel strength of common high hydroscopic resin.
Description
Technical field
The invention belongs to the production field of Sodium Polyacrylate high exhaustion, and in particular to one kind has gradual change type level
Structure is sucked blood with Sodium Polyacrylate high exhaustion and preparation method thereof, meanwhile, it also has general Sodium Polyacrylate high
The water absorbing properties and gel strength of absorbent resin.
Background technology
Sodium Polyacrylate high exhaustion has been widely used for hygienic use due to its excellent water imbibition and absorbency
Product, such as sanitary napkin, paper diaper, also have in the field such as agricultural, industry, building, medicine, light industry, chemical industry have been widely used in addition.
Typically require it when contacting the waterborne liquid such as body fluid with higher absorbency, excellent for high hydroscopic resin
Infiltration rate, logical fluidity and higher gel strength.But after particulate water-absorbing resin contacts the aqueous solution, its surface is easily glued
Tie and granular polymer is formed caking, be also easy to produce " flake ", i.e. gel blockage effect, so as to hinder the further of hydrone
Penetrate into, be unfavorable for resin and give full play to water absorbing properties, influence its water absorbent rate and rate of water absorption.Its another deficiency is exactly solidifying
Glue intensity is not high, can not meet to use needs.In view of the foregoing, people improve the performance of water-absorbing resin using a variety of methods,
Surface-crosslinked technology is exactly one kind therein.This method to water-absorbing resin by carrying out chemical surface treatment to improve its water suction
The shortcomings that speed and low gel strength, it is set to have more application value.
Such as disclose in US4051086 using alcohols material as dispersant, can be significantly improved by crosslinking agent of glyoxal
The rate of water absorption and gel strength of resin, but the environmental issue of aldehyde material is especially dfficult to apply to the mankind than more prominent
Amenities.Japan Patent JP91302895.7, which is disclosed, is placed in water-absorbing resin in high speed agitator, and polyalcohols are crosslinked
The treatment fluid that agent is prepared is sprayed on water-absorbent resin surfaces by stirring, is subsequently placed into baking oven heating and carries out cross-linking reaction.This method
Rate of water absorption is drastically increased, but needs the equipment for using costliness.Japan Patent JP7242709 is disclosed aftertreatment fluid
It is dissolved in hydrophilic solvent, heating becomes thermal current, thermal current is carried out by the toner under heated condition with its surface
Reaction.This method considerably improves water absorbent rate, but handling process is more complicated, it is difficult to operates.And above technology institute
The cross-linking treatment method of use typically all uses single handling process, and surface-crosslinked is all to form single cross-linked layer, it is difficult to
Realize gel strength and rate of water absorption and the perfect unity of protection against the tide.
In addition, polyalcohol or epoxy compounds chemical crosslinking and multivalent metal salt are employed in CN 1696181A
Coordination cross-linked two ways processing Sodium Polyacrylate high exhaustion, obtain relatively good effect, but this two class is handed over
There is the problem of compatibility between connection mode, simply the physics superposition of two kinds of crosslinking methods, does not carry out necessary structure design, lead
Cause its combination property unsatisfactory, it is impossible to while ensure gel strength, Smoking indexes and rate of water absorption.
Importantly, when these high exhaustions are used for sanitary napkin, operation is sucked blood etc. occasion, only have due to general
There are stronger water absorbing properties, be easy to condense blocking after blood dehydration, hamper its comfort, that is, do not reach performance side of sucking blood
The requirement in face.
The content of the invention
Therefore, an object of the present invention is to provide and a kind of there is sucking blood for gradual change type hierarchical structure to use Sodium Polyacrylate
High exhaustion and preparation method thereof.The organic crosslinking and inorganic crosslinking that high hydroscopic resin surface is modified by the present invention combine
Sucking blood with Sodium Polyacrylate high exhaustion with gradual change type hierarchical structure is made.The formation of this structure, ensureing
While resin is to the high-absorbable of blood, can also have excellent rate of liquid aspiration and solidifying as common super absorbent resin
Glue intensity, while do not sacrifice its water absorbent rate and Smoking indexes substantially again.
For the above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of preparation method sucked blood with Sodium Polyacrylate high exhaustion with gradual change type hierarchical structure, including such as
Lower step：
(1) Metal aluminum salt is configured to water solution A；
(2) compound containing epoxide group is configured to solution B；
(3) 80-95 DEG C of water solution A is sprayed onto after Sodium Polyacrylate high exhaustion and be incubated at 50-60 DEG C, so
60-75 DEG C of solution B is sprayed afterwards, is incubated at 40-60 DEG C；
(4) resin obtained by step (3) is subjected to cross-linking reaction, the surface modification for obtaining having gradual change type hierarchical structure gathers
PAA high exhaustion.
The organic crosslinking and inorganic crosslinking that high hydroscopic resin surface is modified by the present invention combine, and this combination is not
It is simple physics superposition, but the combination of a kind of innovative " organic ".Successively it is sprayed on using two kinds of modified solutions of A and B
On the surface of high hydroscopic resin, based on A modification liquids are crosslinked with inorganic coordination, this crosslinking compares more loose, can form ratio
Compared with the cross-linked layer of " soft ", and B modification liquids are the epoxides for being prone to chemical crosslinking, and this crosslinking can form the degree of cross linking
The cross-linked layer of bigger relatively " hard ".A, after B treatment fluids spray respectively, the heat treatment of certain time is all carried out respectively, is made
Its is partial cross-linked and no fully crosslinked, and last another rise heats the complete cross-linking reaction of progress.Due to this charging
The smart design of technique and aftertreatment technology, both cross-linked layers of one side have inside and outside sequentially, i.e., comparatively dense cross-linked layer exists
Outside, the gel strength of resin is ensure that, and more loose cross-linked layer is inside, ensure that water absorption channel, also ensures that
Rate of water absorption；On the other hand due to using multi step strategy technique, this two layers distribution is presented a kind of due to the result of diffusion
Gradual change type hierarchical structure, rather than completely isolated double-layer structure, it is achieved thereby that rate of water absorption and the perfect knot of gel strength
Close, meanwhile, the formation of this gradual change type hierarchical structure, also enable the macromoleculars such as the protein in blood to pass through its microcosmic hole
Road is penetrated into inside resin together with moisture, other small molecules, ensure that its excellent performance of sucking blood.Obvious this process synthesis
The advantage of prior art, and its technique is simpler, it is easily operated, without special processing equipment, so as to greatly reduce
Cost.
Preferably, the Metal aluminum salt described in step (1) is one kind in aluminium chloride, aluminum sulfate, aluminum nitrate and alum
Or two or more combination.
The effect of Metal aluminum salt is to be formed on the surface of resin coordination cross-linked, and its dosage is too low, will cause cross-linked layer excessively
It is loose, do not realize cross-linking modified effect；Too high dosage then causes cross-linked layer too closely, and aperture reduces, and causes washing lotion
The reduction of amount and rate of liquid aspiration.Preferably, the mass concentration of Metal aluminum salt is 3-30%, preferably 5%-20% in the aqueous solution.
Preferably, the compound containing epoxide group described in step (2) is epoxy resin, epoxychloropropane, ring
Combination more than one or both of Ethylene Oxide, glycidol ether, ethylene glycol diglycidylether.
Preferably, the solvent of solution B is combination more than one or both of alcohol, ketone.
Preferably, the solvent of solution B is group more than one or both of methanol, ethanol, isopropanol, acetone, butanone
Close.
The content of epoxide group determines the content of resin densification cross-linked layer and the size in duct, and too low content can cause
Cross-linked layer it is loose, gel strength can not be ensured, too high dosage, can make it that cross-linked layer is excessively fine and close, although gel strength increase
Add, but have a strong impact on liquid absorption.Preferably, the compound quality concentration containing epoxide group is 5-35% in solution B, preferably
For 10%-25%.
Step (1) and (2) do not have sequencing, can first prepare solution A, can also first prepare solution B, can also be simultaneously
Prepare two kinds of solution.
In order to form the suitable cross-linked layer of crosslink density in resin surface, ensure that resin has stronger combination property, make
To be preferred, the mass ratio of solution A and Sodium Polyacrylate high exhaustion described in step (3) is 1:1.5-15, it is preferably
1:3-10。
In order to form the suitable cross-linked layer of crosslink density in resin surface, ensure that resin has stronger combination property, it is excellent
The mass ratio of selection of land, solution B and Sodium Polyacrylate high exhaustion is 1:2-20, preferably 1:4-1:12.
Preferably, it is stirred during insulation, the time being preferably stirred is more than 5 minutes, preferably 15-25 minutes,
So that solution and resin are well mixed.Insulation after sprinkling water solution A and solution B meets above-mentioned restriction, it is preferable that spray water
Solution A is identical with the time being stirred under the insulation after solution B, to obtain hierarchical structure evenly.Stirring can pass through height
Fast agitator is carried out, if mixing speed is the agitator of 200-380 revs/min of agitator, preferably more than 300 revs/min.
In a preferred embodiment, the process of step (3) is as follows：Sodium Polyacrylate high exhaustion is taken to be placed at a high speed
In agitator, it would be heated to 80 DEG C -95 DEG C for the treatment of fluid A and be sprayed onto on resin, be incubated 50-60 DEG C, be stirred 15-25 points
Clock；It would be heated to 60 DEG C -75 DEG C for the treatment of fluid B to be sprayed onto on resin, 40-60 DEG C of insulation is stirred 15-25 minutes.
Preferably, the temperature of cross-linking reaction is 100-150 DEG C in step (4), the time is 60-90 minutes.Cross-linking reaction
It can carry out in an oven.
In a preferred embodiment, the process of step (4) is as follows：Well mixed resin is put into pallet, entered
Baking oven carries out cross-linking reaction, and reaction temperature is 100-150 DEG C, and the reaction time is 60-90 minutes, that is, has obtained having gradual change type layer
The surface modified polyacrylate sodium high exhaustion of level structure.
Preferably, the preparation method of the present invention comprises the following steps：
(1) treatment fluid A is prepared：Metal aluminum salt is configured to the aqueous solution that concentration is 5%-20%；
(2) treatment fluid B is prepared：From the one or several kinds in methanol, ethanol, isopropanol, acetone, butanone as molten
Agent, the compound containing epoxide group is configured to the solution of 10%-25% weight concentration；
(3) processing of the treatment fluid to resin：
Take quantitative Sodium Polyacrylate high exhaustion to be placed in high speed agitator, would be heated to 80 DEG C -95 DEG C of place
Reason liquid A is sprayed onto on resin, is incubated 50-60 DEG C, is stirred 15-25 minutes；It would be heated to 60 DEG C -75 DEG C for the treatment of fluid B sprays
It is spread across on resin, 40-60 DEG C of insulation is stirred 15-25 minutes.
(4) well mixed resin is put into pallet, cross-linking reaction, reaction temperature 100-150 is carried out into baking oven
DEG C, the reaction time is 60-90 minutes, that is, has obtained the modification of the surface with gradual change type hierarchical structure and sucked blood with Sodium Polyacrylate height
Absorbent resin.
An object of the present invention also reside in provide prepared by a kind of the method for the invention there is gradual change type hierarchical structure
Suck blood with Sodium Polyacrylate high exhaustion.
The present invention forms soft or hard property using two kinds of different surface conditioning agents on Sodium Polyacrylate super absorbent resin surface
Different cross-linked layers, it is soft interior hard outer, and by the design of crosslinking Treatment technique, that is, after spraying treatment fluid, at a certain temperature
Carry out partial cross-linked and phase counterdiffusion, this cross-linking reaction can only be carried out partly because temperature is relatively low, while treatment fluid A and B it
Between phase counterdiffusion, they also to some extent towards resin surface spread, finally carry out complete cross-linking reaction at high temperature again,
So as to form the hierarchical structure of gradual change type, it finally ensure that resin has very high rate of water absorption (less than 45 seconds), gel strength
It is excellent, Smoking indexes can reach 60 or so.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
(1) water solution A that aluminum sulfate is formulated as 15% mass concentration is weighed；
(2) the acetone soln B that epoxychloropropane is formulated as 12% mass concentration is weighed；
(3) take quantitative Sodium Polyacrylate high exhaustion to be placed in 300 revs/min of high speed agitator, would be heated to
90 DEG C for the treatment of fluid A is 1 according to weight resin ratio:5 ratio is sprayed onto on resin, is incubated 60 DEG C, is stirred 20 minutes；
It is 1 that 70 DEG C for the treatment of fluid B, which be would be heated to, according to weight resin ratio:6 ratio is sprayed onto on resin, and 50 DEG C of insulation is stirred
20 minutes；
(4) well mixed resin is put into pallet, carries out cross-linking reaction into baking oven, reaction temperature is 120 DEG C, instead
It is 70 minutes between seasonable, that is, has obtained the high exhaustion of surface modification.
Embodiment 2
Treatment fluid A and B in embodiment 1 and the mass ratio of resin are changed to 1 respectively:6 and 1:8, other conditions are the same as implementation
Example 1.
Embodiment 3
Treatment fluid A in embodiment 1 is changed to the alum of 20% mass concentration, other are the same as embodiment 1.
Embodiment 4
Treatment fluid A in embodiment 1 is changed to the alum of 20% mass concentration, other are the same as embodiment 2.
Embodiment 5
Treatment fluid B in embodiment 1 is changed to the glycidol ether ethanol solution of 10% mass concentration, other same embodiments
1。
Embodiment 6
By the treatment fluid A and B in embodiment 1 be changed to respectively 18% mass concentration aluminum nitrate aqueous solution and 23% mass it is dense
The acetone soln of the E-51 epoxy resin of degree, other conditions are such as embodiment 3.
Embodiment 7
Treatment fluid A in embodiment 6 and treatment fluid B and resin quality ratio are changed to 1 respectively:7 and 1:9, other are the same as implementation
Example 6.
Embodiment 8
Treatment fluid A and B in embodiment 7 is changed to the aluminum chloride aqueous solution of 18% mass concentration respectively and ethylene glycol two contracts
The methanol solution of 20% mass concentration of water glycerin ether, other are the same as embodiment 7.
Embodiment 9
It is 5% by the concentration of the treatment fluid A in embodiment 1, other conditions are the same as embodiment 1.
Embodiment 10
It is 25% by the concentration of the treatment fluid A in embodiment 1, other conditions are the same as embodiment 1.
Embodiment 11
Step (3), (4) proceed as follows, and remaining is same as Example 1.
(3) take quantitative Sodium Polyacrylate high exhaustion to be placed in high speed agitator, would be heated to 80 DEG C of processing
Liquid A is 1 according to weight resin ratio:3 ratio is sprayed onto on resin, is incubated 50 DEG C, is stirred 25 minutes；It would be heated to 60
DEG C treatment fluid B according to weight resin ratio be 1:12 ratio is sprayed onto on resin, and 40 DEG C of insulation is stirred 15 minutes；
(4) well mixed resin is put into pallet, carries out cross-linking reaction into baking oven, reaction temperature is 100 DEG C, instead
It is 90 minutes between seasonable, that is, has obtained the high exhaustion of surface modification.
Embodiment 12
Step (3), (4) proceed as follows, and remaining is same as Example 1.
(3) take quantitative Sodium Polyacrylate high exhaustion to be placed in 300 revs/min of high speed agitators, would be heated to 95
DEG C treatment fluid A according to weight resin ratio be 1:10 ratio is sprayed onto on resin, is incubated 75 DEG C, is stirred 15 minutes；
It is 1 that 75 DEG C for the treatment of fluid B, which be would be heated to, according to weight resin ratio:4 ratio is sprayed onto on resin, and 60 DEG C of insulation is stirred
15 minutes；
(4) well mixed resin is put into pallet, carries out cross-linking reaction into baking oven, reaction temperature is 150 DEG C, instead
It is 60 minutes between seasonable, that is, has obtained the high exhaustion of surface modification.
Comparative example 1
Detailed process according to the progress disclosed in CN 1696181A, solution A, B concentration and with the ratio of resin according to reality
The setting of example 1 is applied, step is as follows：
1) treatment fluid A, is prepared：
From acetone as dispersant, from epoxychloropropane as crosslinking agent, DMP-30 is as crosslinking accelerator；It will divide
Powder, crosslinking agent, crosslinking accelerator are placed in glass container and stirred, and are configured to treatment fluid A, and the mass concentration of epoxychloropropane is
12%；
2) treatment fluid B, is prepared：
Deionized water is placed in glass container and is heated to 90 DEG C, aluminum sulfate salt is weighed and the second crosslinking agent glycerine adds
State in deionized water and stir, be configured to treatment fluid B, the mass concentration of aluminum sulfate is 15%；
3), processing of the treatment fluid to water-absorbing resin：
Take 60kg water-absorbing resin to be placed in 300 revs/min to mix in device, under agitation by treatment fluid A, treatment fluid B by first
Water-absorbent resin surfaces are sequentially sprayed on afterwards by stirring, and resin is put into pallet, is heated into baking oven and carries out cross-linking reaction, instead
It is 120 DEG C to answer temperature, and the reaction time is 100 minutes, that is, completes modifying surface of absorption resin of sodium polyacrylate.
The performance of modified resin prepared by above example and comparative example is listed in Table 1 below.
The performance of 1. each embodiment of table and the preparation-obtained modified resin of comparative example
The test of liquid measure of sucking blood and speed of sucking blood is carried out according to standard GB/T/T22875-2008 methods；Water absorbent rate and
Rate of water absorption is tested according to standard GB/T 22905-2008 methods；The document that gel strength is reported according to Zhu Youliang et al.
(Zhu Youliang, my country is strong, the synthesis with coreshell type structure water-absorbing resin, plastics, 2005,34 (1) for method：23-26) surveyed
Examination.
Institute's column data from table 1, it is apparent that the present invention outstanding advantages be that there is excellent performance of sucking blood, suck blood
For amount apparently higher than comparative example, speed of sucking blood and rate of liquid aspiration are significantly larger than comparative example, gel strength and liquid absorbency rate and comparative example
Quite.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method sucked blood with Sodium Polyacrylate high exhaustion with gradual change type hierarchical structure, including it is as follows
Step：
(1) Metal aluminum salt is configured to water solution A；
(2) compound containing epoxide group is configured to solution B；
(3) 80-95 DEG C of water solution A is sprayed onto after Sodium Polyacrylate high exhaustion and be incubated at 50-60 DEG C, then sprayed
60-75 DEG C of solution B is spilt, is incubated at 40-60 DEG C；
(4) resin obtained by step (3) is subjected to cross-linking reaction, obtains the polypropylene that there is the surface of gradual change type hierarchical structure to be modified
Sour sodium high exhaustion.
2. preparation method according to claim 1, it is characterised in that Metal aluminum salt described in step (1) is aluminium chloride,
Combination more than one or both of aluminum sulfate, aluminum nitrate and alum.
3. preparation method according to claim 1 or 2, it is characterised in that the matter of step (1) reclaimed water GOLD FROM PLATING SOLUTION category aluminium salt
Amount concentration is 3-30%, preferably 5%-20%.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that contain epoxy described in step (2)
The compound of group is in epoxy resin, epoxychloropropane, expoxy propane, glycidol ether, ethylene glycol diglycidylether
One or more kinds of combinations.
5. according to the preparation method described in claim any one of 1-4, it is characterised in that the solvent of solution B is in step (2)
Combination more than one or both of alcohol, ketone；
Preferably, the solvent of solution B is combination more than one or both of methanol, ethanol, isopropanol, acetone, butanone.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that contain epoxy in solution B in step (2)
The compound quality concentration of group is 5-35%, preferably 10%-25%.
7. according to the preparation method described in claim any one of 1-6, it is characterised in that the solution A described in step (3) is with gathering
The mass ratio of PAA high exhaustion is 1:1.5-15 preferably 1:3-10；
Preferably, the mass ratio of solution B and Sodium Polyacrylate high exhaustion is 1:2-20, preferably 1:4-1:12.
8. according to the preparation method described in claim any one of 1-7, it is characterised in that it is stirred when being incubated in step (3),
It is preferred that the time being stirred is more than 5 minutes, preferably 15-25 minutes.
9. according to the preparation method described in claim any one of 1-8, it is characterised in that the temperature of cross-linking reaction in step (4)
For 100-150 DEG C, the time is 60-90 minutes.
10. a kind of by prepared by any one of claim 1-9 methods described there is sucking blood for gradual change type hierarchical structure to use polypropylene
Sour sodium high exhaustion.
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