CN105924565B - Modified super absorbent polymer and preparation method thereof and the application in cement-based material - Google Patents
Modified super absorbent polymer and preparation method thereof and the application in cement-based material Download PDFInfo
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- CN105924565B CN105924565B CN201610393031.7A CN201610393031A CN105924565B CN 105924565 B CN105924565 B CN 105924565B CN 201610393031 A CN201610393031 A CN 201610393031A CN 105924565 B CN105924565 B CN 105924565B
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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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
Abstract
The invention discloses a kind of preparation method of modified super absorbent polymer, this method, which is included under ultrasonication, is prepared SAP microemulsions, and the super absorbent polymer surface is modified the step of finally obtain super absorbent polymer product and with silane coupling agent the step of must being modified super absorbent polymer.The modification super absorbent polymer being prepared the invention also discloses this method and the application of the modification super absorbent polymer in cement-based material.When the modification super absorbent polymer that the present invention is prepared is used for cement-base composite material, the waterproof of concrete structures, impervious characteristic can be both improved；There is excellent water retention property and suitable gel strength again, even if compressed water is not easy to extrude, further plugging cement sill hole, achievees the purpose that with water sealing, water-saving；It can also ensure its durability after water circulation is released in long-term water suction.
Description
Technical field
The present invention relates to cement-based material technical field, more particularly to a kind of modified super absorbent polymer and preparation method thereof
With the application in cement-based material.
Background technology
High performance cement-based material (HPC) generally use low water-cement ratio technological approaches obtains, therefore, be also easy to produce it is larger from
Shrink and cause structure crack, while the aquation in non-completely hydrated cement later stage can also produce the wet problem of Cracking that rises.Solve above-mentioned
The key of problem is the relative humidity improved inside HPC, promotes hydrated cementitious.But the usual compact structures of HPC, supported using conventional
It is relatively difficult that maintaining method is introduced from outside into curing water.Therefore, some scholars propose that moisture is introduced directly inside HPC carries out autotrophy
Shield.Wherein, super absorbent polymer (SAP) is the common interior curing agent of cement-based material.Have using super absorbent polymer good
The characteristics of water conservation, will fill in cement-based material in it, its later stage is carried out Self-curing to cement-based material, can effectively change
The basic performance of kind cement-based material.In addition, because of water imbibition excellent SAP, make when leakage occurs for the interior cement structures for mixing SAP
Used time, SAP energy water swellings, plugging cement sill hole, forms rigidity water-proofing material, so as to play the mesh of " with water sealing "
's.But traditional SAP prepares rigid cement group water-proofing material, and there are the problem of following several respects：1) traditional SAP is in distilled water
In there is higher imbibition rate, but in brine (such as NaCl solution, CaCl2Solution) in, water absorbent rate can substantially reduce, and make its resistance to
Salt is poor, and water absorption rate significantly reduces in the solution containing ion, and in actual application, this kind of water-absorbing resin is mainly
Absorb the moisture containing electrolyte.Particularly when being applied to extra large work structures, using effect is a greater impact.2) one
High-absorbent material as although influences significantly the working performance of cement-based material, and because water-absorption particle is larger, grain shape is not
Regular uniform, it is difficult to obtain comparatively ideal high-performance water-proof cement sill.3) SAP in long-term water swelling, release water or water
Under pressure effect interface between SAP and cement matrix can be caused to destroy, influence the waterproof of cement structures, the durable spy such as impervious
Property.
The content of the invention
It is an object of the invention to provide a kind of modified super absorbent polymer and its preparation for existing technological deficiency
Method.The modification super absorbent polymer particle is smaller, regular shape is uniform, and salt tolerance is good.
It is a further object to provide application of the above-mentioned modified super absorbent polymer in cement-based material.This changes
After property super absorbent polymer is filled into cement-based material, there is good interface interaction with cement-based material.
To realize above-mentioned first purpose, the technical solution adopted by the present invention is：
A kind of modified super absorbent polymer, the modification super absorbent polymer are prepared as follows to obtain：
(1) using deionized water as dispersed phase, addition emulsifying agent, assistant for emulsifying agent, initiator, crosslinking agent are stirred into homogeneous
Phase soap lye；The emulsifying agent is anion emulsifier and nonionic emulsifier.
(2) in 40~60 DEG C, under inert atmosphere, mix monomer is added dropwise within half an hour, opens ultrasonic wave, reaction 1
After~2h, SAP microemulsions are prepared.Reaction was completed, product is dried crude product is made.
(3) gained crude product is put into distilled water, 0.5~1h is stirred at 60~70 DEG C, after filtering, dry, crushing i.e.
The super absorbent polymer product that must be purified.
(4) with absolute ethyl alcohol decentralized medium, super absorbent polymer is disperseed under mechanical agitation, constant pressure funnel will be modified
Agent is added drop-wise in three-necked flask, and being vigorously stirred (300~400r/min) makes it be dispersed in super absorbent polymer surface, to obtain the final product
Modified super absorbent polymer；The modifying agent is silane coupling agent.
In the emulsifying agent addition of anion emulsifier and nonionic emulsifier respectively for mix monomer gross weight 1~
5%.
The nonionic emulsifier is phenethyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, first contracting nonyl phenol
One kind in polyoxyethylene ether or the combination between them；The anion emulsifier is neopelex, 12
One kind or two kinds of combination in sodium alkyl sulfonate.
The assistant for emulsifying agent addition is the 0.5~3% of mix monomer gross weight.
The assistant for emulsifying agent is n-butanol, propyl alcohol, one kind in isopropanol or the combination between them.
The initiator is (NH4)2S2O8, addition is mix monomer gross weight for 0.5~0.7%；Crosslinking agent is
N, N'- methylene-bisacrylamide, addition are the 0.3~0.5% of mix monomer gross weight.
The mix monomer is respectively acrylic acid, acrylamide, the 2- acrylamido -2- methyl after NaOH is neutralized
Propane sulfonic acid and sodium styrene sulfonate, wherein the acrylic acid after NaOH is neutralized accounts for the 65%~80% of mix monomer gross weight, third
Acrylamide accounts for the 10%~15% of mix monomer gross weight, 2- acrylamide-2-methylpro panesulfonic acids and accounts for mix monomer gross weight
5~10%, sodium styrene sulfonate account for the 5~10% of mix monomer gross weight.
The silane coupling agent is one kind or two kinds of combination in KH550, KH560, and addition polymerize for superabsorbent water
The 2~5% of thing weight.
To realize second object of the present invention, the technical solution adopted by the present invention is as follows：
Application of the modified super absorbent polymer in cement-based material, includes the following steps：
Weigh cement, fine sand, water and modified super absorbent polymer；The cement of weighing and the fine sand weighed are poured into stirring
Machine, is stirred 50~80 seconds；It is subsequently poured into the water of weighing and stirs 50~80 seconds；Modified super absorbent polymer is eventually adding, is stirred
60~120 seconds, 28 days are conserved through pouring, vibrating, under the conditions of standard curing to obtain the final product.
The cement, fine sand, water parts by weight are as follows：Cement：Fine sand：Water：Modified super absorbent polymer=1:2:0.4：
(0.001~0.008).
It is of the invention to be had the following advantages compared with traditional super absorbent polymer cement-base composite material：
1) traditional super absorbent polymer is mainly used as internal curing of cement-based materials agent, so as to improve cement-based material early water
The application fields such as change degree, early strength and reduction cement-based material contraction, the present invention is using modified super absorbent polymer preparation
Cement-base composite material, using the hole between modified super absorbent polymer filling concrete hyrate and aggregate, reduces cement and mixes
The hole of soil is coagulated, improves the waterproof of concrete structures, impervious characteristic, in addition, having after modified super absorbent polymer water suction excellent
Good water retention property and suitable gel strength, even if compressed water is not easy to extrude, further plugging cement sill hole,
Achieve the purpose that with water sealing, water-saving.
Although 2) traditional high-absorbent material the working performance of cement-based material is influenced it is notable, because water-absorption particle compared with
Greatly, grain shape is irregularly uniform, it is difficult to obtains comparatively ideal high-performance water-proof cement sill.The present invention is surpassed using microemulsion
Sound polymerization, is designed and improves to the molecular structure and synthesis technique of SAP, prepares SAP microemulsions, further filters, is dry
It is dry, obtain a nanometer SAP particles after purification, obtained SAP water-absorption particles smaller (below 150nm), grain shape regular uniform should
SAP water-absorption particles can improve its interaction with cement interface, overcome and SAP is mixed in tradition after silane coupler modified
The simple physical of cement-based material is scattered the shortcomings that, it is being played waterproof, sealing effect at the same time, moreover it is possible to long-term water suction-
Ensure its durability after releasing water circulation.
3) water absorption rate of traditional super absorbent polymer is influenced to be used for extra large work structures it is obvious that being particularly by salt, because
There are extreme influence super absorbent polymer cement-based material waterproof and durability for salt.Super absorbent polymer provided by the invention contains
There are a variety of hydrophilic radicals (carboxyl, sulfonic group, amide groups etc.), its salt tolerance is greatly improved, except meeting that traditional superabsorbent water gathers
Compound acts on the waterproof for outside, being also particularly suitable extra large work structures, sealing, impervious application.
Brief description of the drawings
Fig. 1 is super absorbent polymer reaction unit in the specific embodiment of the invention.
Fig. 2 is SAP particle shape figures prepared by the embodiment of the present invention 3.
Fig. 3 is SAP particle shape figures prepared by comparative example 1 of the present invention.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but does not limit the present invention.
Embodiment 1：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 2 parts by weight, the n-butanol of 1 the parts by weight, (NH of 0.5 parts by weight4)2S2O8Initiator, 0.5 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 60 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 68%, acrylamide content 12%, styrene sulfonic acid sodium content are 10%, 2- acrylamido -2- methyl-props
Sulfonic acid content is 10%, opens ultrasonic wave, after carrying out reaction 1h, prepares SAP microemulsions.Reaction was completed, and product is dried and is made
Crude product.Gained crude product is put into distilled water, 1h is stirred under 70 DEG C of water-baths, it is super up to purifying after filtering, dry, crushing
Water absorbent polymer product.The reaction unit of super absorbent polymer product is shown in Fig. 1.
Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, mechanical agitation is disperseed,
KH550 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is the 3% of super absorbent polymer weight, acute
Strong stirring makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is the 0.1% of cement consumption；The cement of weighing and the fine sand weighed are poured into mixer, stirred
60 seconds；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, shakes
Smash, 28 days are conserved under the conditions of standard curing to obtain the final product.
Embodiment 2：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 1 parts by weight is added
Ether, the neopelex of 2 parts by weight, the n-butanol of 1 the parts by weight, (NH of 0.7 parts by weight4)2S2O8Initiator, 0.3 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 50 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 80%, acrylamide content 10%, styrene sulfonic acid sodium content are 5%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 5%, opens ultrasonic wave, after carrying out reaction 1.5h, prepares SAP microemulsions.Reaction was completed, and product drying is made thick
Product.Gained crude product is put into distilled water, 0.8h is stirred under 65 DEG C of water-baths, it is super up to purifying after filtering, dry, crushing
Water absorbent polymer product.Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, machinery stirs
Mix scattered, KH560 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is super absorbent polymer weight
2%, being vigorously stirred makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.3%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Embodiment 3：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 3 parts by weight, the n-butanol of 2 the parts by weight, (NH of 0.5 parts by weight4)2S2O8Initiator, 0.5 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 50 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 75%, acrylamide content 10%, styrene sulfonic acid sodium content are 7%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 8%, opens ultrasonic wave, after carrying out reaction 1.2h, prepares SAP microemulsions.Reaction was completed, and product drying is made thick
Product.Gained crude product is put into distilled water, 1h is stirred under 60 DEG C of water-baths, up to purifying superabsorbent after filtering, dry, crushing
Aqueous polymer product.The super absorbent polymer particle shape figure being prepared is shown in Fig. 2.
Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, mechanical agitation is disperseed,
KH550 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is the 5% of super absorbent polymer weight, acute
Strong stirring makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.5%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Embodiment 4：Using deionized water as dispersed phase in four-hole bottle, the phenethyl phenol polyoxyethylene of 1 parts by weight is added
Ether, the neopelex of 3 parts by weight, the n-butanol of 1 the parts by weight, (NH of 0.5 parts by weight4)2S2O8Initiator, 0.5 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 45 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 70%, acrylamide content 13%, styrene sulfonic acid sodium content are 7%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 10%, opens ultrasonic wave, after carrying out reaction 2h, prepares SAP microemulsions.Reaction was completed, and product drying is made thick
Product.Gained crude product is put into distilled water, 1h is stirred under 70 DEG C of water-baths, up to purifying superabsorbent after filtering, dry, crushing
Aqueous polymer product.Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, mechanical agitation
It is scattered, KH560 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is super absorbent polymer weight
3%, being vigorously stirred makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.8%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Embodiment 5：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 2 parts by weight, the n-butanol of 2 the parts by weight, (NH of 0.7 parts by weight4)2S2O8Initiator, 0.3 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 60 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 78%, acrylamide content 12%, styrene sulfonic acid sodium content are 5%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 5%, opens ultrasonic wave, after carrying out reaction 1h, prepares SAP microemulsions.Reaction was completed, and product drying is made thick production
Product.Gained crude product is put into distilled water, 1h is stirred under 70 DEG C of water-baths, up to purifying superabsorbent water after filtering, dry, crushing
Polymeric articles.Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, mechanical agitation point
Dissipating, KH550 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is the 2% of super absorbent polymer weight,
Being vigorously stirred makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.5%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Embodiment 6：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 3 parts by weight, the n-butanol of 1 the parts by weight, (NH of 0.5 parts by weight4)2S2O8Initiator, 0.5 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 60 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 72%, acrylamide content 10%, styrene sulfonic acid sodium content are 8%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 10%, opens ultrasonic wave, after carrying out reaction 1h, prepares SAP microemulsions.Reaction was completed, and product is made in 102 DEG C
Crude product.Gained crude product is put into distilled water, 1h is stirred under 70 DEG C of water-baths, it is super up to purifying after filtering, dry, crushing
Water absorbent polymer product.Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, machinery stirs
Mix scattered, KH560 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is super absorbent polymer weight
5%, being vigorously stirred makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.3%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Comparative example 1：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 3 parts by weight, the n-butanol of 2 the parts by weight, (NH of 0.5 parts by weight4)2S2O8Initiator, 0.5 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 50 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 75%, acrylamide content 10%, styrene sulfonic acid sodium content are 7%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 8%, after carrying out reaction 1h, prepares SAP microemulsions.Reaction was completed, product is dried crude product is made.Gained is thick
Product is put into distilled water, 1h is stirred under 60 DEG C of water-baths, up to purifying super absorbent polymer product after filtering, dry, crushing.
The super absorbent polymer particle shape figure being prepared is shown in Fig. 3.
Suitable super absorbent polymer is weighed in three-necked flask, using absolute ethyl alcohol as decentralized medium, mechanical agitation is disperseed,
KH550 modifying agent is added drop-wise in three-necked flask with constant pressure funnel, addition is the 2% of super absorbent polymer weight, acute
Strong stirring makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer.
Cement, fine sand, water and modified super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4,
Modified super absorbent polymer volume is cement consumption 0.5%；The cement of weighing and the fine sand weighed are poured into mixer, stirring 60
Second；The water for being subsequently poured into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates,
28 days are conserved under the conditions of standard curing to obtain the final product.
Comparative example 2：In four-hole bottle, using deionized water as dispersed phase, the phenethyl phenol polyoxyethylene of 2 parts by weight is added
Ether, the neopelex of 2 parts by weight, the n-butanol of 2 the parts by weight, (NH of 0.7 parts by weight4)2S2O8Initiator, 0.3 weight
The N of part is measured, N'- methylene-bisacrylamides are stirred into homogeneous phase soap lye.In the four-hole boiling flask that bath temperature is 60 DEG C,
Under nitrogen protection, the mix monomers of 100 parts by weight is added dropwise within half an hour, in mix monomer, the propylene that is neutralized through NaOH
Acid content is 75%, acrylamide content 10%, styrene sulfonic acid sodium content are 7%, 2- acrylamido -2- methyl-prop sulphurs
Acid content is 8%, opens ultrasonic wave, after carrying out reaction 1h, prepares SAP microemulsions.Reaction was completed, and product drying is made thick production
Product.Gained crude product is put into distilled water, 1h is stirred under 70 DEG C of water-baths, up to purifying superabsorbent water after filtering, dry, crushing
Polymeric articles.
Cement, fine sand, water and super absorbent polymer are weighed, wherein, cement, fine sand, the ratio of water are 1:2:0.4, superabsorbent
Aqueous polymer volume is cement consumption 0.5%；The cement of weighing and the fine sand weighed are poured into mixer, stirred 60 seconds；Then
The water for pouring into weighing stirs 60 seconds；Modified super absorbent polymer is eventually adding, is stirred 90 seconds, is then poured, vibrates, standard curing
Under the conditions of conserve 28 days to obtain the final product.
Figure it is seen that the SAP particle size uniformities being prepared by supersound process, shape is regular, and
Below 150nm.From figure 3, it can be seen that not only homogeneity is poor for the SAP particles without ultrasonication, but also particle is larger.
The present invention is using country " JC/T 984-2011, JC/T 951-2005 and GB50728-2011 " standards, to implementing
(modification) super absorbent polymer and the performance of cement mortar sample prepared by example 1~6 and comparative example 1~2 is tested, it is surveyed
Test result is see table 1.Wherein, what embodiment 1~6 and comparative example 2 were tested is the salt tolerance of modified super absorbent polymer, comparative example
What is tested is the salt tolerance of super absorbent polymer.
1 super absorbent polymer of table or the performance test results of modified super absorbent polymer and cement mortar sample
As it can be seen from table 1 super absorbent polymer prepared by ultrasound is after modified relative to the superabsorbent without supersonic modifying
When for cement mortar sample, properties have significantly to be improved aqueous polymer；And even if sonicated, if without
Silane coupler modified, obtained super absorbent polymer when for cement mortar sample, also can by the performance such as impermeability, durability
Significantly reduce.
Claims (5)
- A kind of 1. application of modified super absorbent polymer in cement-based material, it is characterised in that：Include the following steps：Weigh cement, fine sand, water and modified super absorbent polymer；The cement of weighing and the fine sand weighed are poured into mixer, stirred Mix 50~80 seconds；It is subsequently poured into the water of weighing and stirs 50~80 seconds；It is eventually adding modified super absorbent polymer, stirring 60~ 120 seconds, 28 days are conserved through pouring, vibrating, under the conditions of standard curing to obtain the final product；The cement, fine sand, water parts by weight are as follows：Cement：Fine sand：Water：Modified super absorbent polymer=1:2:0.4： (0.001~0.008)；The modified super absorbent polymer is prepared as follows：(1) using deionized water as dispersed phase, emulsifying agent, assistant for emulsifying agent, initiator, crosslinking agent is added and is stirred into homogeneous phase soap Liquid；The emulsifying agent is anion emulsifier and nonionic emulsifier；(2) in 40~60 DEG C, under inert atmosphere, mix monomer is added dropwise within half an hour, opens ultrasonic wave, reacts 1~2h Afterwards, SAP microemulsions are prepared；Reaction was completed, product is dried crude product is made；(3) gained crude product is put into distilled water, 0.5~1h is stirred at 60~70 DEG C, up to pure after filtering, dry, crushing The super absorbent polymer product of change；(4) with absolute ethyl alcohol decentralized medium, super absorbent polymer is disperseed under mechanical agitation, constant pressure funnel drips modifying agent It is added in three-necked flask, being vigorously stirred makes it be dispersed in super absorbent polymer surface, up to modified super absorbent polymer；Institute It is silane coupling agent to state modifying agent；The initiator is (NH4)2S2O8, addition is mix monomer gross weight for 0.5~0.7%；Crosslinking agent is N, N'- Methylene-bisacrylamide, addition are the 0.3~0.5% of mix monomer gross weight；The mix monomer is respectively acrylic acid, acrylamide, the 2- acrylamido -2- methyl-prop sulphurs after NaOH is neutralized Acid and sodium styrene sulfonate, wherein the acrylic acid after NaOH is neutralized accounts for the 65%~80% of mix monomer gross weight, acryloyl Amine account for the 10%~15% of mix monomer gross weight, 2- acrylamide-2-methylpro panesulfonic acids account for mix monomer gross weight 5~ 10%th, sodium styrene sulfonate accounts for the 5~10% of mix monomer gross weight；The silane coupling agent is super absorbent polymer weight for one kind in KH550, KH560 or two kinds of combination, addition The 2~5% of amount.
- 2. application of the modified super absorbent polymer according to claim 1 in cement-based material, it is characterised in that：The addition of anion emulsifier and nonionic emulsifier is respectively the 1~5% of mix monomer gross weight in the emulsifying agent.
- 3. application of the modified super absorbent polymer according to claim 1 or 2 in cement-based material, it is characterised in that：The nonionic emulsifier is phenethyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, first contracting polyoxyethylene nonyl phenyl One kind in vinethene or the combination between them；The anion emulsifier is neopelex, dodecyl One kind or two kinds of combination in sodium sulfonate.
- 4. application of the modified super absorbent polymer according to claim 1 or 2 in cement-based material, it is characterised in that：The assistant for emulsifying agent addition is the 0.5~3% of mix monomer gross weight.
- 5. application of the modified super absorbent polymer according to claim 1 in cement-based material, it is characterised in that：The assistant for emulsifying agent is n-butanol, propyl alcohol, one kind in isopropanol or the combination between them.
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| CN116041011B (en) * | 2022-12-29 | 2024-03-29 | 河北高速集团工程咨询有限公司 | Anti-freezing concrete containing micro-nano SAP holes and preparation method thereof |
| CN116496022A (en) * | 2023-06-27 | 2023-07-28 | 石家庄市长安育才建材有限公司 | Thickening agent for coarse sand concrete and preparation method thereof |
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