CN102675557A - Slow-release type concrete slump retaining agent and preparation method thereof - Google Patents
Slow-release type concrete slump retaining agent and preparation method thereof Download PDFInfo
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- CN102675557A CN102675557A CN2012101525652A CN201210152565A CN102675557A CN 102675557 A CN102675557 A CN 102675557A CN 2012101525652 A CN2012101525652 A CN 2012101525652A CN 201210152565 A CN201210152565 A CN 201210152565A CN 102675557 A CN102675557 A CN 102675557A
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Abstract
The invention discloses a slow-release type concrete slump retaining agent and a preparation method thereof. The preparation method comprises the following steps of: a, dissolving unsaturated alkyl polyoxyethylene ether into water, adding unsaturated carboxylic acid monomer and a molecular-weight adjusting agent, stirring and mixing uniformly, and heating; b, adding an initiator and the slow-release type comonomer and carrying out insulating polymerization; c, supplementing the initiator during the insulating polymerization so as to reach full reaction; and d, after insulation, reducing temperature and neutralizing. The preparation method disclosed by the invention has the advantages that the cross-linking step which is very difficult to operate and control in the original synthetic process is avoided; and since the slow-release monomer is used, the production is easy and the slump retaining effect can be improved. The slow-release type concrete slump retaining agent prepared by the method has the characteristic of increase of water reducing rate along with the time, and can be used singly or can be combined with the polycarboxylic-acid slump retaining agent for use so as to achieve the slump retaining effect.
Description
Technical field
The present invention relates to a kind of concrete slump retaining agent and preparation method thereof, particularly a kind of sustained-release polycarboxylic concrete slump retaining agent.
Background technology
Along with being in full swing of China's construction work, architectural concrete amounts such as railway, highway, bridge increase greatly.Simultaneously, the production of high performance concrete such as durable, weather-proof, high-strength more and more depends on high-performance water reducing agent, and this popularizes in an all-round way and use in the whole nation, just high performance water reducing agent of polyocarboxy acid.
Polycarboxylate water-reducer, be by unsaturated fatty acids and polyoxyethylene glycol through graft polymerization, the high branched polymer dispersion agent that obtains.Compare with water reducer in the past, it has the water-reducing rate height, and slump-loss waits plurality of advantages slowly; But this all is embodied on the stoste, and aspect composite, polycarboxylate water-reducer is difficult for finding the complex material that matches with it; So often in practical engineering application, the advantage of its net effect is not obvious.
Compare with traditional high efficiency water reducing agent; Though having, polycarboxylic acids dehydragent protects the advantages such as ability is strong, water-reducing rate is high, molecular structure is flexible of collapsing; But in the face of domestic cement complicated and changeable and concrete material, polycarboxylic acids dehydragent often can not embody its high performance advantage.In some engineering, polycarboxylic acids dehydragent can often run into problems such as water-reducing rate is low, slump-loss very fast, concrete workability is poor, cement adaptability is bad.
Wherein the most scabrous problem is that slump-loss is too fast.To on this problem, the admixture worker is usually with the composite guarantors that improve water reducer of retardant such as polycarboxylic acids dehydragent and glucose (sour sodium), sucrose, the molasses ability of collapsing.Protect the weak shortcoming of the ability of collapsing but the adding of retardant can not fundamentally solve, too much volume can make prolong concrete time of coagulation on the contrary, reduces concrete quality, influences construction speed.So the strong polycarboxylic acids dehydragent that perhaps can improve of ability that a kind of flexibility is good, the guarantor is collapsed is protected the research focus that the admixture of the ability of collapsing has just become concrete admixture.
Some prior aries, the shortcoming and defect part of comparing with the present invention:
Patent documentation:
Cn 1667009 a difference: the water reducer of the low diminishing of no slowly-releasing, the guarantor is collapsed relatively poor; Naphthalene system is composite with carboxylic acid, in actual experiment, does not operate successful precedent.
Cn 101066851 differences: cross-linking type, epoxy cross-linking, possible in theory only kept by 90 minutes.
Cn 101817657 differences: cross-linking type, having under the situation of water, use the cis-butenedioic anhydride esterification and crosslinking, in actual experiment, do not operate successful precedent.
Cn 101831037 differences: cross-linking type, crosslinked with the PEG double methacrylate, effect should be unable to be above 40 minutes.
Cn 102093521 differences: be cross-linking type, come acid esters crosslinked with the PEG span, commercially available carboxylic acid water reducer is almost not loss all, the effect and not obvious it is thus clear that its guarantor is collapsed.
Non-patent literature:
" research and the application of high-performance poly carboxylic-acid slump retaining agent " difference: cross-linking type, the PEG double methyl methacrylate is crosslinked, and the slump of saying so 2 hours there is not loss, but divergence do not say, we can say that divergence is bad.
" development and the application of the efficient diminishing slump retaining agent of poly carboxylic acid " difference: no slowly-releasing, compound method does not have reagent, and carboxylic acid and naphthalene are the composite successful precedent of in actual experiment, not operating.
" application of poly carboxylic acid series water reducer in ready mixed concrete " difference: be summary of Application property article, do not research and develop content, do not have the concrete operations step.
" the synthetic and application of new and effective slump retaining agent " difference: the old level in 98 years.The carboxylic acid water reducer is mixed to 0.2% and self just can have been reached performance like this now.Mix naphthalene and tie up in the actual experiment the successful precedent of operation.
" green of novel graftomer slump retaining agent synthetic and performance study " difference: no slowly-releasing, old level in 2002, water reducer is not mixed slump retaining agent and can be kept 2 hours in the same old way under 0.8% volume.
" performance study of the efficient slump retaining agent of novel carboxylic acid quasi-graft copolymer " difference: cross-linking type, the difunctionality polyethers is crosslinked, and concrete keeps both slightly losses in a hour.
" the process for cleanly preparing performance and the practical applications of novel carboxylic acid class graftomer slump retaining agent " difference: delay absorption but not slowly-releasing with the acid anhydrides complexing.Acid anhydrides can not complexing, and be hydrolyzed into acid could complexing, and effect possibly have, but poor effect.
In recent years, the special-purpose slump retaining agent of poly carboxylic acid begins to occur, and its mechanism of action mostly is through linking agent, molecule crosslinked the poly carboxylic acid slump retaining agent, and slowly separate crosslinkedly, protect the purpose of collapsing thereby reach.But the difficult control of the degree of crosslinking of this technology, the cement adaptability of product is bad.Based on this present situation, the present invention has researched and developed slow release type non-crosslinked poly carboxylic acid slump retaining agent.
Summary of the invention
Technical problem to be solved by this invention is, does not use linking agent, and synthesizes the poly carboxylic acid slump retaining agent with slow release effect.The present invention is according to " absorption-dispersion " mechanism of action of water reducer; Prepared a kind of high polycarboxylic acid slump retaining agent of protecting the ability of collapsing that has; This slump retaining agent has tangible slow release effect; Use separately or an amount of slump hold facility that can obviously improve common polycarboxylic acids dehydragent with common polycarboxylic acids dehydragent after composite, and it is to having no adverse effect concrete time of coagulation and strength development.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of slow release type concrete slump retaining agent, may further comprise the steps:
A. the unsaturated alkyl Soxylat A 25-7 is dissolved in the water, adds unsaturated carboxylic acid monomer and molecular weight regulator, stirring makes it mix, and is heated to certain temperature;
B. drop into initiator and slow release type comonomer, the insulation polymerization;
C. between the insulation polymerization period, add initiator, make its sufficient reacting;
D. insulation finishes back cooling neutralization.
In said step a, the unsaturated alkyl in the said unsaturated alkyl Soxylat A 25-7 is preferably: one or more in isopentene group, isobutenyl, allyl group, the vinyl.
In said step a, the molecular weight of said unsaturated alkyl Soxylat A 25-7 can be 500 to 5000, is preferably 800 to 2500.
In said step a; Said unsaturated carboxylic acid monomer can be the unsaturated carboxylic acid and/or the unsaturated acid anhydride of 3～6 carbon, is preferably: one or more in vinylformic acid, methylacrylic acid, maleic acid, MALEIC ANHYDRIDE, methylene-succinic acid, FUMARIC ACID TECH GRADE, the 3-carboxyl-2-propene dicarboxylic acid.
In said step a; Said molecular weight regulator is preferably the chain-transfer agent that all chain transfers such as methallylsulfonic acid sodium, thioglycolic acid, sulfo-lactic acid, vinyl-acetic ester surpass Virahol for the chain-transfer agent of all chain transfers above Virahol.
In said step a, be heated to certain stablizing, can be 30 ℃ to 90 ℃, be preferably 40 ℃ to 65 ℃.
In said step a, the consumption of the water that is added is 25% to 50% to be as the criterion with the control total concn.
In said step b, the initiator of input is preferably one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ydrogen peroxide 50, tertbutyl peroxide, potassium permanganate, the SRM 935a.
In said step b, described slow release type comonomer can hydrolysis in alkaline aqueous solution, the saturated alcohol ester of unsaturated carboxylic acid, fragrant alcohol ester, oxa-alcohol ester or acid amides, and intramolecularly only contains 4～15 carbon atoms.Be preferably in Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, isopropyl acrylate, Bing Xisuandingzhi, vinylformic acid p-aminophenyl phenolic ester, vinylformic acid acetyl triethyl, Rocryl 400, Rocryl 410, TEB 3K, Jia Jibingxisuanyizhi, isopropyl methacrylate, NSC 20956, dimethyl maleate, diethyl maleate, acrylic amide, the NMA one or more.
In said step b, insulation polymeric temperature fluctuation range can be positive and negative 10 ℃ of temperature among the step a, is preferably positive and negative 5 ℃.
In said step b, the said insulation polymeric time can be 2 hours to 5 hours.
In said step c, the described initiator of adding is preferably ydrogen peroxide 50 or ammonium persulphate.
In said step c, saidly add time of initiator between polymerization period in insulation, the said time of adding initiator, be preferably and add once soaking time two/a period of time, or soaking time 1/3rd and three/two o'clock respectively add once.
In said step c, the said consumption of adding initiator is preferably 20～80% of initiator mole number described in the step b.
In said steps d, the actual temp of said cooling is preferably below 50 ℃.
In said steps d, said neutralization procedure can for: add mass percent concentration and be 40% sodium hydroxide solution, making said solvent be neutralized to pH value is 4-7 or 7-9, is preferably 6-7 or 7-8.
The preparation method of said slow release type concrete slump retaining agent may further include following steps: e. adds 2～5% Sunmorl N 60S or the Trisodium Citrate account for said slow release type concrete slump retaining agent gross weight.
The preparation method of said slow release type concrete slump retaining agent also may further include following steps: e. and adds 1～2.5% the Sunmorl N 60S account for said slow release type concrete slump retaining agent gross weight and 1～2.5% Trisodium Citrate.
For solving the problems of the technologies described above, the present invention also provides a kind of slow release type concrete slump retaining agent of preparing method's preparation of the concrete slump retaining agent of slow release type as stated.
For solving the problems of the technologies described above, the present invention provides the application of a kind of concrete slump retaining agent of slow release type as stated in concrete construction again.
Beneficial technical effects of the present invention is: avoided in the past in the building-up process, be very difficult to operate and control cross-linking step, change into and use the slowly-releasing monomer, promptly be easy to produce, can improve again and protect the effect of collapsing.Slump retaining agent of the present invention has the advantages that water-reducing rate amplifies in time, can be separately or with the composite use of poly carboxylic acid slump retaining agent, reach and protect the effect of collapsing.
Embodiment
After common polycarboxylic acids dehydragent joins in the concrete mortar, in the cement initial hydration phase, the water reducer molecule will exist with four kinds of forms: 1. be adsorbed on hydrated cementitious product surface; 2. be adsorbed in unhydrated cement particle surface; 3. be wrapped in the hydrated cementitious product; 4. remain in the liquid phase part that promptly is not adsorbed.Along with the aggravation of hydrated cementitious, the water reducer molecule of first kind and second kind form existence will change the third form gradually into, and the water reducer molecule that former two kinds of forms exist is to the dispersing property decisive role.Therefore; Common polycarboxylic acids dehydragent is in adding concrete mortar behind 1～2h; The water reducer molecule that exists owing to second kind of form disappears and a large amount of minimizings of first kind of form water reducer molecule make its dispersiveness to concrete mortar descend, and causes concrete flowability to descend.
If concrete mortar still obtained behind 1～2h better even be superior to initial flowability; Just need there be more water reducer molecule " to replenish "; Replacement is continued to be adsorbed onto performance dispersive effect on the hydrated cementitious product by the water reducer molecule that the hydrated cementitious product covers.For common polycarboxylic acids dehydragent, these molecules that " replenish " are mainly derived from the water reducer molecule that remains in the liquid phase.And the adsorption group of polycarboxylate water-reducer is a hydroxy-acid group, and in this strong basicity environment of grout, hydroxy-acid group exists with anionic form.Because this anionic group, stronger electrostatic attraction takes place in the cement particle that can have positive charge, so in the short period of time, can reach the adsorption-desorption balance, promptly residue in the liquid phase the water reducer molecule seldom.Just because of this; In the concrete flowability variation; After the water reducer molecule that just plays water-reduction was embedded in the hydrated cementitious product, the water reducer molecular amounts that can play supplementary function was less, is not enough to make concrete mortar behind 1～2h, still to obtain good flowability.And if can synthesize a kind of on chemical structure, very similar polycarboxylic acids dehydragent, but can not produce anionic molecule, the adsorption of so this molecule will weaken greatly, promptly major part all remains in the liquid phase.If this molecule can also issue biochemical reaction at concrete alkalescence environmental activity; Constantly produce the water reducer molecule that has anionic group; Thereby " replenish " the water reducer molecule performance dissemination that is covered by the hydrated cementitious product; Then can keep highly beneficial, the guarantor that can obviously the improve polycarboxylate water-reducer ability of collapsing to the flowability behind cement concrete slurry 1～2h.
According to above hydrated cementitious and water reducer adsorption theory, the invention provides a kind of high-performance sustained-release polycarboxylic class slump retaining agent.This slump retaining agent is a comb shaped molecular structure, has on the main chain chemical reaction can take place in grout, and generates the release structures of adsorption group such as carboxyl.Because its initial stage adsorption group is few, thus adsorptive power well below common polycarboxylic acids dehydragent, thereby cause its most of molecules, all remain in the cement slurry liquid phase and do not adsorbed by the cement particle.At the hydrated cementitious initial stage, the grout liquid phase becomes the strong basicity environment very soon, so the slowly-releasing group begins reaction; Gradually be transformed into adsorption group; Behind 1～2h, nearly all slowly-releasing group all is transformed into adsorption group, so slump retaining agent is transformed into conventional water reducer; And be adsorbed on cement particle and the hydrated product thereof, thereby make concrete mortar continue to keep good mobility.
The preparation method of slow release type concrete slump retaining agent of the present invention may further comprise the steps: a. is dissolved in the water the unsaturated alkyl Soxylat A 25-7, adds unsaturated carboxylic acid monomer and molecular weight regulator, stirs to make it mix, and is heated to certain temperature; B. drop into initiator and the slow release type comonomer makes its polymerization; C. be incubated polymerization, and add the part initiator, make its sufficient reacting; The d insulation finishes back cooling neutralization.
Described concrete polycarboxylate slump retaining agent preparation method, in step a, the unsaturated alkyl in the described unsaturated alkyl Soxylat A 25-7 is preferably in isopentene group, isobutenyl, allyl group, the vinyl one or more.
The concrete polycarboxylate slump retaining agent preparation method who states, in step a, the molecular weight of said unsaturated alkyl Soxylat A 25-7 can be 500 to 5000, is preferably 800 to 2500.
Said concrete polycarboxylate slump retaining agent preparation method; In step a; Said comonomer can be 3～6 unsaturated carboxylic acid and/or unsaturated acid anhydride for carbon number, is preferably in vinylformic acid, methylacrylic acid, maleic acid, MALEIC ANHYDRIDE, methylene-succinic acid, FUMARIC ACID TECH GRADE, the 3-carboxyl-2-propene dicarboxylic acid one or more.
Said concrete polycarboxylate slump retaining agent preparation method; In step a, described molecular weight regulator can be preferably the chain-transfer agent that all chain transfers such as methallylsulfonic acid sodium, sodium allyl sulfonate, thioglycolic acid, sulfo-lactic acid, vinyl-acetic ester surpass Virahol.
Said concrete polycarboxylate slump retaining agent preparation method, in step a, the described certain temperature that is heated to can be 30 to 90 ℃, is preferably 40 to 65 ℃.
Said concrete polycarboxylate slump retaining agent preparation method, in step a, the consumption of the water that is added is 25% to 50% to be as the criterion with control total mass percentage concentration.
Said concrete polycarboxylate slump retaining agent preparation method, the initiator that in step b, drops into is preferably one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ydrogen peroxide 50, tertbutyl peroxide, potassium permanganate, the SRM 935a.
Said concrete polycarboxylate slump retaining agent preparation method; In step b, described slow release type comonomer can hydrolysis in alkaline aqueous solution; The saturated alcohol ester of unsaturated carboxylic acid, fragrant alcohol ester, oxa-alcohol ester or acid amides, and intramolecularly only contains 4～15 carbon atoms.Be preferably in Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl acrylate, ethyl propenoate, isopropyl acrylate, Bing Xisuandingzhi, vinylformic acid p-aminophenyl phenolic ester, vinylformic acid acetyl triethyl, Rocryl 400, Rocryl 410, TEB 3K, Jia Jibingxisuanyizhi, isopropyl methacrylate, NSC 20956, dimethyl maleate, diethyl maleate, acrylic amide, the NMA one or more.
Said concrete polycarboxylate slump retaining agent preparation method, in step b, said insulation polymeric temperature fluctuation range can be positive and negative 10 ℃ of temperature among the step a, is preferably positive and negative 5 ℃.。
Said concrete polycarboxylate slump retaining agent preparation method, in step b, the said insulation polymeric time can be 2 hours to 5 hours.
Said concrete polycarboxylate slump retaining agent preparation method, in step c, the described initiator of adding is preferably ydrogen peroxide 50 or ammonium persulphate.
Said concrete polycarboxylate slump retaining agent preparation method in step c, the said time of adding initiator, is preferably and adds once soaking time two/a period of time, or soaking time 1/3rd and three/two o'clock respectively adds once.
Said concrete polycarboxylate slump retaining agent preparation method, in step c, the said consumption of adding initiator is preferably 20～80% of initiator mole number described in the step b.
Said concrete polycarboxylate slump retaining agent preparation method, in said steps d, the actual temp of said cooling is preferably below 50 ℃.
Said concrete polycarboxylate slump retaining agent preparation method, said neutralization procedure can for: add mass percent concentration and be 40% sodium hydroxide solution, make said solvent be neutralized to the pH value more than or equal to 7.
The present invention also may further include following steps: e. and adds 1～2.5% the Sunmorl N 60S account for said slow release type concrete slump retaining agent gross weight and 1～2.5% Trisodium Citrate.
The present invention can further include following steps: e. adds 2～5% Sunmorl N 60S or the Trisodium Citrate account for said slow release type concrete slump retaining agent gross weight.
Below will combine form and specific embodiment to specify embodiment of the present invention, how the utilisation technology means solve technical problem to the present invention whereby, and the implementation procedure of reaching technique effect can make much of and implement according to this.
The raw material umber is the parts by weight ratio among all embodiment.
Embodiment 1:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 90 parts of entry, 60 parts of isopentene Soxylat A 25-7s, 3 parts in vinylformic acid, 1.5 parts of vinyl-acetic esters constantly stir so that it all is dissolved in the water and heats up; Add 0.2 part of acrylic amide in the time of 70 ℃, 2 parts of Hydroxyethyl acrylates, 0.6 part of ammonium persulphate, and insulation.When being incubated 2 hours, add 0.2 part of ammonium persulphate.Be incubated cooling after 4 hours, 9 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 2:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 90 parts of entry, 60 parts of isopentene Soxylat A 25-7s, 5.2 parts of methylacrylic acids, 1.3 parts in methallylsulfonic acid sodium constantly stirs so that it all is dissolved in the water and heats up; Add 1 part of N-p-sulfonic acid Phenyl Acrylamide in the time of 80 ℃, 3.5 parts of NMAs, 0.6 part of Sodium Persulfate, and insulation.Be incubated 1 hour and 2 hours the time, respectively add 0.15 part of ammonium persulphate.Be incubated cooling after 3 hours, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 3:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 110 parts of entry, 60 parts of iso-butylene Soxylat A 25-7s, 4.8 parts of methylacrylic acids, 1.2 parts in methallylsulfonic acid sodium constantly stirs so that it all is dissolved in the water and heats up; Add 0.4 part of Hydroxyethyl acrylate in the time of 35 ℃, 0.9 part of Propylene glycol monoacrylate, 0.6 part in potassium permanganate, and insulation.Be incubated 45 minutes and 110 minutes the time, respectively add 0.11 part of ammonium persulphate.Be incubated cooling after 3 hours, 8 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 4:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 90 parts of entry, 60 parts of iso-butylene Soxylat A 25-7s, 5.3 parts in vinylformic acid, 1.3 parts of thioglycolic acids constantly stir so that it all is dissolved in the water and heats up; Add 0.7 part of ethyl propenoate in the time of 90 ℃, 0.2 part of isopropyl acrylate, 1.0 parts in ydrogen peroxide 50,0.3 part of Potassium Persulphate, and insulation.Be incubated 1.5 hours, respectively add 0.4 part in ydrogen peroxide 50.Be incubated cooling after 180 minutes, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 5:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 120 parts of entry, 60 parts of allyl polyethenoxy ethers, 5.8 parts of MALEIC ANHYDRIDEs, 1.1 parts of vinyl-acetic esters constantly stir so that it all is dissolved in the water and heats up; Add 1.2 parts of dimethyl maleates in the time of 45 ℃, 0.8 part of NMA, 1.6 parts in ydrogen peroxide 50, and insulation.Be incubated 1 hour and 2 hours the time, respectively add 0.25 part of ammonium persulphate.Be incubated cooling after 3 hours, 6 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 6:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 100 parts of entry, 60 parts of allyl polyethenoxy ethers, 4.9 parts of methylene-succinic acids, 1.1 parts of sulfo-lactic acids constantly stir so that it all is dissolved in the water and heats up; Add 0.3 part of TEB 3K in the time of 65 ℃, 0.5 part of vinylformic acid p-aminophenyl phenolic ester, 0.5 part of tertbutyl peroxide, and insulation.Be incubated 50 minutes and 140 minutes the time, respectively add 0.12 part of ammonium persulphate.Be incubated cooling after 200 minutes, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 7:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 120 parts of entry, 60 parts of allyl polyethenoxy ethers; 3.9 parts of methylene-succinic acids; 1.2 parts of 3-carboxyls-2-propene dicarboxylic acid, 1.1 parts of sulfo-lactic acids constantly stir so that it all is dissolved in the water and heats up; Add 0.8 part of vinylformic acid acetyl triethyl in the time of 60 ℃, 1.5 parts of vinylformic acid p-aminophenyl phenolic esters, 1.2 parts of tertbutyl peroxides, and insulation.When insulation 50 minutes and 140 minutes, respectively add 0.3 part of ammonium persulphate.Be incubated cooling after 180 minutes, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 8:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 110 parts of entry, 60 parts of allyl polyethenoxy ethers, 3.9 parts of maleic anhydrides, 2.5 parts of 3-carboxyls-2-propene dicarboxylic acid, 0.8 part of sulfo-lactic acid constantly stirs so that it all is dissolved in the water and heats up; Add 1.5 parts of vinylformic acid acetyl triethyls in the time of 50 ℃, 1.5 parts of Propylene glycol monoacrylates, 2.2 parts of SRM 935as, and insulation.When insulation 50 minutes and 140 minutes, respectively add 0.3 part of ammonium persulphate, 1.2 parts in ydrogen peroxide 50.Be incubated cooling after 200 minutes, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 9:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 110 parts of entry, 60 parts of allyl polyethenoxy ethers; 5.2 parts of FUMARIC ACID TECH GRADE, 1.5 parts of acrylic amides, 0.8 part of sulfo-lactic acid; 0.4 part of vinyl-acetic ester constantly stirs so that it all is dissolved in the water and heats up; Add 0.5 part of isopropyl acrylate in the time of 50 ℃, 1.8 parts of dimethyl maleates, 2.2 parts in ydrogen peroxide 50, and insulation.When insulation 50 minutes and 140 minutes, respectively add 0.5 part of ammonium persulphate.Be incubated cooling after 200 minutes, 7 parts of the sodium hydroxide solutions of adding 40%, continuing to stir promptly obtains product.
Embodiment 10:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 90 parts of entry, 60 parts of vinyl Soxylat A 25-7s; 3.5 parts of FUMARIC ACID TECH GRADE; 3.8 parts of 3-carboxyls-2-propene dicarboxylic acid, 1.4 parts of sodium allyl sulfonates constantly stir so that it all is dissolved in the water and heats up; Add 0.6 part of dimethyl maleate in the time of 70 ℃, 0.1 part of diethyl maleate, 1.2 parts of SRM 935as, 0.3 part of tertbutyl peroxide, and insulation.Be incubated 40 minutes and 90 minutes the time, respectively add 0.11 part of ammonium persulphate.Be incubated after 160 minutes cooling, add 6 parts of 40% sodium hydroxide solutions, continue to stir, add 2～5% Sunmorl N 60S or the Trisodium Citrate that account for said slow release type concrete slump retaining agent gross weight and promptly obtain product.
Embodiment 11:
During normal temperature, in the four-hole boiling flask that TM, whisking appliance are housed, add 90 parts of entry, 54 parts of iso-butylene Soxylat A 25-7s, 5.4 parts of FUMARIC ACID TECH GRADE, 1.1 parts of thioglycolic acids constantly stir so that it all is dissolved in the water and heats up; Add 0.3 part of acrylic amide in the time of 50 ℃, 0.5 part of NMA, 0.4 part of Potassium Persulphate, 0.5 part of tertbutyl peroxide, and insulation.Be incubated 45 minutes and 100 minutes the time, respectively add 0.5 part in ydrogen peroxide 50.Be incubated after 170 minutes cooling, add 6 parts of 40% sodium hydroxide solutions, continue to stir, add 1～2.5% the Sunmorl N 60S that accounts for said slow release type concrete slump retaining agent gross weight and 1～2.5% Trisodium Citrate and promptly obtain product.
Comparative Examples 1:
In the four-necked bottle that whisking appliance, TM, constant pressure funnel are housed, add a certain amount of zero(ppm) water, maleic anhydride, methylallyl polyethers and ammonium persulphate earlier; When rising to 70～80 ℃; Begin to drip the mixing solutions of sodium sulfite anhy 96, molecular weight regulator and polyoxyethylene glycol double methyl methacrylate, 2～3h dropwises, and continues below the reaction 2h postcooling to 40 ℃; NaOH solution adjust pH with 30% is 5～6, obtains yellow transparent liquid.Thin up to solid content is 20%, obtains the polycarboxylic acid slump retaining agent.
Comparative Examples 2:
The TK-502 modifying agent of Shanghai Hualian Construction Admixture Manufactory Co., Ltd.'s research and development.
Comparative Examples 3:
With toxilic acid liquor-saturated with vinyl monomer (carry out copolymerization like vinylformic acid, methylacrylic acid, vinylbenzene, iso-butylene, acrylic amide, sodium allyl sulfonate, Hydroxyethyl acrylate etc., binary or terpolymer, make to have pendant carboxylic group and sulfonic group on the copolymer chain.Utilize pendant carboxylic group and polyoxyethylene glycol on the polymeric chain to carry out grafting, on polymeric chain, introduce activity hydroxy, synthetic slump retaining agent.
Comparative Examples 4:
Unsaturated carboxylic acid monomer, a small amount of stopper and catalyzer monoalkyl polyethers and the quantitative difunctionality polyethers with certain amount of substance ratio joined in the three-necked bottle; Be warming up to (145 ± 5) and ℃ carry out graft reaction; Cool then, and in reaction flask, add a certain amount of distilled water diluting cooling, add maleic anhydride again; After being warming up to 80～95 ℃ after the dissolving, begin to drip composite initiator solution (K
2S
2O
8+ 30%H
2O
2) (about 90min), insulation 3h naturally cools to below 40 ℃, adds the alkaline solution neutralization and obtains the sticky clear solution of bright red-brown, is concrete slump retaining agent.
Comparative Examples 5:
During normal temperature; In the four-hole boiling flask that TM, whisking appliance, reflux condensate device are housed, add 60 parts of polyoxyethylene glycol-Ucar 35 unregulated polymer, stir and be warmed up to 60 ℃, add 24.5g MALEIC ANHYDRIDE, 3g tosic acid; And continue to stir and be warmed up to 145 ℃, be incubated 3 hours.In the insulating process, get acrylic amide 7.63g, add in the 15g water.Other gets Potassium Persulphate 0.5g, ydrogen peroxide 50 0.8g, also adds in the 15g water.Shake up two parts of solution subsequent use.After insulation finishes, in four-hole bottle, add 60g water, keep 90 ℃ of temperature.After stirring, beginning drips two parts of solution simultaneously, in 1.5 hours, drips off uniformly, and continues to keep 90 ℃, cooling after 1.5 hours.After treating that temperature is lower than 40 ℃, 6 parts of the sodium hydroxide solutions of adding 40% continue to stir, and promptly obtain product.
The cement paste experiment: weigh 300g Lafarge reference cement, slump retaining agent adds water to 87ml, starches stirrer only with standard and stirs, and does clean slurry degree of mobilization after (stirred slowly 2 minutes, stopped 15 seconds, stirred soon 2 minutes), and the clean slurry degree of mobilization of measuring behind the different time changes.The slump retaining agent volume is that 160～170mm is as the criterion with initial stage clean slurry degree of mobilization.
Experimental result sees the following form:
Annotate: "-" expression has no degree of mobilization in the table, can't pour in the mould.
From the test-results of last table, when mixing slump retaining agent of the present invention, the hold-time of starching degree of mobilization only is obviously than length of the prior art.
Concrete slump mixes experiment: concrete mix is C: F: S: G is big: G is little=and 320: 70: 778: 543: 528 (for actual material therefor of site works and proportioning); Fixing water consumption, and as far as possible keep the machine slump close, measure the concrete state through the time changing conditions (C: cement; F: flyash; S: sand, G is big: big stone, G is little: handstone).
Experimental result sees the following form:
Annotate: "-" expression numerical value is too little in the table, does not measure meaning.
From the test-results of last table, when mixing slump retaining agent of the present invention, the hold-time of the slump is obviously than length of the prior art.
All are above-mentioned to be the primary implementation method of this intellecture property, does not set restriction and implements this novel method with other forms.Those skilled in the art will utilize this important information, foregoing revised, to realize similar implementation status.But all are based on modification of the present invention or transform novel method, belong to the right of reservation.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any professional and technical personnel of being familiar with possibly utilize the technology contents of above-mentioned announcement to change or be modified as the equivalent embodiment of equivalent variations.But everyly do not break away from technical scheme content of the present invention,, still belong to the protection domain of technical scheme of the present invention according to any simple modification, equivalent variations and the remodeling that technical spirit of the present invention is done above instance.
Claims (10)
1. the preparation method of a slow release type concrete slump retaining agent is characterized in that, may further comprise the steps:
A. the unsaturated alkyl Soxylat A 25-7 is dissolved in the water, adds unsaturated carboxylic acid monomer and molecular weight regulator, stirring makes it mix, heating;
B. drop into initiator and slow release type comonomer, the insulation polymerization;
C. between the insulation polymerization period, add initiator, make its sufficient reacting;
D. insulation finishes back cooling neutralization.
2. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1; It is characterized in that; In said step a, the unsaturated alkyl of said unsaturated alkyl Soxylat A 25-7 is: one or more in isopentene group, isobutenyl, allyl group, the vinyl.
3. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, the molecular weight of said unsaturated alkyl Soxylat A 25-7 is 500 to 5000.
4. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, the molecular weight of said unsaturated alkyl Soxylat A 25-7 is 800 to 2500.
5. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, said unsaturated carboxylic acid monomer is the unsaturated carboxylic acid and/or the unsaturated acid anhydride of 3～6 carbon.
6. according to the preparation method of the said slow release type concrete slump retaining agent of claim 5; It is characterized in that; In said step a, said unsaturated carboxylic acid monomer is: one or more in vinylformic acid, methylacrylic acid, maleic acid, MALEIC ANHYDRIDE, methylene-succinic acid, FUMARIC ACID TECH GRADE, the 3-carboxyl-2-propene dicarboxylic acid.
7. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, said molecular weight regulator is the chain-transfer agent that chain transfer surpasses Virahol.
8. according to the preparation method of the said slow release type concrete slump retaining agent of claim 7; It is characterized in that; In said step a, said molecular weight regulator is: one or more in methallylsulfonic acid sodium, sodium allyl sulfonate, thioglycolic acid, sulfo-lactic acid, the vinyl-acetic ester.
9. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, the temperature of said heating is 30 ℃ to 90 ℃.
10. according to the preparation method of the said slow release type concrete slump retaining agent of claim 1, it is characterized in that in said step a, the temperature of said heating is 40 ℃ to 65 ℃.
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Application publication date: 20120919 |