CN104031218B - Long chain polycarboxylic acids's based water reducer - Google Patents
Long chain polycarboxylic acids's based water reducer Download PDFInfo
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Abstract
The present invention relates to a kind of long chain polycarboxylic acids's water reducer, it is with Ammonium persulfate. for initiator, formed by the monomer copolymerization including allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid and acrylamide, wherein allyl polyglycol accounts for the 30 ~ 50% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 5 ~ 20% of monomer gross mass, acrylic acid accounts for the 20 ~ 40% of monomer gross mass, acrylamide accounts for the 1 ~ 10% of monomer gross mass, and Ammonium persulfate. consumption accounts for the 2.5 ~ 10.0% of monomer gross mass.The method that the preparation of poly carboxylic acid series water reducer of the present invention adopts radical polymerization, with water for solvent, technique is simple and easy to control, without three industrial wastes；And properties of product are excellent, have that volume is low, water-reducing rate is high, little loss of slump and cement adaptable, increase substantially the advantages such as concrete early stage and later strength.
Description
Technical field
The present invention relates to the technical field of concrete admixture, it is more particularly related to a kind of long chain polycarboxylic acids's based water reducer.
Background technology
Flourish along with China's infrastructure construction, necessary to infrastructure construction, concrete various aspects of performance is also improving constantly, meanwhile that the requirement of cement water reducing agent is also more and more higher.Poly carboxylic acid series water reducer is third generation high-performance water reducing agent, has that volume is low, water-reducing rate is big, loss of slump is little, with the feature such as cement adaptability is good.Poly carboxylic acid series water reducer can increase substantially the consumption improving the composite material such as flyash, breeze, environmental protection, can significantly save cement, configure the advantages such as high-strength, ultra high strength concrete, it is widely used in commerical ready-mixed concrete, high-strength concrete, high performance concrete etc., is particularly well-suited to the concrete works of the high intensity such as high-speed railway, bridge, sea port dock, hydraulic engineering, high-durability, high cement adaptability.
Poly carboxylic acid series water reducer is in preparation process, generally to select the not isoplastic monomer material of band, pass additive reaction in principle according still further to MOLECULE DESIGN and structure and performance water reducer are subscribed in single for polymerizable structure synthesis, it is usually by the monomer two or more containing carboxylic acid group and polyethylene oxide base, synthesized by free radicals copolymerization reaction with some the gathered monomers containing sulfonic group, ester group or other group, its chemical molecular structure contains the construction unit of carboxylic acid group and polyethylene oxide base and other group.In the molecular binding process of polymer, different monomers to condense together at random or regularly, with containing monomers such as carboxyl, polyoxyethylene groups, ester group, sulfonic groups for elementary cell.
CN1772686A discloses a kind of carboxylic acid concrete water reducing agent containing unsaturated polyether, it is by unsaturated carboxylic acid (A), unsaturated sulfonic acid (B), three kinds of polymerization single polymerization monomer copolymerization of unsaturated polyether (C) form, comprise the concrete steps that monomer (B) is first made into aqueous solution to add in reactor, stirring heats up, again monomer (A) and monomer (C) are mixed by a certain percentage and be made into mix monomer aqueous solution, initiator solution and mix monomer aqueous solution is dripped in batches at 60～80 DEG C, interval time is 0.5～1h, heat up after dripping off, reaction 4～5h is continued between 80～90 DEG C, it is neutralized to pH=7～8 with 40% sodium hydroxide solution after cooling, obtain the water reducer of brown color.This cement water reducing agent not only preparation process is loaded down with trivial details, and the percent grafting of product is low, and water-reducing rate also needs to be improved further.
CN101492518A discloses a kind of ethers polycarboxylic acid water reducing agent, it is by the allyl polyethenoxy alcohol ether of 10～70%, the acrylic acid of 20～70%, three kinds of monomer copolymerization in aqueous of the 2-(Acryloyloxy)ethanol of 10～30% form, comprising the concrete steps that first adds in reactor by allyl polyethenoxy ether monomer and deionized water, stirring heats up and logical nitrogen protection simultaneously, mixed aqueous solution and 10% ammonium persulfate aqueous solution of acrylic monomers and hydroxyethyl acrylate monomers it is simultaneously added dropwise when rising to 60～120 DEG C, 4h dropwises, insulation 1～3h, adjusting pH value after cooling is 6.0～7.5, obtain described water reducer.The method adopts 2-(Acryloyloxy)ethanol to adjust polyethers and acrylic acid reactivity, reduces acrylic acid autohemagglutination ratio, makes the molecular structure of product more uniform and molecular weight distribution is narrower.But owing to the restriction of the allyl polyethenoxy reactivity of base ether own, the water-reducing rate of product and dispersion keep performance undesirable.
CN100545118A discloses a kind of poly carboxylic acid series water reducer being raw material with allyl polyglycol; it is by suitable quality proportioning with allyl polyglycol, maleic anhydride, acrylic acid methyl ester., Ammonium persulfate., stannous sulfate, sodium hydroxide and water; when being connected with nitrogen protection; heated reaction and prepare; reaction temperature is 50～100 DEG C, and the response time is 4～10h.The method adopts the initiator of oxidation-reduction system, substantially increase efficiency of initiation, and technical process is simple, but owing to not adding chain-transferring agent to adjust the molecular weight of polymer, the molecular weight of product is excessive, the water-reducing rate of water reducer is relatively low, initial dispersion is indifferent, less with the concrete initial slump of its preparation.
Summary of the invention
In order to solve above-mentioned technical problem, it is an object of the invention to overcome that poly carboxylic acid series water reducer production technology is excessively complicated, relatively costly, water-reducing rate is not high and to problems such as cement adaptability are not high, it is provided that a kind of technique is simple, cost is low, performance is high, the polycarboxylic acid series high efficiency water reducing agent of greening and environmental protection.
A kind of long chain polycarboxylic acids's water reducer, it is characterized in that: it is with Ammonium persulfate. for initiator, formed by the monomer copolymerization including allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid and acrylamide, wherein allyl polyglycol accounts for the 30～50% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 5～20% of monomer gross mass, acrylic acid accounts for the 20～40% of monomer gross mass, acrylamide accounts for the 1～10% of monomer gross mass, and Ammonium persulfate. consumption accounts for the 2.5～10.0% of monomer gross mass.
Wherein, described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid and four kinds of monomer copolymerizations of acrylamide, wherein allyl polyglycol accounts for the 30～50% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 10～20% of monomer gross mass, acrylic acid accounts for the 30～40% of monomer gross mass, and acrylamide accounts for the 5～10% of monomer gross mass.
Wherein, described monomer also includes ethoxylated bisphenol F diacrylate, and described ethoxylated bisphenol F diacrylate accounts for the 3～5% of monomer gross mass.
Wherein, described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid, acrylamide and 5 kinds of monomer copolymerizations of ethoxylated bisphenol F diacrylate, wherein allyl polyglycol accounts for the 40～45% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 15～20% of monomer gross mass, acrylic acid accounts for the 30～35% of monomer gross mass, acrylamide accounts for the 5～10% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 3～5% of monomer gross mass.
Further, described monomer also includes poly-alkoxylation terpenes, and described poly-alkoxylation terpenes accounts for the 1.0～2.0% of monomer gross mass.
Wherein, the molecular formula of described poly-alkoxylation terpenes is: bicyclo-[2,2,1] heptene-OCH2CH2O-[PO]n-[EO]p-[PO]q-CH3；And n is 2-4, p be 12-15, q is 15-20.
Wherein, described water reducer is by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid, acrylamide, ethoxylated bisphenol F diacrylate and 6 kinds of monomer copolymerizations of poly-alkoxylation terpenes form, wherein allyl polyglycol accounts for the 40～45% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 15～20% of monomer gross mass, acrylic acid accounts for the 30～35% of monomer gross mass, acrylamide accounts for the 5～10% of monomer gross mass, ethoxylated bisphenol F diacrylate accounts for the 3～5% of monomer gross mass, poly-alkoxylation terpenes accounts for the 1.0～2.0% of monomer gross mass.
Wherein, the preparation technology of described water reducer is as follows:
(1) by each monomer according to proportioning feeding；Being dissolved in 2～5 times of water as dropping liquid I, Ammonium persulfate. is dissolved in the water by consumption feeding and is made in the solution that mass fraction is 1～10% as dropping liquid II；
(2) equipped with thermometer, agitator, Dropping funnel, condenser four-hole boiling flask in add flask volume 20～30% water, be warming up to 80～90 DEG C；
(3) in flask, it is simultaneously added dropwise dropping liquid I and dropping liquid II, reacts 2～4 hours at 80～90 DEG C after dropwising；
(4) after completion of the reaction, utilize sodium hydrate aqueous solution to regulate pH value to 7～9, obtain described water reducer.
Poly carboxylic acid series water reducer of the present invention compared with prior art, has the advantages that
The method that the preparation of poly carboxylic acid series water reducer of the present invention adopts radical polymerization, with water for solvent, technique is simple and easy to control, without three industrial wastes；And properties of product are excellent, have that volume is low, water-reducing rate is high, little loss of slump and cement adaptable, increase substantially the advantages such as concrete early stage and later strength.
Detailed description of the invention
Below with reference to specific embodiment, long chain polycarboxylic acids's based water reducer of the present invention and preparation method thereof, performance etc. are described further.
Embodiment 1
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 50% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 10% of monomer gross mass, acrylic acid accounts for the 30% of monomer gross mass, and acrylamide accounts for the 10% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-1.
Embodiment 2
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 30% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 20% of monomer gross mass, acrylic acid accounts for the 40% of monomer gross mass, and acrylamide accounts for the 10% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-2.
Embodiment 3
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, and acrylic acid accounts for the 37% of monomer gross mass, and acrylamide accounts for the 5% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-3.
Embodiment 4
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 34% of monomer gross mass, acrylamide accounts for the 5% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 3% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-4.
Embodiment 5
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 32% of monomer gross mass, acrylamide accounts for the 5% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 5% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-5.
Embodiment 6
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 32% of monomer gross mass, acrylamide accounts for the 6% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 4% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-6.
Embodiment 7
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 32% of monomer gross mass, acrylamide accounts for the 5% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 4% of monomer gross mass, poly-alkoxylation terpenes (bicyclo-[2,2,1] heptene-OCH2CH2O-[PO]n-[EO]p-[PO]q-CH3；And n is 2-4, p be 12-15, q is 15-20) account for the 1.0% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-7.
Embodiment 8
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 15% of monomer gross mass, acrylic acid accounts for the 30% of monomer gross mass, acrylamide accounts for the 9% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 4% of monomer gross mass, poly-alkoxylation terpenes (bicyclo-[2,2,1] heptene-OCH2CH2O-[PO]n-[EO]p-[PO]q-CH3；And n is 2-4, p be 12-15, q is 15-20) account for the 2.0% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as SS-8.
Comparative example 1
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Being dissolved in as dropping liquid I in 3 times of water using each monomer according to proportioning feeding, wherein: allyl polyglycol accounts for the 58% of monomer gross mass, acrylic acid accounts for the 37% of monomer gross mass, and acrylamide accounts for the 5% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as DB-1.
Comparative example 2
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Being dissolved in as dropping liquid I in 3 times of water using each monomer according to proportioning feeding, wherein: polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 58% of monomer gross mass, acrylic acid accounts for the 37% of monomer gross mass, and acrylamide accounts for the 5% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as DB-2.
Comparative example 3
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyethenoxy alcohol ether accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 37% of monomer gross mass, and acrylamide accounts for the 5% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as DB-3.
Comparative example 4
Equipped with thermometer, agitator, Dropping funnel, condenser 250mL four-hole boiling flask in add the water of 50g, warming-in-water is to 80 DEG C；Each monomer is dissolved in 3 times of water as dropping liquid I according to proportioning feeding, wherein: allyl polyglycol accounts for the 40% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 18% of monomer gross mass, acrylic acid accounts for the 37% of monomer gross mass, acrylamide accounts for the 3% of monomer gross mass, poly-alkoxylation terpenes (bicyclo-[2,2,1] heptene-OCH2CH2O-[PO]n-[EO]p-[PO]q-CH3；And n is 2-4, p be 12-15, q is 15-20) account for the 2% of monomer gross mass；Ammonium persulfate. is dissolved in the water by consumption feeding and is made into as dropping liquid II in the solution that mass fraction is 7.2%, and wherein Ammonium persulfate. consumption accounts for the 2.5% of monomer gross mass；Being simultaneously added dropwise dropping liquid I and dropping liquid II in flask, time for adding controlled at 4 hours；It is incubated 2h at 85 DEG C of constant temperature after dropwising；After reaction terminates, drip the sodium hydrate aqueous solution that mass fraction is 40% and regulate pH value to about 7, obtain long chain polycarboxylic acids's based water reducer, be labeled as DB-4.
Implementation result
Below by corresponding experiment, the water reducer DB-1～DB-4 prepared in the water reducer SS-1～SS-8 prepared in above-described embodiment 1～8 and comparative example 1-4 is contrasted, to be expanded on further in the embodiment of the present invention performance of the water reducer of preparation.
(1) test is only starched
Adopting reference cement, test the paste flowing degree of cement according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", the ratio of mud is 0.29, and water reducer volume is the solid volume of folding, and result is in Table 1.
Table 1 flowing degree of net paste of cement is tested
Compared with Comparative Example D B-1～DB-3, the water reducer SS-1～SS-8 of preparation in the embodiment of the present invention, initial paste flowing degree is all higher than being equal to 270mm；And the paste flowing degree in 120min loses less (< 40mm), and the initial paste flowing degree of DB-1～DB-3 is not higher than 260, and the paste flowing degree loss relatively big (> 50mm) in 120min, illustrate that the water reducer of the embodiment of the present invention has better initial dispersion performance and dispersion keeps performance.Although additionally, the initial paste flowing degree of DB-4 is more excellent, but the paste flowing degree loss relatively big (> 60mm) in 120min, this, compared with SS-7, SS-8 that embodiment 7 and 8 obtains, defines striking contrast.As shown in Table 1, allyl polyglycol and the composite use of polyethylene glycol monomethyl ethermethacrylic acid esters not only increase initial dispersion performance, also significantly increase dispersion and keep performance；In addition, add poly-alkoxylation terpenes further owing to keeping poor performance, thus be not preferred, but it is found by the applicant that pass through poly-alkoxylation terpenes and the composite use of ethoxylated bisphenol F diacrylate, further increase initial dispersion performance and the effect of dispersion maintenance performance, it is seen that the composite of the two creates good synergism.
(2) concrete test
Adopt little wild water in field mud P.0.42.5, flyash (II level), breeze (S95), medium coarse sand (fluvial sand, moisture content 3%), ovum rubble (particle diameter 5～25mm, continuous size fraction), according to the concrete mix in table 2, the solid volume of the folding of the water reducer in table 3, with reference to GB8076-2008 " concrete admixture " concrete batching, the result of concrete experiments is as shown in table 3.
Table 2 concrete mix (kg/m3)
| Cement | Flyash | Breeze | Sand | Stone |
| 130 | 30 | 35 | 485 | 430 |
Table 3 is by inspection concrete performance index (the solid volume 0.20% of water reducer folding)
Compared with Comparative Example D B-1～DB-3, adopt the concrete of SS-1～SS-8 preparation to have higher initial slump >=220mm and the slump≤20mm of 60min, and there is excellent effect that is early strong and also that can improve later strength.
For the ordinary skill in the art; the present invention is simply exemplarily described by specific embodiment; the obvious present invention implements and is not subject to the restrictions described above; as long as have employed the improvement of the various unsubstantialities that the design of the method for the present invention carries out with technical scheme; or the not improved design by the present invention and technical scheme directly apply to other occasion, all within protection scope of the present invention.
Claims (5)
1. long chain polycarboxylic acids's water reducer, it is characterized in that: it is with Ammonium persulfate. for initiator, by including allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, ethoxylated bisphenol F diacrylate, the monomer copolymerization of acrylic acid and acrylamide forms, wherein allyl polyglycol accounts for the 30 ~ 50% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 5 ~ 20% of monomer gross mass, described ethoxylated bisphenol F diacrylate accounts for the 3 ~ 5% of monomer gross mass, acrylic acid accounts for the 20 ~ 40% of monomer gross mass, acrylamide accounts for the 1 ~ 10% of monomer gross mass, Ammonium persulfate. consumption accounts for the 2.5 ~ 10.0% of monomer gross mass.
2. long chain polycarboxylic acids's water reducer according to claim 1, it is characterized in that: described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid, acrylamide and 5 kinds of monomer copolymerizations of ethoxylated bisphenol F diacrylate, wherein allyl polyglycol accounts for the 40 ~ 45% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 15 ~ 20% of monomer gross mass, acrylic acid accounts for the 30 ~ 35% of monomer gross mass, acrylamide accounts for the 5 ~ 10% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 3 ~ 5% of monomer gross mass.
3. long chain polycarboxylic acids's water reducer according to claim 1, it is characterised in that: described monomer also includes poly-alkoxylation terpenes, and described poly-alkoxylation terpenes accounts for the 1.0 ~ 2.0% of monomer gross mass；And the molecular formula of described poly-alkoxylation terpenes is: bicyclo-[2,2,1] heptene-OCH2CH2O-[PO]n-[EO]p-[PO]q-CH3；And n is 2-4, p be 12-15, q is 15-20.
4. long chain polycarboxylic acids's water reducer according to claim 3, it is characterised in that: described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic acid, acrylamide, ethoxylated bisphenol F diacrylate and 6 kinds of monomer copolymerizations of poly-alkoxylation terpenes；Wherein allyl polyglycol accounts for the 40 ~ 45% of monomer gross mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for the 15 ~ 20% of monomer gross mass, acrylic acid accounts for the 30 ~ 35% of monomer gross mass, acrylamide accounts for the 5 ~ 10% of monomer gross mass, and ethoxylated bisphenol F diacrylate accounts for the 3 ~ 5% of monomer gross mass, poly-alkoxylation terpenes accounts for the 1.0 ~ 2.0% of monomer gross mass.
5. the long chain polycarboxylic acids's water reducer according to any one of claim 1-4, it is characterised in that: the preparation technology of described water reducer is as follows:
(1) by each monomer according to proportioning feeding, being dissolved in 2 ~ 5 times of water as dropping liquid I, Ammonium persulfate. is dissolved in the water by consumption feeding and is made in the solution that mass fraction is 1 ~ 10% as dropping liquid II；
(2) equipped with thermometer, agitator, Dropping funnel, condenser four-hole boiling flask in add flask volume 20 ~ 30% water, be warming up to 80 ~ 90 DEG C；
(3) in flask, it is simultaneously added dropwise dropping liquid I and dropping liquid II, reacts 2 ~ 4 hours at 80 ~ 90 DEG C after dropwising；
(4) after completion of the reaction, utilize sodium hydrate aqueous solution to regulate pH value to 7 ~ 9, obtain described water reducer.
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| CN106749955A (en) * | 2015-11-20 | 2017-05-31 | 衡阳市银利实业有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer |
| CN107033291B (en) * | 2017-03-28 | 2019-04-09 | 江苏超力建材科技有限公司 | Economization agent for concrete and the preparation method and application thereof |
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| CN101906193A (en) * | 2010-08-06 | 2010-12-08 | 天津市飞龙砼外加剂有限公司 | Method for synthesizing polycarboxylic acid water reducing agent |
| CN101935184A (en) * | 2010-08-19 | 2011-01-05 | 上海三瑞高分子材料有限公司 | Reduction and early strength polymer additive |
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| US8623979B2 (en) * | 2003-06-23 | 2014-01-07 | Geo Speciality Chemicals, Inc. | Cement dispersant and methods of making and using the same |
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| US8623979B2 (en) * | 2003-06-23 | 2014-01-07 | Geo Speciality Chemicals, Inc. | Cement dispersant and methods of making and using the same |
| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN101906193A (en) * | 2010-08-06 | 2010-12-08 | 天津市飞龙砼外加剂有限公司 | Method for synthesizing polycarboxylic acid water reducing agent |
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