CN104031218A - Long-chain polycarboxylic acid water reducing agent - Google Patents
Long-chain polycarboxylic acid water reducing agent Download PDFInfo
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- CN104031218A CN104031218A CN201410213055.0A CN201410213055A CN104031218A CN 104031218 A CN104031218 A CN 104031218A CN 201410213055 A CN201410213055 A CN 201410213055A CN 104031218 A CN104031218 A CN 104031218A
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Abstract
The invention relates to a long-chain polycarboxylic acid water reducing agent which is prepared by adopting ammonium persulfate as an initiator and copolymerizing monomers of allyl polyethylene glycol, polyethylene glycol monomethyl ether methacrylate, acrylic acid and acrylamide, wherein allyl polyethylene glycol accounts for 30-50% of the total monomer mass, polyethylene glycol monomethyl ether methacrylate accounts for 5-20% of the total monomer mass, acrylic acid accounts for 20-40% of the total monomer mass, acrylamide accounts for 1-10% of the total monomer mass, and ammonium persulfate accounts for 2.5-10.0% of the total monomer mass. The preparation of the polycarboxylic acid water reducing agent adopts the free radical polymerization method, takes water as a solvent, has simple and easily controlled process, and has no industrial three wastes; and moreover, the product has excellent properties, has the advantages of low mixing amount, high water reducing rate, small slump degree loss, and strong adaptability to cement, and substantially improves early and later strength of concrete.
Description
Technical field
The present invention relates to the technical field of concrete admixture, more particularly, the present invention relates to a kind of long-chain poly carboxylic acid series water reducer.
Background technology
Flourish along with China's infrastructure construction, the necessary concrete various aspects of performance of infrastructure construction is also improving constantly, meanwhile also more and more higher to the requirement of cement water reducing agent.Poly carboxylic acid series water reducer is third generation high-performance water reducing agent, has that volume is low, water-reducing rate is large, 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 of mixing materials such as improving flyash, breeze, environmental protection, can significantly save cement, configure the advantages such as high-strength, ultra high strength concrete, be widely used in commerical ready-mixed concrete, high-strength concrete, high performance concrete etc., be specially adapted to the concrete works of the high strength such as high-speed railway, bridge, sea port dock, hydro project, high-durability, high cement adaptability.
Poly carboxylic acid series water reducer is in preparation process, the general not isoplastic monomer material of select tape of wanting, pass addition reaction in principle by single polymerizable structure synthetic reservation structure and performance water reducer according to molecular designing again, it is normally by containing carboxylic acid group and the two or more monomer of polyoxyethylene thiazolinyl, synthesize by free radicals copolymerization reaction with some the gathered monomers containing sulfonic group, ester group or other group, in its chemical molecular structure, contain the structural unit of carboxylic acid group and polyoxyethylene thiazolinyl and other group.In the molecule cohesive process of polymkeric substance, different monomers is to condense together at random or regularly, to contain the monomers such as carboxyl, polyoxyethylene groups, ester group, sulfonic group as 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, concrete steps are first monomer (B) to be made into the aqueous solution to add in reactor, stir and heat up, again monomer (A) and monomer (C) are mixed and are made into the mix monomer aqueous solution by a certain percentage, drip in batches initiator solution and the mix monomer aqueous solution at 60～80 DEG C, be 0.5～1h interval time, drip off rear intensification, between 80～90 DEG C, continue reaction 4～5h, cooling rear use 40% sodium hydroxide solution is neutralized to pH=7～8, obtain the water reducer of brown color.This cement water reducing agent not only preparation process is loaded down with trivial details, and the percentage of grafting of product is low, and water-reducing rate also needs further to be improved.
CN101492518A discloses a kind of ethers polycarboxylic acid water reducing agent, it is by 10～70% allyl polyethenoxy alcohol ether, 20～70% vinylformic acid, three kinds of monomer copolymerization in the aqueous solution of Hydroxyethyl acrylate of 10～30% form, concrete steps are first allyl polyethenoxy alcohol ether monomer and deionized water to be added in reactor, stir and heat up and logical nitrogen protection simultaneously, while rising to 60～120 DEG C, drip mixed aqueous solution and 10% ammonium persulfate aqueous solution of Acrylic Acid Monomer and Hydroxyethyl acrylate monomer simultaneously, 4h dropwises, insulation 1～3h, after cooling, adjust pH is 6.0～7.5, obtain described water reducer.The method adopts Hydroxyethyl acrylate to adjust polyethers and acrylic acid reactive behavior, has reduced acrylic acid autohemagglutination ratio, makes that the molecular structure of product is more even and molecular weight distribution is narrower.But due to the restriction of the reactive behavior of allyl polyethenoxy base ether own, the water-reducing rate of product and dispersion retention are undesirable.
CN100545118A discloses a kind of poly carboxylic acid series water reducer taking allyl polyglycol as raw material; it is by suitable quality proportioning with allyl polyglycol, maleic anhydride, methyl acrylate, ammonium persulphate, stannous sulfate, sodium hydroxide and water; under the condition that is connected with nitrogen protection; prepare through reacting by heating; temperature of reaction is 50～100 DEG C, and the reaction times is 4～10h.The method adopts the initiator of oxidation-reduction system, greatly improve efficiency of initiation, and technological process is simple, but adjust the molecular weight of polymkeric substance owing to not adding chain-transfer agent, the molecular weight of product is excessive, the water-reducing rate of water reducer is lower, initial dispersion is indifferent, less by the initial slump of concrete of its preparation.
Summary of the invention
In order to solve the problems of the technologies described above, the object of the invention is to overcome that poly carboxylic acid series water reducer production technique is too complicated, cost is higher, water-reducing rate is not high and to problems such as cement adaptability are not high, provide 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 polycarboxylate water-reducer, it is characterized in that: it is taking ammonium persulphate as initiator, formed by the monomer copolymerization that comprises allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid and acrylamide, wherein allyl polyglycol accounts for 30～50% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 5～20% of monomer total mass, vinylformic acid accounts for 20～40% of monomer total mass, acrylamide accounts for 1～10% of monomer total mass, and ammonium persulphate consumption accounts for 2.5～10.0% of monomer total mass.
Wherein, described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid and four kinds of monomer copolymerizations of acrylamide, wherein allyl polyglycol accounts for 30～50% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 10～20% of monomer total mass, vinylformic acid accounts for 30～40% of monomer total mass, and acrylamide accounts for 5～10% of monomer total mass.
Wherein, described monomer also comprises ethoxyquin Bisphenol F diacrylate, and described ethoxyquin Bisphenol F diacrylate accounts for 3～5% of monomer total mass.
Wherein, described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid, acrylamide and 5 kinds of monomer copolymerizations of ethoxyquin Bisphenol F diacrylate, wherein allyl polyglycol accounts for 40～45% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 15～20% of monomer total mass, vinylformic acid accounts for 30～35% of monomer total mass, acrylamide accounts for 5～10% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 3～5% of monomer total mass.
Further, described monomer also comprises poly-alkoxylation terpenes, and described poly-alkoxylation terpenes accounts for 1.0～2.0% of monomer total mass.
Wherein, the molecular formula of described poly-alkoxylation terpenes is: two ring [2,2,1] heptene-OCH
2cH
2o-[PO]
n-[EO]
p-[PO] q-CH
3; And n is 2-4, p is 12-15, and q is 15-20.
Wherein, described water reducer is by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid, acrylamide, 6 kinds of monomer copolymerizations of ethoxyquin Bisphenol F diacrylate and poly-alkoxylation terpenes form, wherein allyl polyglycol accounts for 40～45% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 15～20% of monomer total mass, vinylformic acid accounts for 30～35% of monomer total mass, acrylamide accounts for 5～10% of monomer total mass, ethoxyquin Bisphenol F diacrylate accounts for 3～5% of monomer total mass, poly-alkoxylation terpenes accounts for 1.0～2.0% of monomer total mass.
Wherein, the preparation technology of described water reducer is as follows:
(1) by each monomer according to proportioning feeding; Be dissolved in 2～5 times of water as dropping liquid I, ammonium persulphate is dissolved in the water by consumption feeding, and to be made into massfraction be as dropping liquid II in 1～10% solution;
(2) in the four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of flask volume 20～30%, be warming up to 80～90 DEG C;
(3) in flask, drip dropping liquid I and dropping liquid II simultaneously, after dropwising, react 2～4 hours at 80～90 DEG C;
(4) after completion of the reaction, utilize aqueous sodium hydroxide 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 following beneficial effect:
Poly carboxylic acid series water reducer of the present invention prepare the method that adopts radical polymerization, taking water as solvent, technique is simple and easy to control, without three industrial wastes; And product performance are good, have that volume is low, water-reducing rate is high, a little loss of slump, adaptable with cement, increase substantially the advantages such as concrete early stage and later strength.
Embodiment
Below with reference to specific embodiment, long-chain poly carboxylic acid series water reducer of the present invention and preparation method thereof, performance etc. are described further.
Embodiment 1
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 50% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 10% of monomer total mass, vinylformic acid accounts for 30% of monomer total mass, and acrylamide accounts for 10% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-1.
Embodiment 2
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 30% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 20% of monomer total mass, vinylformic acid accounts for 40% of monomer total mass, and acrylamide accounts for 10% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-2.
Embodiment 3
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 37% of monomer total mass, and acrylamide accounts for 5% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-3.
Embodiment 4
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 34% of monomer total mass, acrylamide accounts for 5% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 3% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-4.
Embodiment 5
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 32% of monomer total mass, acrylamide accounts for 5% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 5% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-5.
Embodiment 6
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 32% of monomer total mass, acrylamide accounts for 6% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 4% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-6.
Embodiment 7
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 32% of monomer total mass, acrylamide accounts for 5% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 4% of monomer total mass, poly-alkoxylation terpenes (two rings [2,2,1] heptene-OCH
2cH
2o-[PO]
n-[EO]
p-[PO] q-CH
3; And n is 2-4, p is 12-15, and q is 15-20) account for 1.0% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-7.
Embodiment 8
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 15% of monomer total mass, vinylformic acid accounts for 30% of monomer total mass, acrylamide accounts for 9% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 4% of monomer total mass, poly-alkoxylation terpenes (two rings [2,2,1] heptene-OCH
2cH
2o-[PO]
n-[EO]
p-[PO] q-CH
3; And n is 2-4, p is 12-15, and q is 15-20) account for 2.0% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as SS-8.
Comparative example 1
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water to 80 DEG C; Each monomer is dissolved in 3 times of water as dropping liquid I, wherein according to proportioning feeding: allyl polyglycol accounts for 58% of monomer total mass, and vinylformic acid accounts for 37% of monomer total mass, and acrylamide accounts for 5% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as DB-1.
Comparative example 2
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water to 80 DEG C; Each monomer is dissolved in 3 times of water as dropping liquid I, wherein according to proportioning feeding: polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 58% of monomer total mass, and vinylformic acid accounts for 37% of monomer total mass, and acrylamide accounts for 5% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as DB-2.
Comparative example 3
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 37% of monomer total mass, and acrylamide accounts for 5% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as DB-3.
Comparative example 4
In the 250mL four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of 50g, warming-in-water 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 40% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 18% of monomer total mass, vinylformic acid accounts for 37% of monomer total mass, acrylamide accounts for 3% of monomer total mass, poly-alkoxylation terpenes (two ring [2,2,1] heptene-OCH
2cH
2o-[PO]
n-[EO]
p-[PO] q-CH
3; And n is 2-4, p is 12-15, and q is 15-20) account for 2% of monomer total mass; Ammonium persulphate by consumption feeding be dissolved in the water be made into massfraction be in 7.2% solution as dropping liquid II, wherein ammonium persulphate consumption accounts for 2.5% of monomer total mass; In flask, drip dropping liquid I and dropping liquid II, time for adding is controlled at 4 hours simultaneously; After dropwising, be incubated 2h at 85 DEG C of constant temperature; After reaction finishes, the aqueous sodium hydroxide solution that dropping massfraction is 40% regulates pH value to 7 left and right, obtains long-chain poly carboxylic acid series water reducer, is labeled as DB-4.
Implementation result
Below by corresponding experiment, the water reducer DB-1～DB-4 making is contrasted, further to set forth the performance of the water reducer of preparing in the embodiment of the present invention in above-described embodiment 1～8 in the water reducer SS-1～SS-8 making and comparative example 1-4.
(1) clean slurry test
Adopt reference cement, according to the clean slurry degree of mobilization of GB/T8077-2000 " Methods for testing uniformity of concrete admixture " test cement, water cement ratio is 0.29, and water reducer volume, for the solid volume of folding, the results are shown in Table 1.
The test of table 1 flowing degree of net paste of cement
Compared with Comparative Example D B-1～DB-3, the water reducer SS-1～SS-8 preparing in the embodiment of the present invention, initial clean slurry degree of mobilization is all more than or equal to 270mm; And the clean slurry fluidity loss less (< 40mm) in 120min, and the initial clean slurry degree of mobilization of DB-1～DB-3 is not higher than 260, and the clean slurry fluidity loss in 120min is large (> 50mm), illustrate that the water reducer of the embodiment of the present invention has better initial dispersion performance and disperses retention.In addition, although the initial clean slurry degree of mobilization of DB-4 is more excellent, the clean slurry fluidity loss in 120min is large (> 60mm), and this SS-7, SS-8 obtaining with 8 with embodiment 7 compares, and has formed striking contrast.As shown in Table 1, the composite use of allyl polyglycol and polyethylene glycol monomethyl ethermethacrylic acid esters has not only improved initial dispersion performance, has also significantly improved dispersion retention; In addition, further add poly-alkoxylation terpenes because retention is poor, cause instead of preferred, but applicant finds to pass through poly-alkoxylation terpenes and the composite use of ethoxyquin Bisphenol F diacrylate, further improved initial dispersion performance and disperseed the effect of retention, the two composite produced good synergy as seen.
(2) concrete test
Adopt little wild water in field mud P.0.42.5, flyash (II level), breeze (S95), medium coarse sand (river sand, water ratio 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/m
3)
| Cement | Flyash | Breeze | Sand | Stone |
| 130 | 30 | 35 | 485 | 430 |
Table 3 is examined 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 there is the higher initial slump >=220mm, and the slump≤20mm of 60min, and have early strong and can improve the excellent effect of later strength.
For the ordinary skill in the art; specific embodiment is just exemplarily described the present invention; obviously specific implementation of the present invention is not subject to the restrictions described above; as long as adopted the improvement of the various unsubstantialities that method of the present invention design and technical scheme carry out; or without improving, design of the present invention and technical scheme are directly applied to other occasion, all within protection scope of the present invention.
Claims (8)
1. a long-chain polycarboxylate water-reducer, it is characterized in that: it is taking ammonium persulphate as initiator, formed by the monomer copolymerization that comprises allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid and acrylamide, wherein allyl polyglycol accounts for 30 ~ 50% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 5 ~ 20% of monomer total mass, vinylformic acid accounts for 20 ~ 40% of monomer total mass, acrylamide accounts for 1 ~ 10% of monomer total mass, and ammonium persulphate consumption accounts for 2.5 ~ 10.0% of monomer total mass.
2. long-chain polycarboxylate 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, vinylformic acid and four kinds of monomer copolymerizations of acrylamide, wherein allyl polyglycol accounts for 30 ~ 50% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 10 ~ 20% of monomer total mass, vinylformic acid accounts for 30 ~ 40% of monomer total mass, and acrylamide accounts for 5 ~ 10% of monomer total mass.
3. long-chain polycarboxylate water-reducer according to claim 1, is characterized in that: described monomer also comprises ethoxyquin Bisphenol F diacrylate, and described ethoxyquin Bisphenol F diacrylate accounts for 3 ~ 5% of monomer total mass.
4. long-chain polycarboxylate water-reducer according to claim 3, it is characterized in that: described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid, acrylamide and 5 kinds of monomer copolymerizations of ethoxyquin Bisphenol F diacrylate, wherein allyl polyglycol accounts for 40 ~ 45% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 15 ~ 20% of monomer total mass, vinylformic acid accounts for 30 ~ 35% of monomer total mass, acrylamide accounts for 5 ~ 10% of monomer total mass, and ethoxyquin Bisphenol F diacrylate accounts for 3 ~ 5% of monomer total mass.
5. long-chain polycarboxylate water-reducer according to claim 3, is characterized in that: described monomer also comprises poly-alkoxylation terpenes, described poly-alkoxylation terpenes accounts for 1.0 ~ 2.0% of monomer total mass.
6. long-chain polycarboxylate water-reducer according to claim 5, is characterized in that: the molecular formula of described poly-alkoxylation terpenes is: two ring [2,2,1] heptene-OCH
2cH
2o-[PO]
n-[EO]
p-[PO] q-CH
3; And n is 2-4, p is 12-15, and q is 15-20.
7. long-chain polycarboxylate water-reducer according to claim 6, is characterized in that: described water reducer is formed by allyl polyglycol, polyethylene glycol monomethyl ethermethacrylic acid esters, vinylformic acid, acrylamide, ethoxyquin Bisphenol F diacrylate and 6 kinds of monomer copolymerizations of poly-alkoxylation terpenes; Wherein allyl polyglycol accounts for 40 ~ 45% of monomer total mass, polyethylene glycol monomethyl ethermethacrylic acid esters accounts for 15 ~ 20% of monomer total mass, vinylformic acid accounts for 30 ~ 35% of monomer total mass, acrylamide accounts for 5 ~ 10% of monomer total mass, ethoxyquin Bisphenol F diacrylate account for monomer total mass 3 ~ 5%, poly-alkoxylation terpenes accounts for 1.0 ~ 2.0% of monomer total mass.
8. according to the long-chain polycarboxylate water-reducer described in claim 1-7 any one, it is characterized in that: the preparation technology of described water reducer is as follows:
(1) by each monomer according to proportioning feeding, be dissolved in 2 ~ 5 times of water as dropping liquid I, ammonium persulphate is dissolved in the water by consumption feeding, and to be made into massfraction be as dropping liquid II in 1 ~ 10% solution;
(2) in the four-hole boiling flask that thermometer, agitator, dropping funnel, condenser are housed, add the water of flask volume 20 ~ 30%, be warming up to 80 ~ 90 DEG C;
(3) in flask, drip dropping liquid I and dropping liquid II simultaneously, after dropwising, react 2 ~ 4 hours at 80 ~ 90 DEG C;
(4) after completion of the reaction, utilize aqueous sodium hydroxide solution to regulate pH value to 7 ~ 9, obtain described water reducer.
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