A kind of to the strong poly carboxylic acid series water reducer of cement adaptability, compound method and method of use
Technical field
The invention belongs to building material technical field, be specifically related to a kind of the strong poly carboxylic acid series water reducer of cement adaptability, compound method and method of use thereof.
Background technology
The poly carboxylic acid series water reducer water-reducing rate is high, and slump-loss is little, an amount of bleed, can improve concrete durability and work-ing life, is the important means of concrete high-performanceization.Cement in China is various in style, complicated component and performance change are big, though poly carboxylic acid series water reducer has the adaptability problem that many premium propertiess also are present in cement, causes it to apply and receives great restriction.
The flexibility of admixture is meant admixture under identical condition, causes result of use that bigger difference or even diverse degree are arranged because of cement is different.Poly carboxylic acid series water reducer is through extensive application in the railway construction engineering over the past two years and the test in the high-speed railway engineering; Prove that its flexibility is relatively poor relatively; The subtle change of factors such as its concrete raw material component, the place of production all can cause fresh mixing concrete property to occur changing, and these characteristics and naphthalene water reducer have completely different with the characteristics of stability than strong adaptability.And address this problem the collocation that can not be confined to test between each component and the more conversion materials aspect of frequency; Must break through the old mode of thinking; Do deep exploration and research from development, integral body, macroscopic angle, could promote the development of poly carboxylic acid series water reducer.
The method of " the big monomer of poly glycol monomethyl ether esterification+mix monomer polymerization " and " allyl polyglycol+mix monomer polymerization " is the synthesis mode that at present more admixture manufacturer adopts, but reasonably " Molecular Structure Design " and admixture and the concrete flexibility research of product science has been ignored by many manufacturers.In order to improve the performance of water reducer; Practice thrift cost; Part producer adopts poly glycol monomethyl ether class poly carboxylic acid series water reducer and allyl polyglycol class poly carboxylic acid series water reducer composite, but composite meeting causes the demixing phenomenon of water reducer in actual procedure, influences the result of use of water reducer.
Now, the research emphasis of poly carboxylic acid series water reducer is a molecular structure reasonable in design, reduces cost, simplifies technology, and different cement is had good flexibility, enhances one's market competitiveness, and also will satisfy the good comprehensive performances requirement simultaneously.The present invention is that main raw material(s) carries out copolymerization with the big monomer of poly glycol monomethyl ether esterification (MPEGMA), allyl polyglycol (APEG); Not only simplify synthesis technique; And have big monomer of ester class and the big monomer of ethers in the poly carboxylic acid series water reducer molecular structure simultaneously; Also introduce carboxamido-group and sulfonic group, make poly carboxylic acid series water reducer all have good flexibility different cement.At present, the domestic not achievement in research of relevant synthesis technique aspect.
Summary of the invention
The object of the present invention is to provide a kind of to the strong poly carboxylic acid series water reducer of cement adaptability, compound method and method of use thereof.
The present invention propose to cement adaptability strong poly carboxylic acid series water reducer, be to be the poly carboxylic acid series water reducer of main raw material with polyethylene glycol monomethyl ethermethacrylic acid esters (MPEGMA) and allyl polyglycol (APEG); Starting material are polyethylene glycol monomethyl ethermethacrylic acid esters (MPEGMA), allyl polyglycol (APEG), methylacrylic acid (MAA), 2-acrylic amide-2-methacrylic sulfonic acid (AMPS), mercaptan type chain transfer agent, ammonium persulphate (initiator), sodium hydroxide and water, and the weight ratio of each component is:
The component weight ratio
MPEGMA 100
APEG 30~70
MAA 15~35
AMPS 0.5~1.5
Mercaptan type chain transfer agent 1~4
Ammonium persulphate 1.5~8.5
Sodium hydroxide 3~7
Water 200~900.
The preferable weight ratio of each component is:
The component weight ratio
MPEGMA 100
APEG 40~60
MAA 20~30
AMPS 0.75~1.25
Mercaptan type chain transfer agent 2~3
Ammonium persulphate 3~7
Sodium hydroxide 4~6
Water 400~600.
Among the present invention, the molecular mass of said polyethylene glycol monomethyl ethermethacrylic acid esters is 800~2000.
Among the present invention, the molecular mass of said allyl polyglycol is 800~2000.
The present invention is the compound method of the poly carboxylic acid series water reducer of main raw material with polyethylene glycol monomethyl ethermethacrylic acid esters (MPEGMA) and allyl polyglycol (APEG), and concrete steps are:
(1) take by weighing polyethylene glycol monomethyl ethermethacrylic acid esters, allyl polyglycol, methylacrylic acid, 2-acrylic amide-2-methacrylic sulfonic acid, mercaptan type chain transfer agent, ammonium persulphate and water by mass ratio:
(2) allyl polyglycol and ammonium persulphate are mixed with the solution of 20%~50% (concentration that refers to the aqueous solution) concentration respectively;
(3) polyethylene glycol monomethyl ethermethacrylic acid esters, methylacrylic acid, 2-acrylic amide-2-methacrylic sulfonic acid and mercaptan type chain transfer agent are mixed, add the monomer mixture solution that water is mixed with 20%~50% (concentration that refers to the aqueous solution) concentration;
(4) in reaction kettle, add the allyl polyglycol solution of step (2) gained, feed shielding gas nitrogen, plug prolong, be warming up to 60~100 ℃, begin to drip the monomer mixture solution of step (3) gained and the ammonium persulfate solution of step (2) gained; The dropping time of monomer mixture solution is 1~5 hour, and the dropping time of ammonium persulfate solution is 1.5~5.5 hours; After ammonium persulfate solution dropwises, isothermal reaction 0.5~1.5 hour;
(5) after the cooling of question response thing, regulate pH value to 6.8~7.2, mix, promptly get required product with sodium hydroxide.
Among the present invention, concentration is 25%~35% described in step (2) and the step (3).
Among the present invention, temperature is 70~90 ℃ described in the step (4).
Among the present invention, the dropping time of monomer mixture solution described in the step (4) is preferably 2~4 hours, and the dropping time of ammonium persulfate solution is preferably 2.5~4.5 hours.
Among the present invention,, both contained the big monomer of ester class in the reaction product molecular structure, contained the big monomer of ethers again, produced the steric restriction effect of physics, prevented the cement granules cohesion, kept good dispersiveness with MPEGMA and APEG copolymerization.The more important thing is MPEGMA, APEG can with MAA, AMPS polymerization reaction take place; Introduce carboxyl, carboxamido-group and sulfonic group, carboxyl has diminishing, slow setting and guarantor effect such as collapse, and carboxamido-group has bleed and disperses thickening power; Sulfonic group has high water-reduction, improves the performance of poly carboxylic acid series water reducer.Big monomer is the primary structure unit of water reducer molecule, and wherein polyethylene oxide chain reduces big monomeric polymerization activity, and its chain length has certain influence to the chainpropagation of water reducer, and mercaptan type chain transfer agent can make the polymkeric substance molecular-weight average reduce.Ammonium persulphate is an initiator, is mainly used in middle temperature (40 ℃~100 ℃) and causes, and can make each monomer participate in polyreaction.Sodium hydroxide is used for the pH value of conditioned reaction product solution.
Synthetic product of the present invention is a light yellow transparent liquid; Concentration is 15%~45%; The water reducer incorporation is 0.10%~0.30% of a cement weight in the clean slurry, and the water reducer incorporation is 0.40%~0.60% of a cement weight in the concrete, can make it have high water reducing rate; Satisfy higher construction requirement, and improve concrete strength to a certain extent.Compare with existing processes; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the synthesis technique reaction times weak point of the poly carboxylic acid series water reducer of main raw material(s); Technology is simple, and the stable performance of reaction product especially all has good flexibility to different cement.
The present invention can supply admixture factory to produce, and one-step polymerization and getting is widely used in the Important Project and the various common engineerings such as high ferro, bridge, dam, airport of different areas.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the poly carboxylic acid series water reducer of main raw material(s); Its weight ratio is: molecular mass is that 800 MPEGMA 100, molecular mass are 1200 APEG 30, MAA 15, AMPS 0.5, mercaptan type chain transfer agent 1; Ammonium persulphate 1.5, sodium hydroxide 3, water 225.It is 40% solution that APEG, monomer mixture and ammonium persulphate are mixed with concentration respectively, adopts following compound method: APEG solution adds reaction kettle, feeds nitrogen protection, is warming up to 60 ℃, begins to drip monomer mixture solution and initiator solution; The dropping time of monomer mixture solution is 1 hour, and the initiator dropping time is 1.5 hours, after agent solution to be triggered dropwises, 60 ℃ of isothermal reactions 0.5 hour, adds sodium hydroxide, regulates pH value to 7, mixes, and promptly gets desired product.Mix this water reducer of by mass of cement 0.30%, wc is 0.29 o'clock, and it is 300mm that reference cement is starched degree of mobilization only, and 2 hours clean slurry degree of mobilization loss is 40mm; The conch flowing degree of net paste of cement is 280mm, and 2 hours clean slurry degree of mobilization loss is 50mm; Three lion flowing degree of net paste of cement are 290mm, and 2 hours clean slurry degree of mobilization loss is 45mm; Wu's flowing degree of net paste of cement is 285mm, and 2 hours clean slurry degree of mobilization loss is 35mm; Evergreen flowing degree of net paste of cement is 295mm, and 2 hours clean slurry degree of mobilization loss is 30mm.In concrete, mix this water reducer of 0.60%, concrete water-reducing ratio reaches 25%, 28 day compressive strength rate and reaches 130%.
Embodiment 2; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the poly carboxylic acid series water reducer of main raw material(s); Its weight ratio is: molecular mass is that 2000 MPEGMA 100, molecular mass are 800 APEG 50, MAA 35, AMPS 1, mercaptan type chain transfer agent 4; Ammonium persulphate 5, sodium hydroxide 5, water 200.It is 50% solution that APEG, monomer mixture and ammonium persulphate are mixed with concentration respectively, adopts following compound method: APEG solution adds reaction kettle, feeds nitrogen protection, is warming up to 80 ℃, begins to drip monomer mixture solution and initiator solution; The dropping time of monomer mixture solution is 3 hours, and the initiator dropping time is 3.5 hours, after agent solution to be triggered dropwises, 80 ℃ of isothermal reactions 1 hour, adds sodium hydroxide, regulates pH value to 6.8, mixes, and promptly gets desired product.Mix this water reducer of by mass of cement 0.20%, wc is 0.29 o'clock, and it is 285mm that reference cement is starched degree of mobilization only, and 2 hours clean slurry degree of mobilization loss is 20mm; The conch flowing degree of net paste of cement is 280mm, and 2 hours clean slurry degree of mobilization loss is 30mm; Three lion flowing degree of net paste of cement are 280mm, and 2 hours clean slurry degree of mobilization loss is 25mm; Wu's flowing degree of net paste of cement is 275mm, and 2 hours clean slurry degree of mobilization loss is 15mm; Evergreen flowing degree of net paste of cement is 285mm, and 2 hours clean slurry degree of mobilization loss is 20mm.In concrete, mix this water reducer of 0.40%, concrete water-reducing ratio reaches 28%, 28 day compressive strength rate and reaches 135%.
Embodiment 3; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the poly carboxylic acid series water reducer of main raw material(s); Its weight ratio is: molecular mass is that 1600 MPEGMA 100, molecular mass are 2000 APEG 60, MAA 30, AMPS 1.25, mercaptan type chain transfer agent 3; Ammonium persulphate 7, sodium hydroxide 6, water 600.It is 25% solution that APEG, monomer mixture and ammonium persulphate are mixed with concentration respectively, adopts following compound method: APEG solution adds reaction kettle, feeds nitrogen protection, is warming up to 60 ℃, begins to drip monomer mixture solution and initiator solution; The dropping time of monomer mixture solution is 4 hours, and the initiator dropping time is 4.5 hours, after agent solution to be triggered dropwises, 90 ℃ of isothermal reactions 1 hour, adds sodium hydroxide, regulates pH value to 7.2, mixes, and promptly gets desired product.Mix this water reducer of by mass of cement 0.10%, wc is 0.29 o'clock, and it is 275mm that reference cement is starched degree of mobilization only, and 2 hours clean slurry degree of mobilization loss is 20mm; The conch flowing degree of net paste of cement is 260mm, and 2 hours clean slurry degree of mobilization loss is 30mm; Three lion flowing degree of net paste of cement are 270mm, and 2 hours clean slurry degree of mobilization loss is 25mm; Wu's flowing degree of net paste of cement is 265mm, and 2 hours clean slurry degree of mobilization loss is 15mm; Evergreen flowing degree of net paste of cement is 280mm, and 2 hours clean slurry degree of mobilization loss is 20mm.In concrete, mix this water reducer of 0.50%, concrete water-reducing ratio reaches 30%, 28 day compressive strength rate and reaches 145%.
Embodiment 4; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the poly carboxylic acid series water reducer of main raw material(s); Its weight ratio is: molecular mass is that 1200 MPEGMA 100, molecular mass are 1000 APEG 40, MAA 20, AMPS 0.75, mercaptan type chain transfer agent 2; Ammonium persulphate 3, sodium hydroxide 4, water 400.It is 20% solution that APEG, monomer mixture and ammonium persulphate are mixed with concentration respectively, adopts following compound method: APEG solution adds reaction kettle, feeds nitrogen protection, is warming up to 70 ℃, begins to drip monomer mixture solution and initiator solution; The dropping time of monomer mixture solution is 2 hours, and the initiator dropping time is 2.5 hours, after agent solution to be triggered dropwises, 70 ℃ of isothermal reactions 1 hour, adds sodium hydroxide, regulates pH value to 7, mixes, and promptly gets desired product.Mix this water reducer of by mass of cement 0.15%, wc is 0.29 o'clock, and it is 280mm that reference cement is starched degree of mobilization only, and 2 hours clean slurry degree of mobilization loss is 30mm; The conch flowing degree of net paste of cement is 270mm, and 2 hours clean slurry degree of mobilization loss is 40mm; Three lion flowing degree of net paste of cement are 275mm, and 2 hours clean slurry degree of mobilization loss is 25mm; Wu's flowing degree of net paste of cement is 265mm, and 2 hours clean slurry degree of mobilization loss is 35mm; Evergreen flowing degree of net paste of cement is 270mm, and 2 hours clean slurry degree of mobilization loss is 25mm.In concrete, mix this water reducer of 0.45%, concrete water-reducing ratio reaches 23%, 28 day compressive strength rate and reaches 125%.
Embodiment 5; With polyethylene glycol monomethyl ethermethacrylic acid esters and allyl polyglycol is the poly carboxylic acid series water reducer of main raw material(s); Its weight ratio is: molecular mass is that 800 MPEGMA 100, molecular mass are 800 APEG 70, MAA35, AMPS 1.5, mercaptan type chain transfer agent 4; Ammonium persulphate 8.5, sodium hydroxide 7, water 900.It is 20% solution that APEG, monomer mixture and ammonium persulphate are mixed with concentration respectively, adopts following compound method: APEG solution adds reaction kettle, feeds nitrogen protection, is warming up to 100 ℃, begins to drip monomer mixture solution and initiator solution; The dropping time of monomer mixture solution is 5 hours, and the initiator dropping time is 5.5 hours, after agent solution to be triggered dropwises, 100 ℃ of isothermal reactions 1.5 hours, adds sodium hydroxide, regulates pH value to 7, mixes, and promptly gets desired product.Mix this water reducer of by mass of cement 0.25%, wc is 0.29 o'clock, and it is 300mm that reference cement is starched degree of mobilization only, and 2 hours clean slurry degree of mobilization loss is 20mm; The conch flowing degree of net paste of cement is 285mm, and 2 hours clean slurry degree of mobilization loss is 35mm; Three lion flowing degree of net paste of cement are 290mm, and 2 hours clean slurry degree of mobilization loss is 25mm; Wu's flowing degree of net paste of cement is 290mm, and 2 hours clean slurry degree of mobilization loss is 30mm; Evergreen flowing degree of net paste of cement is 285mm, and 2 hours clean slurry degree of mobilization loss is 25mm.In concrete, mix this water reducer of 0.55%, concrete water-reducing ratio reaches 26%, 28 day compressive strength rate and reaches 134%.