CN103588414B - High-performance polycarboxylic acid water reducer and special compound admixture containing the water reducer for limestone powder concrete - Google Patents
High-performance polycarboxylic acid water reducer and special compound admixture containing the water reducer for limestone powder concrete Download PDFInfo
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Abstract
The invention relates to a high-performance polycarboxylic acid water reducer and a special compound admixture containing the water reducer for limestone powder concrete. The special compound admixture for limestone powder concrete comprises a high-performance polycarboxylic acid water reducer I 5 to 10wt%, a high-performance polycarboxylic acid water reducer II 10 to 15wt%, retarder 1 to 5wt%, defoamer 0 to 0.2wt%, air entraining agent 0 to 0.1wt%, and water 70 to 80wt%, wherein the sum of mass percents of every component is 100%. The admixture provided by the invention can effectively improve workability of fresh limestone powder concrete, and can prevent 3-hour work performance loss of fresh limestone powder concrete without influencing concrete strength development. The admixture preparation method is unique, simple and feasible, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of concrete admixture, be specifically related to a kind of high performance water reducing agent of polyocarboxy acid and comprise its limestone powder concrete specific complex type admixture.
Background technology
In recent years, along with the high speed development of domestic construction industry, concrete demand goes up year by year, and the trend that supply falls short of demand has appearred in conventional mineral adulterant.Along with the adjustment of national energy strategy and the progress of power domain, thermal power generation will reduce year by year, and fly ash is inevitable day by day deficient.Wingdale as a kind ofly the most easily obtaining, grindability is good, cost is low a kind of material, being become by its grinding limestone powder to replace the conventional fossil adulterants such as flyash is the inevitable development trend of of following Concrete Industry.
Although limestone powder has good application prospect in ready mixed concrete, limestone powder also brings some new problem to concrete: the water-retentivity of limestone powder particle is poor, easily produces excreting water phenomenon when volume is larger in concrete; Limestone powder easily causes concrete work performance loss too fast, not utilizing works construction; Due to the material difference of Wingdale, part limestone powder is comparatively large on concrete serviceability impact, causes concrete admixture volume significantly to improve, and is unfavorable for that the concrete quality of production controls and cost control.
At present, already present polycarboxylate water-reducer has possessed higher water-reducing rate, in the conventional material systems such as cement, flyash, breeze, silicon ash, concrete also can be made to realize good workability and plastic property, but in cement, limestone powder system, but be difficult to realize good workability and plastic property, and, according to existing document and report, so far still not for the special water reducer of the concrete problem of limestone powder.Therefore, for this emerging mineral admixture of limestone powder, it is very necessary for developing a kind of limestone powder concrete specific complex type admixture.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of high performance water reducing agent of polyocarboxy acid and comprise its limestone powder concrete specific complex type admixture, it can improve the concrete workability of limestone powder effectively, especially can improve the concrete water-retentivity of limestone powder, solve that limestone powder is concrete easily secretes water problem.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of limestone powder concrete specific complex type admixture, by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I 5 ~ 10wt%, high performance water reducing agent of polyocarboxy acid II 10 ~ 15wt%, retardant 1 ~ 5wt%, defoamer 0 ~ 0.2wt%, air entrapment agent 0 ~ 0.1wt% and water 70 ~ 80wt%, and the mass percent sum of each component is 100%.
In such scheme, described high performance water reducing agent of polyocarboxy acid I is by monomer a isopentene group Soxylat A 25-7, monomer b unitary unsaturated carboxylic acid and derivative thereof, amount of component b maleic anhydride binary alcohol esters, under initiator, chain-transfer agent effect, copolyreaction 1 ~ 3.5h in the aqueous solution of 40 ~ 90 DEG C, then adds alkali and is neutralized to pH and prepares 7 ~ 8.More specifically step is:
Under an inert atmosphere, by deionized water, monomer a isopentene group Soxylat A 25-7, monomer b unitary unsaturated carboxylic acid and derivative thereof mixing also heated and stirred; After monomer a and b dissolves, when being warmed up to 40 ~ 90 DEG C, drip the aqueous solution of maleic anhydride binary alcohol esters c and the aqueous solution of initiator and chain-transfer agent respectively simultaneously, after the aqueous solution of maleic anhydride binary alcohol esters c dropwises, the aqueous solution of remaining initiator and chain-transfer agent is dropwised in 0.5 ~ 2h, after dripping, is incubated 1 ~ 3.5h again; Then, cooling adds alkali and is neutralized to pH 7 ~ 8, obtains high performance water reducing agent of polyocarboxy acid I.
Wherein, according to the solid content standard of required high performance water reducing agent of polyocarboxy acid I, determine the addition preparing water in high performance water reducing agent of polyocarboxy acid I process, the solid content of described high performance water reducing agent of polyocarboxy acid I is preferably 40 ~ 60wt%.
In such scheme, the mass percent of described monomer a and monomer b, amount of component b is respectively monomer a isopentene group Soxylat A 25-7 70 ~ 90wt%, monomer b unitary unsaturated carboxylic acid and derivative 1 ~ 10wt% thereof, amount of component b maleic anhydride binary alcohol esters 5 ~ 29wt%, and three's mass percent sum is 100%.
In such scheme, described chain-transfer agent is one or more mixtures in any proportion in mercaptoethanol, 2-hydroxyl propylmercaptan, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-dimercaptosuccinic acid, the add-on of described chain-transfer agent is 0.05 ~ 0.2% of the gross weight of monomer a, b and amount of component b by weight.
In such scheme, described initiator can be selected from one or more the mixing in ammonium persulphate, Potassium Persulphate, azo-bis-isobutyl cyanide, described initiator add by weight for reaction monomers a, b and c gross weight 0.2 ~ 0.5%.
In such scheme, as the formula (1), wherein n is the average mol of polyethylene oxide chain to the chemical structural formula of described monomer a isopentene group Soxylat A 25-7, and its value is 9 ~ 100.
In such scheme, the preparation method of described amount of component b maleic anhydride binary alcohol esters is: under an inert atmosphere, by maleic anhydride and binary primary alconol according to 2.5:1 mol ratio in the absence of a solvent, in the maleic anhydride binary primary alconol ester that temperature 30 ~ 60 DEG C of stirring reaction 1 ~ 3h obtain, its reaction formula is such as formula described in (2), n in formula (2) is the average mol of binary primary alconol carbochain, and the value of n is 2 ~ 10.
formula (2)
In such scheme, described monomer b unitary unsaturated carboxylic acid and derivative thereof are one or several mixtures in any proportion in vinylformic acid, methacrylic acid and monovalent base metal-salt thereof, diatomic base metal-salt, ammonium salt.
In such scheme, described high performance water reducing agent of polyocarboxy acid II is ester class or ethers high performance water reducing agent of polyocarboxy acid, and water-reducing rate is not less than 30%; The solid content of described high performance water reducing agent of polyocarboxy acid II is preferably 40 ~ 60wt%.
In such scheme, described retardant is any one or two kinds of mixtures in any proportion in organic retardant, mineral-type retardant.Described organic retardant is selected from glucose, Sunmorl N 60S, sucrose, citric acid, Trisodium Citrate, tartrate, sodium tartrate; Described mineral-type retardant is selected from three coacervation acid sodium, trisodium phosphate, fluoric acid magnesium, borate, zinc salts.
In such scheme, described defoamer is polyethers defoamer.
In such scheme, described air entrapment agent is triterpenoid saponin air entrapment agent.
High performance water reducing agent of polyocarboxy acid I, high performance water reducing agent of polyocarboxy acid II, retardant, defoamer, air entrapment agent and water mix according to the mass percent of 5 ~ 10wt%:10 ~ 15wt%:1 ~ 5wt%:0 ~ 0.2wt%:0 ~ 0.1wt%:70 ~ 80wt% by the preparation method of above-mentioned limestone powder concrete specific complex type admixture, namely obtain limestone powder concrete specific complex type admixture.
Compared with prior art, the invention has the beneficial effects as follows:
(1) high performance water reducing agent of polyocarboxy acid I in the limestone powder concrete specific complex type admixture described in can improve the water retention property of limestone powder particle effectively, significantly improve the concrete workability of limestone powder, and high performance water reducing agent of polyocarboxy acid I has excellent sustained release performance, can ensure that newly mixing limestone powder concrete serviceability under 35 ~ 40 DEG C of high temperature does not lose;
(2) high performance water reducing agent of polyocarboxy acid I and high performance water reducing agent of polyocarboxy acid II (water-reducing rate is not less than 30%) composite use, can ensure the serviceability of initial water-reducing rate and 3h simultaneously; Be used alone compared with high performance water reducing agent of polyocarboxy acid II, high performance water reducing agent of polyocarboxy acid I significantly can reduce the susceptibility of water reducer with the compound product of high performance water reducing agent of polyocarboxy acid II;
(3) in described limestone powder concrete specific complex type admixture, high performance water reducing agent of polyocarboxy acid II belongs to water reducing type mother liquor, high performance water reducing agent of polyocarboxy acid I biases toward raising concrete workability, while they respectively get the collocation of the chief, composite retardant, defoamer and air entrapment agent, make the state that the performance of limestone powder concrete specific complex type admixture reaches optimum;
(4) when limestone powder volume reaches more than 20%, test employs commercially available common high performance water reducing agent of polyocarboxy acid, all can produce excreting water phenomenon in various degree, but when using limestone powder concrete specific complex type admixture provided by the invention, concrete workability is good, without excreting water phenomenon.
Embodiment
In order to production method of the present invention is described better, further describe the present invention below by specific examples, but the present invention includes and non-ly be only limitted to following examples.
embodiment 1
(1) amount of component b maleic anhydride binary alcohol esters, its preparation method is: under an inert atmosphere, is dropped into by ethylene glycol in 1# reactor, heat to 30 DEG C, then maleic anhydride solid is dropped in 1# reactor, stir 3h, obtain carboxylate maleic anhydride binary alcohol esters, label is c1.Wherein, the mol ratio of maleic anhydride and ethylene glycol is 2.5:1.
(2) high performance water reducing agent of polyocarboxy acid I, its preparation method is:
Be that 71wt%, 10wt%, 29wt get the raw materials ready according to the mass percent of monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate and maleic anhydride binary alcohol esters c1; The amount of getting the raw materials ready of ammonium persulphate (initiator) is 0.2% of the gross weight of reaction monomers a, b and c1 by weight; The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is 0.1% of the gross weight of monomer a, b and amount of component b 1 by weight;
Maleic anhydride binary alcohol esters c1 is made into the aqueous solution, and mass concentration is 50%;
Together with being dissolved in Thiovanic acid by ammonium persulphate, mass concentration adds up to 5%;
More than dissolve water used and be deionized water;
Under an inert atmosphere, deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred is dropped into successively to 2# reactor; After monomer a and b dissolves, when being warmed up to 40 DEG C, drip the aqueous solution of maleic anhydride binary alcohol esters c1 and the aqueous solution of ammonium persulphate and Thiovanic acid respectively simultaneously, after the aqueous solution of maleic anhydride binary alcohol esters c1 dropwises, the aqueous solution of remaining ammonium persulphate and Thiovanic acid is dropwised in 2h, after dripping, is incubated 3.5h again; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, and obtain high performance water reducing agent of polyocarboxy acid I, quality solid content is 40%, and label is A1.
Note: the amount of the getting the raw materials ready m of deionized water is 1.5 times of total mass M of monomer a, monomer b, amount of component b 1, Thiovanic acid (chain-transfer agent), ammonium persulphate (initiator) and alkali, namely high performance water reducing agent of polyocarboxy acid I solid content prepared by event is M/(M+m), high performance water reducing agent of polyocarboxy acid I solid content prepared in the present embodiment is 40wt%.
embodiment 2
(1) amount of component b maleic anhydride binary alcohol esters, its preparation method is: under an inert atmosphere, is dropped into by butyleneglycol in 1# reactor, heat to 45 DEG C, then maleic anhydride solid is dropped in 1# reactor, stir 2h, obtain carboxylate maleic anhydride binary alcohol esters, label is c2.Wherein, the mol ratio of maleic anhydride and ethylene glycol is 2.5:1.
(2) high performance water reducing agent of polyocarboxy acid I, its preparation method is:
Be that 80wt%, 1wt%, 19wt get the raw materials ready according to the mass percent of monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate and maleic anhydride binary alcohol esters c2;
Maleic anhydride binary alcohol esters c2 is made into the aqueous solution, and mass concentration is 50%;
The amount of getting the raw materials ready of ammonium persulphate (initiator) is 0.5% of the gross weight of reaction monomers a, b and c2 by weight;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is 0.05% of the gross weight of monomer a, b and amount of component b 2 by weight;
Together with being dissolved in Thiovanic acid by ammonium persulphate, mass concentration is 5%;
More than dissolve water used and be deionized water.
Under an inert atmosphere, deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred is dropped into successively to 2# reactor; After monomer a and b dissolves, when being warmed up to 60 DEG C, drip the aqueous solution of maleic anhydride binary alcohol esters c2 and the aqueous solution of ammonium persulphate and Thiovanic acid respectively simultaneously, after the aqueous solution of maleic anhydride binary alcohol esters c2 dropwises, the aqueous solution of remaining ammonium persulphate and Thiovanic acid is dropwised in 1h, after dripping, is incubated 2h again; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, and obtain high performance water reducing agent of polyocarboxy acid I, quality solid content is 40%, and label is A2.
embodiment 3
(1) amount of component b maleic anhydride binary alcohol esters, its preparation method is: under an inert atmosphere, is dropped into by ethohexadiol in 1# reactor, heat to 60 DEG C, then maleic anhydride solid is dropped in 1# reactor, stir 1h, obtain carboxylate maleic anhydride binary alcohol esters, label is c3.Wherein, the mol ratio of maleic anhydride and ethylene glycol is 2.5:1.
(2) high performance water reducing agent of polyocarboxy acid I, its preparation method is:
Be that 90wt%, 5wt%, 5wt% get the raw materials ready according to the mass percent of monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate and maleic anhydride binary alcohol esters c3;
Maleic anhydride binary alcohol esters c1 is made into the aqueous solution, and mass concentration is 50%;
The amount of getting the raw materials ready of ammonium persulphate (initiator) is 0.3% of the gross weight of reaction monomers a, b and c3 by weight;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is 0.2% of the gross weight of monomer a, b and amount of component b 3 by weight;
Together with being dissolved in Thiovanic acid by ammonium persulphate, mass concentration is 5%;
More than dissolve water used and be deionized water.
Under an inert atmosphere, deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred is dropped into successively to 2# reactor; After monomer a and b dissolves, when being warmed up to 90 DEG C, drip the aqueous solution of maleic anhydride binary alcohol esters c3 and the aqueous solution of ammonium persulphate and Thiovanic acid respectively simultaneously, after the aqueous solution of maleic anhydride binary alcohol esters c3 dropwises, the aqueous solution of remaining ammonium persulphate and Thiovanic acid is dropwised in 0.5h, after dripping, is incubated 1h again; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, and obtain high performance water reducing agent of polyocarboxy acid I, quality solid content is 40%, and label is A3.
embodiment 4
(1) amount of component b maleic anhydride binary alcohol esters, its preparation method is: under an inert atmosphere, is dropped into by decanediol in 1# reactor, heat to 40 DEG C, then maleic anhydride solid is dropped in 1# reactor, stir 1.5h, obtain carboxylate maleic anhydride binary alcohol esters, label is c4.Wherein, the mol ratio of maleic anhydride and ethylene glycol is 2.5:1.
(2) high performance water reducing agent of polyocarboxy acid I, its preparation method is:
Be that 75wt%, 5wt%, 20wt% get the raw materials ready according to the mass percent of monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate and maleic anhydride binary alcohol esters c4.
Maleic anhydride binary alcohol esters c1 is made into the aqueous solution, and mass concentration is 50%.
The amount of getting the raw materials ready of ammonium persulphate (initiator) is 0.25% of the gross weight of reaction monomers a, b and c4 by weight;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is 0.15% of the gross weight of monomer a, b and amount of component b 4 by weight;
Together with being dissolved in Thiovanic acid by ammonium persulphate, mass concentration is 5%;
More than dissolve water used and be deionized water.
Under an inert atmosphere, deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred is dropped into successively to 2# reactor; After monomer a and b dissolves, when being warmed up to 50 DEG C, drip the aqueous solution of maleic anhydride binary alcohol esters c4 and the aqueous solution of ammonium persulphate and Thiovanic acid respectively simultaneously, after the aqueous solution of maleic anhydride binary alcohol esters c4 dropwises, the aqueous solution of remaining ammonium persulphate and Thiovanic acid is dropwised in 0.5h, after dripping, is incubated 1.5h again; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, and obtain high performance water reducing agent of polyocarboxy acid I, quality solid content is 40%, and label is A4.
contrast test
The high performance water reducing agent of polyocarboxy acid I (i.e. A1, A2, A3, A4) prepared by embodiment 1-4 carries out flowing degree of net paste of cement detection respectively.During detection: test cement consumption is 300g, the effective solid content adding water reducer is 0.36g, and slurry water-cement ratio is 0.29.
Choose the high performance water reducing agent of polyocarboxy acid II of different solid content in contrast, numbering is respectively B1, B2, B3, B4, and its solid content is followed successively by 40%, 40%, 50%, 60%.Flowing degree of net paste of cement detected result is as shown in table 1.
As can be seen from Table 1, high performance water reducing agent of polyocarboxy acid I is with the difference of high performance water reducing agent of polyocarboxy acid II: the cement paste initial flow degree of admixture high performance water reducing agent of polyocarboxy acid I is smaller, but 3h fluidity loss is less or free of losses, the initial water-reducing property of high performance water reducing agent of polyocarboxy acid II is better, but protect plasticity can be poor.
embodiment 5
A kind of limestone powder concrete specific complex type admixture, by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I (i.e. A4) 5wt%, high performance water reducing agent of polyocarboxy acid II (solid content 40% prepared by embodiment 1, i.e. B2) 14wt%, Sunmorl N 60S (retardant) 2wt%, polyethers defoamer 0.1wt%, triterpenoid saponin air entrapment agent 0.05wt% and water 78.85wt%, each component is mixed, can obtain limestone powder concrete specific complex type admixture, label is P1.
embodiment 6
A kind of limestone powder concrete specific complex type admixture, by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I (i.e. A4) 8wt%, high performance water reducing agent of polyocarboxy acid II (solid content 40% prepared by embodiment 1, i.e. B2) 10wt%, Sunmorl N 60S (retardant) 3wt%, polyethers defoamer 0.05wt%, triterpenoid saponin air entrapment agent 0.1wt% and water 78.85wt%, each component is mixed, can obtain limestone powder concrete specific complex type admixture, label is P2.
embodiment 7
A kind of limestone powder concrete specific complex type admixture, by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I (i.e. A4) 10wt%, high performance water reducing agent of polyocarboxy acid II (solid content 40% prepared by embodiment 1, i.e. B2) 10wt%, Sunmorl N 60S (retardant) 1wt%, polyethers defoamer 0.05wt%, triterpenoid saponin air entrapment agent 0.1wt% and water 78.85wt%, each component is mixed, can obtain limestone powder concrete specific complex type admixture, label is P3.
embodiment 8
A kind of limestone powder concrete specific complex type admixture, by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I (i.e. A4) 5wt%, high performance water reducing agent of polyocarboxy acid II (solid content 40% prepared by embodiment 1, i.e. B2) 15wt%, Sunmorl N 60S (retardant) 1wt%, polyethers defoamer 0.15wt%, triterpenoid saponin air entrapment agent 0 and water 78.85wt%, each component is mixed, can obtain limestone powder concrete specific complex type admixture, label is P4.
application testing (one)
Limestone powder concrete specific complex type admixture (i.e. sample P 1-P4) prepared by embodiment 5-8 is carried out Performance Detection and the detection of cement slurry degree of mobilization.
In order to beneficial effect of the present invention is better described, chooses commercially available certain hit product X and replace high performance water reducing agent of polyocarboxy acid I (i.e. A4) in contrast.
Control group (1): X, B2, Sunmorl N 60S (retardant), polyethers defoamer, triterpenoid saponin air entrapment agent and water are mixed according to the mass ratio of 8%:10%:3%:0.05%:0.1%:78.85%, obtains experimental control admixture D1.
Control group (2): X, B2, Sunmorl N 60S (retardant), polyethers defoamer, triterpenoid saponin air entrapment agent and water are mixed according to the mass ratio of 5%:15%:1%:0.15%:0%:78.85%, obtains experimental control admixture D2.
Control group (3): B2, Sunmorl N 60S (retardant), polyethers defoamer, triterpenoid saponin air entrapment agent and water are mixed according to the mass ratio of 20%:1%:0.15%:0%:78.85%, obtains Experimental Comparison admixture D3.
Limestone powder concrete specific complex type admixture P1-P4 prepared by embodiment 5-8 and the admixture sample D1-D3 prepared by control group is carried out respectively Performance Detection cement slurry degree of mobilization to detect, cement consumption is 150g, limestone powder consumption is 150g, water-cement ratio is 0.29, make flowing degree of net paste of cement reach 240 ± 5mm, admixture dosage (i.e. the volume of P1, P2, P3, P4, D1, D2 or D3), initial flow degree, 3h degree of mobilization, initial slurry bleeding state, 3h slurry bleeding state are as shown in table 2.
application testing (two)
Limestone powder concrete specific complex type admixture P1 ~ P4 prepared by embodiment 5-8 and the admixture sample D1-D3 prepared by control group is respectively used to preparation limestone powder concrete, detects its impact on concrete performance respectively.
In this application testing, cement used is Lafarge PO42.5, and flyash is first level flour coal ash, and the specific surface area of limestone powder used is 450m
2/ kg, aggregate used is degree of being modulus is the Machine-made Sand of 2.6 and the rubble of 5 ~ 31.5mm continuous grading.Concrete mix is as shown in table 3, and wherein the consumption of admixture is between 3.2 ~ 3.8kg, according to different admixtures adjustment consumption, makes the state that the concrete slump and divergence reach substantially suitable.Test ambient temperature is 36 DEG C, and concrete formation test block is the length of side is the standard test block of 150mm cubes.Concrete fundamental property is as shown in table 4.
As can be seen from Table 4, limestone powder concrete specific complex type admixture prepared by the present invention can improve concrete workability effectively, what especially solve concrete of stone powder easily secretes water problem, and the loss of the serviceability of 3h is less, can reach and mould ability with the guarantor that preferably collapse protective poly-carboxylic acid water reducing agent is suitable in the market; The concrete strength development of limestone powder of the admixture prepared by admixture the present invention and other high performance water reducing agent of polyocarboxy acid are substantially suitable, can not have a negative impact.
Claims (9)
1. a high performance water reducing agent of polyocarboxy acid, it is characterized in that it is by monomer a isopentene group Soxylat A 25-7, monomer b unitary unsaturated carboxylic acid and derivative thereof, amount of component b maleic anhydride binary alcohol esters, under initiator, chain-transfer agent effect, copolyreaction in the aqueous solution of 40 ~ 90 DEG C, then adds alkali and is neutralized to pH and prepares 7 ~ 8;
The mass percent of described monomer a and monomer b, amount of component b is respectively monomer a isopentene group Soxylat A 25-7 70 ~ 90wt%, monomer b unitary unsaturated carboxylic acid and derivative 1 ~ 10wt% thereof, amount of component b maleic anhydride binary alcohol esters 5 ~ 29wt%, and three's mass percent sum is 100%.
2. a kind of high performance water reducing agent of polyocarboxy acid according to claim 1, it is characterized in that the preparation method of described amount of component b maleic anhydride binary alcohol esters is: under an inert atmosphere, by maleic anhydride and binary primary alconol in the absence of a solvent, in the maleic anhydride binary primary alconol ester that temperature 30 ~ 60 DEG C of stirring reaction 1 ~ 3h obtain, the average mol of the carbochain of described binary primary alconol is 2 ~ 10.
3. a kind of high performance water reducing agent of polyocarboxy acid according to claim 1, it is characterized in that described chain-transfer agent is one or more mixtures in any proportion in mercaptoethanol, 2-hydroxyl propylmercaptan, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-dimercaptosuccinic acid, the add-on of described chain-transfer agent is 0.05 ~ 0.2% of the gross weight of monomer a, b and amount of component b by weight; Described initiator is selected from one or more the mixing in ammonium persulphate, Potassium Persulphate, azo-bis-isobutyl cyanide, described initiator add by weight for reaction monomers a, b and c gross weight 0.2 ~ 0.5%.
4. a limestone powder concrete specific complex type admixture, it is characterized in that by mass percentage, it comprises following component: high performance water reducing agent of polyocarboxy acid I 5 ~ 10wt%, high performance water reducing agent of polyocarboxy acid II 10 ~ 15wt%, retardant 1 ~ 5wt%, defoamer 0 ~ 0.2wt%, air entrapment agent 0 ~ 0.1wt% and water 70 ~ 80wt%, and the mass percent sum of each component is 100%;
Described high performance water reducing agent of polyocarboxy acid I is by monomer a isopentene group Soxylat A 25-7, monomer b unitary unsaturated carboxylic acid and derivative thereof, amount of component b maleic anhydride binary alcohol esters, under initiator, chain-transfer agent effect, copolyreaction 1 ~ 3.5h in the aqueous solution of 40 ~ 90 DEG C, then adds alkali and is neutralized to pH and prepares 7 ~ 8.
5. a kind of limestone powder concrete specific complex type admixture according to claim 4, it is characterized in that the preparation method of described amount of component b maleic anhydride binary alcohol esters is: under an inert atmosphere, by maleic anhydride and binary primary alconol in the absence of a solvent, in the maleic anhydride binary primary alconol ester that temperature 30 ~ 60 DEG C of stirring reaction 1 ~ 3h obtain, the average mol of the carbochain of described binary primary alconol is 2 ~ 10.
6. a kind of limestone powder concrete specific complex type admixture according to claim 4, is characterized in that described monomer b unitary unsaturated carboxylic acid and derivative thereof are one or several mixtures in any proportion in vinylformic acid, methacrylic acid and monovalent base metal-salt thereof, diatomic base metal-salt, ammonium salt.
7. a kind of limestone powder concrete specific complex type admixture according to claim 4, it is characterized in that described high performance water reducing agent of polyocarboxy acid II is ester class or ethers high performance water reducing agent of polyocarboxy acid, water-reducing rate is not less than 30%.
8. a kind of limestone powder concrete specific complex type admixture according to claim 4, is characterized in that described retardant is any one or two kinds of mixtures in any proportion in organic retardant, mineral-type retardant; Described defoamer is polyethers defoamer; Described air entrapment agent is triterpenoid saponin air entrapment agent.
9. the preparation method of any one limestone powder concrete specific complex type admixture in claim 4-8, it is characterized in that it is mixed according to the mass percent of 5 ~ 10wt%:10 ~ 15wt%:1 ~ 5wt%:0 ~ 0.2wt%:0 ~ 0.1wt%:70 ~ 80wt% high performance water reducing agent of polyocarboxy acid I, high performance water reducing agent of polyocarboxy acid II, retardant, defoamer, air entrapment agent and water, namely obtain limestone powder concrete specific complex type admixture.
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| CN103588414B true CN103588414B (en) | 2015-03-04 |
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| CN105601155A (en) * | 2015-12-29 | 2016-05-25 | 中建商品混凝土有限公司 | Additive special for limestone powder concrete |
| CN105753360A (en) * | 2016-04-05 | 2016-07-13 | 中铁建设集团设备安装有限公司 | Concrete admixture and preparation method and application thereof |
| CN106749926B (en) * | 2016-11-30 | 2018-09-14 | 东北林业大学 | Improve the additive and its preparation and application of cement mortar bending and compressive strength |
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| CN109293276A (en) * | 2018-10-25 | 2019-02-01 | 湖南中岩建材科技有限公司 | A kind of thickening water-retaining type additive and its preparation method and application |
| CN109867486B (en) * | 2019-03-23 | 2021-09-24 | 杭州构建新型材料有限公司 | Special water-retaining additive for high-temperature-resistant concrete and preparation process and application thereof |
| CN111825365A (en) * | 2019-09-12 | 2020-10-27 | 尧柏特种水泥技术研发有限公司 | Sulphoaluminate cement concrete additive |
| CN111320414B (en) * | 2020-03-31 | 2022-04-19 | 桂林理工大学 | Ultra-high performance concrete dry powder additive and preparation method thereof |
| CN111807750A (en) * | 2020-06-16 | 2020-10-23 | 浙江五龙新材股份有限公司 | Additive for improving appearance of concrete |
| CN113264707A (en) * | 2021-06-08 | 2021-08-17 | 山东华伟银凯建材科技股份有限公司 | High-performance concrete water reducing agent and preparation method thereof |
| CN113480702A (en) * | 2021-07-10 | 2021-10-08 | 南京瑞固聚合物有限公司 | High-plasticity-retention polycarboxylate superplasticizer and preparation method thereof |
| CN113772989B (en) * | 2021-09-16 | 2022-12-16 | 重庆富普新材料有限公司 | Preparation method of special additive mother liquor for limestone-based wet-mixed mortar |
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| CN102659989A (en) * | 2011-12-16 | 2012-09-12 | 天津冶建特种材料有限公司 | Preparation method of low-cost concrete polycarboxylic acid water reducing agent |
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Address after: 430074, 13 tower, 18 high tech building, East Lake high tech Zone, Wuhan, Hubei. Co-patentee after: The construction of the West southwest Construction Co. Ltd. Patentee after: China Construction Commercial Concrete Co., Ltd. Address before: 430074, 13 tower, 18 high tech building, East Lake high tech Zone, Wuhan, Hubei. Co-patentee before: CSCEC Commerical Concrete Chengdu Co., Ltd. Patentee before: China Construction Commercial Concrete Co., Ltd. |