CN103588414A - 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 PDF

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CN103588414A
CN103588414A CN201310587362.0A CN201310587362A CN103588414A CN 103588414 A CN103588414 A CN 103588414A CN 201310587362 A CN201310587362 A CN 201310587362A CN 103588414 A CN103588414 A CN 103588414A
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acid
high performance
reducing agent
limestone powder
monomer
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CN103588414B (en
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王军
陈景
李东来
夏远英
徐庭波
韩周冰
沈浩
张建亮
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China Construction Ready Mixed Concrete Co Ltd
China West Construction Southwest Co Ltd
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China Construction Ready Mixed Concrete Co Ltd
China Construction Ready Mixed Concrete Chengdu Co Ltd
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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

A kind of high performance water reducing agent of polyocarboxy acid and the limestone powder concrete specific complex type admixture that comprises it
Technical field
The present invention relates to a kind of concrete admixture, the limestone powder concrete specific complex type admixture that is specifically related to a kind of high performance water reducing agent of polyocarboxy acid and comprises it.
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 traditional mineral admixture.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 of material a kind ofly the most easily obtaining, grindability is good, cost is low, becomes limestone powder to replace the inevitable development trend that the conventional mineral admixtures such as flyash are following Concrete Industries its grinding.
Although limestone powder has good application prospect in ready mixed concrete, limestone powder has also brought the new problem of some 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, unfavorable with engineering construction; Due to the material difference of Wingdale, part limestone powder is larger on concrete serviceability impact, causes concrete admixture volume significantly to improve, and is unfavorable for concrete quality of production control 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, also can make concrete 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, still there is no so far the special-purpose water reducer for the concrete problem of limestone powder.Therefore,, for this emerging mineral admixture of limestone powder, it is very necessary 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 limestone powder concrete specific complex type admixture that a kind of high performance water reducing agent of polyocarboxy acid is provided and comprises it for the deficiency of above-mentioned prior art existence, it can improve the concrete workability of limestone powder effectively, especially can improve the concrete water-retentivity of limestone powder, solve the problem of the concrete easy bleeding of limestone powder.
The present invention is that the technical scheme that the problem of 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%, 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 monobasic 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 ℃, then adds alkali and is neutralized to pH and prepares 7 ~ 8.More specifically step is:
Under inert atmosphere, deionized water, monomer a isopentene group Soxylat A 25-7, monomer b monobasic unsaturated carboxylic acid and derivative thereof are mixed and heated and stirred; After monomer a and b dissolving, while being warmed up to 40 ~ 90 ℃, drip respectively the aqueous solution of maleic anhydride binary alcohol esters c and the aqueous solution of initiator and chain-transfer agent 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, be incubated again 1 ~ 3.5h; 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 of 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 monobasic 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 monomer a by weight, 0.05 ~ 0.2% of the gross weight of b and amount of component b.
In such scheme, described initiator can be selected from one or more the mixing in ammonium persulphate, Potassium Persulphate, azo-bis-isobutyl cyanide, and adding of described initiator is reaction monomers a by weight, 0.2 ~ 0.5% of the gross weight of b and c.
In such scheme, the chemical structural formula of described monomer a isopentene group Soxylat A 25-7 as the formula (1), the average mol that wherein n is polyethylene oxide chain, its value is 9 ~ 100.
In such scheme, the preparation method of described amount of component b maleic anhydride binary alcohol esters is: under inert atmosphere, by maleic anhydride and binary primary alconol according to the mol ratio of 2.5:1 under solvent-free condition, the maleic anhydride binary primary alconol ester obtaining in 30 ~ 60 ℃ of stirring reaction 1 ~ 3h of temperature, its reaction formula is suc 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.
 
Figure 2013105873620100002DEST_PATH_IMAGE002
formula (2)
In such scheme, described monomer b monobasic 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 salt.
In such scheme, described defoamer is polyethers defoamer.
In such scheme, described air entrapment agent is triterpenoid saponin air entrapment agent.
The preparation method of above-mentioned limestone powder concrete specific complex type admixture mixes 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 according to the mass percent of 5 ~ 10wt%:10 ~ 15wt%:1 ~ 5wt%:0 ~ 0.2wt%:0 ~ 0.1wt%:70 ~ 80wt%, obtain limestone powder concrete specific complex type admixture.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the high performance water reducing agent of polyocarboxy acid I in described limestone powder concrete specific complex type admixture 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 good sustained release performance, can guarantee newly to mix limestone powder concrete serviceability under 35 ~ 40 ℃ of high temperature and not lose;
(2) high performance water reducing agent of polyocarboxy acid I and the composite use of high performance water reducing agent of polyocarboxy acid II (water-reducing rate is not less than 30%) can guarantee the serviceability of initial water-reducing rate and 3h simultaneously; Compare with independent use high performance water reducing agent of polyocarboxy acid II, the composite product of high performance water reducing agent of polyocarboxy acid I and high performance water reducing agent of polyocarboxy acid II can significantly reduce the susceptibility of water reducer;
(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, when they respectively get the chief's collocation, composite retardant, defoamer and air entrapment agent, make the performance of limestone powder concrete specific complex type admixture reach optimum state;
(4) when limestone powder volume reaches 20% when above, commercially available common high performance water reducing agent of polyocarboxy acid has been used in test, all can produce excreting water phenomenon in various degree, but while using limestone powder concrete specific complex type admixture provided by the invention, concrete workability is good, without excreting water phenomenon.
Embodiment
For production method of the present invention is described better, below by specific examples, further describe the present invention, but the present invention includes and the non-following examples that only limit to.
embodiment 1
(1) amount of component b maleic anhydride binary alcohol esters, its preparation method is: under inert atmosphere, ethylene glycol is dropped in 1# reactor, heat to 30 ℃, 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:
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, be that 71wt%, 10wt%, 29wt get the raw materials ready; The amount of getting the raw materials ready of ammonium persulphate (initiator) is reaction monomers a by weight, 0.2% of the gross weight of b and c1; The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is monomer a by weight, 0.1% of the gross weight of b and amount of component b 1;
Maleic anhydride binary alcohol esters c1 is made into the aqueous solution, and mass concentration is 50%;
Together with ammonium persulphate is dissolved in Thiovanic acid, mass concentration adds up to 5%;
More than dissolve institute's water and be deionized water;
Under inert atmosphere, to 2# reactor, drop into successively deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred; After monomer a and b dissolving, while being warmed up to 40 ℃, drip respectively the aqueous solution of maleic anhydride binary alcohol esters c1 and the aqueous solution of ammonium persulphate and Thiovanic acid 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, be incubated again 3.5h; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, obtains high performance water reducing agent of polyocarboxy acid I, and 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, therefore prepared high performance water reducing agent of polyocarboxy acid I solid content 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 inert atmosphere, butyleneglycol is dropped in 1# reactor, heat to 45 ℃, 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:
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, be that 80wt%, 1wt%, 19wt get the raw materials ready;
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 reaction monomers a by weight, 0.5% of the gross weight of b and c2;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is monomer a by weight, 0.05% of the gross weight of b and amount of component b 2;
Together with ammonium persulphate is dissolved in Thiovanic acid, mass concentration is 5%;
More than dissolve institute's water and be deionized water.
Under inert atmosphere, to 2# reactor, drop into successively deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred; After monomer a and b dissolving, while being warmed up to 60 ℃, drip respectively the aqueous solution of maleic anhydride binary alcohol esters c2 and the aqueous solution of ammonium persulphate and Thiovanic acid 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, be incubated again 2h; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, obtains high performance water reducing agent of polyocarboxy acid I, and 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 inert atmosphere, ethohexadiol is dropped in 1# reactor, heat to 60 ℃, 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:
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, be that 90wt%, 5wt%, 5wt% get the raw materials ready;
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 reaction monomers a by weight, 0.3% of the gross weight of b and c3;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is monomer a by weight, 0.2% of the gross weight of b and amount of component b 3;
Together with ammonium persulphate is dissolved in Thiovanic acid, mass concentration is 5%;
More than dissolve institute's water and be deionized water.
Under inert atmosphere, to 2# reactor, drop into successively deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred; After monomer a and b dissolving, while being warmed up to 90 ℃, drip respectively the aqueous solution of maleic anhydride binary alcohol esters c3 and the aqueous solution of ammonium persulphate and Thiovanic acid 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, be incubated again 1h; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, obtains high performance water reducing agent of polyocarboxy acid I, and 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 inert atmosphere, decanediol is dropped in 1# reactor, heat to 40 ℃, 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:
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, be that 75wt%, 5wt%, 20wt% get the raw materials ready.
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 reaction monomers a by weight, 0.25% of the gross weight of b and c4;
The amount of getting the raw materials ready of Thiovanic acid (chain-transfer agent) is monomer a by weight, 0.15% of the gross weight of b and amount of component b 4;
Together with ammonium persulphate is dissolved in Thiovanic acid, mass concentration is 5%;
More than dissolve institute's water and be deionized water.
Under inert atmosphere, to 2# reactor, drop into successively deionized water, monomer a isopentene group Soxylat A 25-7, monomer b methyl acrylate heated and stirred; After monomer a and b dissolving, while being warmed up to 50 ℃, drip respectively the aqueous solution of maleic anhydride binary alcohol esters c4 and the aqueous solution of ammonium persulphate and Thiovanic acid 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, be incubated again 1.5h; Then, cooling adds alkali and is neutralized to pH between 7 ~ 8, obtains high performance water reducing agent of polyocarboxy acid I, and quality solid content is 40%, and label is A4.
contrast test
High performance water reducing agent of polyocarboxy acid I prepared by embodiment 1-4 (being A1, A2, A3, A4) is carried out respectively flowing degree of net paste of cement detection.During detection: test cement consumption is 300g, the effective solid content that adds 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 contents 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.
Figure 701209DEST_PATH_IMAGE003
As can be seen from Table 1, the difference of high performance water reducing agent of polyocarboxy acid I and high performance water reducing agent of polyocarboxy acid II is: 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 high performance water reducing agent of polyocarboxy acid I (being A4) 5wt%, the high performance water reducing agent of polyocarboxy acid II (solid content 40% of following component: embodiment 1 preparation, be 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 high performance water reducing agent of polyocarboxy acid I (being A4) 8wt%, the high performance water reducing agent of polyocarboxy acid II (solid content 40% of following component: embodiment 1 preparation, be 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 high performance water reducing agent of polyocarboxy acid I (being A4) 10wt%, the high performance water reducing agent of polyocarboxy acid II (solid content 40% of following component: embodiment 1 preparation, be 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 high performance water reducing agent of polyocarboxy acid I (being A4) 5wt%, the high performance water reducing agent of polyocarboxy acid II (solid content 40% of following component: embodiment 1 preparation, be 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)
The prepared limestone powder concrete specific complex type admixture (being sample P 1-P4) of embodiment 5-8 is carried out to Performance Detection and the detection of cement slurry degree of mobilization.
For beneficial effect of the present invention is better described, chooses certain commercially available hit product X and replace high performance water reducing agent of polyocarboxy acid I (being 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%, obtain 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%, obtain 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%, obtain Experimental Comparison admixture D3.
Limestone powder concrete specific complex type admixture P1-P4 and the prepared admixture sample D1-D3 of control group that embodiment 5-8 is prepared carry out respectively the detection of Performance Detection cement slurry degree of mobilization, 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 (being 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.
Figure 2013105873620100002DEST_PATH_IMAGE004
application testing (two)
Limestone powder concrete specific complex type admixture P1 ~ P4 and the prepared admixture sample D1-D3 of control group that embodiment 5-8 is prepared are respectively used to prepare limestone powder concrete, detect respectively its impact on concrete performance.
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 the being modulus Machine-made Sand that is 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, between 3.2 ~ 3.8kg, is adjusted consumption according to different admixtures, makes the concrete slump and divergence reach substantially suitable state.Test ambient temperature is 36 ℃, and concrete formation test block is that the length of side is the standard test block of 150mm cubes.Concrete fundamental property is as shown in table 4.
Figure 902383DEST_PATH_IMAGE005
As can be seen from Table 4, the prepared limestone powder concrete specific complex type admixture of the present invention can improve concrete workability effectively, especially solved the problem of the easy bleeding of concrete of stone powder, and the loss of the serviceability of 3h is less, can reach with the guarantor that preferably collapse protective poly-carboxylic acid water reducing agent is suitable in the market and mould ability; The concrete strength development of limestone powder and other high performance water reducing agent of polyocarboxy acid of the admixture that admixture the present invention is prepared are substantially suitable, can not have a negative impact.

Claims (10)

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 monobasic 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 ℃, then adds alkali and is neutralized to pH and prepares 7 ~ 8.
2. a kind of high performance water reducing agent of polyocarboxy acid according to claim 1, the mass percent that it is characterized in that described monomer a and monomer b, amount of component b is respectively monomer a isopentene group Soxylat A 25-7 70 ~ 90wt%, monomer b monobasic 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%.
3. a kind of high performance water reducing agent of polyocarboxy acid according to claim 1 and 2, the preparation method who it is characterized in that described amount of component b maleic anhydride binary alcohol esters is: under inert atmosphere, by maleic anhydride and binary primary alconol under solvent-free condition, the maleic anhydride binary primary alconol ester obtaining in 30 ~ 60 ℃ of stirring reaction 1 ~ 3h of temperature, the average mol of the carbochain of described binary primary alconol is 2 ~ 10.
4. 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 monomer a by weight, 0.05 ~ 0.2% of the gross weight of b and amount of component b; Described initiator can be selected from one or more the mixing in ammonium persulphate, Potassium Persulphate, azo-bis-isobutyl cyanide, and adding of described initiator is reaction monomers a by weight, 0.2 ~ 0.5% of the gross weight of b and c.
5. 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 monobasic 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 ℃, then adds alkali and is neutralized to pH and prepares 7 ~ 8.
6. a kind of limestone powder concrete specific complex type admixture according to claim 5, the preparation method who it is characterized in that described amount of component b maleic anhydride binary alcohol esters is: under inert atmosphere, by maleic anhydride and binary primary alconol under solvent-free condition, the maleic anhydride binary primary alconol ester obtaining in 30 ~ 60 ℃ of stirring reaction 1 ~ 3h of temperature, the average mol of the carbochain of described binary primary alconol is 2 ~ 10.
7. a kind of limestone powder concrete specific complex type admixture according to claim 5, is characterized in that described monomer b monobasic 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.
8. a kind of limestone powder concrete specific complex type admixture according to claim 5, 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, and water-reducing rate is not less than 30%.
9. a kind of limestone powder concrete specific complex type admixture according to claim 5, 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.
10. the preparation method of any one limestone powder concrete specific complex type admixture in claim 5-9, it is characterized in that it is that 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 are mixed according to the mass percent of 5 ~ 10wt%:10 ~ 15wt%:1 ~ 5wt%:0 ~ 0.2wt%:0 ~ 0.1wt%:60 ~ 80wt%, obtain limestone powder concrete specific complex type admixture.
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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
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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
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CN113772989A (en) * 2021-09-16 2021-12-10 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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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
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CN111320414A (en) * 2020-03-31 2020-06-23 桂林理工大学 Ultra-high performance concrete dry powder additive and preparation method thereof
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