CN103396028A - High-early-strength polycarboxylate water reducer and preparation method thereof - Google Patents

High-early-strength polycarboxylate water reducer and preparation method thereof Download PDF

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CN103396028A
CN103396028A CN2013103463458A CN201310346345A CN103396028A CN 103396028 A CN103396028 A CN 103396028A CN 2013103463458 A CN2013103463458 A CN 2013103463458A CN 201310346345 A CN201310346345 A CN 201310346345A CN 103396028 A CN103396028 A CN 103396028A
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polycarboxylate water
acid
preparation
strength type
type polycarboxylate
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廖声金
王伟
胡铁刚
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CHANGSHA KAMILE-SU CHEMICAL Co Ltd
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CHANGSHA KAMILE-SU CHEMICAL Co Ltd
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Abstract

The invention discloses a high-early-strength polycarboxylate water reducer and a preparation method thereof. The high-early-strength polycarboxylate water reducer is a liquid, and has a solid content of 40%. The water reducer containing an esterified alcohol amine group, a sulfonic group, an amido group, a carboxyl group and a methylallyl polyoxyethylene ether side chain is prepared through polymerizing monomers comprising methylallyl polyoxyethylene ether, acrylamide, sodium methylallyl sulfonate, acrylic acid or methacrylic acid, acrylated amine and the like under the action of a molecular weight chain initiator and a chain transferring agent, and neutralizing. The high-early-strength polycarboxylate water reducer has the advantages of low alkali content, high water reduction rate, short coagulation time, suitableness for the construction of prefabricated components, pile tubes, duct pieces and bridges, simple production technology, easily controlled reaction condition, and no environmental pollution.

Description

A kind of high early-strength type polycarboxylate water-reducer and preparation method thereof
Technical field
The invention belongs to the concrete admixture field, specifically a kind of high early-strength type polycarboxylate water-reducer and preparation method thereof.
Background technology
Polycarboxylate water-reducer has that volume is low, water-reducing rate is high (25%~45%), the fresh concrete workability is good, slump hold facility is good, little, low alkali is shunk in concrete hardening, without advantages such as chlorine, formaldehydeless clean environment firendlies, be called as high-performance water reducing agent.Hardening accelerator is to accelerate hydrated cementitious, improves early age strength of concrete, and the admixture that later strength is not made significant difference.Present hardening accelerator itself is without water-reducing rate, and volume large (1%~2%).Early powerful polycarboxylate water-reducer can solve effectively in the winter construction process that early strength is low, concrete is subjected to the problems such as freeze injury, can improve form cycling rate, reduces and even removes the vapor cure expense from, and accelerating construction progress, increase economic efficiency.
Along with further developing of engineering construction, large-scale high quality requires engineering more and more, and concrete performance has also just been had to higher requirement, and also can be more and more extensive for the application of the early-strength type polycarboxylate water-reducer that high diminishing, high early epistasis energy are arranged.But lack for a long time the research with the synthetic early-strength type polycarboxylate water-reducer of molecular designing mode, this has limited the application of polycarboxylate water-reducer in common prefabricated components concrete and high-strength pipe pile concrete greatly.By the relation of research polycarboxylate water-reducer molecular structure and performance, synthesize and have the early more excellent polycarboxylate water-reducer of powerful, will have great importance.
Summary of the invention
In order to meet the needs of prior art, the object of the present invention is to provide a kind of high early-strength type polycarboxylate water-reducer and preparation method thereof, described high early-strength type polycarboxylate water-reducer overcomes the simple composite production technique of early strength water-reducing agent in the past, by molecular designing, synthesized the early-strength type polycarboxylate water-reducer with excellent diminishing and high early epistasis energy, constant product quality, excellent performance.
For achieving the above object, the invention provides following technical scheme:
A kind of high early-strength type polycarboxylate water-reducer, molecular weight 20000~40000, chemical structural formula is:
Figure 693615DEST_PATH_IMAGE001
Wherein: R is methyl, n=40~75; OR ' is pure amido-0CH 2CH 2N (CH 2CH 2OH) e, e=0~2; R 〞 is hydroxyl or amino.
As the further scheme of the present invention: described n=40~45 o'clock, water reducer have best performance.
The preparation method of described high early-strength type polycarboxylate water-reducer, comprise the steps:
(1) esterification: under 100~140 ℃ of conditions, as catalyzer, Resorcinol is as stopper with sulfuric acid by vinylformic acid and hydramine, and esterification 4~8h obtains the acroleic acid esterification hydramine with unsaturated link(age); Described vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.02~0.6:0.002~0.01;
(2) polymerization: add organic acid, acrylamide and methylpropene sodium sulfonate and acroleic acid esterification hydramine in the methacrylic Soxylat A 25-7 aqueous solution, with ammonium persulphate or Sodium Persulfate as initiator, Thiovanic acid or thiohydracrylic acid are as chain-transfer agent, at 65~80 ℃, carry out polyreaction, described initiator adds at 90~150min, continues reaction 2 ± 0.5h; Described methacrylic Soxylat A 25-7: acrylamide: methylpropene sodium sulfonate: organic acid: the molar ratio of acroleic acid esterification hydramine is 1:1~2:0.5~1.0:1.0~4.0:0.2~0.8; Initiator amount is 1%~8% of polymerization single polymerization monomer total moles; Chain-transfer agent is 0.5%~2.0% of polymerization single polymerization monomer total moles; Described organic acid is a kind of in vinylformic acid and methacrylic acid or both mixtures;
(3) after reaction completes, with sodium hydroxide solution or ethylenediamine solution pH=6~7 that neutralize, obtain high early-strength type polycarboxylate water-reducer.
As the further scheme of the present invention: in step (1), esterification reaction temperature is 120 ℃, and the time is 6h.
As the further scheme of the present invention: vinylformic acid described in step (1): hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005.
As the further scheme of the present invention: in step (2), polymeric reaction temperature is 70 ± 5 ℃, and the continuation reaction times is 2h.
As the further scheme of the present invention: methacrylic Soxylat A 25-7 described in step (2): acrylamide: methylpropene sodium sulfonate: organic acid: the molar ratio of acroleic acid esterification hydramine is 1:1.5:0.8:3.0:0.5.
As the further scheme of the present invention: described in step (2), initiator amount is 6% of polymerization single polymerization monomer total moles.
As the further scheme of the present invention: described in step (2), chain-transfer agent is 1.0% of polymerization single polymerization monomer total moles.
As the further scheme of the present invention: described in step (3), the mass concentration of sodium hydroxide solution is 40%.
Compared with prior art, the invention has the beneficial effects as follows: poly carboxylic acid series water reducer of the present invention is for concrete batching, when this water reducer volume of 18wt% concentration be cement weight 1.2% the time, more than the concrete mix slump can reach 18cm; When volume was 1.2%, water-reducing rate can reach 25%; Ultimate compression strength can reach 22MPa in 1 day.Chloride ion-containing not, to the reinforcing bar non-corrosiveness; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 20% than naphthalene; The adaptation of product is strong, is adapted to the cement (especially southern cement) of plurality of specifications, model, and product performance are stable, stores for a long time not stratified, nothing precipitation, and winter is without crystallization; The advantages such as the product nontoxic pollution-free, do not contain formaldehyde, and is environmentally safe.
The applicant found through experiments, in situation preferably, be that molecular weight is 20000-40000, R is methyl CH3, during n=40-45, described polycarboxylic acid series water reducing agent is for concrete batching, when this water reducer volume of 18wt% concentration be cement weight 1.2% the time, more than the concrete mix slump can reach 20cm; When volume was 1.2%, water-reducing rate can reach 32%; Ultimate compression strength can reach 25MPa in 1 day.Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 40% than naphthalene.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment that obtains, belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of preparation method of high early-strength type polycarboxylate water-reducer comprises the following steps:
(1) esterification: by vinylformic acid and hydramine under 120 degree conditions, with sulfuric acid as catalyzer, Resorcinol is as stopper, and vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005, and esterification 6h obtains the acroleic acid esterification hydramine with unsaturated link(age);
(2) polymerization: be that 2400 methacrylic Soxylat A 25-7 and water are some by 120.00 parts of molecular weight, put into reaction vessel, heat up, at 70 ± 5 ℃ of temperature, stirring is dissolved reactant fully, in container, add 10.80 parts of vinylformic acid again, 6.33 part methylpropene sodium sulfonate, 5.33 part acrylamide, 5.01 part acroleic acid esterification hydramine, drip again 93.00 parts of mass percents and be 5% ammonium persulfate solution and 7.2 parts of mass percents and be 5% thin basic propionic acid solution, control rate of addition, at 120 ± 10 minutes, drip off, maintain the temperature at 70 ± 2 ℃, continue reaction 2h,
(3) after cooling, adding 2.53 parts of mass percents is that 40% sodium hydroxide solution is regulated pH=6.5 ± 0.5 again, obtains high early-strength type polycarboxylate water-reducer of the present invention.
Embodiment 2
In the embodiment of the present invention, a kind of preparation method of high early-strength type polycarboxylate water-reducer comprises the following steps:
(1) esterification: by vinylformic acid and hydramine under 120 degree conditions, with sulfuric acid as catalyzer, Resorcinol is as stopper, and vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005, and esterification 6h obtains the acroleic acid esterification hydramine with unsaturated link(age);
(2) polymerization: be that 2400 methacrylic Soxylat A 25-7 and water are some by 120.00 parts of molecular weight, put into reaction vessel, heat up, at 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, in container, add 10.80 parts of vinylformic acid again, 6.33 part methylpropene sodium sulfonate, 5.33 part acrylamide, 5.01 part acroleic acid esterification hydramine, drip again 93.00 parts of mass percents and be 5% ammonium persulfate solution and 7.2 parts of mass percents and be 5% Thioglycolic acid solution, control rate of addition, at 120 ± 10 minutes, drip off, maintain the temperature at 70 ± 2 ℃, continue reaction 2h,
(3) after cooling, adding 2.53 parts of mass percents is that 40% sodium hydroxide solution is regulated pH=6.5 ± 0.5 again, obtains high early-strength type polycarboxylate water-reducer of the present invention.
Embodiment 3
In the embodiment of the present invention, a kind of preparation method of high early-strength type polycarboxylate water-reducer comprises the following steps:
(1) esterification: by vinylformic acid and hydramine under 120 degree conditions, with sulfuric acid as catalyzer, Resorcinol is as stopper, and vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005, and esterification 6h obtains the acroleic acid esterification hydramine with unsaturated link(age);
(2) polymerization: 120.00 parts of molecular weight are that 2400 methacrylic Soxylat A 25-7 and water are some, put into reaction vessel, heat up, at 70 ± 5 ℃ of temperature, stirring is dissolved reactant fully, in container, add 10.80 parts of vinylformic acid again, 5.1 part methylpropene sodium sulfonate, 6.2 part acrylamide, 7.0 part acroleic acid esterification hydramine, drip again 93.00 parts of mass percents and be 5% ammonium persulfate solution and 7.2 parts of mass percents and be 5% thin basic propionic acid solution, control rate of addition, at 120 ± 10 minutes, drip off, maintain the temperature at 70 ± 2 ℃, continue reaction 2h,
(3) after cooling, add again 2.53 parts of ethylenediamine solutions to regulate pH=6.5 ± 0.5, obtain high early-strength type polycarboxylate water-reducer of the present invention.
Embodiment 4
In the embodiment of the present invention, a kind of preparation method of high early-strength type polycarboxylate water-reducer comprises the following steps:
(1) esterification: by vinylformic acid and hydramine under 120 degree conditions, with sulfuric acid as catalyzer, Resorcinol is as stopper, and vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005, and esterification 6h obtains the acroleic acid esterification hydramine with unsaturated link(age);
(2) polymerization: be that 2400 methacrylic Soxylat A 25-7 and water are some by 120.00 parts of molecular weight, put into reaction vessel, heat up, at 70 ± 5 ℃ of temperature, stirring is dissolved reactant fully, in container, add 10.80 parts of vinylformic acid again, 6.33 part methylpropene sodium sulfonate, 5.33 part acrylamide, 5.01 part acroleic acid esterification hydramine, drip again 93.00 parts of mass percents and be 5% ammonium persulfate solution and 7.2 parts of mass percents and be 5% thin basic propionic acid solution, control rate of addition, at 90 ± 10 minutes, drip off, maintain the temperature at 70 ± 2 ℃, continue reaction 2h,
(3) after cooling, adding 2.53 parts of mass percents is that 40% sodium hydroxide solution is regulated pH=6.5 ± 0.5 again, obtains high early-strength type polycarboxylate water-reducer of the present invention.
The above-mentioned high early-strength type polycarboxylate water-reducer that the present invention provides, according to clean slurry degree of mobilization, test (GB/T8077-2000): adopt reference cement, according to GB/T8077-87 test flowing degree of net paste of cement, detected result is as shown in table 1 below.
Table 1: performance test results
The above-mentioned high early-strength type polycarboxylate water-reducer that the present invention provides, as shown in table 2 below by the concrete test comparing result with market product of the same type.
Table 2: concrete performance examination result
Figure 518056DEST_PATH_IMAGE003
Concrete formulation: southern cement: flyash: sand: cobble: water: admixture=374:66:701:1097:120:5.28.
In concrete test, find, BASF-411 is early strong, and serviceability is better than this product, the initial slump and divergence are all good than the present embodiment product, but 1 day ultimate compression strength and 3 days ultimate compression strength are starkly lower than this product, and this product shows excellent properties in the intensity aspect in early days.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that do not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.

Claims (10)

1. one kind high early-strength type polycarboxylate water-reducer, is characterized in that, molecular weight 20000~40000, and chemical structural formula is:
Wherein: R is methyl, n=40~75; OR ' is pure amido-0CH 2CH 2N (CH 2CH 2OH) e, e=0~2; R 〞 is hydroxyl or amino.
2. high early-strength type polycarboxylate water-reducer according to claim 1, is characterized in that described n=40~45.
3. the preparation method of a high early-strength type polycarboxylate water-reducer as claimed in claim 1, is characterized in that, comprises the steps:
(1) esterification: under 100~140 ℃ of conditions, as catalyzer, Resorcinol is as stopper with sulfuric acid by vinylformic acid and hydramine, and esterification 4~8h obtains the acroleic acid esterification hydramine with unsaturated link(age); Described vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.02~0.6:0.002~0.01;
(2) polymerization: add organic acid, acrylamide and methylpropene sodium sulfonate and acroleic acid esterification hydramine in the methacrylic Soxylat A 25-7 aqueous solution, with ammonium persulphate or Sodium Persulfate as initiator, Thiovanic acid or thiohydracrylic acid are as chain-transfer agent, at 65~80 ℃, carry out polyreaction, described initiator adds at 90~150min, continues reaction 2 ± 0.5h; Described methacrylic Soxylat A 25-7: acrylamide: methylpropene sodium sulfonate: organic acid: the molar ratio of acroleic acid esterification hydramine is 1:1~2:0.5~1.0:1.0~4.0:0.2~0.8; Initiator amount is 1%~8% of polymerization single polymerization monomer total moles; Chain-transfer agent is 0.5%~2.0% of polymerization single polymerization monomer total moles; Described organic acid is a kind of in vinylformic acid and methacrylic acid or both mixtures;
(3) after reaction completes, with sodium hydroxide solution or ethylenediamine solution pH=6~7 that neutralize, obtain high early-strength type polycarboxylate water-reducer.
4. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, in step (1), esterification reaction temperature is 120 ℃, and the time is 6h.
5. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, vinylformic acid described in step (1): hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005.
6. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, in step (2), polymeric reaction temperature is 70 ± 5 ℃, and the continuation reaction times is 2h.
7. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, it is characterized in that methacrylic Soxylat A 25-7 described in step (2): acrylamide: methylpropene sodium sulfonate: organic acid: the molar ratio of acroleic acid esterification hydramine is 1:1.5:0.8:3.0:0.5.
8. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, described in step (2), initiator amount is 6% of polymerization single polymerization monomer total moles.
9. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, described in step (2), chain-transfer agent is 1.0% of polymerization single polymerization monomer total moles.
10. the preparation method of high early-strength type polycarboxylate water-reducer according to claim 3, is characterized in that, described in step (3), the mass concentration of sodium hydroxide solution is 40%.
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CN103936934A (en) * 2014-05-06 2014-07-23 武汉理工大学 Preparation method of triisopropanolamine modified early strength polycarboxylate superplasticizer
CN103951796A (en) * 2014-05-06 2014-07-30 武汉理工大学 Preparation method of triethanolamine modified early-strength polylactic acid water-reducing agent
CN104150807A (en) * 2014-07-29 2014-11-19 太仓新亚逊生物科技有限公司 Polycarboxylic acid water reducer for pre-stressed high-strength concrete pipe pile and application of polycarboxylic acid water reducer
CN104817658A (en) * 2015-05-21 2015-08-05 苏州市湘园特种精细化工有限公司 Acrylic acid water reducing agent and preparation method thereof
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CN106397685A (en) * 2016-09-21 2017-02-15 武汉奥克化学有限公司 Early strength water reducing agent and preparation method thereof
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CN110606924A (en) * 2019-09-04 2019-12-24 西安建筑科技大学 Polycarboxylate superplasticizer mother liquor for hydraulic concrete and preparation method thereof
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CN109575198B (en) * 2018-11-15 2022-02-15 福建路桥翔通建材科技有限公司 Enhanced polycarboxylate superplasticizer and preparation method thereof
CN110407985A (en) * 2019-07-30 2019-11-05 广州建盛建材有限公司 A kind of polycarboxylate water-reducer of Narrow Molecular Weight Distribution and preparation method thereof
CN110606924A (en) * 2019-09-04 2019-12-24 西安建筑科技大学 Polycarboxylate superplasticizer mother liquor for hydraulic concrete and preparation method thereof
CN110606924B (en) * 2019-09-04 2021-11-05 西安建筑科技大学 Polycarboxylate superplasticizer mother liquor for hydraulic concrete and preparation method thereof
CN112500533A (en) * 2020-11-06 2021-03-16 湖北天安新型建材股份有限公司 Preparation process of water reducing agent

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Application publication date: 20131120