CN109399992A - A kind of aqua retarder - Google Patents
A kind of aqua retarder Download PDFInfo
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- CN109399992A CN109399992A CN201811470452.0A CN201811470452A CN109399992A CN 109399992 A CN109399992 A CN 109399992A CN 201811470452 A CN201811470452 A CN 201811470452A CN 109399992 A CN109399992 A CN 109399992A
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- Prior art keywords
- calcium
- retarder
- agent
- reducer
- solution
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of aqua retarder, according to parts by weight, the retarder includes polycarboxylate water-reducer 70-85, Quadrafos 1-10, organic acid 5-20, antifreezing agent 1-5 and calcium increasing agent 1-10, the Quadrafos be calgon or sodium tripolyphosphate, the calcium increasing agent be include calcium hydroxide, calcium oxide and calcium carbonate.Solves the deferred action in the prior art to improve water-reducing agent, cause auxiliary agent addition type and additive amount it is higher and caused by environmental pollution, product in the present invention has the characteristics that high-thin arch dam, high water reduction, high intensity, slow setting, improve the workability of concrete, improve every mechanical property of concrete, it is good to various cement adaptabilities, the concrete surface made using the present invention is without bleeding line, bubble-free, color difference is small, presentation quality is good, environment temperature influences it small, and convenient for construction, production method simply easily grasps.
Description
Technical field
The invention belongs to concrete admixture fields, and in particular to a kind of aqua retarder.
Background technique
Concrete admixture, abbreviation additive refer to that incorporation is to change before mixing concrete mixing or during mix
The substance of kind concrete performance.Since additive can effectively improve the performance of concrete, and it is with good economic efficiency,
It is widely used in many countries, the application in engineering is increasingly taken seriously, and becomes indispensable in concrete
Material.Retarder is a kind of additive that can extend concrete coagulating time, and retarder is mainly used for delaying the water of cement
Change setting rate, in favor of the transport of concrete, to pour and vibrate so that fresh concrete keeps plasticity in a long time；
The time of temperature peak of hydration appearance can be postponed, temperature peak of hydration value is reduced, prevents mass concrete from thermal cracking occur；It can adjust
The adaptability of whole high efficiency water reducing agent and cement reduces concrete mix slump-loss.
Currently, the concrete retarder of domestic and international application is divided into two major classes, inorganic and organic.Inorganic mainly includes
Borax, zinc oxide, phosphate and metaphosphate etc., organic mainly include lignosulfonates, hydroxycarboxylic acid (salt), carbohydrate and
Carbohydrate, polyalcohol and its derivative etc..Organic retarder application is relatively more.But these current retarder have one
A little disadvantages, one, only common retarder, after volume is more than certain value, the problems such as concrete not will appear solidifying, intensity declines；
Two, retarder and all kinds of water-reducing agent adaptability being widely used at present are poor, when being used in combination sometimes with water-reducing agent, or even can produce
Raw blood coagulation enhancing effect；Third is that the problems such as not strong to the more cement type adaptability in the country.Mainly there is innovation wood in cement water reducing agent market
The different types of coagulations such as mahogany sulfonate system, naphthalene sulfonate system, sulfonated melamine system, sulfamate system, polycarboxylic-acid
Native water-reducing agent, in engineer application, concrete retarder is often used together with cement water reducing agent, be widely used in underground,
Therefore the construction of the mass concrete engineerings such as dam develops multi-functional, Composite, high performance concrete admixture to coagulation
Native technology development has great importance.
Existing patent CN104119027A discloses a kind of retardation water reducing agent, by the raw material mixing of following parts by weight
At: beta-naphthalenesulfonic-acid salt formaldehyde condensation products 35-45, sulfonated acetone-formaldehyde condensation products 20-30, hydroxypropyl methyl cellulose 10-15,
Casein 6-12, saltcake 3-6, sulfonated coal tar 4-8, borax 2-4, calcium hydroxide 5-10, activated sludge 8-14, prodan 5-
10, oil foot 2.5-4.5, tartaric acid 2-3, zinc molybdate 3-5, triethyl phosphate 4-6, maltodextrin 2-4, methacrylic sulfonic acid 4-8,
Auxiliary agent 3-6.The retarding effect of the invention water-reducing agent is good, and setting time can extend 2-4 hours, and water-reducing rate 15%-20% can change
The workability of kind concrete, it is good to various cement adaptabilities, it can be used for various reinforced concrete works, but water-reducing agent in the invention
Water-reducing rate be not too high, and auxiliary component is complex.Existing patent CN108609901A discloses a kind of highly effective coagulation
Native retardation water reducing agent is made of the raw material of following parts by weight: polycarboxylic acids mother liquor 40-60 parts by weight, sodium gluconate 5-15 weight
Measure part, maltodextrin polyacrylamide graft copolymer 3-8 parts by weight, asbestos wool 1-5 parts by weight, aluminium polychloride 2-6 weight
Part, anhydrous sodium sulfate 3-8 parts by weight, calcium chloride 2-5 parts by weight, polyethyleneglycol ether 5-12 parts by weight, p-aminobenzene sulfonic acid
1-5 parts by weight, chitin 3-10 parts by weight, poly (sodium aspartate) 0.2-3 parts by weight, ammonium citrate 10-20 parts by weight, acetone 3-
8 parts by weight, water 40-60 parts by weight.The setting time of the adjustable concrete of the retardation water reducing agent of the invention, the invention belong to poly-
Carboxylic acid type water reducing agent, it is lower to the adaptability of soil.So being badly in need of providing a kind of water-reducing agent the case where reducing the use of auxiliary agent
Under, it both can guarantee higher water-reducing rate, while can also improve the adaptability of soil, and other function is also maintained at normal water
It is flat.
Summary of the invention
The purpose of the present invention is to provide a kind of aqua retarder, to solve the slow setting to improve water-reducing agent in the prior art
Effect, cause auxiliary agent addition type and additive amount it is higher and caused by environmental pollution.Specific technical solution adopted by the present invention
It is as follows:
A kind of aqua retarder, including polycarboxylate water-reducer, Quadrafos, organic acid, antifreezing agent and calcium increasing agent.
Specifically, according to parts by weight, the retarder includes polycarboxylate water-reducer 70-85, Quadrafos 1-10, has
Machine acid 5-20, antifreezing agent 1-5 and calcium increasing agent 1-10.
Preferably, the retarder includes polycarboxylate water-reducer 75-85, Quadrafos 5-10, organic acid 10-20, prevents
Freeze agent 2-5 and calcium increasing agent 5-10.
Preferably, the retarder include polycarboxylate water-reducer 80, Quadrafos 6, organic acid 15, antifreezing agent 3 and
Calcium increasing agent 7.
The preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring to assigned temperature；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, after 5min starts that minor comonomer solution 3h is slowly added dropwise,
Initiator solution 3.5h keeps assigned temperature to react 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains
Faint yellow sticky shape high-molecular copolymer solution, i.e. polycarboxylate water-reducer.
Specifically, the assigned temperature in the step 1) and step 2) is 40 DEG C.
Specifically, the minor comonomer solution in the step 2) is in acrylic acid, methacrylic acid, fumaric acid or itaconic acid
It is one or more.
Specifically, the initiator solution in the step 2) is at least one of ammonium persulfate, potassium peroxydisulfate.
Specifically, the antifreezing agent be at least one of sodium nitrite, carbonate, calcium chloride, calcium nitrite, methanol,
Preferably methanol.
Specifically, the Quadrafos is calgon or sodium tripolyphosphate.
Specifically, the calcium increasing agent includes calcium hydroxide, calcium oxide and calcium carbonate, and the calcium hydroxide, calcium oxide
Weight ratio with calcium carbonate is 20-50:30-50:1-60；Optionally, the fineness of the calcium increasing agent is 325 mesh.
The preparation method of the retarder is the following steps are included: by the polycarboxylate water-reducer of the parts by weight, tripolyphosphate
Sodium, citric acid and calcium increasing agent mixing, stirring into slurry without granular material, stand 10 minutes to get.
Retarder is one kind organic high molecular compound as made of the copolymerization of several functional monomers, molecule in the present invention
Contain a large amount of hydroxy functional group in structure, can be complexed to form stable complex compound with the calcium ion in cement slurry, covers
On the surface of hydrolysis product of cement, hydrated cementitious is prevented.On the other hand, the hydroxyl in retarder structure also can be straight by hydrogen bond
It connects and is adsorbed on cement particle surface, prevent cement granules from contacting with the direct of water, prevent the progress of aquation.With hydration process
It carries out, this adsorption layer will gradually use up, and aquation will normally continue, therefore not influence cement further hydration.It is resulting slow
Solidifying agent and polycarboxylate water-reducer adaptability are preferable, can also be used in compounding therewith.
The invention has the following advantages:
One, Product Green environmental protection, formaldehydeless content belong to low alkali product, the discharge of no three wastes；
Two, product has the characteristics that high-thin arch dam, high water reduction, high intensity, slow setting；
Three, the workability for substantially improving concrete improves every mechanical property of concrete, suitable to various cement
Answering property is good；
Four, the concrete surface made by the present invention is without bleeding line, bubble-free, and color difference is small, and presentation quality is good, environment temperature
It is influenced small, convenient for construction, production method simply easily grasps.
Specific embodiment
Embodiment 1
A kind of aqua retarder, according to parts by weight, the retarder include polycarboxylate water-reducer 70, sodium tripolyphosphate
1, citric acid 5, sodium nitrite 1 and calcium increasing agent 1, the weight ratio of calcium hydroxide, calcium oxide and calcium carbonate is in the calcium increasing agent
20:30:1.The preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring is to 40 DEG C；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, after 5min starts that fumaric acid solution 3h is slowly added dropwise,
Ammonium persulfate solution 3.5h keeps 40 DEG C of reaction 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains
Faint yellow sticky shape high-molecular copolymer solution, i.e. polycarboxylate water-reducer.
The polycarboxylate water-reducer of the parts by weight, sodium tripolyphosphate, citric acid, sodium nitrite and calcium increasing agent are mixed,
Stirring into slurry without granular material, stand 10 minutes to get.
Embodiment 2
A kind of aqua retarder, according to parts by weight, the retarder include polycarboxylate water-reducer 75, sodium tripolyphosphate
5, citric acid 10, calcium nitrite 2 and calcium increasing agent 5, the weight ratio of calcium hydroxide, calcium oxide and calcium carbonate is in the calcium increasing agent
30:40:10.The preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring is to 40 DEG C；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, after 5min starts that itaconic acid solution 3h is slowly added dropwise,
Ammonium persulfate solution 3.5h keeps 40 DEG C of reaction 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains
Faint yellow sticky shape high-molecular copolymer solution, i.e. polycarboxylate water-reducer.
The polycarboxylate water-reducer of the parts by weight, sodium tripolyphosphate, citric acid, calcium nitrite and calcium increasing agent are mixed,
Stirring into slurry without granular material, stand 10 minutes to get.
Embodiment 3
A kind of aqua retarder, according to parts by weight, the retarder include polycarboxylate water-reducer 80, calgon
6, citric acid 15, methanol 3 and calcium increasing agent 7, the weight ratio of calcium hydroxide, calcium oxide and calcium carbonate is 30 in the calcium increasing agent:
40:15.The preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring is to 40 DEG C；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, starts after 5min methacrylic acid is slowly added dropwise molten
Liquid 3h, potassium persulfate solution 3.5h keep 40 DEG C of reaction 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains
Faint yellow sticky shape high-molecular copolymer solution, i.e. polycarboxylate water-reducer.
The polycarboxylate water-reducer of the parts by weight, calgon, citric acid, methanol and calcium increasing agent are mixed, stirring
Into slurry without granular material, stand 10 minutes to get.
Embodiment 4
A kind of aqua retarder, according to parts by weight, the retarder include polycarboxylate water-reducer 85, calgon
10, citric acid 20, methanol 5 and calcium increasing agent 10, the weight ratio of calcium hydroxide, calcium oxide and calcium carbonate is in the calcium increasing agent
30:40:15.The preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring is to 40 DEG C；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, after 5min starts that acrylic acid solution 3h is slowly added dropwise,
Potassium persulfate solution 3.5h keeps 40 DEG C of reaction 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains
Faint yellow sticky shape high-molecular copolymer solution, i.e. polycarboxylate water-reducer.
The polycarboxylate water-reducer of the parts by weight, calgon, citric acid, methanol and calcium increasing agent are mixed, stirring
Into slurry without granular material, stand 10 minutes to get.
Comparative example 1
A kind of aqua retarder, according to parts by weight, the retarder include polycarboxylate water-reducer 80, calgon
6, citric acid 15, methanol 3 and calcium increasing agent 7, the weight ratio of calcium hydroxide, calcium oxide and calcium carbonate is 30 in the calcium increasing agent:
40:15, the polycarboxylate water-reducer are common commercially available 40% polycarboxylate water-reducer of solid content.The polycarboxylic acids of the parts by weight is subtracted
Aqua, calgon, citric acid, methanol and calcium increasing agent mixing, stirring, without granular material, stand 10 minutes into slurry,
To obtain the final product.
Experimental example 1
The service performance of retarder prepared in embodiment 1-4 and comparative example 1 is tested, is wherein delayed in concrete
The additive amount of solidifying agent is 1.5wt%, and experimental result is as shown in table 1.
The performance table of each retarder in 1 embodiment 1-4 of table and comparative example 1
From table 1 it follows that embodiment 3 is optimum embodiment, i.e., according to the type of the constituent in embodiment 3 and
Ratio, the properties of retarder can achieve best.It can also be seen that the properties of embodiment are better than comparative example, because
The ingredient of polycarboxylate water-reducer is only changed in comparative example, so the setting time of comparative example is not much different with each embodiment.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of aqua retarder, including polycarboxylate water-reducer, Quadrafos, organic acid, antifreezing agent and calcium increasing agent.
2. retarder according to claim 1, which is characterized in that according to parts by weight, the retarder includes poly- carboxylic
Sour water-reducing agent 70-85, Quadrafos 1-10, organic acid 5-20, antifreezing agent 1-5 and calcium increasing agent 1-10.
3. retarder according to claim 1, which is characterized in that the retarder include polycarboxylate water-reducer 75-85,
Quadrafos 5-10, organic acid 10-20, antifreezing agent 2-5 and calcium increasing agent 5-10.
4. retarder according to claim 1, which is characterized in that the preparation step of the polycarboxylate water-reducer are as follows:
1) methyl allyl polyoxyethylene ether is added in three-neck flask, heating stirring to assigned temperature；
2) 30% hydrogen peroxide solution is added, instills mercaptoacetic acid solution, after 5min starts that minor comonomer solution 3h is slowly added dropwise, cause
Agent solution 3.5h keeps assigned temperature to react 1.5h after being added dropwise；
3) after reaction, cooling to reaction product, 30% sodium hydroxide solution is added, adjusts pH value to neutrality, obtains yellowish
The sticky shape high-molecular copolymer solution of color, i.e. polycarboxylate water-reducer.
5. retarder according to claim 4, which is characterized in that the assigned temperature in the step 1) and step 2) is 40
℃。
6. retarder according to claim 4, which is characterized in that minor comonomer solution in the step 2) be acrylic acid,
One of methacrylic acid, fumaric acid or itaconic acid are a variety of, and the initiator solution in the step 2) is ammonium persulfate, mistake
At least one of potassium sulfate.
7. retarder according to claim 1, which is characterized in that the antifreezing agent is sodium nitrite, carbonate, chlorination
At least one of calcium, calcium nitrite, methanol.
8. retarder according to claim 1, which is characterized in that the Quadrafos is calgon or tripolyphosphate
Sodium.
9. retarder according to claim 1, which is characterized in that specifically, the calcium increasing agent includes calcium hydroxide, oxidation
Calcium and calcium carbonate, and the weight ratio of the calcium hydroxide, calcium oxide and calcium carbonate is 20-50:30-50:1-60；Optionally,
The fineness of the calcium increasing agent is 325 mesh.
10. retarder according to claim 1-3, which is characterized in that the preparation method of the retarder includes
Following steps: the polycarboxylate water-reducer of the parts by weight, Quadrafos, organic acid, antifreezing agent and calcium increasing agent are mixed, stirring
Into slurry without granular material, stand 10 minutes to get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811470452.0A CN109399992A (en) | 2018-12-04 | 2018-12-04 | A kind of aqua retarder |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811470452.0A CN109399992A (en) | 2018-12-04 | 2018-12-04 | A kind of aqua retarder |
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| CN109399992A true CN109399992A (en) | 2019-03-01 |
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| CN201811470452.0A Pending CN109399992A (en) | 2018-12-04 | 2018-12-04 | A kind of aqua retarder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925147A (en) * | 2020-07-10 | 2020-11-13 | 中国科学院合肥物质科学研究院 | Novel water-resistant quick-hardening retarder for inorganic cementing material and preparation method thereof |
| CN115259728A (en) * | 2022-08-15 | 2022-11-01 | 四川奥克化学有限公司 | Gypsum retarder and preparation method thereof |
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| CN101812163B (en) * | 2010-04-19 | 2011-09-14 | 河北铁园科技发展有限公司 | Method for preparing polycarboxylic acid retarding water reducer |
| CN104059199A (en) * | 2014-04-16 | 2014-09-24 | 广东红墙新材料股份有限公司 | Polycarboxylic acid super-retarding water reducer and preparation method and application thereof |
| CN104119027A (en) * | 2014-06-25 | 2014-10-29 | 芜湖市三兴混凝土外加剂有限公司 | Retarding and water reducing agent |
| CN108659174A (en) * | 2017-03-28 | 2018-10-16 | 北新集团建材股份有限公司 | A kind of method preparing polycarboxylate water-reducer and a kind of retarder and preparation method thereof |
-
2018
- 2018-12-04 CN CN201811470452.0A patent/CN109399992A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812163B (en) * | 2010-04-19 | 2011-09-14 | 河北铁园科技发展有限公司 | Method for preparing polycarboxylic acid retarding water reducer |
| CN104059199A (en) * | 2014-04-16 | 2014-09-24 | 广东红墙新材料股份有限公司 | Polycarboxylic acid super-retarding water reducer and preparation method and application thereof |
| CN104119027A (en) * | 2014-06-25 | 2014-10-29 | 芜湖市三兴混凝土外加剂有限公司 | Retarding and water reducing agent |
| CN108659174A (en) * | 2017-03-28 | 2018-10-16 | 北新集团建材股份有限公司 | A kind of method preparing polycarboxylate water-reducer and a kind of retarder and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925147A (en) * | 2020-07-10 | 2020-11-13 | 中国科学院合肥物质科学研究院 | Novel water-resistant quick-hardening retarder for inorganic cementing material and preparation method thereof |
| CN111925147B (en) * | 2020-07-10 | 2022-07-01 | 中国科学院合肥物质科学研究院 | Water-resistant rapid-hardening retarder for inorganic cementing material and preparation method thereof |
| CN115259728A (en) * | 2022-08-15 | 2022-11-01 | 四川奥克化学有限公司 | Gypsum retarder and preparation method thereof |
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