CN102241488B - Cement slump-retaining grinding aid as well as preparation method and application thereof - Google Patents
Cement slump-retaining grinding aid as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102241488B CN102241488B CN 201110137780 CN201110137780A CN102241488B CN 102241488 B CN102241488 B CN 102241488B CN 201110137780 CN201110137780 CN 201110137780 CN 201110137780 A CN201110137780 A CN 201110137780A CN 102241488 B CN102241488 B CN 102241488B
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- China
- Prior art keywords
- cement
- grinding aid
- sodium
- phenol
- phenylformic acid
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Classifications
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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
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
Abstract
The invention relates to a cement slump-retaining grinding aid as well as a preparation method and an application thereof. The cement slump-retaining grinding aid is composed of the following components in percentage by weight: 4.0-7.0% of sodium tripolyphosphate, 10.0-21.0% of sodium hexametaphosphate, 4.0-10% of ethylene glycol, 0.5-2.0% of carboxylic-group-containing amino sulfonate water reducing agent and 60.0-81.5% of water, wherein the carboxylic-group-containing amino sulfonate water reducing agent is formed by condensation of phenol, sodium p-amino benzene sulfonate and formaldehyde in a molar ratio of (1.1-1.5): (0.9-1.2): (3.5-3.7) with a benzoic acid sulfonation monomer. The addition amount of the cement slump-retaining grinding aid provided by the invention is 0.03-0.1% of the total weight of cement; and the cement slump-retaining grinding aid has the characteristics of simple preparation process and low cost, and can effectively improve the adaptability of cement and additives.
Description
Technical field
The present invention relates to a kind of cement and protect the grinding aid that collapses, particularly relate to a kind of adaptive guarantor who is used to improve cement and admixture grinding aid and preparation method thereof that collapses.
Background technology
The development trend of Cement industry from the world, the growth that future world Cement Production and consumption still keep certain speed.The cement output of some developed countries begins to descend, and the center of gravity of manufacture of cement progressively shifts to developing country.Estimate that Future in China will become cement exit big country.But because the industrial structure is unreasonable, it is uneven cement quality to occur, and oeverall quality is relatively poor, and comparing with external cement mainly is that the blending amount of mixture material of cement is bigger, and the fineness of cement is thicker, and then causes the early stage intensity of cement on the low side.And will address this problem, the simplest and effective way just is to use cement grinding aid.
At present; Research, the production unit of cement in China grinding aid are a lot; But all be confined to study grinding-aid effect, the reinforced effects of grinding aid and improve on the conventional study content such as grain composition and flowability of cement, mixing of cement grinding aid influenced cement and the adaptive research of admixture seldom.Yet; Because the introducing of cement grinding aid; Make the quality of cement that variation take place, the performance that causes commerical ready-mixed concrete especially serviceability has produced fluctuation, and some commerical ready-mixed concrete manufacturers are to the cement of mixing grinding aid and the flexibility statement into question of superplasticizer.Domestic existing investigator proves that there is detrimentally affect in grinding aid commonly used to the flexibility of cement and admixture.
Concrete the insider know, and just there is the adaptability problem with concrete admixture in cement itself.How to improve the flexibility of cement and admixture; And solving the concrete slump loss problem simultaneously, is scientific research personnel's goal in research in the industry, therefore; If can obtain a kind of grinding aid reinforced effects of existing traditional grinding aid; Can effectively improve the flexibility of cement and admixture again, solve the grinding aid of concrete slump loss problem simultaneously, will technical guarantee be provided for extensively promoting the use of of cement grinding aid.
CN101831037A discloses a kind of carboxylic acid copolymer concrete slump retaining agent; This slump retaining agent adopts redox system and initiator synthetic molecular weight to form for the 10000-100000 copolymer by modified polyether and unsaturated carboxylic acid and linking agent; This invention has protects the effect of collapsing preferably, but can not solve above-mentioned adaptability problem.
CN101065338A discloses a kind of aqueous compsn that contains polymer A also can the making cement grinding aid; The combination of this polymer A and common cement grinding aid; Can correct or significantly reduce the shortcoming of known grinding aid; Polymer A can contain hydroxy-acid group or carboxylic acid sodium group, but this method for producing polymer is complicated, thereby it is also higher to contain the cement grinding aid cost of this polymkeric substance.
Summary of the invention
The technical problem that the present invention will solve provides that a kind of manufacture craft is simple, cost is low, can effectively improve the flexibility of cement and admixture, the guarantor who the solves the concrete slump loss problem simultaneously grinding aid that collapses.
A kind of cement of the present invention is protected the grinding aid that collapses; Sulfamate based water reducer and 60.0%～81.5% water by weight percent 4.0%～7.0% tripoly phosphate sodium STPP, 10.0%～21.0% Sodium hexametaphosphate 99,4.0%～10% terepthaloyl moietie, 0.5%～2.0% carboxy-containing acid group are formed, and preferably are made up of weight percent 6.0% tripoly phosphate sodium STPP, 19.0% Sodium hexametaphosphate 99,8.0% terepthaloyl moietie, 1.0% carboxy-containing acid group's sulfamate based water reducer and 66.0% water.
The present invention is a kind of to prepare the collapse method of grinding aid of above-mentioned guarantor, may further comprise the steps:
(1) prepares said raw material in said ratio;
(2),, tripoly phosphate sodium STPP evenly adds Sodium hexametaphosphate 99 after dissolving fully while stirring with tripoly phosphate sodium STPP and water mixing and stirring;
(3) adding terepthaloyl moietie and carboxy-containing acid group's sulfamate based water reducer after said Sodium hexametaphosphate 99 dissolves fully stirs.
The present invention prepares the collapse method of grinding aid of said guarantor; Wherein said carboxy-containing acid group's sulfamate based water reducer is (1.1～1.5) by phenol, Sodium sulfanilate and formaldehyde with mol ratio: (0.9～1.2): (3.5～3.7) and the condensation of phenylformic acid sulfonated monomers form, and the consumption of said phenylformic acid sulfonated monomers is 60%～80% of said phenol and a Sodium sulfanilate quality sum.
Said phenylformic acid sulfonated monomers by phenylformic acid, phenol and the vitriol oil with mol ratio (0.9～1.2): (0.3～0.6): (1.3～1.7) made at 130 ℃ of sulfonation 2-3 hours.
Said setting-up point is 83～87 ℃, and the pH value is 8～11, and the reaction times is 4-6 hour.
Said formaldehyde joins in the condensation system with the dropping mode; The dropping time is 1-1.5 hour, drip formaldehyde after, kept reaction system constant 1 hour; Add auxiliary agent Sodium sulfanilate, naphthalenesulfonate formaldehyde condensation compound and water; The volume of Sodium sulfanilate and naphthalenesulfonate formaldehyde condensation compound is initial 10%～30% of phenol, Sodium sulfanilate and the sulfonated monomers quality that add, and water an amount of (confirming according to the amount of adding auxiliary agent) continues reaction 5-6 hour afterwards.
The collapse application of grinding aid of guarantor of the present invention is incorporated into it in cement, to improve the performance of cement.
The said guarantor incorporation that grinding aid mixes in the cement that collapses is 0.03%～0.1% of a cement gross weight.
Cement of the present invention is protected the grinding aid that collapses, and selects proper raw material and proportioning thereof for use, and has added carboxy-containing acid group's sulfamate based water reducer in the raw material; This carboxy-containing acid group's sulfamate based water reducer; On molecular backbone chain, introduce reactive group-carboxyl, improved molecular structure, and adopted the distinctive process method condensation of the present invention to form; Can guarantee that carboxylic group can be grafted to suitable ratio on the molecular backbone chain; Promptly, improved the performance of water reducer, improved the flexibility of cement and admixture through water reducer is carried out chemical modification; Effectively reduce the loss that cement collapses, overcome that traditional grinding aid performance is single, bad adaptability, shortcoming that cost is high.The present invention prepares the method that cement is protected the grinding aid that collapses, and has the advantages that operation is simple.
Embodiment
Below in conjunction with embodiment, contrast and effect test data, do more detailed explanation with other technical characterictic and advantage to the present invention is above-mentioned.
Carboxy-containing acid group's of the present invention sulfamate based water reducer, its concrete preparation method is following:
The phenylformic acid sulfonated monomers was made 130 ℃ of sulfonation by 122g phenylformic acid, 47g phenol and the 147g vitriol oil in 3 hours.
In reaction kettle, carry out condensation reaction by 112.8g phenol, 195.1g Sodium sulfanilate, 108g formaldehyde, 585g water, 10g catalyzer and 184.7g phenylformic acid sulfonated monomers; Setting-up point is 85 ℃; Reacting solution pH value is 10; Wherein formaldehyde joins in the condensation system with the dropping mode, and the dropping time is 1 hour.After dripping formaldehyde, kept reaction system constant 1 hour, add Sodium sulfanilate and naphthalenesulfonate formaldehyde condensation compound 98.5g and water 20g, continue reaction 6 hours afterwards, total reaction time is about 8 hours, obtains carboxy-containing acid group's sulfamate.
Embodiment 1: prepare following raw materials by weight percentage: tripoly phosphate sodium STPP 4g, Sodium hexametaphosphate 99 21g, terepthaloyl moietie 10g, above-mentioned carboxy-containing acid group's sulfamate based water reducer 2.0g and tap water 63g.With tripoly phosphate sodium STPP and water mixing and stirring,, tripoly phosphate sodium STPP evenly adds Sodium hexametaphosphate 99 after dissolving fully while stirring; After said Sodium hexametaphosphate 99 dissolves fully, add terepthaloyl moietie and carboxy-containing acid group's sulfamate based water reducer, stir, obtain No. 1 and protect the grinding aid that collapses.
Embodiment 2: prepare following raw materials by weight percentage: 6.0g tripoly phosphate sodium STPP, 19.0g Sodium hexametaphosphate 99,8.0g terepthaloyl moietie, 1.0g carboxy-containing acid group's sulfamate based water reducer and 66.0g water.The preparation method obtains No. 2 and protects the grinding aid that collapses with embodiment 1.
Embodiment 3: prepare following raw materials by weight percentage: 7.0g tripoly phosphate sodium STPP, 10.0g Sodium hexametaphosphate 99,4.0g terepthaloyl moietie, 0.5g carboxy-containing acid group's sulfamate based water reducer and 78.5g water.The preparation method obtains No. 3 and protects the grinding aid that collapses with embodiment 1.
Embodiment 4: prepare following raw materials by weight percentage: 6.0g tripoly phosphate sodium STPP, 19.0g Sodium hexametaphosphate 99,8.0g terepthaloyl moietie and 67.0g water.The preparation method obtains No. 4 and protects the grinding aid that collapses with embodiment 1.
Use this area ordinary method measure the above embodiment of the present invention protect the grinding-aid effect of grinding aid that collapses, to the influence of cement performance, to cement and the adaptive influence of admixture, shown in table 1, table 2, table 3.(annotate: kind hurdle " blank " is meant in the cement that admixture is not protected the grinding aid that collapses in the following table, and " 1 " is meant to add in the cement and protects the grinding aid that collapses No. 1, in like manner analogize that " 4 " are meant to add in the cement and protect the grinding aid that collapses No. 4.)
Mensuration to concrete slump: the used mass ratio of cement, flyash, sand and stone is in the concrete: 281: 109: 752: 1082.The concrete initial slump (being the concrete elemental height) is 180mm, after 1 hour, measures blank and has mixed the concrete slump (the concrete height after promptly 1 hour) of protecting the grinding aid that collapses for 1,2,3, No. 4 respectively, and the result sees table 3.
Obtain with embodiment 2 to protect the grinding aid that collapses No. 2 be example, checking volume scope is to the influence of cement effect, that the volume of protecting the grinding aid that collapses for No. 2 is respectively is blank, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, the result sees table 4.
Table 1 the present invention protects the grinding aid grinding-aid effect that collapses
Table 2 the present invention protects the influence of grinding aid to cement performance of collapsing
Table 3 the present invention protects collapses grinding aid to cement and the adaptive influence of admixture
Table 4 the present invention protects the influence of grinding aid volume to grinding-aid effect of collapsing
Through facts have proved, it is 0.03%～0.1% that cement of the present invention is protected the grinding aid volume that collapses, its grinding-aid effect: specific surface area increases by 10～50m
2Between/the kg, 80 μ m tail over and reduce by 0.2%～1.1%; Improve strength of cement: 3d and improve 3～8Mpa, 28d improves 3～7Mpa; 5～25 yuan of reduction cement costs per ton; Overcome the shortcoming of traditional grinding aid, effectively improved the flexibility of cement and admixture.This test grinding-aid effect adopts " cement grinding aid " JC/T667-2004 standard test, and cement performance adopts " general purpose portland cement " GB175-2007 standard test.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (9)
1. a cement is protected the grinding aid that collapses, and it is characterized in that: sulfamate based water reducer and 60.0%～81.5% water by weight percent 4.0%～7.0% tripoly phosphate sodium STPP, 10.0%～21.0% Sodium hexametaphosphate 99,4.0%～10% terepthaloyl moietie, 0.5%～2.0% carboxy-containing acid group are formed;
Wherein said carboxy-containing acid group's sulfamate based water reducer is (1.1～1.5) by phenol, Sodium sulfanilate and formaldehyde with mol ratio: (0.9～1.2): (3.5～3.7) and the condensation of phenylformic acid sulfonated monomers form, and the consumption of said phenylformic acid sulfonated monomers is 60%～80% of said phenol and a Sodium sulfanilate quality sum;
Said phenylformic acid sulfonated monomers by phenylformic acid, phenol and the vitriol oil with mol ratio (0.9～1.2): (0.3～0.6): (1.3～1.7) made at 130 ℃ of sulfonation 2-3 hours.
2. the guarantor according to claim 1 grinding aid that collapses, it is characterized in that: sulfamate based water reducer and 66.0% water by weight percent 6.0% tripoly phosphate sodium STPP, 19.0% Sodium hexametaphosphate 99,8.0% terepthaloyl moietie, 1.0% carboxy-containing acid group are formed.
3. one kind prepares the collapse method of grinding aid of claim 1 or 2 described guarantors, it is characterized in that: may further comprise the steps:
(1) prepares said raw material in said ratio;
(2),, tripoly phosphate sodium STPP evenly adds Sodium hexametaphosphate 99 after dissolving fully while stirring with tripoly phosphate sodium STPP and water mixing and stirring;
(3) adding terepthaloyl moietie and carboxy-containing acid group's sulfamate based water reducer after said Sodium hexametaphosphate 99 dissolves fully stirs.
4. method according to claim 3; It is characterized in that: said carboxy-containing acid group's sulfamate based water reducer is (1.1～1.5) by phenol, Sodium sulfanilate and formaldehyde with mol ratio: (0.9～1.2): (3.5～3.7) and the condensation of phenylformic acid sulfonated monomers form, and the consumption of said phenylformic acid sulfonated monomers is 60%～80% of said phenol and a Sodium sulfanilate quality sum.
5. method according to claim 4 is characterized in that: said phenylformic acid sulfonated monomers by phenylformic acid, phenol and the vitriol oil with mol ratio (0.9～1.2): (0.3～0.6): (1.3～1.7) made at 130 ℃ of sulfonation 2-3 hours.
6. method according to claim 4 is characterized in that: said setting-up point is 83～87 ℃, and the pH value is 8～11, and the reaction times is 4-6 hour.
7. method according to claim 4 is characterized in that: said formaldehyde joins in the condensation system with the dropping mode, and the dropping time is 1-1.5 hour.
8. claim 1 or the 2 described guarantors application of grinding aid of collapsing is incorporated into it in cement, to improve the performance of cement.
9. the collapse application of grinding aid of guarantor according to claim 8 is characterized in that: the said guarantor incorporation that grinding aid mixes in the cement that collapses is 0.03%～0.1% of a cement gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201110137780 CN102241488B (en) | 2011-05-25 | 2011-05-25 | Cement slump-retaining grinding aid as well as preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110137780 CN102241488B (en) | 2011-05-25 | 2011-05-25 | Cement slump-retaining grinding aid as well as preparation method and application thereof |
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| CN102241488A CN102241488A (en) | 2011-11-16 |
| CN102241488B true CN102241488B (en) | 2012-11-21 |
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Families Citing this family (6)
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| CN102863176B (en) * | 2012-10-17 | 2014-06-04 | 南京永能新材料有限公司 | High grinding temperature compound liquid grinding aid and preparation method thereof |
| CN103755165B (en) * | 2013-12-18 | 2016-03-02 | 北京东方建宇混凝土科学技术研究院有限公司 | Modification silicon manganese slag and the concrete utilizing this silicon manganese slag to prepare and concrete method for making |
| CN106007449A (en) * | 2015-12-19 | 2016-10-12 | 济南源盛化工科技有限公司 | Cement grinding aid |
| CN106007458B (en) * | 2016-05-20 | 2019-01-01 | 江苏苏博特新材料股份有限公司 | A kind of preparation method and applications of gas tracting subtractive agent |
| CN109021188B (en) * | 2018-08-29 | 2021-04-20 | 江苏苏博特新材料股份有限公司 | Modified phenolic aldehyde amine polycondensate cement grinding aid, and preparation method and application thereof |
| CN109503023A (en) * | 2018-12-27 | 2019-03-22 | 山西黄腾化工有限公司 | A kind of pumping agent for concrete and its production technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080227890A1 (en) * | 2004-06-21 | 2008-09-18 | Sika Technology Ag | Cement Grinding Aid |
| CN101830662B (en) * | 2010-03-30 | 2012-10-10 | 中钢集团洛阳耐火材料研究院有限公司 | Compound early strength antifreezing agent of unshaped refractory for aluminate cement |
| CN101831037A (en) * | 2010-04-14 | 2010-09-15 | 深圳市五山建材实业有限公司 | Carboxylic acid copolymer concrete slump retaining agent |
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