Cement is protected the grinding aid and its production and application that collapses
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
From the development trend of world's Cement industry, 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, China's Research on cement additive, production unit are a lot, but all be confined to study grinding-aid effect, the reinforced effects of grinding aid and improve the grain composition of cement and conventional study content such as flowability on, 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 adaptability statement into question of superplasticizer.Domestic existing investigator proves that there is detrimentally affect in grinding aid commonly used to the adaptability 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 adaptability of cement and admixture, and solve the concrete slump loss problem simultaneously, it 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 adaptability of cement and admixture again, solve the grinding aid of concrete slump loss problem simultaneously, will provide technical guarantee 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 composition 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 to be solved in the present invention provides that a kind of manufacture craft is simple, cost is low, can effectively improve the adaptability of cement and admixture, the guarantor who the solves the concrete slump loss problem simultaneously grinding aid and its production and application 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% ethylene glycol, 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% ethylene glycol, 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 described raw material in described ratio;
(2), after dissolving fully, tripoly phosphate sodium STPP evenly adds Sodium hexametaphosphate 99 while stirring with tripoly phosphate sodium STPP and water mixing and stirring;
(3) adding ethylene glycol and carboxy-containing acid group's sulfamate based water reducer after described Sodium hexametaphosphate 99 dissolves fully stirs.
The present invention prepares the collapse method of grinding aid of described 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 described phenylformic acid sulfonated monomers is 60%~80% of described phenol and a Sodium sulfanilate quality sum.
Described 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.
Described setting-up point is 83~87 ℃, and the pH value is 8~11, and the reaction times is 4-6 hour.
Described formaldehyde joins in the condensation system in the dropping mode, the dropping time is 1-1.5 hour, after dripping formaldehyde, 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 (determining 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 described 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, select proper raw material and proportioning thereof for use, and 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, introduced active group-carboxyl, improved molecular structure, and adopt the distinctive processing 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 by water reducer is carried out chemical modification, improved the performance of water reducer, improved the adaptability of cement and admixture, effectively reduce the loss that cement collapses, it is single to have overcome traditional grinding aid performance, bad adaptability, the 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, be described in more detail with other technical characterictic and advantage the present invention is above-mentioned.
Carboxy-containing acid group's of the present invention sulfamate based water reducer, its concrete preparation method is as follows:
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 reactor, 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 in 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, ethylene glycol 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, after dissolving fully, tripoly phosphate sodium STPP evenly adds Sodium hexametaphosphate 99 while stirring; After described Sodium hexametaphosphate 99 dissolves fully, add ethylene glycol 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 ethylene glycol, 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 ethylene glycol, 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 ethylene glycol 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, the results are shown in 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 results are shown in 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 adaptability 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 is described 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.