A kind of polycarboxylate water-reducer and application thereof and preparation method
Technical field
The invention belongs to chemosynthesis technical field, especially belong to the additional high performance water-reducer preparing technical field of concrete, particularly a kind of polycarboxylate water-reducer and application thereof and preparation method.
Background technology
Along with the quickening of nation-building development, traditional concrete is replaced by high performance concrete, green concrete gradually, occur in process at new concrete, concrete admixture plays an important role, and water reducer is topmost integral part in concrete admixture, in concrete production technology, progressively play the effect of core, play huge effect.After mixing admixture, among every cubic meter of concrete, approximately can save cement 15% ~ 20%, making full use of of the agglutinate such as flyash, breeze can also be assisted.
Water reducer is also known as fluidizer or dispersion agent.Add appropriate water reducer when mixing and stirring concrete, mainly play a part three different: 1. when maintenance concrete mix is constant, improve its workability; Or reduce water consumption when keeping workability constant, improve concrete strength; 2. reducing cement consumption when keeping intensity constant, saving cement, reducing costs; 3. after adding water reducer, concrete is more evenly closely knit, improves series of physical chemical property, as impermeability, frost resistance, resistance to fouling etc., improves concrete weather resistance.
High performance water reducing agent of polyocarboxy acid has the advantage of its uniqueness: volume is low, and have super dispersing property to cement molecule, water-reducing rate is large; The mobility of concrete mix and retentivity good, slump-loss is low; Low to construction environment temperature requirement; Under identical degree of mobilization, delay time of coagulation less; On molecular structure, degree of freedom is large, and in admixture manufacturing technology, controllable parameter is many, and really accomplish the mechanism of action design the most effective various molecular structure according to dispersion cement, the potential of high performance is large.The consistency of high performance water reducing agent of polyocarboxy acid and cement is better, can more utilize the blended material such as slag or flyash, thus reduce concrete cost on the whole, in addition, high performance water reducing agent of polyocarboxy acid also has the features such as production greenization, green productive process, is the prior development direction of water reducer industry.
China's research high performance water reducing agent of polyocarboxy acid is started late, and since the middle and later periods nineties in last century, many R&D institutions, institution of higher learning, strong admixture manufacturing enterprise etc., by large quantity research, achieve many scientific payoffss.Compared to external high-level admixture technology, the particularly enterprise such as catalyst, BASF, also there is very large gap in the admixture application technology of China, especially shows the aspects such as the maintenance of ready mixed concrete dispersing property, water-retentivity, workability.
Summary of the invention
The present invention discloses a kind of polycarboxylate water-reducer and application thereof and preparation method according to the deficiencies in the prior art, the object of the present invention is to provide a kind ofly have that volume is low, protect plasticity can good, the high performance water reducing agent of polyocarboxy acid that effectively can improve the advantages such as concrete workability and application thereof and preparation method.
The present invention synthesizes a kind of polycarboxylate water-reducer, and its general formula of molecular structure is as follows:
The compound molecular weight of described general formula is 10000 ~ 100000; Wherein, R
1for
or
; R
2for hydrogen or carboxyl; R
3for hydrogen or methyl; N=1 ~ 200; A, b, c are all less than 1000.
Water reducer is made up of the component of following parts by weight:
Polymeric monomer 100 parts;
Minor comonomer
*3.2 ~ 13.2 parts;
0.3 ~ 3 part, oxygenant;
Minor comonomer
*4.5 ~ 12.7 parts;
Reductive agent 0.14 ~ 2 part;
Molecular weight regulator 0.2 ~ 1 part;
72 ~ 190 parts, water;
Described polymeric monomer is: any one in isopentenol polyoxyethylene ether, prenol polyethenoxy ether, and molecular weight is 1000 ~ 5000; Preferred polymeric monomer molecular weight is 2200 ~ 2600.
Described minor comonomer
*for: N-carbamyl toxilic acid;
Described oxygenant is: hydrogen peroxide;
Described minor comonomer
*for any one or two kinds of in vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE;
Described reductive agent is: any one in xitix, S-WAT, sodium hypophosphite, glucose, rongalite;
Described molecular weight regulator is: any one or two kinds of in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid.
The synthesis preparation method of above-mentioned polycarboxylate water-reducer is specially:
(1) take polymeric monomer, minor comonomer by described parts by weight
*and water, add in the reactor with agitator, thermometer and reflux exchanger, stirring heating makes it dissolve;
(2), at 30 ~ 60 DEG C of temperature, in reactor, add oxygenant, stir;
(3) keep temperature 30 ~ 60 DEG C, drip minor comonomer
*, reductive agent and molecular weight regulator preparation mixed aqueous solution, time for adding is 1 ~ 6h;
(4), after dripping, at 30 ~ 60 DEG C of temperature, continue insulation reaction 1 ~ 3h;
(5) react end, be cooled to room temperature discharging, obtain described polycarboxylate water-reducer, solid content 40 ~ 60%.
Described step (2) to step (4) in design temperature be preferably 50 ~ 55 DEG C.
Described step (3) in the material dropping time be preferably 3 ~ 4h.
Described step (4) in the insulation reaction time be preferably 1 ~ 2h.
The application method of polycarboxylate water-reducer: the water reducer of above-mentioned preparation and commercially available polycarboxylate water-reducer are pressed part by weight 10 ~ 30 ︰ 90 ~ 70 converted as solid content used in combination.Preferred proportion is 20 ~ 30 ︰ 80 ~ 70.
Helpfulness of the present invention: the invention provides a kind of new water reducer and application thereof and preparation method, after contrast experiment detects and proves that water reducer of the present invention and conventional commercial polycarboxylic acids water reducing agent compositional use, the initial dispersion of cement is decreased, but has improvement in various degree to dispersion retention; Use water reducer of the present invention to make the workability of fresh concrete obtain improvement to a certain extent, the slump, divergence retention and concrete crushing strength get a promotion.Water reducer raw materials of the present invention is easy to get, synthesis preparation method safely, stablize controlled, raw material and finished product use cost low, safety and environmental protection.
Embodiment
Below by embodiment, the present invention is specifically described; the present embodiment is only for being further detailed the present invention; but can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art makes according to the content of the invention described above and adjustment also belong to the scope of protection of the invention.
Embodiment 1
In the 1000ml four-hole boiling flask being furnished with agitator, thermometer, reflux exchanger and Dropping feeder, add isopentenol polyoxyethylene ether 500g, N-carbamyl toxilic acid 32.9g and deionized water 286.7g, stirring heating makes it dissolve.
When temperature is 50 DEG C, adding 2g concentration is 30% hydrogen peroxide, stirs.Then, start the mixture dripping 39g vinylformic acid, 0.8g xitix, 1.6g Thiovanic acid and 286.7g deionized water composition in four-hole boiling flask, time for adding is 3h.After material dropping is complete, at 50 DEG C, continue insulation reaction 1h.
Reaction terminates, and cools to room temperature discharging, is diluted to desired concn with deionized water, obtain product P C-1.
Embodiment 2
In the 1000ml four-hole boiling flask being furnished with agitator, thermometer, reflux exchanger and Dropping feeder, add isopentenol polyoxyethylene ether 500g, N-carbamyl toxilic acid 49.3g and deionized water 291.2g, stirring heating makes it dissolve.
When temperature is 55 DEG C, adding 2g concentration is 30% hydrogen peroxide, stirs.Then, start the mixture dripping 31.5g vinylformic acid, 0.8g xitix, 1.6g Thiovanic acid and 291.2g deionized water composition in four-hole boiling flask, time for adding is 3h.After material dropping is complete, at 55 DEG C, continue insulation reaction 1h.
Reaction terminates, and cools to room temperature discharging, is diluted to desired concn with deionized water, obtain product P C-2.
Embodiment 3
In the 1000ml four-hole boiling flask being furnished with agitator, thermometer, reflux exchanger and Dropping feeder, add isopentenol polyoxyethylene ether 500g, N-carbamyl toxilic acid 49.3g and deionized water 296.9g, stirring heating makes it dissolve.
When temperature is 55 DEG C, adding 2.7g concentration is 30% hydrogen peroxide, stirs.Then, start the mixture dripping 37.6g methacrylic acid, 0.95g xitix, 1.9g3-thiohydracrylic acid and 296.9g deionized water composition in four-hole boiling flask, time for adding is 3h.After material dropping is complete, at 55 DEG C, continue insulation reaction 1h.
Reaction terminates, and cools to room temperature discharging, is diluted to desired concn with deionized water, obtain product P C-3.
Test experience
High performance water reducing agent of polyocarboxy acid PC-1, PC-2, PC-3 prepared by above 3 embodiments are used with commercially available polycarboxylic acids water reducing agent compositional respectively, carry out flowing degree of net paste of cement experiment and concrete performance experiment, and contrast when being used alone with commercially available polycarboxylate water-reducer.Compound proportion is polycarboxylate water-reducer prepared by the embodiment of the present invention: the solid weight ratio of effective folding of commercially available polycarboxylate water-reducer=20 ︰ 80, except these two kinds of polycarboxylate water-reducers, all test experiments do not use other the third admixtures.Commercially available polycarboxylate water-reducer has multiple product, mainly distinguishes according to molecular structure and molecular weight, and as the gradation composition of high performance water reducing agent of polyocarboxy acid of the present invention, all polycarboxylate water-reducers can bought at present all can use.In the description which follows also referred to as conventional polycarboxylate water-reducer.
1. flowing degree of net paste of cement Experimental comparison
Flowing degree of net paste of cement test reference examination criteria: GB8077-2000 " concrete admixture homogeneity test method ", cement: Yadong P.O42.5R, water: 87g, water cement ratio=0.29.Test result is in table 1.
Table 1 flowing degree of net paste of cement test result
Test result as can be seen from table 1, after using according to the polycarboxylate water-reducer of preparation of the present invention and conventional polycarboxylic acids water reducing agent compositional, decreases to the initial dispersion of cement, but has improvement in various degree to dispersion retention.
2. fresh mixing concrete property experiment
Concrete performance experiment is with reference to examination criteria: GB8076-2008 " concrete admixture " and GB50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ".Cement: Lafarge P.O42.5R, sand is the medium sand of fineness modulus M=2.65, and cobble-stone diameter is 5 ~ 25mm continuous size fraction rubble.Concrete mix is in table 2.
Table 2 concrete mix (unit: kg/m
3)
According to above-mentioned condition and proportioning fresh concrete, and measure concrete initial slump, initial extension degree, the slump and divergence loss after 1h, test result is in table 3.
Table 3 fresh mixing concrete property (the solid volume of folding: 0.16%)
In table 3, testing concrete performance result shows, according to the high performance water reducing agent of polyocarboxy acid of preparation of the present invention, with conventional polycarboxylic acids water reducing agent compositional after use, make the workability of fresh concrete obtain improvement to a certain extent, the slump, divergence retention and concrete crushing strength get a promotion.