CN102030494A - High-performance polycarboxylate water reducing agent and low-temperature one-step preparation method thereof - Google Patents
High-performance polycarboxylate water reducing agent and low-temperature one-step preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance polycarboxylate water reducing agent and a low-temperature one-step preparation method thereof. In the invention, high-activity isopentene alcohol polyethenoxy ether or isobutylene alcohol polyethenoxy ether large monomer and acrylic acid react in a water solution at a low temperature (30-50 DEG C) to obtain the high-performance polycarboxylate water reducing agent in a two-dropping one-step mode. The water reducing agent has the advantages of high water reducing rate, low doped amount, high dispersity, favorable slump retaining property, wide applicability and high cost performance, and is suitable for various types of cement; and when the water reducing agent is used, more powdered ores and fly ash can substitute cement. The preparation method is simple for operation, and has the advantages of low energy consumption and environmental protection; three wastes are not discharged in the whole production process; and thus, the preparation method is a green synthesis method.
Description
Technical field
The present invention relates to a kind of concrete admixture, especially a kind of polycarboxylate high performance dehydragent and low temperature one-step preppn process thereof.
Background technology
In recent years, China's building cause fast development, country's constructions great, priority project such as civilian, railway, highway, bridge, tunnel, water power, harbour, harbour, airport all be unable to do without high performance concrete, self-compacting concrete, strong concrete, high-flowing concrete.And increasing to concrete demand, specification of quality is more and more higher, and performance requriements is more and more synthesization and variation also.The concrete that satisfies above requirement just be unable to do without high performance water reducer.
At present, high performance water reducer is exactly polycarboxylic acid salt's water reducer.Polycarboxylate high performance dehydragent has many advantages than the water reducer of other type, and, good dispersity low such as water-reducing rate height, volume, slump retaining be good, applied widely, be applicable to that various cement, low, the available more breeze of concrete cost or flyash replace cement, environmental protection, do not use objectionable impurities, whole process of production not to have " three wastes " discharging.Polycarboxylate high performance dehydragent has become the inexorable trend of 21 century research and development.
Abroad, polycarboxylate high performance dehydragent was just succeeded in developing from the nineties in last century, and formal suitability for industrialized production, began to be used for construction engineering, and development in recent years is swifter and more violent.Great, the priority project of Guo Jia some a few years ago, the polycarboxylate high performance dehydragent of use all is an imported product.Since the beginning of this century, development in recent years is rapider to the research of polycarboxylic acid salt's water reducer in China, and research level is constantly upgraded, and product performance are also improving constantly.2004, China began to build high-speed railway, required to adopt technology of high performance concrete, Tie Keyuan, iron to build institute completely and had done a large amount of basic works at high performance concrete.Ministry of Railways's science and technology base [2005] No. 101 " the provisional technical qualification of Line for Passenger Transportation high performance concrete " has required high-performance water reducing agent relevant technologies index, proposed 13 technical indicators, clearly stipulated durability of HPC with high index (as sodium sulphate content, chloride ion content, shrinkage ratio and relative durability index) requirement.After this, the notice about " Line for Passenger Transportation high performance concrete admixture standard detailed rules and regulations " has been assigned by science and technology office of the Ministry of Railways in 2006.Issued enforcement " polycarboxylate high performance dehydragent " JG/T223-2007 in 2007 again, for production, check and the use of polycarboxylate high performance dehydragent product provides foundation.State Administration for Quality Supervision and Inspection and Quarantine in 2008 and national standardization management committee are at the technical characterstic of water reducer, on the basis of a large amount of experiments, proposed specific performance and required and test method, united and issued " concrete admixture " GB8076-2008.The beginning that sign polycarboxylate high performance dehydragent substance is applied.
At present, producing polycarboxylic acid salt's water reducer has two kinds of methods, and a kind of is single stage method, and another kind is a two-step approach.Single stage method mainly is to be the product that major ingredient is produced with allyl alcohol Soxylat A 25-7, cis-butenedioic anhydride, and custom is referred to as the polyethers water reducer.This method production time is long, the temperature of reaction height.Its product early strength is low, and function of slump protection is poor, deficiencies such as bad adaptability.Two-step approach, the first step methoxy polyoxyethylene ether and methacrylic acid or vinylformic acid carry out esterification, prepare methoxy polyoxyethylene ether metacrylic acid ester or acrylate, and the ester of second step with preparation carries out polymerization with minor comonomer again.This method technology relative complex, reaction time is long, temperature of reaction height, production cost height.
Summary of the invention
Problem at the prior art existence, the object of the present invention is to provide a kind ofly have the water-reducing rate height, volume is low, dispersing property good, the slump keeps advantages such as performance is good polycarboxylate high performance dehydragent, another object of the present invention provides a kind of low temperature one-step preppn process of this water reducer.
For achieving the above object, a kind of polycarboxylate high performance dehydragent of the present invention, its general formula of molecular structure is as follows:
Wherein, R
1For-CH
2-CH
2-or
R
2, R
3, R
4Represent hydrogen or methyl respectively; R
5Expression hydrogen or methyl or carboxymethyl; R
6Expression hydrogen; R
7Expression hydrogen or carboxyl; M represents hydrogen, monovalent metallic ion, divalent-metal ion, ammonium ion; Y represents hydrogen or methyl; M=1～1000, n=1～1000, o=1～1000.
Further, the molecular weight of described polycarboxylate high performance dehydragent is 10000～100000.
A kind of low temperature one-step preppn process of above-mentioned polycarboxylate high performance dehydragent is specially:
1) minor comonomer, the water that takes by weighing big monomer and partly measure by setting weight drops in the reactor, and stirring heating makes its dissolving;
2) under design temperature, add initiator, stir;
3) under agitation, adopt two modes to drip minor comonomer and the aqueous solution of chain-transfer agent mixture and the aqueous solution of reductive agent of residual content respectively, or drip the aqueous solution of the residue minor comonomer aqueous solution and reductive agent and chain-transfer agent mixture;
4) drip off after, under design temperature, insulation reaction 1～5 hour;
5) add liquid caustic soda and neutralize, obtain the polycarboxylate high performance dehydragent product.
Further, described big monomer is: vinylcarbinol Soxylat A 25-7, isobutene alcohol Soxylat A 25-7, prenol Soxylat A 25-7; Described minor comonomer is: vinylformic acid, methacrylic acid, methylene-succinic acid, cis-butenedioic anhydride; Described initiator is: ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide; Described reductive agent is: S-WAT, sodium hypophosphite, glucose, xitix, rongalite; Described chain-transfer agent is: Thiovanic acid, mercaptoethanol, 2 mercaptopropionic acid, 3-thiohydracrylic acid; Described solvent is: tap water, deionized water.
Further, described big monomer consumption accounts for gross activity multipolymer mole number and is: 10～30%; The minor comonomer consumption accounts for gross activity multipolymer mole number: 70～80%; Initiator amount accounts for gross activity multipolymer mole number: 1.0～20%; The reductive agent consumption accounts for gross activity multipolymer mole number: 0.5～5.5%; The chain-transfer agent consumption accounts for gross activity multipolymer mole number: 1.0～10%.
Further, described step 2) and the design temperature in the step 4) be 30～50 ℃, this temperature is preferably 35～40 ℃; The insulation reaction time in the step 4) is preferably 2～3 hours.
Further, the dropping time in the described step 3) is 2～6 hours, and it is preferably 3～4 hours;
Further, adopt sodium hydroxide, ammoniacal liquor, organic bases, Ionic Membrane to neutralize in the described step 5), it is preferably Ionic Membrane.
Further, the reaction density of system is controlled at 20～70% among the described preparation method, and its preferred value is 40～50%.
Further, the concentration of the polycarboxylate high performance dehydragent product that obtains in the described step 5) is 30～60%.
The present invention adopts active high prenol Soxylat A 25-7 or big monomer of isobutene alcohol Soxylat A 25-7 and vinylformic acid, and in the aqueous solution, low temperature (30～50 ℃) adopts the high performance polycarboxylate dehydragent of two modes, one step preparation down.The water reducer of present method preparation has the water-reducing rate height, volume is low, dispersing property good, the slump keeps good, applied widely, the suitable various cement of performance, available more breezes and flyash to replace cement, cost performance height.This preparation method is easy and simple to handle, and energy consumption is low, environmental protection, whole process of production do not have " three wastes " discharging, is a kind of synthetic method of green.
Embodiment
Below in conjunction with specific embodiment, the process that the inventive method prepares polycarboxylate high performance dehydragent is described in more detail.
Embodiment 1
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer vinylcarbinol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 40 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 40 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-1.
Embodiment 2
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer isobutene alcohol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 40 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 40 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-2.
Embodiment 3
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer prenol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 40 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 40 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-3.
Embodiment 4
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer prenol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 30 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 30 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-4.
Embodiment 5
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer prenol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 50 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 50 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-5.
Embodiment 6
In disposing the 1000mL four-hole boiling flask of electric mixer, thermometer, prolong, Dropping feeder, add deionized water 345.6g, big monomer prenol Soxylat A 25-7 433.7g, heated and stirred makes it dissolving.
Under 60 ℃ of temperature, adding 16.05g concentration is 27.5% hydrogen peroxide, stirs.
Thereafter, dripping 94.7g concentration in 3 hours in reaction flask is 70% acrylic acid aqueous solution.Meanwhile, in 3.5 hours, in reaction flask, drip the mixed solution that 1.25g xitix and 2.3g Thiovanic acid and 110g deionized water are formed.
After dripping off, continue reaction 2.5 hours down at 60 ℃.
Regulate pH 6.0～7.0 with 32% Ionic Membrane.After be diluted with water to desired concn, promptly get product P CA-6.
Polycarboxylate high performance dehydragent to above 6 embodiment preparation carries out cement paste experiment and concrete performance experiment respectively.
1. product of the present invention and the contrast of product cement paste experiment both at home and abroad
Flowing degree of net paste of cement test is with reference to the GB/T8077-2000 standard, cement be bent stockaded village P.042.5,300g, amount of water is 87g, stir slowly stirred 2 minutes soon in 2 minutes after, on sheet glass, measure flowing degree of net paste of cement, and degree of mobilization changing conditions after measuring 1 hour, experimental result sees Table 1.
Table 1 flowing degree of net paste of cement experimental result
As seen from Table 1, the vinylcarbinol Soxylat A 25-7 be the water reducer prepared of big monomer than isobutene alcohol Soxylat A 25-7 or prenol Soxylat A 25-7 is that the water reducer dispersiveness prepared of big monomer is very different.Be the water reducer prepared of big monomer than isobutene alcohol Soxylat A 25-7 with the prenol Soxylat A 25-7 be that the water reducer prepared of big monomer is quite a lot of.This just illustrated compound structures shape its performance, the character that is to say compound is by its structures shape.
2. concrete experiments
Concrete experiments of the present invention, cement are the bent P.O of stockaded village 42.5, and sand is the medium sand of fineness modulus M=2.65, and cobble-stone diameter is the rubble of 5～25mm continuous grading.Concrete mix sees Table 2.
Table 2 concrete experiments proportioning
Mix concrete under above-mentioned condition and proportioning, and measure the concrete initial slump, slump-loss and air content after 1 hour, experimental result sees Table 3.
Table 3 concrete experiments result
Annotate: slump retention value is slump value/initial slump value * 100% after concrete is placed 60min.
Concrete experiments result shows, is big monomer with the prenol Soxylat A 25-7, and at 40 ℃ of polycarboxylate dehydragents that prepare down, concrete experiments result is best.
In sum, the polycarboxylate dehydragent that (except that PCA-1) makes in the embodiment of the invention, use volume in concrete is few, has high water reducing rate, and the slump keeps performance good, and air content is low, can satisfy the requirement of higher construction.
A. used various big monomers are Liaoning AoKe Chemical Co., Ltd and provide among the embodiment.
B. used vinylformic acid provides for the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing among the embodiment.
C. other raw materials are industrial goods among the embodiment.
Explanation at last, protection domain of the present invention is not limited to the above scope of embodiments, and protection domain of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. a polycarboxylate high performance dehydragent is characterized in that, the general formula of molecular structure of this water reducer is as follows:
Wherein, R
1For-CH
2-CH
2-or
R
2, R
3, R
4Represent hydrogen or methyl respectively; R
5Expression hydrogen or methyl or carboxymethyl; R
6Expression hydrogen; R
7Expression hydrogen or carboxyl; M represents hydrogen, monovalent metallic ion, divalent-metal ion, ammonium ion; Y represents hydrogen or methyl; M=1～1000, n=1～1000, o=1～1000.
2. polycarboxylate high performance dehydragent as claimed in claim 1 is characterized in that, the molecular weight of described polycarboxylate high performance dehydragent is 10000～100000.
3. low temperature one-step preppn process of polycarboxylate high performance dehydragent according to claim 1 is characterized in that this method is specially:
1) minor comonomer, the water that takes by weighing big monomer and partly measure by setting weight drops in the reactor, and stirring heating makes its dissolving;
2) under design temperature, add initiator, stir;
3) under agitation, adopt two modes to drip minor comonomer and the aqueous solution of chain-transfer agent mixture and the aqueous solution of reductive agent of residual content respectively, or drip the aqueous solution of the residue minor comonomer aqueous solution and reductive agent and chain-transfer agent mixture;
4) drip off after, under design temperature, insulation reaction 1～5 hour;
5) add liquid caustic soda and neutralize, obtain the polycarboxylate high performance dehydragent product.
4. low temperature one-step preppn process as claimed in claim 3 is characterized in that, described big monomer is: vinylcarbinol Soxylat A 25-7, isobutene alcohol Soxylat A 25-7, prenol Soxylat A 25-7; Described minor comonomer is: vinylformic acid, methacrylic acid, methylene-succinic acid, cis-butenedioic anhydride; Described initiator is: ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide; Described reductive agent is: S-WAT, sodium hypophosphite, glucose, xitix, rongalite; Described chain-transfer agent is: Thiovanic acid, mercaptoethanol, 2 mercaptopropionic acid, 3-thiohydracrylic acid; Described solvent is: tap water, deionized water.
5. low temperature one-step preppn process as claimed in claim 3 is characterized in that, described big monomer consumption accounts for gross activity multipolymer mole number and is: 10～30%; The minor comonomer consumption accounts for gross activity multipolymer mole number: 70～80%; Initiator amount accounts for gross activity multipolymer mole number: 1.0～20%; The reductive agent consumption accounts for gross activity multipolymer mole number: 0.5～5.5%; The chain-transfer agent consumption accounts for gross activity multipolymer mole number: 1.0～10%.
6. low temperature one-step preppn process as claimed in claim 3 is characterized in that, described step 2) and step 4) in design temperature be 30～50 ℃, this temperature is preferably 35～40 ℃; The insulation reaction time in the step 4) is preferably 2～3 hours.
7. low temperature one-step preppn process as claimed in claim 3 is characterized in that, the dropping time in the described step 3 is 2～6 hours, and it is preferably 3～4 hours.
8. low temperature one-step preppn process as claimed in claim 3 is characterized in that, adopts sodium hydroxide, ammoniacal liquor, organic bases, Ionic Membrane to neutralize in the described step 5), and it is preferably Ionic Membrane.
9. low temperature one-step preppn process as claimed in claim 3 is characterized in that the reaction density of system is controlled at 20～70% among the described preparation method, and its preferred value is 40～50%.
10. low temperature one-step preppn process as claimed in claim 3 is characterized in that, the concentration of the polycarboxylate high performance dehydragent product that obtains in the described step 5) is 30～60%.
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