CN1330600C - Maleic acid anhydride series concrete water-reducing agent and preparation process thereof - Google Patents
Maleic acid anhydride series concrete water-reducing agent and preparation process thereof Download PDFInfo
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- CN1330600C CN1330600C CNB2005100198761A CN200510019876A CN1330600C CN 1330600 C CN1330600 C CN 1330600C CN B2005100198761 A CNB2005100198761 A CN B2005100198761A CN 200510019876 A CN200510019876 A CN 200510019876A CN 1330600 C CN1330600 C CN 1330600C
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Abstract
The present invention relates to maleic anhydride series concrete water-reducing agent and a preparation method thereof. Methoxypolyethylene glycol reacts with maleic anhydride to generate maleic acid single methoxypolyethylene glycol ester monomer; the synthesized large monomer is polymerized together with 2-acrylamide-2 methyl propyl sodium sulfonate to form macromolecule containing carboxy groups, sulfonic groups and side chains of a polyoxyethylene chain, more especially the maleic anhydride series concrete water-reducing agent. The maleic anhydride series concrete water-reducing agent prepared by the present invention has the advantages of low alkali content and high water-reducing rate. When 0.6 to 1.5 percent of the quality of gelled material is added, the concrete operation has the advantages of labor saving, cement mixture has high flowability and good placeability, the loss of slump degree is effectively inhibited, and sufficient early strength is in the hardening initial stage. The present invention has the advantages of simple production technology, easy control of reaction conditions, no environment pollution and low cost. The product can be used as important constituent of high-performance concrete and is widely applied to the field of industry, civil architecture, water conservancy and road traffic engineering, and furthermore, the present invention has obvious economic and social benefits.
Description
Technical field
The invention belongs to a kind of preparation method of maleic anhydride series concrete water-reducing agent.
Technical background
As everyone knows, when the cement mixture operation, effective for making rapid operation, and the early stage demoulding requires cement mixture to have high workability with the reduction of erection time, effectively the loss of inhibition of slump, and there is sufficient early strength at the sclerosis initial stage, and this just needs a kind of high performance concrete water reducer.Along with the concrete the reach of science, polymer chemistry and material molecule design theory constantly make further progress, and cement water reducing agent is also had higher requirement.And the cement water reducing agent of China is a product based on naphthalene system and melamine at present, and the cement mixture workability of this series products is bad, has the problem that water-reducing rate is not high, slump-loss is big.Though use water-soluble ethylene copolymer cement dispersant slump-loss little, prolong time of coagulation greatly, causes early strength low, can not well satisfy the needs of engineering, and complex manufacturing.Domestic closely during the last ten years, the research and development main products of new and effective water reducer and superplasticizer still is naphthalenesulfonate formaldehyde condensation compound and sulfamate condenses etc., and to polycarboxylic acid series, no matter the research of maleic anhydride based water reducer is to select from starting material, production technique or raising aspect of performance are all started late, though domestic investigator explores polycarboxylic acid series by molecular pathways, maleic anhydride based water reducer product has been obtained certain effect, but it is domestic to polycarboxylic acid series, the research and development of maleic anhydride based water reducer product are in the experiment development stage mostly, the producer of real formation product also seldom far can not satisfy the needs of high performance concrete development.And maleic anhydride series, the vinylformic acid system high-performance water reducing agent of the development of states such as Japan have high water reducing rate, and numerous premium propertiess such as low slump loss have obtained using widely, and technology is ripe.
The synthetic method of Japan report maleic anhydride high performance concrete water reducer was divided into for two steps and finishes.The first step: behind the nitrogen purge autoclave; under the nitrogen protection condition; make catalyzer with sodium methylate; slowly feed oxyethane in the methyl alcohol in reaction vessel, keep 140 ℃, the reaction down of 0.05-0.5 MPa pressure, then; reaction mixture is cooled to room temperature; in reaction vessel, add NaOH, be warming up to 110 ℃, keep the dehydration of 20mmHg pressure.Subsequently, nitrogen pressure is increased to 0.1 MPa, slowly in mixture, add a certain amount of chlorallylene and stirring.After 4 hours, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt from the reaction beginning, the separating by-products salt can obtain allyl ethers, as the raw material of next step reaction.Second the step: with toluene as solvent; under nitrogen protection; in having the reaction vessel of condensation; the allyl ethers and the maleic anhydride that are generated with the first step reaction carry out polyreaction; polymerization temperature is 80 ℃, stir make it to react 4 hours after, under 110 ℃, 10mmHg pressure; steam and remove toluene solvant, obtaining transparent viscous liquid is final product.Introduce among the Te Kaiping 9-286648, taking by weighing polyoxyethylene (oxyethane) 33mol, monomethyl monoallyl ether 1mol, allyl sodium sulfonate 1mol and Maleic Acid, Anhydrous 3mol in the four-hole boiling flask that agitator, thermometer, prolong, nitrogen ingress pipe are housed is dissolved in the 1480g water, add ammonium persulphate 0.75mol as polymerization starter, 50 ± 2 ℃ were reacted 12 hours under nitrogen atmosphere, obtained interpolymer X.
This shows, maleic anhydride series high-performance cement water reducing agent process for producing complexity, severe reaction conditions is wayward, and is very high to equipment requirements, is unfavorable for industrial production.
Summary of the invention:
The objective of the invention is to overcome water reducer complex manufacturing in the past, to the equipment requirements height, a kind of preparation method of maleic anhydride series concrete water-reducing agent is provided, have polymolecularity and disperse retentivity with this method synthetic water reducer, and synthesis technique is simple, reaction conditions is simple and easy to control, do not pollute, cost hangs down advantages such as being easy to suitability for industrialized production.
The present invention realizes by the following technical solutions:
A kind of maleic anhydride series concrete water-reducing agent, its molecular weight are 10000～60000, and its molecular formula is:
In the formula: m=6～23
n＝10～60
Above-mentioned molecular formula represents it is the molecular structure of using present method synthetic maleic anhydride series concrete water-reducing agent, its synthesis technique was divided into for two steps, the first step: with maleic anhydride and methoxy poly (ethylene glycol) mol ratio is to be raw material at 1.1～1.8: 1, make catalyzer at tosic acid, cuprous chloride and Resorcinol are made stopper, toluene is done to react under the condition of solvent, 80～120 ℃ of controlled temperature react and generated toxilic acid mono methoxy polyethylene glycol ester and the big monomer mixture of toxilic acid Varonic DM 55 ester in 10～15 hours;
In the formula: m=6～23
Second step: use ammonium persulphate as initiator, mercaptoethanol is as chain-transfer agent, the mass ratio that slowly adds on one side big monomer mixture that the first step obtains and 2-acrylamide-2 methyl-propyl sodium sulfonate is 17.5～31: 1 mixed aqueous solution, slowly add initiator and chain-transfer agent on one side, controlled temperature is intact to adding material at 80～85 ℃, then 80～85 ℃ of insulations 1 hour, temperature is elevated to 95～100 ℃ of insulations 2 hours, be cooled to 15～30 ℃ of room temperatures, neutralizing with sodium hydroxide, to obtain mass concentration be 30% the high-molecular copolymer aqueous solution in pH=6.5 ± 0.5, be the cement water reducing agent that present method makes, the principal reaction formula is;
In the formula: m=6～23
n＝10～60。
The first step catalyzer tosic acid consumption is 2%～8% of maleic anhydride and a methoxy poly (ethylene glycol) total mass; The hydroquinone of polymerization retarder consumption is 0.5%～2% of a maleic anhydride quality, and the cuprous chloride consumption is 0.5%～1.5% of a maleic anhydride quality; Reaction solvent toluene consumption is 80%～150% of maleic anhydride and a methoxy poly (ethylene glycol) total mass; The second step polymerization is 1.8%～8% of maleic acid ester and 2-acrylamide-2 a methyl-propyl sodium sulfonate monomer total mass with initiator ammonium sulfate quality; Polymerization is 0.1%～2% of maleic acid ester and 2-acrylamide-2 a methyl-propyl sodium sulfonate monomer total mass with chain-transfer agent mercaptoethanol quality; The aqueous solution, the chain-transfer agent mercaptoethanol aqueous solution and the initiator ammonium persulfate aqueous solution of big monomer mixture and 2-acrylamide-2 methyl-propyl sodium sulfonate slowly added at 2.5～3.5 hours in second step.
Maleic anhydride series concrete water-reducing agent of the present invention is to be reacted under certain condition by methoxy poly (ethylene glycol) and maleic anhydride to generate the big monomer of maleic acid ester, utilize the synthetic carboxyl that contains of big monomer of synthetic and the copolymerization of 2-acrylamide-2 methyl-propyl sodium sulfonate, sulfonic group, the polymer of polyoxyethylene chain side chain.Need not nitrogen protection in the building-up process, the temperature of reaction substantially constant, reinforced program is simple, and reaction conditions is easy to control; And cost is lower than the acrylic acid series cement water reducing agent.The maleic anhydride series concrete water-reducing agent that adopts the inventive method to make, volume (mass concentration is 30% maleic anhydride series concrete water-reducing agent) is at 1.0% o'clock of cement weight, water-reducing rate can reach 30%; The concrete surface of preparation does not have bleeding line, no air pocket, aberration is little, Surface Quality of Concrete good; Alkali content is low; Chloride ion-containing not is to the reinforcing bar non-corrosiveness; Freeze-thaw-ability and anti-carbonization ability significantly improve than normal concrete; Can effectively restrain hydration heat, prevent the inner cracking that heats up; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 20% than naphthalene; The adaptation of product is strong, is adapted to the cement of plurality of specifications, model, and especially suitable and high-quality fly ash, the compatible preparation of slag isoreactivity adulterant are high-strength, high-durability, the contour performance concrete of self-compacting; Product is aqueous solution stable performance, and long storage is not stratified, do not have precipitation, do not have crystallization winter, nontoxic pollution-free, advantage such as environmentally safe.
Embodiment
Embodiment 1～7
Toxilic acid mono methoxy polyethylene glycol ester and toxilic acid Varonic DM 55 ester are big monomeric synthetic:
Press listed each inventory in the table 1, take by weighing maleic anhydride, methoxy poly (ethylene glycol), Resorcinol, cuprous chloride, tosic acid, toluene (seeing Table 1) respectively and put into there-necked flask, be heated with stirring to 62.5 ± 25 ℃, wait to dissolve complete back insulation 0.75 ± 0.25 hour, slowly be warming up to 85 ± 5 ℃ again, insulation reaction 4.5 ± 0.5 hours is warming up to 115 ± 5 ℃ again, insulation reaction 7 ± 1 hours; Be cooled to 20 ± 5 ℃ of room temperatures, remove solvent toluene, obtain toxilic acid mono methoxy polyethylene glycol ester and the big monomer of toxilic acid Varonic DM 55 ester.
Table 1 each reactant consumption in big monomeric synthesizing
| Embodiment number | Maleic anhydride (g) | Methoxy poly (ethylene glycol) (1000) (g) | Resorcinol (g) | Cuprous chloride (g) | Tosic acid (g) | Toluene (g) |
| 1 | 10.8 | 100 | 0.21 | 0.11 | 4.43 | 132 |
| 2 | 14.7 | 100 | 0).29 | 0.15 | 4.59 | 137 |
| 3 | 17.6 | 100 | 0.35 | 0.18 | 4.70 | 141 |
| 4 | 14.7 | 100 | 0.44 | 0.08 | 4.59 | 137 |
| 5 | 14.7 | 100 | 0.08 | 0.22 | 4.59 | 137 |
| 6 | 14.7 | 100 | 0.29 | 0 14 | 2.29 | 137 |
| 7 | 14.7 | 100 | 0.29 | 0.14 | 4.59 | 92.8 |
Embodiment 8～12
Maleic anhydride series concrete water-reducing agent high molecular polymerization:
Press listed each inventory in the table 2, taking by weighing the dissolving of toxilic acid mono methoxy polyethylene glycol ester and the big monomer of toxilic acid Varonic DM 55 ester, 2-acrylamide-2 methyl-propyl sodium sulfonate respectively, to be mixed with mass concentration be 60% the aqueous solution, as titrating solution 1; Take by weighing the ammonium persulphate dissolving and be mixed with the aqueous solution, as titrating solution 2; Take by weighing mercaptoethanol and be mixed with the aqueous solution, as titrating solution 3 (each material consumption sees Table 2).Put into suitable quantity of water in the there-necked flask, stirring heating keeps 82.5 ± 2.5 ℃, and slowly titrating solution 1 and titrating solution 2 treat that polyreaction began the back about 0.4 ± 0.1 hour, and beginning slowly drips titrating solution 3, and speed is dripped in control, all drips off in 3.0 ± 0.5 hours; 82.5 ± 2.5 ℃ of time insulations are 1 hour then, are warming up to 97.5 ± 2.5 ℃ again, are incubated 2 hours, are cooled to 20 ± 5 ℃ of room temperatures then, and neutralizing with sodium hydroxide, to obtain mass concentration be 30% the high-molecular copolymer aqueous solution in pH=6.5 ± 0.5.
Table 2 polymerizable maleimide acid anhydride series concrete water-reducing agent is with each reactant consumption
| Embodiment number | The big monomer of maleic acid ester (g) | 2-acrylamide-2 methyl-propyl sodium sulfonate (g) | Ammonium persulphate (g) | Mercaptoethanol (g) | Water (g) |
| 8 | (17.5 embodiment 3 in the table 1) | 1.0 | 0.93 | 0.19 | 45.76 |
| 9 | (25.0 embodiment 4 in the table 1) | 1.0 | 1.30 | 0.26 | 64.31 |
| 10 | (31.0 embodiment 5 in the table 1) | 1.0 | 1.60 | 0.32 | 79.15 |
| 11 | (25.0 embodiment 6 in the table 1) | 1.0 | 0.78 | 0.13 | 62.79 |
| 12 | (25.0 embodiment 7 in the table 1) | 1.0 | 1.82 | 0.34 | 65.70 |
With the inventive method synthetic high-molecular copolymer is that the maleic anhydride series concrete water-reducing agent has dispersed preferably and the dispersion retentivity.Carry out the quiet slurry test of cement with national standard, volume is 0.15% o'clock of solid content quality, and quiet slurry degree of mobilization lost greater than 250mm in 1 hour hardly, loss 20～30% in 4 hours (the quiet slurry of cement is tested with little wild field 525 silicate cements).Mixing mass concentration of the present invention in concrete is 30% maleic anhydride series concrete water-reducing agent, and volume is 1.0% o'clock of gelling material quality, and water-reducing rate can be up to 30%.
Claims (7)
1. a maleic anhydride series concrete water-reducing agent is characterized in that molecular weight is 10000～60000, and molecular formula is:
In the formula: m=6～23
n＝10～60。
2. the preparation method of the described maleic anhydride series concrete water-reducing agent of claim 1, it is characterized in that: synthesis technique was divided into for two steps,
The first step: with maleic anhydride and methoxy poly (ethylene glycol) mol ratio is to be raw material at 1.1～1.8: 1, make catalyzer at tosic acid, cuprous chloride and Resorcinol are made stopper, toluene is done to react under the condition of solvent, 80～120 ℃ of controlled temperature, reacted 10～15 hours, solvent toluene is removed in cooling, obtains toxilic acid mono methoxy polyethylene glycol ester and the big monomer mixture of toxilic acid Varonic DM 55 ester;
Second step: use ammonium persulphate as initiator, mercaptoethanol is as chain-transfer agent, the mass ratio that adds on one side big monomer mixture that the first step obtains and 2-acrylamide-2 methyl-propyl sodium sulfonate is 17.5～31: 1 mixed aqueous solution, add initiator and chain-transfer agent on one side, the aqueous solution of big monomer mixture and 2-acrylamide-2 methyl-propyl sodium sulfonate, initiator and chain-transfer agent slowly added at 2.5～3.5 hours, controlled temperature is intact to adding material at 80～85 ℃, then 80～85 ℃ of insulations 1 hour, temperature is elevated to 95～100 ℃ of insulations 2 hours, be cooled to 15～30 ℃ of room temperatures, neutralizing with sodium hydroxide, to obtain mass concentration be 30% the high-molecular copolymer aqueous solution in pH=6.5 ± 0.5, is the maleic anhydride series concrete water-reducing agent that makes.
3. the preparation method of maleic anhydride series concrete water-reducing agent as claimed in claim 2 is characterized in that the catalyzer tosic acid consumption in the described the first step is 2%～8% of a total mass.
4. the preparation method of maleic anhydride series concrete water-reducing agent as claimed in claim 2, it is characterized in that the hydroquinone of polymerization retarder consumption in the described the first step is 0.5%～3% of a maleic anhydride quality, the cuprous chloride consumption is 0.5%～1.5% of a maleic anhydride quality.
5. the preparation method of maleic anhydride series concrete water-reducing agent as claimed in claim 2 is characterized in that the reaction solvent toluene consumption in the described the first step is 50%～150% of a total mass.
6. the preparation method of maleic anhydride series concrete water-reducing agent as claimed in claim 2 is characterized in that the initiator ammonium persulfate quality that polymerization is used in described second step is 1.8%～8% of maleic acid ester and 2-acrylamide-2 a methyl-propyl sodium sulfonate monomer mass.
7. the preparation method of maleic anhydride series concrete water-reducing agent as claimed in claim 2 is characterized in that the chain-transfer agent mercaptoethanol quality that polymerization is used in described second step is 0.1%～2% of maleic acid ester and 2-acrylamide-2 a methyl-propyl sodium sulfonate monomer mass.
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