CN104261719A - High-performance polycarboxylate water reducing agent and preparation method thereof - Google Patents
High-performance polycarboxylate water reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance polycarboxylate water reducing agent. The polycarboxylate water reducing agent has a structural general formula shown as a structural formula (I). The invention further provides a preparation method of the high-performance polycarboxylate water reducing agent. Apart from a polyether macromonomer and an unsaturated carboxylic acid monomer, an unsaturated phosphate monomer is added to obtain a product, namely, the high-performance polycarboxylate water reducing agent having a phosphate structure. The polycarboxylate water reducing agent disclosed by the invention is safe and simple in preparation process, environmentally friendly, low in energy consumption, low in cost, and suitable for industrial large-scale production. In the structural formula (I), R1 is -H, -COO- or -CH2COO-; R2 is -H or -CH3; R3 is -H or -CH3; R4 is -H or -CH3; R5 is -H or -CH3; R6 is -CH2- or -CH2CH2-; X, Y, Z and n are integers; X=1-100; Y=1-100; Z=1-100; and n=22-53.
Description
Technical field
The present invention relates to technical field of concrete, refer to a kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof particularly.
Background technology
High performance concrete, because of high workability, the high-strength and characteristic such as high-durability and volume stability, is widely used in the engineering constructions such as each large bridge, highway, tunnel and heavy construction, and wherein, water reducer forms one of indispensable component of high performance concrete.Polycarboxylate water-reducer has that volume is low, water-reducing rate is high, slump-retaining good, Molecular Structure Design degree of freedom large, advantages of environment protection, be described as third generation Concrete superplastizer, become the focus of concrete admixture area research and the emphasis of exploitation.
At present, domestic and international polycarboxylate water-reducer product has two large classes, ethers and ester class, complex manufacturing, the temperature of reaction of ester class are high, the production cycle is long, energy consumption is large, cost is high, and is that the volatile organic solvent that raising esterification yield uses is many, and hazardness is high, environmental pollution is large, also ethers is lower relatively for the water-reducing rate of product, but slump retaining and adaptability better.Ethers then has that production operation is safe and simple, with short production cycle, energy consumption is low, cost is low and the feature such as environmental friendliness, and the water-reducing rate of product is higher, but protect collapse and adaptability slightly poor.Therefore, while guarantee ethers polycarboxylic acid water reducing agent advantage, lot of domestic and international reports that main research emphasis is to improve its slump retaining and adaptability.
Metallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methyl propane sulfonic, methacrylic acid and ammonium persulphate are carried out aqueous free radical polymerization by patent CN 102268121 A at 60-100 DEG C of temperature, have prepared the high slump-retaining polycarboxylate water-reducer of a kind of high water reducing rate.Patent CN 103788310 A with prenol polyoxyethylene poly-oxygen propylene aether, maleic anhydride, Hydroxyethyl acrylate for raw material, take hydrogen peroxide as initiator, sodium formaldehyde sulphoxylate, ferrous sulfate are work catalyzer, with thiohydracrylic acid or Thiovanic acid for molecular weight regulator, at 5-40 DEG C of temperature, cause radical polymerization, prepare a kind of polycarboxylic acid series sustained-release water reducing agent.Patent CN 103641959 A is reacted 3 hours at 80 DEG C of temperature by the hydrogen peroxide and 1-10 part massfraction 10% mercaptoethanol solution using 5-50 part polyoxyethylene ether, 1-10 part vinylformic acid, 1-10 part methacrylic ester, 0.3-3 part massfraction 30%, has prepared a kind of sustained-release polycarboxylic water reducer.Although by above-mentioned research, solve the problem that ethers poly carboxylic acid slump retaining is poor relative to ethers with adaptability, but weaken the advantage that volume is low, water-reducing rate is high that ethers self has to a certain extent, such that its volume improves, concrete over-all properties is influenced, construction quality is difficult to ensure.
Summary of the invention
Object of the present invention is exactly the deficiency that will solve above-mentioned background technology, provides a kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof.
Technical scheme of the present invention is: a kind of high-performance polycarboxylic acids water reducing agent, and this polycarboxylate water-reducer has the general structure of structure formula I:
Wherein, R
1for-H ,-COO-or-CH
2cOO-; R
2for-H or-CH
3; R
3for-H or-CH
3; R
4for-H or-CH
3; R
5for-H or-CH
3; R
6for-CH
2-or-CH
2cH
2-; X, Y, Z and n are integer, X=1-100, Y=1-100, Z=1-100, n=22-53.
Preferably, the molecular weight of this polycarboxylate water-reducer is 30000-80000.
The present invention also provides a kind of preparation method of high-performance polycarboxylic acids water reducing agent, it is characterized in that, step is:
A. raw material polyether macromonomer, unsaturated phosphate ester monomer, unsaturated carboxylic acid monomer, initiator and chain-transfer agent is got, wherein the molar content of each raw material is respectively: polyether macromonomer 15-25%, unsaturated phosphate ester monomer 1-10%, unsaturated carboxylic acid monomer 65-70%, initiator 1-5%, chain-transfer agent 1-3%, and each feed molar percentage composition sum is 100%;
B. above-mentioned raw materials and water are reacted 4-6 hour at 40-80 DEG C, quality and the above-mentioned raw materials total mass ratio of water used are 1-10:1, are then cooled to 35-40 DEG C, and add neutralizing agent, adjust ph, to 6-8, obtains product and is the high-performance polycarboxylic acids water reducing agent with phosphate ester structure.
Preferably, described polyether macromonomer is the one in allyl polyethenoxy base ether, methacrylic polyoxyethylene ether or the isopentene group polyoxyethylene ether of molecular weight between 1000-3000.
Preferably, described unsaturated phosphate ester monomer is one or more in acrylyl oxy-ethyl phosphoric acid ester, acryloxypropyl phosphoric acid ester, methylacryoyloxyethyl phosphoric acid ester or methacryloxypropyl phosphoric acid ester.
Preferably, described unsaturated carboxylic acid monomer is one or more in vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid or methylene-succinic acid.
Preferably, described initiator is one or more in ammonium persulphate, hydrogen peroxide-xitix, ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite, hydrogen peroxide-rongalite, hydrogen peroxide-sodium hypophosphite.
Preferably, described chain-transfer agent is one or more in Thiovanic acid, thiohydracrylic acid, mercaptoethanol, n-dodecyl mereaptan, methylpropene sodium sulfonate.
Preferably, described water is tap water or deionized water.
Preferably, described neutralizing agent is the sodium hydroxide solution of massfraction 32%, ammoniacal liquor or ethylenediamine solution.
Preferably, polyether macromonomer, unsaturated phosphate ester monomer, unsaturated carboxylic acid monomer, initiator and chain-transfer agent molar percentage are respectively: polyether macromonomer 15-20%, unsaturated phosphate ester monomer 6-8%, unsaturated carboxylic acid monomer 68-70%, initiator 2-4%, chain-transfer agent 2-3%, and each feed molar percentage composition sum is 100%.
Preferably, polyether macromonomer, unsaturated phosphate ester monomer, unsaturated carboxylic acid monomer, initiator and chain-transfer agent molar percentage are respectively: polyether macromonomer 20.2%, unsaturated phosphate ester monomer 6.6%, unsaturated carboxylic acid monomer 68.5%, initiator 3.5%, chain-transfer agent 1.2%.
Preferably, in step b, the quality of water used and step a Raw total mass ratio are 1.5:1.Now the solid content of obtained polycarboxylate water-reducer is about 40%.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) on polycarboxylate water-reducer molecular side chain disclosed by the invention with phosphate radical, there are two negative charges, than traditional polycarboxylate water-reducer, there is stronger adsorptive power, be enough to resist the competitive adsorption to polycarboxylate water-reducer such as Sulphur in Cement hydrochlorate, make polycarboxylate water-reducer performance not by the impact of vitriol etc., substantially increase the dispersive ability of this polycarboxylate water-reducer.
(2) ester bond in polycarboxylate water-reducer molecular side chain disclosed by the invention can be hydrolyzed under concrete strong alkali environment, sustained release go on a tour from phosphate radical and containing two hydroxyl small molecules glycol, phosphate anion meeting and hydrolysis product of cement react, the phosphoric acid salt thin layer of fine and close indissoluble is formed at cement particle surface, inhibit entering of water molecules, hinder the carrying out of the normal hydrated effect of cement, extend the inductive phase of hydrated cementitious, the hydration rate of C3S (tricalcium silicate) is slowed down, thus the aquation of C3A (tricalcium aluminate) and the forming process of ettringite are delayed and play the effect protected and collapse.Meanwhile, in water reducer molecule, also discharge a large amount of carboxyls, continue the effect playing dispersion, make water reducer protect ability of collapsing and significantly promote.The small molecules glycol discharged in addition also has certain delayed coagulation, and the guarantor that the synergy of three aspects improves this polycarboxylate water-reducer is greatly collapsed ability.
(3) safe and simple, the environmental protection of polycarboxylate water-reducer preparation technology disclosed by the invention, energy consumption is low, cost is low, is applicable to industrial scale and produces.
Embodiment
Below with reference to specific embodiment, the present invention will be further described.
Embodiment 1
Water 25.0mol, polymeric monomer isopentene group polyoxyethylene ether 0.202mol is added in the 2000mL four-hole boiling flask being configured with electric mixing device, constant temperature heating device, peristaltic pump, isopentene group polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 60 DEG C, is uniformly dissolved.In 3 hours, at the uniform velocity drip the mixing solutions be made up of 0.685mol vinylformic acid, 0.066mol acrylyl oxy-ethyl phosphoric acid ester, 0.012mol Thiovanic acid, 3.333mol water and the mixing solutions be made up of 0.035mol ammonium persulphate, 6.667mol water respectively, temperature controls between 60-65 DEG C; After being added dropwise to complete, continue reaction 2 hours, then 35-40 DEG C is cooled to, adding massfraction is 32% sodium hydroxide solution and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P1 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 30000-50000.
Embodiment 2
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer methacrylic polyoxyethylene ether 0.15mol, methacrylic polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 40 DEG C, be uniformly dissolved and directly add hydrogen peroxide 0.045mol afterwards, and at the uniform velocity dripped respectively by 0.7mol methacrylic acid in 3.5 hours, 0.07mol methylacryoyloxyethyl phosphoric acid ester, 3.333mol water composition mixing solutions and by 0.03mol thiohydracrylic acid, 0.005mol xitix, the mixing solutions of 6.667mol water composition, temperature controls between 40-45 DEG C, after being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is the ammoniacal liquor of 32% and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P2 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 50000-60000.
Embodiment 3
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer allyl polyethenoxy base ether 0.25mol, allyl polyethenoxy base ether molecular weight used is 1000-3000, stirring is warming up to 60 DEG C, add 0.5mol maleic anhydride, the solution that 0.01mol ammonium persulphate is dissolved in 3.333mol water is directly added after stirring and dissolving is even, and at the uniform velocity dripped in 3.0 hours by 0.015mol vinylformic acid, 0.08mol acryloxypropyl phosphoric acid ester, 0.01mol Thiovanic acid, the mixing solutions of 6.667mol water composition, temperature controls between 75-80 DEG C, after being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is the quadrol of 32% and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P3 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 60000-80000.
Embodiment 4
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer allyl polyethenoxy base ether 0.16mol, allyl polyethenoxy base ether molecular weight used is 1000-3000, stirring is warming up to 60 DEG C, add 0.1mol fumaric acid, hydrogen peroxide 0.035mol is directly added after stirring and dissolving is even, and at the uniform velocity dripped respectively by 0.58mol vinylformic acid in 3 hours, 0.1mol methacryloxypropyl phosphoric acid ester, 5.556mol water composition mixing solutions and by 0.02mol mercaptoethanol, 0.005mol rongalite, the mixing solutions of 6.667mol water composition, temperature controls between 60-65 DEG C, after being added dropwise to complete, continue reaction 2 hours, then 35-40 DEG C is cooled to, adding massfraction is 32% sodium hydroxide solution and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P4 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 40000-60000.
Embodiment 5
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer methacrylic polyoxyethylene ether 0.2mol, methacrylic polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 40 DEG C, be uniformly dissolved and directly add hydrogen peroxide 0.016mol afterwards, and at the uniform velocity dripped respectively by 0.35mol vinylformic acid in 3.5 hours, 0.35mol methylene-succinic acid, 0.05mol acrylyl oxy-ethyl phosphoric acid ester, 3.333mol water composition mixing solutions and by 0.03mol methylpropene sodium sulfonate, 0.004mol sodium hypophosphite, the mixing solutions of 6.667mol water composition, temperature controls between 40-45 DEG C, after being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is 32% ammoniacal liquor and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P5 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 50000-70000.
Embodiment 6
Water 25.0mol, polymeric monomer isopentene group polyoxyethylene ether 0.220mol is added in the 2000mL four-hole boiling flask being configured with electric mixing device, constant temperature heating device, peristaltic pump, isopentene group polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 40 DEG C, is uniformly dissolved directly to add 0.005mol S-WAT afterwards.In 4.0 hours, at the uniform velocity drip the mixing solutions be made up of 0.67mol vinylformic acid, 0.015mol methylacryoyloxyethyl phosphoric acid ester, 0.015 acryloxypropyl phosphoric acid ester, 0.03mol mercaptoethanol, 3.333mol water and the mixing solutions be made up of 0.045mol ammonium persulphate, 6.667mol water respectively, temperature controls between 40-45 DEG C; After being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is 32% quadrol and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P6 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 40000-50000.
Embodiment 7
Water 25.0mol, polymeric monomer isopentene group polyoxyethylene ether 0.19mol is added in the 2000mL four-hole boiling flask being configured with electric mixing device, constant temperature heating device, peristaltic pump, isopentene group polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 40 DEG C, is uniformly dissolved directly to add 0.01mol sodium bisulfite afterwards.In 3 hours, at the uniform velocity drip the mixing solutions be made up of 0.70mol vinylformic acid, 0.05mol acryloxypropyl phosphoric acid ester, 0.03mol n-dodecyl mereaptan, 3.333mol water and the mixing solutions be made up of 0.02mol ammonium persulphate, 6.667mol water respectively, temperature controls between 40-45 DEG C; After being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is 32% liquid caustic soda and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P7 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 60000-70000.
Embodiment 8
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer allyl polyethenoxy base ether 0.24mol, allyl polyethenoxy base ether molecular weight used is 1000-3000, stirring is warming up to 60 DEG C, be uniformly dissolved and directly add hydrogen peroxide 0.031mol afterwards, and at the uniform velocity dripped respectively by 0.69mol vinylformic acid in 3.5 hours, 0.01mol methacryloxypropyl phosphoric acid ester, 3.333mol water composition mixing solutions and by 0.02mol thiohydracrylic acid, 0.009mol xitix, the mixing solutions of 6.667mol water composition, temperature controls between 60-65 DEG C, after being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is 32% ammoniacal liquor and a small amount of dilution water, obtaining pH value is the high-performance polycarboxylic acids water reducing agent PC-P8 with phosphate ester structure that the solid content of 6-8 is about 40%, and its molecular weight is 30000-40000.
Comparative example 1
Be configured with electric mixing device, constant temperature heating device, water 27.28mol is added in the 2000mL four-hole boiling flask of peristaltic pump, polymeric monomer methacrylic polyoxyethylene ether 0.210mol, methacrylic polyoxyethylene ether molecular weight used is 1000-3000, stirring is warming up to 40 DEG C, be uniformly dissolved and directly add hydrogen peroxide 0.034mol afterwards, and at the uniform velocity dripped respectively by 0.670mol vinylformic acid in 3.5 hours, 3.333mol water composition mixing solutions and by 0.020mol Thiovanic acid, 0.006mol xitix, the mixing solutions of 6.667mol water composition, temperature controls between 40-45 DEG C, after being added dropwise to complete, continue reaction 2 hours, be then cooled to 35-40 DEG C, adding massfraction is 32% sodium hydroxide solution and a small amount of dilution water, and obtaining pH value is the high-performance polycarboxylic acids water reducing agent that the solid content of 6-8 is about 40%, and its molecular weight is 40000-70000.
Implementation result is verified:
Polycarboxylate water-reducer of the present invention measures paste flowing degree according to GB/T8077-2000 " concrete admixture homogeneity test method ", and cement is reference cement.Experimental result is in table 1.
Table 1 flowing degree of net paste of cement test result
Wherein, comparative example 1 is the polycarboxylate water-reducer not introducing unsaturated phosphate ester monomer, and comparative example 2 is commercially available ethers polycarboxylic acid water reducing agent.
As seen from the results in Table 1, compare ratio 1,2, embodiment 1-8 is obviously better than the two in initial flow degree and 60min, 120min degree of mobilization gradual loss, as can be seen here, the introducing of unsaturated phosphate ester monomer substantially increases water-reducing rate and the slump retaining of polycarboxylate water-reducer, compared with commercially available ethers polycarboxylic acid water reducing agent, there is more excellent water reducing ability and degree of mobilization retentivity.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; everyly do not depart from technical solution of the present invention content; according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a high-performance polycarboxylic acids water reducing agent, is characterized in that: this polycarboxylate water-reducer has the general structure of structure formula I:
Wherein, R
1for-H ,-COO-or-CH
2cOO-; R
2for-H or-CH
3; R
3for-H or-CH
3; R
4for-H or-CH
3; R
5for-H or-CH
3; R
6for-CH
2-or-CH
2cH
2-; X, Y, Z and n are integer, X=1-100, Y=1-100, Z=1-100, n=22-53.
2. high-performance polycarboxylic acids water reducing agent as claimed in claim 1, is characterized in that: the molecular weight of this polycarboxylate water-reducer is 30000-80000.
3. the preparation method of a kind of high-performance polycarboxylic acids water reducing agent as claimed in claim 1 or 2, is characterized in that, step is:
A. raw material polyether macromonomer, unsaturated phosphate ester monomer, unsaturated carboxylic acid monomer, initiator and chain-transfer agent is got, wherein the molar content of each raw material is respectively: polyether macromonomer 15-25%, unsaturated phosphate ester monomer 1-10%, unsaturated carboxylic acid monomer 65-70%, initiator 1-5%, chain-transfer agent 1-3%, and each feed molar percentage composition sum is 100%;
B. above-mentioned raw materials and water are reacted 4-6 hour at 40-80 DEG C, quality and the above-mentioned raw materials total mass ratio of water used are 1-10:1, are then cooled to 35-40 DEG C, and add neutralizing agent, adjust ph, to 6-8, obtains product and is the high-performance polycarboxylic acids water reducing agent with phosphate ester structure.
4. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described polyether macromonomer is the one in allyl polyethenoxy base ether, methacrylic polyoxyethylene ether or the isopentene group polyoxyethylene ether of molecular weight between 1000-3000.
5. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described unsaturated phosphate ester monomer is one or more in acrylyl oxy-ethyl phosphoric acid ester, acryloxypropyl phosphoric acid ester, methylacryoyloxyethyl phosphoric acid ester or methacryloxypropyl phosphoric acid ester.
6. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described unsaturated carboxylic acid monomer is one or more in vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid or methylene-succinic acid.
7. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described initiator is one or more in ammonium persulphate, hydrogen peroxide-xitix, ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite, hydrogen peroxide-rongalite, hydrogen peroxide-sodium hypophosphite.
8. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described chain-transfer agent is one or more in Thiovanic acid, thiohydracrylic acid, mercaptoethanol, n-dodecyl mereaptan, methylpropene sodium sulfonate.
9. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described water is tap water or deionized water.
10. the preparation method of high-performance polycarboxylic acids water reducing agent as claimed in claim 3, is characterized in that: described neutralizing agent is the sodium hydroxide solution of massfraction 32%, ammoniacal liquor or ethylenediamine solution.
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