CN101717220B - Polycarboxylic acid water-reducing agent and preparation method thereof - Google Patents
Polycarboxylic acid water-reducing agent and preparation method thereof Download PDFInfo
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- CN101717220B CN101717220B CN 200910154139 CN200910154139A CN101717220B CN 101717220 B CN101717220 B CN 101717220B CN 200910154139 CN200910154139 CN 200910154139 CN 200910154139 A CN200910154139 A CN 200910154139A CN 101717220 B CN101717220 B CN 101717220B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 54
- 239000002253 acid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 34
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 22
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 229920001427 mPEG Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000007518 monoprotic acids Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000004568 cement Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 0 CC(C)(C(C)(*)*)N Chemical compound CC(C)(C(C)(*)*)N 0.000 description 2
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a polycarboxylic acid water-reducing agent and a preparation method thereof. The polycarboxylic acid water-reducing agent has the molecular weight between 1,000 and 100,000, and has the structure composition shown in (7), wherein X represents polyether groups, and M is Na or K. The polycarboxylic acid water-reducing agent is prepared by the method comprising the following steps: subjecting polyether X-H and excessive unsaturated fatty acid to esterification so as to obtain esterified substances; subjecting the esterified substances and remaining unsaturated fatty acid to copolymerization so as to obtain carboxylic acid polymer; and neutralizing the obtained carboxylic acid polymer with alkali solution so as to obtain the polycarboxylic acid water-reducing agent. The polycarboxylic acid water-reducing agent has high plastic-retaining property, low fluidity loss of cement paste, high water-reducing rate, low production cost and other excellent performance.
Description
(1) technical field
The present invention relates to concrete admixture, relate in particular to a kind of high protect plasticity ability polycarboxylate water-reducer and preparation method thereof.
(2) background technology
Along with the development of concrete technology, the usefulness of water reducer to be had higher requirement, traditional in the past water reducer exists shortcoming and defect separately, and water-reducing rate is low, and protect plasticity is poor, and is wideless or the like to the flexibility of cement.Since the nineties in 20th century, poly carboxylic acid has developed into a kind of new variety of high efficiency water reducing agent.It has excellent properties such as the high and thermotolerance of intensity, weather resistance, good weatherability.At present with unsaturated carboxylic acid prepare polycarboxylate water-reducer method mainly contain propylene acid system, methacrylic acid system, maleic anhydride method etc.
In patent CN1636922, disclose a kind of preparation method of polycarboxylic acid series water reducing agent, under the catalysis of catalyzer, reacted synthetic carboxylate, again with methylpropene sodium sulfonate and the synthetic water reducer of acrylic acid copolymer by polyoxyethylene glycol and vinylformic acid.Though the vinylformic acid in this method is cheap, monomer whose self characteristics of molecular structure makes that the protect plasticity of its product can not get improving all the time.
A kind of preparation method of polycarboxylate high-efficiency water-reducing agent is disclosed in patent CN101353404; Esterification is taken place in polyethers and methylacrylic acid obtain esterification products in the presence of stopper, catalyzer, again esterification products and thiohydracrylic acid, initiator polymerization are obtained polycarboxylate water-reducer.Though the water reducer protect plasticity of this method preparation increases than the propylene acid system, water-reducing rate is low, and production cost is higher relatively.
A kind of method for preparing polycarboxylate water-reducer with maleic anhydride is disclosed in patent CN1948209B; Obtain polyoxyethylene glycol maleic anhydride ester and the mixture that remains maleic anhydride through polyoxyethylene glycol and maleic anhydride generation esterification, this mixture vinylformic acid, methylpropene sodium sulfonate copolymerization obtain polycarboxylate water-reducer then.In this method; Though maleic anhydride is prone to and alcohols generation esterification; But do not reach the effect of normal water reducer with other polymer of monomers, can only carry out a small amount of admixture, and maleic anhydride is difficult to participate in polyreaction as polymerization single polymerization monomer as a kind of raw material that reduces cost.
(3) summary of the invention
One of technical problem that the present invention will solve provides a kind of new polycarboxylate water-reducer; It has high protect plasticity can, better steric hindrance effect is arranged, cement paste through the time loss little; Problems such as it is good to the control of cement plasticizing effect to overcome the prior art water reducer, and water-reducing rate is not high.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of polycarboxylate water-reducer, its molecular weight are 1000～100000, and structure is formed shown in (7):
In the formula (7), R
4Be selected from C
1～C
3Alkylidene group, R
5Be selected from hydrogen or C
1～C
3Alkyl, M are Na or K; A, b, c, d are integer, and wherein a is 1～80, and b is 0～300, and c is 0～80, and d is 1～200; When c=0, b=0; Wherein X represents polyether group, and the polyether group X in each structural unit independently is selected from shown in following formula (8-1), formula (8-3), the formula (8-3) a kind of in the group separately:
In formula (8-1), formula (8-2) or the formula (8-3), R
1Be selected from C
1～C
3Alkyl, R
2, R
3Independently be selected from C
1～C
3Alkylidene group, m, n, p, q are natural number, wherein the m value is 8～72, is preferably 18～56; The n value is 5～35; The p value is 1～71, and the q value is 1～71, and p+q=8～72, preferred p+q=18～56.
Further, the molecular weight of preferred described polyether group is 600～3000.
Need to prove that what formula (7) was represented is the structural unit composition of polycarboxylate water-reducer, does not represent the true ordering of structural unit.
The present invention to solve another technical problem provide a kind of preparation method of above-mentioned polycarboxylate water-reducer; It is under the prerequisite of guaranteeing the polymkeric substance water-reducing property; Esterification yield is high, synthesis technique is simple, easily-controlled reaction conditions, and can also reduce the production cost of polycarboxylate water-reducer.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of method for preparing described polycarboxylate water-reducer comprises the steps:
Steps A: in the presence of stopper and catalyzer, polyethers X-H and excessive unsaturated fatty acids carried out esterification 3～7 hours in 120～140 ℃, obtained carboxylate; Described unsaturated fatty acids is the unsaturated dibasic acid shown in the formula (2), perhaps is the mixing acid that the unsaturated monoprotic acid shown in unsaturated dibasic acid shown in the formula (2) and the formula (3) is formed; Described polyethers X-H is selected from a kind of or any several kinds combination in the compound shown in formula (1-1), formula (1-2), the formula (1-3);
In formula (1-1), formula (1-2) or the formula (1-3), R
1Be selected from C
1～C
3Alkyl, R
2, R
3Independently be selected from C
1～C
3Alkylidene group, m, n, p, q are natural number, wherein the m value is 8～72; The n value is 5～35; The p value is 1～71, and the q value is 1～71, and p+q=8～72;
In formula (2) or the formula (3), R
4Be C
1～C
3Alkylidene group, R
5Be hydrogen or C
1～C
3Alkyl;
Step B: in the aqueous solution, under action of evocating, carboxylate that steps A is made and remaining unsaturated fatty acids carried out copolymerization 2～5 hours in 55～100 ℃, made the carboxylic acid polyalcohol of formula (6);
In the formula (6), a, b, c, d are integer, and wherein a is 1～80, and b is 0～300, and c is 0～80, and d is 1～200; When c=0, b=0; R
4, R
5, X definition the same;
Step C: the carboxylic acid polyalcohol that step B is made neutralizes with alkaline solution, and control pH is 6～8, gets the polycarboxylate water-reducer product; Said alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
Further, when the described unsaturated fatty acids of steps A was unsaturated dibasic acid, the present invention specifically recommended the mass ratio that feeds intake of polyethers and unsaturated dibasic acid to be: 65～96%: 35～4%, be preferably 70～90%: 30～10%.
Further; When the described unsaturated fatty acids of steps A was unsaturated dibasic acid and unsaturated monacid mixing acid, it was 55～96%: 35～1.5% that the present invention specifically recommends polyethers and unsaturated dibasic acid and the unsaturated monacid mass ratio that feeds intake: 33～1%.Preferably, described polyethers and unsaturated dibasic acid and the unsaturated monacid mass ratio that feeds intake are 65～95%: 30～3%: 30～2%.
Need to prove that the feed ratio of above-mentioned polyethers and unsaturated fatty acids is that the total mass in polyethers and unsaturated fatty acids is 100%.
The preferred 600-3000 of the molecular weight of polyethers according to the invention; Preferred following a kind of or any several kinds mixing: methoxy poly (ethylene glycol), oxyethyl group polyoxyethylene glycol, propoxy-polyoxyethylene glycol, structure suc as formula the compound shown in (9-2), structure suc as formula the compound shown in (9-3); In its Chinese style (9-2) or the formula (9-3), R
1Be selected from methyl, ethyl or propyl group.Said polyethers more preferably use methoxy poly (ethylene glycol), structure suc as formula the compound shown in (9-2), structure suc as formula a kind of or any several kinds mixing in the compound shown in (9-3), its Chinese style (9-2) or (9-3) in, R
1Be methyl.
The preferred methylene-succinic acid of unsaturated dibasic acid (methylene-succinic acid) shown in the described formula (2).
The preferred acrylic or methacrylic acid of unsaturated monoprotic acid shown in the described formula (3).
Catalyzer described in the concrete recommendation step A of the present invention is the vitriol oil or tosic acid, and the adding weight of described catalyzer is recommended as 0.5～5.0% of polyethers and unsaturated fatty acids gross weight, is preferably 0.5～3.5%.
Stopper described in the concrete recommendation step A of the present invention is one or both in thiodiphenylamine, the Resorcinol, and its consumption is recommended as 0.05～0.5% of unsaturated fatty acids gross weight, is preferably 0.1～0.5%.
Initiator described in the step B of the present invention can be selected from one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, SPC-D, Diisopropyl azodicarboxylate, the azo-bis-isobutyrate hydrochloride; Its add-on is recommended as 0.1～10% of polyethers and unsaturated fatty acids gross weight, is preferably 1～6%.
In the described copolymerization of step B, when the reaction system mass concentration was higher than 25%, for preventing crosslinking reaction, the present invention recommended to add chain-transfer agent, with the size of regulate polymer molecular weight.The add-on of chain-transfer agent is recommended as 0.2～1.5% of polyethers and unsaturated fatty acids gross weight; Said chain-transfer agent can be selected from one or more in thiohydracrylic acid, mercaptoethanol, n-butyl mercaptan, Virahol, 2 mercapto ethanol, 3-thiohydracrylic acid, the Thiovanic acid.If the reaction solution strength of solution is lower than 25%, then need not add chain-transfer agent.
Polymeric articles of the present invention can with existing carboxylic acid water reducing agent, the compound use of thionamic acid based water reducer, not only effectively concrete slump-loss is newly blocked in improvement, and improves dispersing property, increases water-reducing rate.In addition, the water reducer that the present invention makes can also with compound uses such as other air entrapment agents, retardant, hardening accelerator, skimmer, improve The comprehensive performance.
Poly carboxylic acid series water reducer of the present invention can be used as high performance concrete, the high slump keeps coagulating the important component of soil, high-flowing concrete, anticorrosion concrete; Be widely used in the concrete workses such as construction work, water conservancy, maritime works, bridge, tunnel remarkable economic efficiency and promotional value being arranged.
The present invention compared with prior art has advantage:
1. the present invention adopts unsaturated dibasic acid and polyethers to carry out esterification; In the macromole carboxylate that generates, both contained ester group, poly carboxylic acid macromole long-chain branch can be provided; The main steric hindrance that rises in the application; Contain carboxyl again, play in the application to protect and mould effect, the slump that can also improve polycarboxylate water-reducer keeps effect; And the unsaturated dibasic acid that the present invention adopted is cheap, contains two carboxyls, and this more helps carrying out esterification with polyethers, can reach higher esterification yield.
2. the present invention uses unsaturated monoprotic acid and unsaturated dibasic acid to synthesize jointly, on molecular structure, has considered to improve in the product molecule length of the density of carboxyl and adjustment side chain on the main chain, and the water-reducing rate of water reducer and protect plasticity can be improved greatly.
3. the chloride ion-containing not of the polycarboxylate water-reducer among the present invention, to the reinforcing bar non-corrosiveness, flexibility is strong, and applicable to the cement of plurality of specifications, model, standing storage is not stratified, do not have deposition.
4, use feeds nitrogen like the unsaturated dibasic acid of general formula (2) in the esterification of the present invention in the process, has not only protected reaction system but also played the effect of band water, has improved the esterification yield of product.
Polycarboxylate water-reducer of the present invention, it have protect plasticity height, cement paste through the time loss little, excellent properties such as water-reducing rate is higher, production cost is low.
(4) embodiment
Below the reference implementation example is described in more detail the present invention, the purpose of said embodiment only is to illustrate the present invention, and absolutely not the present invention is carried out any qualification.
Embodiment 1
Get the 150g molecular weight and be and put into the 500mL four-hole boiling flask after 1500 methoxy poly (ethylene glycol) melts, stir and add Resorcinol 0.12g, methylene-succinic acid 22.12g, 98% sulfuric acid 1.53g down, feed nitrogen and heat up, 125～128 ℃ of reactions 6 hours down; Being cooled to adding 89g water below 50 ℃ and 1.01g chain-transfer agent mercaptoethanol stirs as dropping liquid (1); Get 2.74g ammonium persulphate and 48g deionized water, wiring solution-forming is as dropping liquid (2); In the 500mL four-hole boiling flask, add the 89g deionized water, be warming up to 95 ℃, beginning drips above-mentioned dropping liquid (1) and (2) simultaneously; And under this temperature, at the uniform velocity drip and made it to add in 1.5 hours; Be incubated 1 hour down at 96～98 ℃, cooling, sodium hydroxide solution neutralization with 10%; Regulating the pH value is 7, finally makes polycarboxylate water-reducer of the present invention.
Embodiment 2
Get the 100g molecular weight and be and put into the 500mL four-hole boiling flask after 1000 methoxy poly (ethylene glycol) (0.1mol) melts; Stir and add Resorcinol 0.1g, thiodiphenylamine 0.04g, methylene-succinic acid 6.51g, vinylformic acid 23.06g, tosic acid 1.55g down; Feed nitrogen and intensification, reacted 5 hours down at 125～128 ℃; Being cooled to the 131.5g of adding below 50 ℃ water stirs as dropping liquid (3); Get 2.92g ammonium persulphate and 97g deionized water, wiring solution-forming is as dropping liquid (4); In the 1000mL four-hole boiling flask, add the 263g deionized water, be warming up to 65 ℃, beginning drips above-mentioned dropping liquid (3) and (4) simultaneously; And under this temperature, at the uniform velocity drip and made it to add in 3 hours; Be incubated 1 hour down at 68～70 ℃, cooling, sodium hydroxide solution neutralization with 10%; Regulating the pH value is 7, finally makes polycarboxylate water-reducer of the present invention.
Embodiment 3
Get the 120g molecular weight and be and put into the 500mL four-hole boiling flask after 1200 methoxy poly (ethylene glycol) melts; Stir and add Resorcinol 0.12g, methylene-succinic acid 13.2g, methylacrylic acid 34.5g, 98% sulfuric acid 1.22g down; Feed nitrogen and intensification, reacted 6 hours down at 122～125 ℃; Being cooled to the 165g of adding below 50 ℃ water stirs as dropping liquid (5); Get 7.4g ammonium persulphate and 124g deionized water, wiring solution-forming is as dropping liquid (6); In the 1000mL four-hole boiling flask, add the 332g deionized water, be warming up to 95 ℃, beginning drips above-mentioned dropping liquid (5) and (6) simultaneously; And under this temperature, at the uniform velocity drip and made it to add in 4 hours; Be incubated 1 hour down at 96～98 ℃, cooling, sodium hydroxide solution neutralization with 10%; Regulating the pH value is 7, finally makes polycarboxylate water-reducer of the present invention.
Comparing embodiment 4
Get the 155g molecular weight and be and put into the 500mL four-hole boiling flask after 1200 methoxy poly (ethylene glycol) melts, stir and add Resorcinol 0.21g, methylacrylic acid 42.61g, 98% sulfuric acid 1.53g down, feed nitrogen and heat up, 122～125 ℃ of reactions 6 hours down; Being cooled to adding 155g water below 50 ℃ and 1.55g chain-transfer agent mercaptoethanol stirs as dropping liquid (7); Get 5.83g ammonium persulphate and 94g deionized water, wiring solution-forming is as dropping liquid (8); In the 1000mL four-hole boiling flask, add the 355g deionized water, be warming up to 65 ℃, beginning drips above-mentioned dropping liquid (7) and (8) simultaneously; And under this temperature, at the uniform velocity drip and made it to add in 3 hours; Be incubated 1 hour down at 68～70 ℃, cooling, sodium hydroxide solution neutralization with 10%; Regulating the pH value is 7, the final polycarboxylate water-reducer that obtains routine.
Embodiment 5
By embodiment 1～4 prepared polycarboxylate water-reducer, the water reducer of gained is carried out flowing degree of net paste of cement and the test of mortar water-reducing rate according to GB/T8077-2000.Test cement is local conch 42.5R, wc 0.29, and the water reducer volume is gives money as a gift 0.25%, measuring result such as table 1:
Table 1
Above data show that independent methylene-succinic acid and the polyethers of using carries out esterification among the embodiment 1, and the protect plasticity of its product can be relatively good, protect to mould to change in time in the test to lose from clean slurry to be negative value; Use among the embodiment 2 that vinylformic acid and methylene-succinic acid are common to carry out esterification with polyethers, the initial clean slurry dispersiveness of its product is better, but loses relatively large; Use among the embodiment 3 methylacrylic acid and methylene-succinic acid jointly and polyethers carry out esterification, it is very little that its product is starched loss only, water-reducing rate is also higher; Be the preparation method who generally acknowledges at present in the comparing embodiment 4, the clean slurry retentivity of its product is poor, and water-reducing rate is also relatively low simultaneously.
Claims (10)
1. polycarboxylate water-reducer, its molecular weight is 1000～100000, structure is formed shown in (7):
In the formula (7), R
4Be selected from C
1～C
3Alkylidene group, R
5Be selected from hydrogen or C
1～C
3Alkyl, M are Na or K; A, b, c, d are integer, and wherein a is 1～80, and b is 0～300, and c is 0～80, and d is 1～200; When c=0, b=0; Wherein X represents polyether group, and the polyether group X in each structural unit independently is selected from shown in following formula (8-1), formula (8-2), the formula (8-3) a kind of in the group separately:
In formula (8-1), formula (8-2) or the formula (8-3), R
1Be selected from C
1～C
3Alkyl, R
2, R
3Independently be selected from C
1～C
3Alkylidene group, m, n, p, q are natural number, wherein the m value is 8～72; The n value is 5～35; The p value is 1～71, and the q value is 1～71, and p+q=8～72.
2. polycarboxylate water-reducer as claimed in claim 1, the molecular weight that it is characterized in that described polyether group is 600～3000.
3. the preparation method of a polycarboxylate water-reducer as claimed in claim 1 comprises the steps:
Steps A: in the presence of stopper and catalyzer, polyethers X-H and excessive unsaturated fatty acids carried out esterification 3～7 hours in 120～140 ℃, obtained carboxylate; Described unsaturated fatty acids is the unsaturated dibasic acid shown in the formula (2), perhaps is the mixing acid that the unsaturated monoprotic acid shown in unsaturated dibasic acid shown in the formula (2) and the formula (3) is formed; Described polyethers X-H is selected from a kind of or any several kinds combination in the compound shown in formula (1-1), formula (1-2), the formula (1-3);
In formula (1-1), formula (1-2) or the formula (1-3), R
1Be selected from C
1～C
3Alkyl, R
2, R
3Independently be selected from C
1～C
3Alkylidene group, m, n, p, q are natural number, wherein the m value is 8～72; The n value is 5～35; The p value is 1～71, and the q value is 1～71, and p+q=8～72;
In formula (2) or the formula (3), R
4Be C
1～C
3Alkylidene group, R
5Be hydrogen or C
1～C
3Alkyl;
Step B: in the aqueous solution, under action of evocating, carboxylate that steps A is made and remaining unsaturated fatty acids carried out copolymerization 2～5 hours in 55～100 ℃, made the carboxylic acid polyalcohol of formula (6);
In the formula (6), a, b, c, d are integer, and wherein a is 1～80, and b is 0～300, and c is 0～80, and d is 1～200; When c=0, b=0; R
4, R
5, X definition the same;
Step C: the carboxylic acid polyalcohol that step B is made neutralizes with alkaline solution, and control pH is 6～8, gets the polycarboxylate water-reducer product; Said alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
4. the preparation method of polycarboxylate water-reducer as claimed in claim 3 it is characterized in that described unsaturated fatty acids is a unsaturated dibasic acid, and the mass ratio that feeds intake of polyethers and unsaturated dibasic acid is: 65～96%: 35～4%.
5. the preparation method of polycarboxylate water-reducer as claimed in claim 3; It is characterized in that described unsaturated fatty acids is unsaturated dibasic acid and unsaturated monacid mixing acid, polyethers and unsaturated dibasic acid and the unsaturated monacid mass ratio that feeds intake are 55～96%: 35～1.5%: 33～1%.
6. like the preparation method of the described polycarboxylate water-reducer of one of claim 3～5, it is characterized in that said polyethers is selected from following a kind of or any several kinds mixing: methoxy poly (ethylene glycol), oxyethyl group polyoxyethylene glycol, propoxy-polyoxyethylene glycol, structure suc as formula the compound shown in (9-2), structure suc as formula the compound shown in (9-3); Its Chinese style (9-2) or (9-3) in, R
1Be selected from methyl, ethyl or propyl group;
7. like the preparation method of the described polycarboxylate water-reducer of one of claim 3～5; It is characterized in that the catalyzer described in the steps A is the vitriol oil or tosic acid, the adding weight of described catalyzer is 0.5～5.0% of polyethers and unsaturated fatty acids gross weight.
8. like the preparation method of the described polycarboxylate water-reducer of one of claim 3～5, it is characterized in that the stopper described in the steps A is one or both in thiodiphenylamine, the Resorcinol, its consumption is 0.05～0.5% of a unsaturated fatty acids gross weight.
9. like the preparation method of the described polycarboxylate water-reducer of one of claim 3～5; It is characterized in that the initiator described in the step B is selected from one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, SPC-D, Diisopropyl azodicarboxylate, the azo-bis-isobutyrate hydrochloride, its add-on is 0.1～10% of polyethers and a unsaturated fatty acids gross weight.
10. like the preparation method of the described polycarboxylate water-reducer of one of claim 3～5; It is characterized in that in the described copolymerization of step B; The reaction system mass concentration is higher than at 25% o'clock, adds chain-transfer agent, and its add-on is 0.2～1.5% of polyethers and a unsaturated fatty acids gross weight; In said chain-transfer agent selected from mercapto propionic acid, mercaptoethanol, n-butyl mercaptan, Virahol, 2 mercapto ethanol, 3-thiohydracrylic acid, the Thiovanic acid one or more.
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| CN101531744A (en) * | 2009-04-28 | 2009-09-16 | 中国水利水电科学研究院 | Method for synthesizing polycarboxylic acid series concrete hyper-dispersant |
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