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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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N alpha-mercaptopropionic acid Natural products CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 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
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000010881 fly ash Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 abstract 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000004567 concrete Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004574 high-performance concrete Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- -1 Tie Keyuan Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011376 self-consolidating concrete Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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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Application publication date: 20110427 |