CN102660037B - Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer - Google Patents
Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 57
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000013268 sustained release Methods 0.000 title abstract 2
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- 239000000463 material Substances 0.000 claims description 35
- 229920005646 polycarboxylate Polymers 0.000 claims description 29
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- 238000003756 stirring Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 229920001427 mPEG Polymers 0.000 claims description 12
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000004160 Ammonium persulphate Substances 0.000 claims description 9
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000004567 concrete Substances 0.000 abstract description 13
- 238000005886 esterification reaction Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 12
- 230000032050 esterification Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
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- 230000008569 process Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000002170 ethers Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 6
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A preparation method of a super-sustained release ester-ether crosslinking polycarboxylic acid water reducer is provided. The method which combines synthesis of an ester water reducer and synthesis of an ether water reducer allows the polycarboxylic acid water reducer synthesized from large monomers containing different chain lengths and simultaneously containing long side chains and short side chains to be researched and developed, and the method which can guarantee good dispersity and good fluidity keeping ability brings conveniences for the concrete construction process. In the esterification reaction process, hydroxyethyl methacrylate is introduced to increase active hydroxy side chains, and the activity of methacrylic acid is effectively controlled, so the esterification rate of a reaction system is high, product performances are high, and the synthetic method of optimized ester polycarboxylic acid water reducer intermediates is researched and developed through utilizing above principles. A certain synergistic effect is reached by introducing high activity ester monomers in the copolymerization process and combining the long side chains and the short side chains of produced polycarboxylic acid, so performances of the ester-ether crosslinking polycarboxylic acid water reducer of the invention are better than the performances of common ester and ether polycarboxylic acids, and the water reducing rate and the fluidity keeping ability are improved.
Description
Technical field
The present invention relates to a kind of concrete admixture, be specially the preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether.
Background technology
Water reducer has become the indispensable component of concrete, is bringing into play more and more important effect aspect concrete performance improving.Polycarboxylate water-reducer is as a kind of novel concrete additive, very high water-reducing rate is not only arranged, higher protect plasticity, strong adaptability with cement, formation of concrete intensity is high, and the later stage drying shrinkage is little, the erosion resistance each side all than first and second in generation water reducer good, the energy-conserving and environment-protective Green Chemistry, other kinds water reducer is incomparable especially for these.
Along with the development of commerical ready-mixed concrete, people require more and more higher to the function of slump protection of poly carboxylic acid series water reducer.Concrete flow through the time loss not only directly have influence on the result of use of water reducer, also greatly restricted the service radius of concrete mixing plant, and the height and distance of concrete pumping, bring a lot of inconvenience to engineering construction.In order to improve the market competitiveness, must further improve the slow release action and the effect that keeps slurry to flow of poly carboxylic acid series water reducer, and further improve slump retaining.
The performance of polycarboxylate water-reducer depend on length, the side chain of main chain length, molecular composition, functional group type and connect the factors such as Zhi Midu.According to the dispersion mechanism of water reducer, generally can think and use the large monomer copolymerization of polyoxyethylene glycol that contains two kinds of different chain length, can obtain dispersed very high poly carboxylic acid series water reducer, can solve preferably the concrete slump loss problem simultaneously.The synthetic poly carboxylic acid series water reducer that contains simultaneously ester class and two kinds of side chains of ethers, the ester class is combined with ethers, control simultaneously the ethers side chain lengths, can reduce the loss of slump of concrete in construction process, can improve again adsorptive power and the absorption stability of water reducer on cement granules.The copolymerization product of MPEG 1200 and APEG 1200 can produce better mobility due to synergistic effect, and MPEG 1200 can produce more superior effect with the copolymerization of TPEG 2400.
The synthetic two step method that is essentially of ester class polycarboxylate water-reducer, the first step is carried out esterification with methoxy poly (ethylene glycol) monomethyl ether and (methyl) vinylformic acid under the effect of high temperature, catalyzer, obtain the large monomer of polycarboxylate water-reducer; Second step carries out copolymerization with above-mentioned large monomer and (methyl) vinylformic acid, methacrylic sulfonic acid, chain-transfer agent etc. under the effect of heating, initiator, by the time ester class polycarboxylate water-reducer.But all more expensive, many need imports of the starting material that adopt, the esterification cycle is long, and production technique is comparatively complicated simultaneously, and the quality of product but can not get stablizing, and performance is compared ethers larger gap aspect diminishing.Ethers polycarboxylic acid water reducing agent is synthetic is single stage method substantially, polyethers is carried out copolymerization with (methyl) vinylformic acid, initiator, chain-transfer agent etc. obtain ethers polycarboxylic acid water reducing agent under the certain temperature environment.Production technique is fairly simple, and the product diminishing is higher.
Summary of the invention
Technical problem solved by the invention is to provide the preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether, the method is synthetic in conjunction with ester class and ethers water reducer, develop a kind of large monomer composite synthesis by containing different chain length, the polycarboxylate water-reducer that contains simultaneously long side chain and short-side chain, can guaranteed good dispersiveness can guarantee good protect plasticity again, give in concrete construction and brought more facility.
Technical problem solved by the invention realizes by the following technical solutions:
The preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether comprises the steps:
(1) in the reactor of good leak tightness, under constantly stirring, drop into successively methoxy poly (ethylene glycol) and catalyzer, described catalyzer is one or more mixture in tosic acid, Resorcinol, thiodiphenylamine; Stir 30min when then being heated to 80～90 ℃, fully slowly add the mixed solution of methacrylic acid and hydroxyethyl methylacrylate after dissolving, and heat to 100 ℃, all gas valves of off-response still, and pass into rare gas element and make reacting kettle inner pressure remain on 0.05～0.2MPa, continue to be warming up to 125～130 ℃, and be incubated 4～8 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, is namely polycarboxylic acid water reducer intermediate;
(2) add methacrylic Soxylat A 25-7, methylpropene sodium sulfonate and water in closed reactor, open and stir and be warming up to 75～85 ℃, fully after dissolving, drip simultaneously comonomer solution A material and B material; The A material is made into by Thiovanic acid and methoxy polyethylene glycol methacrylate-styrene polymer, and 3.5h is added dropwise to complete; The B material is made into by ammonium persulphate and water, and 4h is added dropwise to complete; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 20%～40% concentration, obtained solid content and be 40% the crosslinked class polycarboxylate water-reducer of super slow release type ester ether.
Each reactant accounts for the massfraction of reactant total mass in following ranges:
Methoxy poly (ethylene glycol) 50%～55%
Methacrylic acid 15%～20%
Hydroxyethyl methylacrylate 3.5%～4.0%
Methacrylic Soxylat A 25-7 25%～30%
Methylpropene sodium sulfonate 1.5%～2.0%
Thiovanic acid 0.1%～0.5%
Ammonium persulphate 1%～2%
The summation that each reactant accounts for the massfraction of reactant total mass is 100%.
Described methoxy poly (ethylene glycol) molecular weight is 1200.
Described methacrylic Soxylat A 25-7 molecular weight is 1200～3600.
The incorporation of described catalyzer is 0.1%～2.0% of reactant total mass.
Beneficial effect:
Due to the rising along with pressure, the boiling point of water also constantly raises, in airtight reactor, pass into certain rare gas element, make and produce certain pressure in reactor, along with temperature raises, the water that produces in esterification process, add a certain amount of water extracter and by the form of water with hot steam, carry out to positive dirction thereby make to react, having improved esterification yield.In esterification reaction process, the present invention is by introducing hydroxyethyl methylacrylate, increase the activity hydroxy side chain, and effectively control the activity of methacrylic acid, the reaction system esterification yield is high, product performance are better, and the present invention utilizes these principles to research and develop a kind of synthetic method of more optimizing ester class polycarboxylic acid water reducer intermediate.In polymerization process, by introducing active higher ethers monomer, the long side chain of the poly carboxylic acid of production combines with short-side chain, reaches certain synergistic effect, is better than common ester class and ethers poly carboxylic acid performance, has improved water-reducing rate and protect plasticity.The present invention has technique and is easy to control, and conversion unit is simple, finished product cost performance advantages of higher, and simultaneously, stable reaction not only has higher water-reducing rate with the polycarboxylate water-reducer of its preparation, and workability is good, and has high slump retaining, basic no loss in an and a half hours.
Embodiment
In order to make technique means of the present invention, creation characteristic, workflow, using method reach purpose and effect is easy to understand, below further set forth the present invention.
Embodiment 1
(1) large monomer is synthetic: in the reactor of good leak tightness, under constantly stirring, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg successively, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20kg, stir 30min when being heated to 80～90 ℃, fully dissolving, then slowly add methacrylic acid 550kg, and beginning heat temperature raising, when temperature reaches 100 ℃, all gas valves of off-response still, and pass into nitrogen and make reacting kettle inner pressure remain on 0.1MPa, continue to be warming up to 125～130 ℃, and be incubated 6 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, it is namely polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: adding molecular weight in closed reactor is 1200 allyl polyethenoxy ether 350kg, methylpropene sodium sulfonate 55.23kg and 1544kg water, open and stir and be warming up to 85 ℃, fully after dissolving, drip comonomer solution A material and B material; The A material is made into by Thiovanic acid 12kg and methoxy polyethylene glycol methacrylate-styrene polymer 2022.5kg, and 3.5h is added dropwise to complete; The B material is made into by ammonium persulphate 44.6kg and water 618.5kg, and 4h is added dropwise to complete; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 30% concentration, obtained flaxen solid content and be 40% the crosslinked class polycarboxylate water-reducer of super slow release type ester ether.
Embodiment 2
(1) large monomer is synthetic: in the reactor of good leak tightness, under constantly stirring, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg successively, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20 kg, stir 30min when being heated to 80～90 ℃, fully dissolving, then slowly add methacrylic acid 550kg, and beginning heat temperature raising, when temperature reaches 100 ℃, all gas valves of off-response still, and pass into nitrogen and make reacting kettle inner pressure remain on 0.1MPa, continue to be warming up to 125～130 ℃, and be incubated 6 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, it is namely polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: adding molecular weight in closed reactor is 2400 methacrylic Soxylat A 25-7 750kg, methylpropene sodium sulfonate 55.23kg and 1544kg water, open and stir and be warming up to 85 ℃, fully after dissolving, drip comonomer solution A material and B material; The A material is made into by Thiovanic acid 12kg and methoxy polyethylene glycol methacrylate-styrene polymer 2022.5kg, and 3.5h is added dropwise to complete; The B material is made into by ammonium persulphate 44.6kg and water 618.5kg, and 4h is added dropwise to complete; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 30% concentration, obtained flaxen solid content and be 40% the crosslinked class polycarboxylate water-reducer of super slow release type ester ether.
Embodiment 3
(1) large monomer is synthetic: in the reactor of good leak tightness, under constantly stirring, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg successively, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20kg, stir 30min when being heated to 80～90 ℃, fully dissolving, then the mixed solution that slowly adds methacrylic acid 550kg and hydroxyethyl methylacrylate 1.06kg, and beginning heat temperature raising, when temperature reaches 100 ℃, all gas valves of off-response still, and pass into nitrogen and make reacting kettle inner pressure remain on 0.1MPa, continue to be warming up to 125～130 ℃, and be incubated 6 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, it is namely polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.84%.
(2) polycarboxylate water-reducer is synthetic: adding molecular weight in closed reactor is 2400 methacrylic Soxylat A 25-7 750kg, methylpropene sodium sulfonate 55.23kg and water 1544kg, open and stir and be warming up to 85 ℃, fully after dissolving, drip comonomer solution A material and B material; The A material is made into by Thiovanic acid 12kg and methoxy polyethylene glycol methacrylate-styrene polymer 2022.5kg, and 3.5h is added dropwise to complete; By being made into, 4h is added dropwise to complete by ammonium persulphate 44.6kg and water 618.5kg for B material; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 30% concentration, obtained flaxen solid content and be 40% the crosslinked class polycarboxylate water-reducer of super slow release type ester ether.
Embodiment 4
(1) large monomer is synthetic: in the reactor of good leak tightness, under constantly stirring, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20 kg successively, stir 30min when being heated to 80～90 ℃, fully dissolving, then the mixed solution that slowly adds methacrylic acid 550kg and hydroxyethyl methylacrylate 1.06kg, and beginning heat temperature raising, when temperature reaches 100 ℃, all gas valves of off-response still, and pass into nitrogen and make reacting kettle inner pressure remain on 0.1MPa.Continue to be warming up to 125～130 ℃, and be incubated 6 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, is namely polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.84%.
(2) polycarboxylate water-reducer is synthetic: adding molecular weight in closed reactor is 3600 methacrylic Soxylat A 25-7 1125kg, methylpropene sodium sulfonate 55.23kg and water 1544kg, open and stir and be warming up to 85 ℃, fully after dissolving, drip comonomer solution A material and B material; The A material is made into by Thiovanic acid 12kg and methoxy polyethylene glycol methacrylate-styrene polymer 2022.5kg, and 3.5h is added dropwise to complete; By being made into, 4h is added dropwise to complete by ammonium persulphate 44.6kg and water 618.5kg for B material; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 30% concentration, obtained flaxen solid content and be 40% the crosslinked class polycarboxylate water-reducer of super slow release type ester ether.
Comparative example
(1) large monomer is synthetic: in the reactor of good leak tightness, under constantly stirring, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg successively, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20 kg, stir 30min when being heated to 80～90 ℃, fully dissolving, then slowly add methacrylic acid 550kg, and beginning heat temperature raising, when temperature reaches 100 ℃, all gas valves of off-response still, and pass into nitrogen and make reacting kettle inner pressure remain on 0.1MPa, continue to be warming up to 125～130 ℃, and be incubated 6 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, it is namely polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: add methylpropene sodium sulfonate 55.23kg and 1544kg water in closed reactor, open and stir and be warming up to 85 ℃, fully after dissolving, drip comonomer solution A material and B material; The A material is made into by Thiovanic acid 12kg and methoxy polyethylene glycol methacrylate-styrene polymer 2022.5kg, and 3.5h is added dropwise to complete; By being made into, 4h is added dropwise to complete by ammonium persulphate 44.6kg and water 618.5kg for B material; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 30% concentration, obtained henna solid content and be 40% ester class polycarboxylate water-reducer.
Adopt above-mentioned technique, under certain copolymerization conditions, prepare polycarboxylate water-reducer, press the examination criteria of GB/T8077～2000, its test experience result such as following table:
The above is only most preferred embodiment of the present invention, and result proves, the present invention reacts simply, stable, is fit to scale operation, and cost is low, and the polycarboxylate water-reducer water-reducing rate of production is high, and slump retaining is good.
Above demonstration and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. the preparation method of the crosslinked class polycarboxylate water-reducer of super slow release type ester ether, is characterized in that, comprises the steps:
(1) in the reactor of good leak tightness, under constantly stirring, drop into successively methoxy poly (ethylene glycol) and catalyzer, described catalyzer is tosic acid; Stir 30min when then being heated to 80～90 ℃, fully slowly add the mixed solution of methacrylic acid and hydroxyethyl methylacrylate after dissolving, and heat to 100 ℃, all gas valves of off-response still, and pass into rare gas element and make reacting kettle inner pressure remain on 0.05～0.2MPa, continue to be warming up to 125～130 ℃, and be incubated 4～8 hours at this temperature, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, is namely polycarboxylic acid water reducer intermediate;
(2) add methacrylic Soxylat A 25-7, methylpropene sodium sulfonate and water in closed reactor, open and stir and be warming up to 75～85 ℃, fully after dissolving, drip simultaneously comonomer solution A material and B material; The A material is made into by Thiovanic acid and polyethylene glycol monomethyl ethermethacrylic acid esters, and 3.5h is added dropwise to complete; The B material is made into by ammonium persulphate and water, and 4h is added dropwise to complete; After B material was added dropwise to complete, insulation 1.5h when being cooled to 40 ℃, added the NaOH solution neutralization of 20%～40% concentration, obtained solid content and be 40% the crosslinked class polycarboxylate water-reducer of ester ether;
Each reactant accounts for the massfraction of reactant total mass in following ranges:
Methoxy poly (ethylene glycol) 50%～55%
Methacrylic acid 15%～20%
Hydroxyethyl methylacrylate 3.5%～4.0%
Methacrylic Soxylat A 25-7 25%～30%
Methylpropene sodium sulfonate 1.5%～2.0%
Thiovanic acid 0.1%～0.5%
Ammonium persulphate 1%～2%
The summation that each reactant accounts for the massfraction of reactant total mass is 100%.
2. the preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether according to claim 1, is characterized in that, described methoxy poly (ethylene glycol) molecular weight is 1200.
3. the preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether according to claim 1, is characterized in that, described methacrylic Soxylat A 25-7 molecular weight is 1200～3600.
4. the preparation method of the crosslinked class polycarboxylate water-reducer of a kind of super slow release type ester ether according to claim 1, is characterized in that, the incorporation of described catalyzer is 0.1%～2.0% of reactant total mass.
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| CN110172129A (en) * | 2019-06-24 | 2019-08-27 | 长沙加美乐素化工有限公司 | A kind of synthetic method of the polycarboxylic acids collapse protection type mother liquor of super sustained release |
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| CN103588655B (en) * | 2013-10-31 | 2016-06-29 | 上海台界化工有限公司 | Polycarboxylate water-reducer of amino acid esterification product modification and preparation method thereof |
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| CN105174782B (en) * | 2015-09-02 | 2017-07-25 | 马清浩 | A kind of Etheric ester type water reducer and preparation method thereof |
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| CN107189026A (en) * | 2017-05-15 | 2017-09-22 | 安徽森普新型材料发展有限公司 | A kind of preparation method of ester ether composite polymeric polycarboxylate water-reducer |
| CN108948284B (en) * | 2018-06-11 | 2020-11-20 | 清远市德诚化工科技有限公司 | Polyether ester modified polyether water reducer and preparation method thereof |
| CN110407510A (en) * | 2019-08-03 | 2019-11-05 | 徐州巨龙新材料科技有限公司 | A kind of polycarboxylate high performance water-reducing agent and preparation method thereof |
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| CN101412790B (en) * | 2008-10-31 | 2012-07-25 | 山东华伟银凯建材科技股份有限公司 | Method for preparing polycarboxylic acid water reducing agent |
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