CN102660037A - 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 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004132 cross linking Methods 0.000 title abstract 3
- 238000013268 sustained release Methods 0.000 title abstract 2
- 239000012730 sustained-release form Substances 0.000 title abstract 2
- 150000002148 esters Chemical class 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005646 polycarboxylate Polymers 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 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 compound 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
- 239000000203 mixture 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 16
- 238000005886 esterification reaction Methods 0.000 abstract description 13
- 230000032050 esterification Effects 0.000 abstract description 11
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- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 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
- 238000010189 synthetic method Methods 0.000 abstract 1
- 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
- 150000001735 carboxylic acids 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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- 238000005516 engineering process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003467 diminishing effect Effects 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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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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 crosslinked type of polycarboxylate water-reducer of a kind of ultra 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 the concrete performance improving.Polycarboxylate water-reducer not only has very high water-reducing rate as a kind of novel concrete additive, higher protect plasticity; Strong with the flexibility of cement; The moulding concrete strength 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, these other kinds especially water reducers are incomparable.
Along with the development of commerical ready-mixed concrete, people require increasingly high 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 restricted the service radius of concrete mixing plant greatly, 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 maintenance slurry mobile effect 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 factors such as Zhi Midu.According to the dispersion mechanism of water reducer, generally can think and use the big 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 the concrete slump loss problem preferably simultaneously.The synthetic poly carboxylic acid series water reducer that contains ester class and two kinds of side chains of ethers simultaneously; The ester class is combined with ethers; Control the ethers side chain lengths simultaneously, can reduce the loss of slump of concrete in construction process, can improve adsorptive power and the absorption stability of water reducer on cement granules again.The copolymerization product of MPEG 1200 and APEG 1200 can be owing to synergistic effect produces preferable flowability, 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 big monomer of polycarboxylate water-reducer; Second step was carried out copolymerization with above-mentioned big monomer and (methyl) vinylformic acid, methacrylic sulfonic acid, chain-transfer agent etc. under heating, action of evocating, by the time ester class polycarboxylate water-reducer.But the starting material that adopted all compare expensive, the many import that needs, and the esterification cycle is long, and production technique is comparatively complicated simultaneously, and the quality of product but can not get stablizing, and the performance ethers has aspect diminishing than big gap.Ethers polycarboxylic acid water reducing agent is synthetic to be single stage method basically, 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 than higher.
Summary of the invention
The technical problem that the present invention solved is to provide the preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether; This method combines ester class and ethers water reducer to synthesize; Develop a kind of by the compound synthetic of big monomer that contains different chain length; The polycarboxylate water-reducer that contains long side chain and short-side chain simultaneously can guaranteed good dispersiveness can guarantee good protect plasticity again, gives in the concrete construction and has brought more facility.
The technical problem that the present invention solved adopts following technical scheme to realize:
The preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether comprises the steps:
(1) in the reaction kettle of good leak tightness, constantly stir down, drop into methoxy poly (ethylene glycol) and catalyzer successively, said catalyzer is one or more a mixture in tosic acid, Resorcinol, the thiodiphenylamine; Stir 30min when being heated to 80～90 ℃ then, fully the dissolving back slowly adds the mixed solution of methylacrylic acid and Rocryl 400, and heats to 100 ℃; All gas valves of off-response still; And feed rare gas element and make reacting kettle inner pressure remain on 0.05～0.2MPa, continue to be warming up to 125～130 ℃, and under this temperature, be incubated 4～8 hours; Reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate;
(2) in closed reactor, add methacrylic Soxylat A 25-7, methylpropene sodium sulfonate and water, open stirring and be warming up to 75～85 ℃, fully after the dissolving, drip comonomer solution A material and B material simultaneously; 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 20%～40% concentration, obtains solid content and be crosslinked type of polycarboxylate water-reducer of ultra slow release type ester ether of 40%.
Each reactant accounts for the massfraction of reactant total mass in following ranges:
Methoxy poly (ethylene glycol) 50%～55%
Methylacrylic acid 15%～20%
Rocryl 400 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%.
Said methoxy poly (ethylene glycol) molecular weight is 1200.
Said methacrylic Soxylat A 25-7 molecular weight is 1200～3600.
The incorporation of said catalyzer is 0.1%～2.0% of a reactant total mass.
Beneficial effect:
Because along with the rising of pressure, the boiling point of water also constantly raises, in closed reaction kettle; Feed certain rare gas element, make and produce certain pressure in the reaction kettle, along with temperature raises; The water that in esterification process, produces; Add a certain amount of water extracter and pass through the form of water, thereby reaction is carried out to positive dirction, improved esterification yield with hot steam.In esterification reaction process; The present invention is through introducing Rocryl 400; Increase the activity hydroxy side chain, and effectively control the activity of methylacrylic 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 compound method of optimizing ester class polycarboxylic acid water reducer intermediate more.Through 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 superior to common ester class and ethers poly carboxylic acid performance, has improved water-reducing rate and protect plasticity in the polymerization process.The present invention has technology 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
Be easy to understand and understand in order to make technique means of the present invention, creation characteristic, workflow, method of use reach purpose and effect, below further set forth the present invention.
Embodiment 1
(1) big monomeric synthetic: in the reaction kettle of good leak tightness, constantly stir down, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20kg successively; Stir 30min when being heated to 80～90 ℃, fully dissolving slowly adds methylacrylic acid 550kg then; And beginning heat temperature raising; When treating that temperature reaches 100 ℃, all gas valves of off-response still, and feeding nitrogen makes reacting kettle inner pressure remain on 0.1MPa; Continue to be warming up to 125～130 ℃; And under this temperature, being incubated 6 hours, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: the adding molecular weight is 1200 allyl polyethenoxy ether 350kg, methylpropene sodium sulfonate 55.23kg and 1544kg water in closed reactor; Open stirring and be warming up to 85 ℃; Fully after the 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 30% concentration, obtains flaxen solid content and be crosslinked type of polycarboxylate water-reducer of ultra slow release type ester ether of 40%.
Embodiment 2
(1) big monomeric synthetic: in the reaction kettle of good leak tightness, constantly stir down, 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 slowly adds methylacrylic acid 550kg then; And beginning heat temperature raising; When treating that temperature reaches 100 ℃, all gas valves of off-response still, and feeding nitrogen makes reacting kettle inner pressure remain on 0.1MPa; Continue to be warming up to 125～130 ℃; And under this temperature, being incubated 6 hours, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: the adding molecular weight is 2400 methacrylic Soxylat A 25-7 750kg, methylpropene sodium sulfonate 55.23kg and 1544kg water in closed reactor; Open stirring and be warming up to 85 ℃; Fully after the 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 30% concentration, obtains flaxen solid content and be crosslinked type of polycarboxylate water-reducer of ultra slow release type ester ether of 40%.
Embodiment 3
(1) big monomeric synthetic: in the reaction kettle of good leak tightness, constantly stir down, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20kg successively; Stir 30min when being heated to 80～90 ℃, fully dissolve, slowly add the mixed solution of methylacrylic acid 550kg and Rocryl 400 1.06kg then; And beginning heat temperature raising; When treating that temperature reaches 100 ℃, all gas valves of off-response still, and feeding nitrogen makes reacting kettle inner pressure remain on 0.1MPa; Continue to be warming up to 125～130 ℃; And under this temperature, being incubated 6 hours, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.84%.
(2) polycarboxylate water-reducer is synthetic: the adding molecular weight is 2400 methacrylic Soxylat A 25-7 750kg, methylpropene sodium sulfonate 55.23kg and water 1544kg in closed reactor; Open stirring and be warming up to 85 ℃; Fully after the 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 30% concentration, obtains flaxen solid content and be crosslinked type of polycarboxylate water-reducer of ultra slow release type ester ether of 40%.
Embodiment 4
(1) big monomeric synthetic: in the reaction kettle of good leak tightness; Constantly stir down, the input molecule amount is 1200 methoxy poly (ethylene glycol) 1500kg, Resorcinol 1.5kg, thiodiphenylamine 0.5 kg, tosic acid 20 kg successively, stirs 30min when being heated to 80～90 ℃; Fully dissolving; The mixed solution that slowly adds methylacrylic acid 550kg and Rocryl 400 1.06kg then, and beginning heat temperature raising are when treating that temperature reaches 100 ℃; All gas valves of off-response still, and feeding nitrogen makes reacting kettle inner pressure remain on 0.1MPa.Continue to be warming up to 125～130 ℃, and under this temperature, be incubated 6 hours, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.84%.
(2) polycarboxylate water-reducer is synthetic: the adding molecular weight is 3600 methacrylic Soxylat A 25-7 1125kg, methylpropene sodium sulfonate 55.23kg and water 1544kg in closed reactor; Open stirring and be warming up to 85 ℃; Fully after the 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 30% concentration, obtains flaxen solid content and be crosslinked type of polycarboxylate water-reducer of ultra slow release type ester ether of 40%.
Comparative example
(1) big monomeric synthetic: in the reaction kettle of good leak tightness, constantly stir down, 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 slowly adds methylacrylic acid 550kg then; And beginning heat temperature raising; When treating that temperature reaches 100 ℃, all gas valves of off-response still, and feeding nitrogen makes reacting kettle inner pressure remain on 0.1MPa; Continue to be warming up to 125～130 ℃; And under this temperature, being incubated 6 hours, reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate.Recording esterification yield after reaction finishes is 99.55%.
(2) polycarboxylate water-reducer is synthetic: in closed reactor, add methylpropene sodium sulfonate 55.23kg and 1544kg water, open stirring and be warming up to 85 ℃, fully after the 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 30% concentration, obtains henna solid content and be 40% ester class polycarboxylate water-reducer.
Adopt above-mentioned technology, 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 merely most preferred embodiment of the present invention, and the result proves that the present invention reacts simply, stablizes, and 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.
More than show 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 the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (5)
1. the preparation method of crosslinked type of polycarboxylate water-reducer of a ultra slow release type ester ether is characterized in that, comprises the steps:
(1) in the reaction kettle of good leak tightness, constantly stir down, drop into methoxy poly (ethylene glycol) and catalyzer successively, said catalyzer is one or more a mixture in tosic acid, Resorcinol, the thiodiphenylamine; Stir 30min when being heated to 80～90 ℃ then, fully the dissolving back slowly adds the mixed solution of methylacrylic acid and Rocryl 400, and heats to 100 ℃; All gas valves of off-response still; And feed rare gas element and make reacting kettle inner pressure remain on 0.05～0.2MPa, continue to be warming up to 125～130 ℃, and under this temperature, be incubated 4～8 hours; Reaction finishes to obtain polyethylene glycol monomethyl ethermethacrylic acid esters, promptly is polycarboxylic acid water reducer intermediate;
(2) in closed reactor, add methacrylic Soxylat A 25-7, methylpropene sodium sulfonate and water, open stirring and be warming up to 75～85 ℃, fully after the dissolving, drip comonomer solution A material and B material simultaneously; 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 treating that the B gob adds completion, insulation 1.5h when being cooled to 40 ℃, adds the NaOH solution neutralization of 20%～40% concentration, obtains solid content and is 40% ester ether and mix a type polycarboxylate water-reducer.
2. the preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether according to claim 1 is characterized in that each reactant accounts for the massfraction of reactant total mass in following ranges:
Methoxy poly (ethylene glycol) 50%～55%
Methylacrylic acid 15%～20%
Rocryl 400 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%.
3. the preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether according to claim 1 and 2 is characterized in that said methoxy poly (ethylene glycol) molecular weight is 1200.
4. the preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether according to claim 1 and 2 is characterized in that said methacrylic Soxylat A 25-7 molecular weight is 1200～3600.
5. the preparation method of crosslinked type of polycarboxylate water-reducer of a kind of ultra slow release type ester ether according to claim 1 is characterized in that the incorporation of said catalyzer is 0.1%～2.0% of a reactant total mass.
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