CN104945568A - Method for preparing maleic anhydride post-addition method low-temperature polycarboxylate superplasticizer - Google Patents
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Abstract
The invention provides maleic anhydride post-addition method low-temperature polycarboxylate superplasticizer and a preparation method thereof. The method includes the following steps that 1, methyl allyl polyethenoxy ether/TPEG and water at a certain proportion are added into a reaction kettle and are stirred to be dissolved; 2, an oxidizing agent and an initiating agent are added at a time at the temperature of 5-15 DEG C, and the mixture is fully stirred till the temperature is stable or slightly rises; 3, a mixed solution with an appropriate proportion of reducing agent, initiating agent and chain transfer agent and a comonomer solution are dipped, and dripping is completed in 1-4 hours; 4, after dripping is conducted in the comonomer solution for 0.5-2 hours, a maleic anhydride solution is added, and dripping is completed in 0-2 hours; 5, curing is conducted for 1-2 hours, an alkaline solution is added, and accordingly the maleic anhydride post-addition method low-temperature polycarboxylate superplasticizer can be obtained. The preparation method is simple in technology, the obtained water reducing agent can have high dispersing performance and dispersing holding capacity with a low mixing amount, a low-temperature heat-source-free process is adopted according to the climate of the northeastern regions in winter, production can be promoted and the method is simple and feasible.
Description
Technical field
The invention belongs to concrete admixture field, particularly relate to a kind of low temperature preparation method of high-adaptability polycarboxylate water-reducer.
Background technology
Polycarboxylate water-reducer a kind ofly to be formed with containing the unsaturated monomer copolymerization of other functional groups by the unsaturated monomer containing carboxyl, and concrete can be made at diminishing, a kind of high molecular polymer protecting the premium properties that collapses, has in environmental protection etc.The advantage such as low-dosage, high water reducing rate, controlled molecular structure, good dispersiveness, environmental protection, strong adaptability of high performance water reducing agent of polyocarboxy acid, be subject to attention and the research of numerous scholars and expert, be widely used in every field engineering construction, thus become concrete admixture development trend from now on.Current Chinese scholars is selected from monomer the research of polycarboxylate water-reducer, determine synthesis technique, improve polycarboxylate water-reducer performance, has transferred to the mechanism aspect on the impact of polycarboxylate water-reducer absorption dispersing property such as anionic charge density, branch lengths, molecular weight.
Polycarboxylate water-reducer synthesis selects maleic anhydride, polymerizable sulfonate or acrylic acid or the like, acrylamide usually, propenyl Soxylat A 25-7, polyoxyethylene glycol acrylic monoester, the direct aqueous solution copolymerization of the polymeric monomer such as poly glycol monomethyl ether, carrys out the water reducer that synthesis performance is good.MA has the carbon-carbon double bond for chain polymerization reactive behavior, but the space steric effect of cyclic anhydride group reduces double bond reactive behavior in MA molecule, make that MA is more difficult carries out self-polymeric reaction, but MA can carry out copolyreaction with other sterically hindered less monomers, and may upset other minor comonomer polymerization effect.
Patent CN 103508696 A discloses a kind of Mud-resistant polycarboxylic acid water reducer, it is made up of following component raw material: allylic polyoxyethylene poly-oxygen propylene aether, component R, R1, R2, chain-transfer agent, initiator R3 and water, and component R is one or more in maleic anhydride, methylpropene sodium sulfonate, vinyl acetate, methylene-succinic acid, itaconic anhydride, fumaric acid; R1 is the mixture of a kind of in vinylformic acid, methacrylic acid or two kinds; R2 is xitix, hang in mortar block, ferrous sulfate, stannous sulfate, sodium hypophosphite, sodium bisulfite, oxalic acid one or more; Also disclose its preparation method.This beneficial effect of the invention is: effectively maintain the water-soluble and sterically hindered of poly carboxylic acid, simultaneously a large amount of on side chain non-hydrophilic structures serves when asking intercalation absorption in the face of dirt bed and effectively obstructs, the speed of suction sun and effect are declined greatly, thus reaches the anti-object containing mud.
Patent CN 103804610 A mono-kind, without the preparation method of the high-performance polycarboxylic acids water reducing agent of thermal source technique, comprises the following steps: 1) join in reactor by a certain proportion of unsaturated Soxylat A 25-7 and water, stirs and makes it dissolve; 2) at 5-30 DEG C, disposablely add aqueous oxidizing agent solution, and stir; 3) drip the promotor of suitable proportion and the mixing solutions of chain-transfer agent and comonomer respectively, 2-4h drips off, and drip after terminating, slaking 1.5 hours, finally, adds alkaline conditioner, makes it neutralize, and namely obtains described polycarboxylate water-reducer.The described preparation method's technique of this invention is simple, and adopts without thermal source technique, decreases the step of heating, makes production easier, though obtained water reducer water-reducing rate is high, still there is slump-loss problem to some cement.
Patent CN 104311754 A provides a kind of room temperature to prepare the method for high density polycarboxylate water-reducer fast, step is as follows: be dissolved in distilled water after being mixed with initiator, chain-transfer agent, promotor by raw material monomer, be mixed with the reaction soln of mass concentration 50-80%; Stirred by gained reaction soln and be placed on irradiation 10-60min under high voltage mercury lamp, the pH of the copolymerization product obtained after being terminated by irradiation is adjusted to 7 ~ 8; Described raw material monomer is that vinylformic acid and prenol polyoxyethylene are by the mixture leading two kinds of monomers.This inventive method reaction process does not need heating, shorter than traditional thermal polymerization method production cycle, and can preparation quality concentration be directly more than 60%.
As can be seen from above three patents, water reducer production technique is comparatively complicated, and water reducer performance is single, fails to make full use of maleic anhydride characteristic, and requires very high to equipment, starting material.
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, provides a kind of preparation method realizing low temperature synthesizing polyether class polycarboxylate water-reducer.
The present invention solves the technical scheme that its technical problem adopts: have electron-withdrawing because maleic anhydride has symmetrical structure simultaneously, when adding supplied for electronic polyethers in polymerization system, first complex compound should be formed, so carry out free-radical polymerized just generation again there is the multipolymer of crosslinking structure, addition after maleic anhydride, the grafting of grafted chain functional group can be caused even, and mix sulfonate minor comonomer is as extra chain-transfer agent effect, polyethers long-chain branch and maleic anhydride short-chain branch can be impelled to keep grafting space distance, due to being alternately distributed of main chain ether and acid anhydrides, polymkeric substance under this synthetic method has stronger adaptability and high dispersive ability and disperses hold facility.As preferably, the method comprises the following steps:
1) in mass parts, join in reactor by 100 parts of methacrylic Soxylat A 25-7/isopentenol polyoxyethylene ether and 60-100 part water, stir, churning time controls stablize constant to reactor temperature or slightly rise; According to different zones weather real-time characteristic, measure temperature in the kettle, disposable input 0.5-2.5 part oxygenant and 0-2 part initiator;
2) 8-15 part unsaturated carboxylic acid, 0-5 part unsaturated sulfonic acid salt and 5-20 part water are configured to mixed solution A;
3) 0.1-1.0 parts of reductive agents, 0-1.0 part chain-transfer agent and 25-30 part water are configured to mixing solutions B;
4), after dropping into oxygenant and initiator in reactor, drip mixed solution A and mixing solutions B respectively, time for adding is 1-4h simultaneously;
5) after mixed solution A and mixing solutions B drip 0.5-2h, disposable or add maleic anhydride solution in dropping mode, control time for adding is 0-2h;
6), after dropping terminates, slaking 1 ~ 2h, finally adds basic solution, makes it neutralize, and control ph is 5-6.
As preferably, described methacrylic Soxylat A 25-7/isopentenol polyoxyethylene ether is preferably Losec 501/ goodization SPEG, and its color is micro-Huang extremely light yellow sheet, degree of unsaturation >=0.30, hydroxyl value is 22.50 ± 2.5 mgKOH/g, and pH value (1% aqueous solution) is 4.5-7.0.
As preferably, described oxygenant is the mixture of one or more in hydrogen peroxide, sodium peroxide, lithium peroxide, Potassium peroxide, ammonium peroxide, persulfuric acid, permanganic acid, potassium permanganate or peracetic acid.
As preferably, described initiator is the mixture of one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, Sodium persulfate, peroxide potassium borate, rongalite, inferior sodium phosphate.
As preferably, described reductive agent is the mixture of one or more in methyl alcohol, methylamine, quadrol, xitix, S-WAT, sodium bisulfite, rongalite, ferrous sulfate, inferior sodium phosphate, oxalic acid.
As preferably, described unsaturated carboxylic acid is one or both the mixture in vinylformic acid, methacrylic acid.
As preferably, described chain-transfer agent is the mixture of one or more in methallylsulfonic acid sodium, thioglycolic acid, sulfo-lactic acid, vinyl-acetic ester, Thiovanic acid, thiohydracrylic acid.
As preferably, described unsaturated sulfonic acid salt is the mixture of one or more in sodium vinyl sulfonate, sodium allyl sulfonate, methylpropene sodium sulfonate or Sodium styrene sulfonate.
As preferably, described mixed solution A time for adding is preferably 1h.
As preferably, described mixing solutions B time for adding is preferably 1h10min.
As preferably, the disposable input amount of described oxygenant adjusts flexibly according to temperature of charge in still.When preferably in still, mixing of materials liquid temp is 10 DEG C, input amount is 2 parts of oxygenants; When preferably in still, mixing of materials liquid temp is 5 DEG C, input amount is 2 parts of oxygenants and 1 part of initiator.
As preferably, described maleic anhydride adopts dropping method to add, and is preferably after mixed solution A drips 0.5h and instills, and time for adding controls the time for mixed solution A remainder drips.
The present invention takes the synthesis mode delaying to add MA, can guarantee MA and AA, sulfonate minor comonomer, polymeric monomer terpolymer, can not be subject to the impact of polymeric monomer and impurities in water.Adopt low temperature synthesizing polyether class polycarboxylate water-reducer of the present invention, not only reduce energy consumption, also reduce maleic anhydride to side reactions such as backbone polymerization and the upsets of length side chain, improve polyethers poly carboxylic acid water-reducing rate and guarantor as far as possible and to collapse the polyethers polycarboxylate water-reducer low-temperature synthetic method of ability.
Embodiment
Embodiment 1:
350g polymeric monomer, 300g water are added four-hole boiling flask, fixes instrument, stir equilibrium temperature to 5 DEG C, add oxygenant and initiator, and start to drip A, B material, after 30min, add 2g maleic anhydride, B dropwises after expecting 40min, and insulation 1h, obtains the mother liquor of 40% after moisturizing.
embodiment 2:
345g polymeric monomer, 250g water are added four-hole boiling flask, fixes instrument, stir equilibrium temperature to 15 DEG C, add oxygenant and initiator, and start to drip A, B material, after 1h, add 3g maleic anhydride, B dropwises after expecting 1h10min, and insulation 2h, obtains the mother liquor of 40% after moisturizing.
embodiment 3:
350g polymeric monomer, 250g water are added four-hole boiling flask, fix instrument, stir equilibrium temperature to 10 DEG C, add oxygenant and initiator, and start to drip A, B material, after 1h, drip 2.5g maleic anhydride and 50g water, time for adding controls as 1h, B dropwises after expecting 2h10min, and insulation 1h, obtains the mother liquor of 40% after moisturizing.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.
Claims (12)
1. the preparation method of addition low temperature polycarboxylate water-reducer after maleic anhydride, is characterized in that comprising the following steps:
1) in mass parts, join in reactor by 100 parts of methacrylic Soxylat A 25-7/isopentenol polyoxyethylene ether and 60-100 part water, stir, churning time controls stablize constant to reactor temperature or slightly rise; According to different zones weather real-time characteristic, measure temperature in the kettle, disposable input 0.5-2.5 part oxygenant and 0-2 part initiator;
2) 8-15 part unsaturated carboxylic acid, 0-5 part unsaturated sulfonic acid salt and 5-20 part water are configured to mixed solution A;
3) 0.1-1.0 parts of reductive agents, 0-1.0 part chain-transfer agent and 25-30 part water are configured to mixing solutions B;
4), after dropping into oxygenant and initiator in reactor, drip mixed solution A and mixing solutions B respectively, time for adding is 1-4h simultaneously;
5) after mixed solution A and mixing solutions B drip 0.5-2h, disposable or add maleic anhydride solution in dropping mode, control time for adding is 0-2h;
6), after dropping terminates, slaking 1 ~ 2h, finally adds basic solution, makes it neutralize, and control ph is 5-6.
2. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, it is characterized in that: described methacrylic Soxylat A 25-7/isopentenol polyoxyethylene ether is Losec 501/ goodization SPEG, its color is that micro-Huang is to light yellow sheet, degree of unsaturation >=0.30, hydroxyl value is 22.50 ± 2.5 mgKOH/g, pH value (1% aqueous solution) is 4.5-7.0, and its structural formula is shown in following general formula:
Wherein R
1, R
2represent hydrogen or methyl, R
1and R
2can not be hydrogen, m, n be the average addition mole numbers of group of oxidation of alkyl, and m represents the arbitrary integer in 20-120, and n represents arbitrary integer in 0-70 simultaneously.
3. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described oxygenant is the mixture of one or more in hydrogen peroxide, sodium peroxide, lithium peroxide, Potassium peroxide, ammonium peroxide, persulfuric acid, permanganic acid, potassium permanganate or peracetic acid.
4. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described initiator is the mixture of one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, Sodium persulfate, peroxide potassium borate, rongalite, inferior sodium phosphate.
5. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described reductive agent is the mixture of one or more in methyl alcohol, methylamine, quadrol, xitix, S-WAT, sodium bisulfite, rongalite, ferrous sulfate, inferior sodium phosphate, oxalic acid.
6. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described unsaturated carboxylic acid is one or both the mixture in vinylformic acid, methacrylic acid.
7. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described chain-transfer agent is the mixture of one or more in methallylsulfonic acid sodium, thioglycolic acid, sulfo-lactic acid, vinyl-acetic ester, Thiovanic acid, thiohydracrylic acid.
8. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 1, is characterized in that: described unsaturated sulfonic acid salt is the mixture of one or more in sodium vinyl sulfonate, sodium allyl sulfonate, methylpropene sodium sulfonate or Sodium styrene sulfonate.
9. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 2, is characterized in that: described mixed solution A time for adding is 1h.
10. the preparation method of addition low temperature polycarboxylate water-reducer after a kind of maleic anhydride according to claim 2, is characterized in that: described mixing solutions B time for adding is 1h10min.
The preparation method of addition low temperature polycarboxylate water-reducer after 11. a kind of maleic anhydrides according to claim 2, is characterized in that: the disposable input amount of described oxygenant adjusts flexibly according to temperature of charge in still; When preferably in still, mixing of materials liquid temp is 10 DEG C, input amount is 2 parts of oxygenants; When preferably in still, mixing of materials liquid temp is 5 DEG C, input amount is 2 parts of oxygenants and 1 part of initiator.
The preparation method of addition low temperature polycarboxylate water-reducer after 12. a kind of maleic anhydrides according to claim 2, it is characterized in that: described maleic anhydride adopts dropping method to add, instill after mixed solution A drips 0.5h, time for adding controls the time for mixed solution A remainder drips.
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| CN105418856A (en) * | 2015-12-18 | 2016-03-23 | 中建商品混凝土有限公司 | Preparation method of synthesis of polycarboxylate superplasticizer at room temperature in wide temperature range |
| CN105566572A (en) * | 2015-12-19 | 2016-05-11 | 桂林理工大学 | Maleic-anhydride-grafted polycarboxylic acid plasticity-maintaining agent and preparation method thereof |
| CN105645810A (en) * | 2016-01-05 | 2016-06-08 | 河南新汉材料科技有限公司 | Early-strength polycarboxylate type high-performance water reducing agent and preparation method |
| CN106749957A (en) * | 2016-11-15 | 2017-05-31 | 湖北工业大学 | A kind of low-temperature synthetic method of polynary initiation polycarboxylate water-reducer |
| CN106946494A (en) * | 2017-04-15 | 2017-07-14 | 青岛理工大学 | Polycarboxylate superplasticizer |
| CN109762160A (en) * | 2018-12-25 | 2019-05-17 | 常熟耐素生物材料科技有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN115304719A (en) * | 2019-11-21 | 2022-11-08 | 四川宇砼建材有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418856A (en) * | 2015-12-18 | 2016-03-23 | 中建商品混凝土有限公司 | Preparation method of synthesis of polycarboxylate superplasticizer at room temperature in wide temperature range |
| CN105566572A (en) * | 2015-12-19 | 2016-05-11 | 桂林理工大学 | Maleic-anhydride-grafted polycarboxylic acid plasticity-maintaining agent and preparation method thereof |
| CN105645810A (en) * | 2016-01-05 | 2016-06-08 | 河南新汉材料科技有限公司 | Early-strength polycarboxylate type high-performance water reducing agent and preparation method |
| CN105645810B (en) * | 2016-01-05 | 2018-05-25 | 河南新汉材料科技有限公司 | A kind of early strength type polycarboxylic acid series high-performance dehydragent and preparation method |
| CN106749957A (en) * | 2016-11-15 | 2017-05-31 | 湖北工业大学 | A kind of low-temperature synthetic method of polynary initiation polycarboxylate water-reducer |
| CN106749957B (en) * | 2016-11-15 | 2019-01-18 | 湖北工业大学 | A kind of polynary low-temperature synthetic method for causing polycarboxylate water-reducer |
| CN106946494A (en) * | 2017-04-15 | 2017-07-14 | 青岛理工大学 | Polycarboxylate superplasticizer |
| CN109762160A (en) * | 2018-12-25 | 2019-05-17 | 常熟耐素生物材料科技有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN115304719A (en) * | 2019-11-21 | 2022-11-08 | 四川宇砼建材有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method and application thereof |
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