CN104140503A - Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature - Google Patents
Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature Download PDFInfo
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Abstract
The invention provides a method for synthesizing a high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature. The method comprises the steps of material preparation, wherein 0.1-5% of chain transfer agents, 0.02-0.15% of reducing agents and water are mixed to obtain a dripping material A according to a mass percentage ratio, 6-15% of unsaturated acids or one or more types of the unsaturated acids and water are mixed to obtain a dripping material B, and the dripping material A and the dripping material B are reserved; polymerization, wherein 1% (by mass percentage) of raw material, namely macromonomer unsaturated methyl alkenyl epoxy vinyl ether is added into a reaction kettle and stirred, 0.01%-0.5% of oxidizing agents are added, the temperature is controlled between 5 DEG C and 30 DEG C, the dripping material A is dripped, the dripping material B is dripped five minutes after the dripping material A is dripped, the dripping time lasts for 2-3 hours, still standing is carried out for 1 hour after the dripping is finished, the polymerization reaction is completed, 0-10% of neutralizers are added for stirring neutralization, and the water reducer can be obtained. The water reducer has the advantages of being low in dosage, high in water-reducing rate, good in adaptability to cement and high in slumping retaining capacity. The method does not depend on the reaction temperature, greatly simplifies the operation steps, and has the advantages of being low in energy consumption, shortening the production period and effectively reducing the product cost.
Description
Technical field
The present invention relates to a kind of synthetic method of water reducer, particularly a kind of normal temperature synthesis method of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent.
Background technology
Cement water reducing agent (claims again superplasticizer, Superplasticizer) refers under the constant condition of concrete workability, cement consumption, can reduce mixing water amount, improve the admixture of concrete strength; Water reducer is hindered or is destroyed the flucculation structure of cement granules by surface-active action, complexing action, electrostatic repulsion forces or steric repulsion power etc., thereby can, when saving cement consumption, guarantee concrete workability and intensity.The mechanism of action of cement water reducing agent is as follows:
Dissemination: after cement blunge, due to the effect of cement granules molecular attraction, make grout form flucculation structure, 10% 30% mixing water is wrapped among cement granules, can not participate in unrestricted flow and lubrication, thereby affect the mobility of concrete mix.After adding water reducer, because water reducer molecular energy oriented adsorption is in cement particle surface, make cement particle surface with same electric charge (being generally negative charge), form electrostatic repulsion, impel cement granules mutually to disperse, flucculation structure is destroyed, discharges wrapped part moisture, participate in flowing, thereby effectively increased the mobility of concrete mix.
Lubrication: the hydrophilic group polarity in water reducer is very strong, therefore the water reducer adsorption film of cement particle surface can form the stable solvation moisture film of one deck with water molecules, this layer of moisture film has good lubrication, can effectively reduce the sliding resistance between cement granules, thereby concrete flowability is further improved.
Sterically hindered effect: there is hydrophilic polyether lateral chain in water reducer structure, be stretched in the aqueous solution, thereby be formed with the three-dimensional adsorption layer of certain thickness wetting ability at adsorbed cement particle surface.When cement granules near time, adsorption layer starts overlapping, between cement granules, produces sterically hindered effect, overlapping more, sterically hindered repulsion is larger, also just larger to the obstruction of cohesion between cement granules, makes the concrete slump keep good.
The slow releasing function of graft copolymerization side chain: novel water reducer is if polycarboxylate water-reducer is in the process of preparation, some side chains in grafting on the molecule of water reducer, this side chain not only can provide space steric effect, and, in the high alkalinity environment of hydrated cementitious, this side chain also can slowly be cut off, thereby discharges the poly carboxylic acid with dissemination, so just can improve the dispersion effect of cement particle, and control slump loss.
Traditional water reducer, can be divided into sulfomethylated lignin acids, Ppolynuclear aromatic salt and water soluble resin sulphonic acids according to composition material, as patent CN101665337 discloses a kind of lignin sulfonate modified aliphatic high-efficiency water reducing agent that utilizes; Patent CN101007719 discloses a kind of polycyclic aromatic hydrocarbon sulfonate polymer concrete water reducing agent; Patent CN101575186 discloses a kind of aliphatic concrete water reducing agent and the disclosed thionamic acid cement water reducing agent of patent CN101723615A etc.Wherein, traditional high efficiency water reducing agent main products has naphthalenesulfonate formaldehyde condensation compound (NSF) and melamine sulfonate and formaldehyde condenses (MSF), although this series products water-reducing rate is higher, but slump loss is fast, weather resistance is poor and can not reach the object of preparation high-performance and ultra-high performance concrete.
Than above-mentioned water reducer, polycarboxylate high performance water-reducing agent is that current scientific and technological content is in the world higher, a kind of cement water reducing agent of high comprehensive performance.The composite product that polycarboxylate high performance water-reducing agent is comprised of carboxylic-acid grafting multiple copolymer and other effective auxiliary agent; Poly carboxylic acid series water reducer has that water-reducing rate is high, reinforced effects is remarkable, concrete workability better, does not affect concrete Young's modulus, while slightly caving in through time the advantages such as loss is less, in various engineerings, be widely used in recent years.
The performance of polycarboxylate high performance water-reducing agent excellence is to be determined by its special molecular structure: the molecular structure of polycarboxylate high performance water-reducing agent is comb shape, is characterized in that on main chain, with more active group, these groups have sulfonic acid group (S0
3h), hydroxy-acid group (COOH), oh group (OH) etc., side chain is the polyoxy protective embankment base thiazolinyl group-(CH growing
2cH
20) m-R etc.Each group is brought into play different effects to the dissemination of cement, it is generally acknowledged, with negative electricity sulfonic group and carboxylic acid group, can be adsorbed onto cement particle surface, plays anchorage effect, also plays certain electrostatic repulsion.Long side chain stretches the stronger sterically hindered effect of playing in solution, sterically hindered effect is stronger to the dissemination of cement granules, and responsive unlike electrostatic interaction on electrolytical impact, therefore polycarboxylate high performance water-reducing agent has good dissemination, also relatively good to the adaptability of cement type.High performance water reducing agent of polyocarboxy acid is is abroad just researched and developed since the eighties, and it is upper to put into gradually engineering application, has obtained good economic benefit.The the 80's novel polycarboxylate high performance water-reducing agent researched and developed first of Japan is a kind of comparatively desirable water reducer that is different from NSF, MSF completely, even if also can make concrete there is high workability when low-dosage, and when low water-cement ratio, there is low viscosity and slump retention, and having better consistency from different cement, is the indispensable material of current high-strength high-flowing concrete.Along with concrete is to high-strength, high-performance future development, polymer chemistry and material molecule design theory constantly make further progress, and water reducer is had higher requirement.Current research direction is developed to novel carboxylic acid polyalcohol water reducing agent by water reducers such as traditional naphthalene system, melamine series, and carboxylic acid polyalcohol water reducing agent has become the staple product in concrete material.
Apply in the market more polycarboxylate water-reducer and mainly contain two classes: a class is the ester type polycarboxylate water-reducer of two step synthesis, it is to adopt methoxy poly (ethylene glycol) MPEG and excessive methacrylic acid (or vinylformic acid, maleic anhydride, furoate clothing) first to carry out esterification, use water as again solvent and bed material, drip at a certain temperature the aqueous solution of peroxide aqueous solution and methoxy poly (ethylene glycol) MPEG carboxylate simultaneously, carry out copolymerization, be incubated slaking certain hour, cooling neutralization obtains ester type polycarboxylate water-reducer again.Another kind of is ether type polycarboxylic acid water reducer, adopting unsaturated alcohol polyethers is raw material, using unsaturated alcohol polyethers and water as bed material, (sometimes also add part containing other monomer of activated double bonds), drop into superoxide and make catalyzer, at a certain temperature, drip the chain-transfer agent aqueous solution simultaneously and carry out copolymerization containing the comonomer of activated double bonds, after insulation slaking certain hour, cooling neutralization obtains ether type polycarboxylic acid water reducer.The cement type that these two kinds of water reducers adapt to is different, respectively has relative merits, sometimes carries out composite use.The common ground of these two kinds of synthetic methods, is all need in process of production to keep temperature and drip reactive monomer, needs continual stirring, so that the abundant hybrid reaction of material in dropping process.
CN101215119A has introduced and has adopted single stage method to prepare the method for high-performance polycarboxylic acids water reducing agent, the method employing first drops into water and alkenyl polyether is bed material, after being warming up to temperature of reaction, drop into peroxide catalyst, drip comonomer and chain-transfer agent, carry out synthesized high-performance polycarboxylate water-reducer.Although the method one-step synthesis water reducer, more simple to operate than two-step approach, facility investment is larger, and the dropping process need of comonomer and chain-transfer agent is strictly controlled, and production process needs insulation, and energy consumption is larger.The preparation method of the disclosed polycarboxylate water-reducer of patent CN101708974A, the method first passes into nitrogen in solvent, is warming up to 70 ° of C, in solvent, drips monomer solution and initiator solution simultaneously, is then warming up to 85 ° of C reactions.
The preparation method of the disclosed polyether grafting concrete water reducer of patent CN101486783A; the method first heats and carries out esterification under nitrogen protection; during copolymerization; temperature need be controlled at 80 110 ° of C; then be heated to 120 160 ° of C, in copolymerization product, add sulphonating agent to carry out high temperature sulfonation.The method operation steps is many, and institute responds and all at high temperature carry out, and difficulty is controlled in reaction.
The preparation technology of the disclosed a kind of ethers water reducer of patent CN101492518A drips mixing solutions and the catalyzer of vinylformic acid and Hydroxyethyl acrylate insulation reaction in 60 120 ° of C temperature ranges.
The preparation technology of the disclosed water reducer of patent CN101024566A, first added poly glycol monomethyl ether, methacrylic acid, tosic acid and Resorcinol, 80 140 ° of C reactions 46 hours; Then at 60 ° of C temperature, add allylsulfonate; At 65 95 ° of C temperature, add initiator to carry out polyreaction.The method step is more complicated, and the control difficulty to temperature.
CN101050083A has introduced take the synthetic method of the high performance water reducing agent of polyocarboxy acid that water is solvent, first uses the air in inert gas replacement reactor, adds water and allyl sulphonic acid salt monomer, 80 ° of C of heating in water bath to 55; Monomer mixed solution and initiator are added drop-wise to respectively in reactor, time for adding is 12 hours simultaneously; Be warming up to 80 90 ° of C reactions.
The disadvantages such as the preparation method of comprehensive aforementioned water reducer, generally exists investment of production equipment larger, require to use professional device fabrication, and technology controlling and process is complicated, and production process energy consumption is high, and during production human input is large.
Summary of the invention
Its object of the present invention is just to provide a kind of normal temperature synthesis method of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent, this water reducer has the advantages that volume is low, water-reducing rate is high, good to cement adaptability, slump hold facility is strong, this processing method does not rely on temperature of reaction, greatly simplified operation steps, had the advantages that energy consumption is low, save the production cycle, effectively reduce production costs.
The technical scheme that realizes above-mentioned purpose and take, comprises step:
1) get the raw materials ready, proportioning is mixed 0.1 5% chain-transfer agent to make and is dripped material A with 0.02 0.15% reductive agent, water by mass percentage, and one or more aqueous solution that mix with water of 6 15% unsaturated acid or unsaturated acid, make dropping and expect B, standby;
2) polymerization, the unsaturated methyl thiazolinyl of the large monomer of the raw material oxyethylene ether that is 1 by mass percent adds reactor, stirring makes it to be dissolved in completely in solvent, add 0.01 0.5% oxygenant, stir, temperature is controlled at 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is 23 hours, guarantees that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, finally adds 0 10% neutralizing agent to stir neutralization, obtains the high high performance water reducing agent of polyocarboxy acid that collapses of protecting of high diminishing.
Compared with prior art the present invention has the following advantages.
1) the present invention forms redox system by chain-transfer agent, the Oxidizing and Reducing Agents adding, can reduce the activation energy that decomposition of initiator becomes free radical, accelerate the decomposition of initiator, thereby also can carry out polyreaction under cold condition, accelerated polymerization velocity simultaneously;
2) preparation technology of the present invention is simple, under normal temperature, can complete polyreaction, has cancelled boiler heating or electric, the gas heating in traditional technology, and energy-conserving and environment-protective, reaction process are easy to control, environmental protection, clean development;
3) the present invention, by the design of molecular weight, can fully regulate poly carboxylic acid molecular backbone chain, side chain lengths, with this, regulates water-reducing property and the function of slump protection of polycarboxylate water-reducer, thereby makes the high water reducer collapsing of protecting of high diminishing.
Embodiment
Comprise step:
1) get the raw materials ready, proportioning is mixed 0.1 5% chain-transfer agent to make and is dripped material A with 0.02 0.15% reductive agent, water by mass percentage, and one or more aqueous solution that mix with water of 6 15% unsaturated acid or unsaturated acid, make dropping and expect B, standby;
2) polymerization, the unsaturated methyl thiazolinyl of the large monomer of the raw material oxyethylene ether that is 1 by mass percent adds reactor, stirring makes it to be dissolved in completely in solvent, add 0.01 0.5% oxygenant, stir, temperature is controlled at 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is 23 hours, guarantees that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, finally adds 0 10% neutralizing agent to stir neutralization, obtains the high high performance water reducing agent of polyocarboxy acid that collapses of protecting of high diminishing.
The large monomer of described raw material is the compound that contains unsaturated group; Can be one or more in the ester, unsaturated amine, unsaturated amides, alkene, hydrocarbon of unsaturated alcohol polyethers, unsaturated acid, comprise methacrylic Soxylat A 25-7 TPEG/HPEG, allyl polyethenoxy ether APEG and poly glycol monomethyl ether MPEG.
Described unsaturated acid, can be one or more mixtures of unsaturated acid, unsaturated acid derivative, comprises one or more mixtures of methacrylic acid, vinylformic acid, maleic anhydride, toxilic acid and acrylamide.
Described oxygenant can be one or more of superoxide, persulfide; Be included as one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen peroxide.
Described chain-transfer agent can be one or more in mercaptan or unsaturated hydrocarbons compound; One or more mixtures that comprise thiohydracrylic acid, Thiovanic acid, methylpropene sodium sulfonate, sodium allyl sulfonate.
Described reductive agent is one or more mixtures in xitix, quadrol, sodium metabisulphite, S-WAT.
Described neutralizing agent is alkali, can be one or more in metal hydroxides, organic amine, inorganic ammonia.
Described solvent is one or more in water, alcohol, ester or ketone, comprises deionized water, distilled water.
The synthetic water reducer product of the present invention comprises that constituent monomers is unsaturated methyl thiazolinyl Soxylat A 25-7, unsaturated acid, chain-transfer agent, oxygenant, reductive agent, neutralizing agent.The synthetic method of cement water reducing agent, step is as follows:
1) by proportioning, chain-transfer agent is mixed with reductive agent, water and make dropping material A, one or more aqueous solution that mix with water of unsaturated acid or unsaturated acid, make and drip material B; Standby;
2) the unsaturated methyl thiazolinyl of the large monomer of raw material oxyethylene ether is added to reactor, stir and make it to be dissolved in completely in solvent, add oxygenant, stir, temperature is controlled within the scope of 5 30 ° of C, drips A material, and A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, finally add neutralizing agent to stir neutralization, obtain the high high performance water reducing agent of polyocarboxy acid that collapses of protecting of high diminishing.
Described solvent can be one or more in water, alcohol, ester or ketone, preferably deionized water, distilled water.
The large monomer of described raw material is the compound that contains unsaturated group; Can be one or more in the ester, unsaturated amine, unsaturated amides, alkene, hydrocarbon of unsaturated alcohol polyethers, unsaturated acid, preferable methyl allyl polyethenoxy ether (TPEG/HPEG), allyl polyethenoxy ether (APEG) and poly glycol monomethyl ether (MPEG).
Described unsaturated acid, can be one or more mixtures of unsaturated acid, unsaturated acid derivative, one or more mixtures of preferable methyl vinylformic acid, vinylformic acid, maleic anhydride, toxilic acid and acrylamide.
Described chain-transfer agent can be one or more in mercaptan or unsaturated hydrocarbons compound; One or more mixtures of preferred thiohydracrylic acid, Thiovanic acid, methylpropene sodium sulfonate, sodium allyl sulfonate.
Described reductive agent is one or more mixtures that are selected from xitix, quadrol, sodium metabisulphite, S-WAT.
Described oxygenant can be one or more of superoxide, persulfide; And be preferably one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen peroxide.
Described neutralizing agent is alkali, can be one or more in metal hydroxides, organic amine, inorganic ammonia, liquid caustic soda is the most frequently used neutralizing agent, sometimes part neutralizing agent can also be added in reaction process, sometimes the height for polycarboxylate water-reducer concentration is tried one's best, also can add sheet alkali or organic amine to neutralize.
According to the embodiment of above-mentioned synthetic method, wherein, the large monomer of reaction raw materials, unsaturated acid, oxygenant, chain-transfer agent, reductive agent and neutralizing agent consumption mass percent are: 1: 6 15%:0.01 0.5%:0.1 5%:0.02 0.15%:0 10%.Further preferable range is: 1: 10 15%:0.05 0.3%:0.5 4%:0.08 0.15%:0 5%.
Embodiment 1
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: thiohydracrylic acid 1.5g, xitix 15g, 120 grams of deionized waters, mix, and A material is standby; Vinylformic acid 90g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (HPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add persulfuric acid by 1.2g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Embodiment 2
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: Thiovanic acid 2.25g, xitix 12g, 120 grams of deionized waters, mix, and A material is standby; Vinylformic acid 90g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (HPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add persulfuric acid by 1.2 g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Embodiment 3
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: thiohydracrylic acid 1.5g, xitix 1g, methylpropene sodium sulfonate 12g, 120 grams of deionized waters, mix, and A material is standby; Methacrylic acid 85g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (TPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add hydrogen peroxide 2.0 g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Embodiment 4
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: Thiovanic acid 2.25g, xitix 1g, methylpropene sodium sulfonate 13g, 120 grams of deionized waters, mix, and A material is standby; Methacrylic acid, 85g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (HPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add hydrogen peroxide 2.0 g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Embodiment 5
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: Thiovanic acid 2.25g, methylpropene sodium sulfonate 14g, 120 grams of deionized waters, mix, and A material is standby; Vinylformic acid 86g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (HPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add persulfuric acid by 4.0 g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Embodiment 6
By following material quantity and technique, prepare high-performance polycarboxylic acids water reducing agent, be specially
1) get the raw materials ready: Thiovanic acid 2.25g, xitix 5g, 8 grams of S-WATs, 120 grams of deionized waters, mix, and A material is standby; Vinylformic acid 90g, adds 80 grams of deionized waters to mix, and B material is standby;
2) polymerization: add deionized water 500 g and unsaturated methyl thiazolinyl Soxylat A 25-7 (HPEG 2400) 700 g to being furnished with in the glass reactor of thermometer and electric blender, stir after fully dissolving, add hydrogen peroxide 4.0 g, stir, temperature is controlled within the scope of 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is controlled at 23 hours, guarantee that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, with aqueous sodium hydroxide solution, be neutralized to pH value to 7, obtain poly-shuttle acid high efficiency water reducing agent, its solid content is about 40%.
Comparative example
By above-described embodiment and the synthetic various water reducers of domestic and international traditional technology, for cement, contrast.
Test material: Yadong, cement selection Jiangxi foreign-style house cement: P042.5.Water reducer is selected 40% embodiment, volume 0.35%
(1) only starch mobility comparison and detection:
Clean slurry mobility contrast (mm)
| ? | Initial flow degree | 1H degree of mobilization |
| Embodiment 1 | 283 | 254 |
| Embodiment 2 | 250 | 211 |
| Embodiment 3 | 305 | 285 |
| Embodiment 4 | 263 | 254 |
| Embodiment 5 | 254 | 222 |
| Embodiment 6 | 316 | 302 |
| Comparative example 1 | 292 | 260 |
| Comparative example 2 | 266 | 232 |
(2) instrument that fluidity of cement mortar comparison and detection-fluidity of cement mortar comparison and detection is used is common glue sand agitator.Because glue sand detects, more approach concrete, and detect the reproducible of data.
Fluidity of cement mortar contrast (mm)
| ? | Initial flow degree | 1H degree of mobilization |
| Embodiment 1 | 196 | 167 |
| Embodiment 2 | 189 | 172 |
| Embodiment 3 | 192 | 165 |
| Embodiment 4 | 185 | 170 |
| Embodiment 5 | 180 | 168 |
| Embodiment 6 | 190 | 175 |
| Comparative example 1 | 182 | 166 |
| Comparative example 2 | 189 | 165 |
Claims (8)
1. a normal temperature synthesis method for high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent, is characterized in that, comprises step:
1) get the raw materials ready, proportioning is mixed 0.1 5% chain-transfer agent to make and is dripped material A with 0.02 0.15% reductive agent, water by mass percentage, and one or more aqueous solution that mix with water of 6 15% unsaturated acid or unsaturated acid, make dropping and expect B, standby;
2) polymerization, the unsaturated methyl thiazolinyl of the large monomer of the raw material oxyethylene ether that is 1 by mass percent adds reactor, stirring makes it to be dissolved in completely in solvent, add 0.01 0.5% oxygenant, stir, temperature is controlled at 5 30 ° of C, drip A material, A gob starts to drip B material after adding 5 minutes, time for adding is 23 hours, guarantees that A material B material drips simultaneously, dropwise latter standing 1 hour, polyreaction is complete, finally adds 0 10% neutralizing agent to stir neutralization, obtains the high high performance water reducing agent of polyocarboxy acid that collapses of protecting of high diminishing.
2. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, is characterized in that, the large monomer of described raw material is the compound that contains unsaturated group; Can be one or more in the ester, unsaturated amine, unsaturated amides, alkene, hydrocarbon of unsaturated alcohol polyethers, unsaturated acid, comprise methacrylic Soxylat A 25-7 TPEG/HPEG, allyl polyethenoxy ether APEG and poly glycol monomethyl ether MPEG.
3. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, it is characterized in that, described unsaturated acid, can be one or more mixtures of unsaturated acid, unsaturated acid derivative, comprise one or more mixtures of methacrylic acid, vinylformic acid, maleic anhydride, toxilic acid and acrylamide.
4. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, is characterized in that, described oxygenant can be one or more of superoxide, persulfide; Be included as one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen peroxide.
5. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, is characterized in that, described chain-transfer agent can be one or more in mercaptan or unsaturated hydrocarbons compound; One or more mixtures that comprise thiohydracrylic acid, Thiovanic acid, methylpropene sodium sulfonate, sodium allyl sulfonate.
6. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, it is characterized in that, described reductive agent is one or more mixtures in xitix, quadrol, sodium metabisulphite, S-WAT.
7. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, is characterized in that, described neutralizing agent is alkali, can be one or more in metal hydroxides, organic amine, inorganic ammonia.
8. the normal temperature synthesis method of a kind of high diminishing high collapse protection type high-performance polycarboxylic acids water reducing agent according to claim 1, is characterized in that, described solvent is one or more in water, alcohol, ester or ketone, comprises deionized water, distilled water.
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Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104497230A (en) * | 2014-12-16 | 2015-04-08 | 上海台界化工有限公司 | Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof |
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| CN104497230A (en) * | 2014-12-16 | 2015-04-08 | 上海台界化工有限公司 | Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof |
| CN104774293A (en) * | 2014-12-17 | 2015-07-15 | 厦门路桥翔通建材科技有限公司 | Mud-resistant polycarboxylic acid water reducer and preparation method thereof |
| CN104774293B (en) * | 2014-12-17 | 2018-03-20 | 福建路桥翔通建材科技有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof |
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| CN106007456A (en) * | 2016-05-17 | 2016-10-12 | 浙江广天构件股份有限公司 | Water reducing agent capable of improving concrete performance |
| CN106084150A (en) * | 2016-06-08 | 2016-11-09 | 柳州市强威锻造厂 | A kind of trimellitic anhydride class polycarboxylate water-reducer |
| CN106065051A (en) * | 2016-06-08 | 2016-11-02 | 江苏新光环保工程有限公司 | A kind of normal temperature preparation method of polycarboxylic acid series high efficiency water reducing agent |
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