CN102911320B - Method for preparing powder polycarboxylic acid superplasticizer - Google Patents
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Abstract
The invention discloses a method for preparing a powder polycarboxylic acid superplasticizer, belonging to the field of concrete admixtures. The method comprises the following steps: by using persulfate, oxydol or a redox system using persulfate and oxydol as oxidizers as an initiator and unsaturated ester or ether large monomer a, unsaturated carboxylic acid or acid anhydride thereof b and unsaturated amide and derivatives thereof c as reaction monomers, adding a chain-transfer agent d, carrying out water solution polymerization at 20-80 DEG C to prepare a liquid product of which the solid content is 40-80%; and carrying out powder spray drying on the liquid product with a centrifugal spray drier to obtain the powder polycarboxylic acid superplasticizer. The powder polycarboxylic acid superplasticizer can be widely used in grouting materials, dry powder mortar and powder paint. A certain amount of epoxypropane is introduced into the reaction large monomers to regulate the HLB (hydrophile-lipophile balance) value of the polycarboxylic acid superplasticizer, so that the finally synthesized superplasticizer has necessary hydrophilicity and lower water retaining capacity; and the superplasticizer can be easily dehydrated in the drying process, can not easily absorb water in the storage process, and is convenient for storage, transportation and use.
Description
Technical field
The present invention relates to the technical field preparing mortar and the reinforcement of concrete powdery high-performance superplasticizer, be specifically related to a kind of concrete preparation method of powder polycarboxylic acid superplasticizer.
Background technology
Poly carboxylic acid series super plasticizer is as the high-performance superplasticizer of a new generation, there is high water reducing rate, low-dosage, fresh concrete slump retention ability is good, maturing contraction is little, alkali content is low, without the characteristic such as chlorine and clean environment firendly, a large amount of for various concrete structure engineering, particularly prepare high performance concrete.But what use at present is all liquid water reducer product, needs special packaging, transport and storing unit, in the liquid product wherein transported containing 50 ~ 60% be the moisture be available anywhere, not only complicated operation, and be unfavorable for energy-saving and emission-reduction and reduce costs.In addition, along with the development of grouting, dry-mix and powder coating industry, market is to the expanded demand of powder superplasticizer, and the liquid application of polycarboxylic acid super-plasticizer in these industries is restricted.Due to the carboxyl containing a large amount of high-hydrophilic energy in polycarboxylic acid super-plasticizer molecular structure, sulfonic group and oxyethane, therefore its water-retentivity and water absorbing properties high compared with the efficient superplasticizer of other type, adopt general spray drying procedures to prepare powder polycarboxylic acid superplasticizer and there is insoluble technical problem, such as drying process easily occurs that wall sticking phenomenon, drying efficiency are low, inflammable under powder high temperature, the easy moisture absorption of powder-like product becomes sticky and powder-like product particle trickling property difference etc.
For the problems referred to above that preparation powder polycarboxylic acid superplasticizer exists, the investigator of domestic and international association area has carried out specific aim research, and achieves some achievements, but does not also have essence to solve the problem.Patent CN101824125A describes a kind of preparation method of powder poly-carboxylic high-performance superplasticizer.Its preparation method is: under initiator and chain-transfer agent existent condition, the macromolecule monomer of certain mol proportion and small-molecular-weight monomer, stir in the aqueous solution of certain temperature, carry out polyreaction, after polyreaction terminates, in reaction solution, add basic cpd, adjusted to ph is 7 ± 1, spraying dry and obtain powder poly-carboxylic high-performance superplasticizer.Described initiator is ammonium persulphate, and chain-transfer agent is lauryl mercaptan or thiohydracrylic acid, and the mol ratio of macromolecule monomer and small-molecular-weight monomer controls in 1:2.5 ~ 5, and temperature is 75 ~ 85 DEG C.Described spraying dry is that polycarboxylic acid super-plasticizer solution throws away formation droplet at a high speed by the centrifugal pan of atomizer siccative, inlet temperature 180 ~ 230 DEG C, air outlet temperature 80 ~ 120 DEG C, and add a certain amount of calcium carbonate superfine powder powder or talcum powder prevents powdered granule from boning at intake stack simultaneously.Although the present invention solves liquid poly-carboxylic high-performance superplasticizer and makes powdery problem, containing a large amount of antiseized flours in the powder-like product made, the effective constituent of powdery water-reducing agent reduces, and has insolubles precipitation when being again dissolved into liquid.In addition, the present invention does not solve the problem that the easy moisture absorption of powder polycarboxylic acid superplasticizer becomes sticky.Patent CN 101962273 A describes the preparation method of another powdery polycarboxylic acid hyperdispersant.Specifically ultrafine inorganic powder or colloidal sol are joined in polycarboxylic acid polymer solution, and make its Homogeneous phase mixing, obtain poly carboxylic acid slurry, then the poly carboxylic acid slurry obtained is made powder-like product by spray drying process; While poly carboxylic acid slurry atomization drying, also need to add inorganic separant in kiln, prevent the powder formed from gluing wall and caking, obtain powdery polycarboxylic acid hyperdispersant, wherein the weight of ultrafine inorganic powder may up to 20%; The method basic simlarity that this invention is mentioned with patent CN 101824125A, there is low, the irreversible dissolving of powdery water-reducing agent active constituent content and makes liquid product problem in the program mixed with inorganic powder by liquid water reducer before only increasing spraying equally.Also describe a kind of preparation method of powder polycarboxylic acids water reducing agent at patent CN 1919772A, it, to the effect that by improving spray-dryer, avoids the wall sticking phenomenon of material in pulverizing process.Be 120 ~ 200 DEG C in inlet temperature, air outlet temperature is under 50 ~ 110 DEG C of processing condition, dryly can obtain powder polycarboxylic acids water reducing agent.The problems such as the present invention is actually and modifies to Frequency Conversion Technique of Centrifugal Spraying Drying Equipment, but under processing condition of the present invention, and the low and energy consumption of production efficiency is high do not solve, and powdered product inflammable problem in moisture eliminator still exists, and should not realize suitability for industrialized production.
In sum, the root problem existed when preparing powder polycarboxylic acid superplasticizer is not also resolved.The various problems of the present invention by existing in further investigation polycarboxylic acid super-plasticizer drying process, find the intrinsic relation of ubiquitous polycarboxylic acid super-plasticizer dehydration difficulty and its molecular structure, start with from the molecule hydrophile-lipophile balance value (HLB) changing polycarboxylic acid super-plasticizer, by propylene oxide being introduced in the specific position of the strong side-chain structure of wetting ability, not affecting under the overall hydrophilic prerequisite of polycarboxylic acid super-plasticizer, improve the dewatering of superplasticizer to a certain extent.While guarantee polycarboxylic acid super-plasticizer utilisation technology performance, overcome the drawback that polycarboxylic acid super-plasticizer not easily becomes powder, common Frequency Conversion Technique of Centrifugal Spraying Drying Equipment can be adopted to carry out the preparation of powdery polycarboxylic acid water reducer, and the active constituent content of the powdery water-reducing agent made is high, the unsuitable moisture absorption, trickling property are good, avoids the powder moisture absorption in production process and glue wall and the ignition issues caused piled up by powder.The powder-like product made can directly use when transporting to onsite application, also water-soluble for powdery water-reducing agent liquid of making again can be used, solve the problem such as transportation cost and packaging, for its further genralrlization provides good prerequisite.
Summary of the invention
The present invention be intended to not reduce poly carboxylic acid high dispersive, diminishing and guarantor collapse effect prerequisite under, by changing side chain composition structure in polycarboxylic acid super-plasticizer molecular structure, improve its easy dewatering, and then improve productive rate and the production efficiency of polycarboxylic acid super-plasticizer powder process, prevent from gluing the problems such as wall, coking and spontaneous combustion in production process.Concrete preparation method is as follows:
With persulphate, hydrogen peroxide or the redox system that formed for oxygenant with persulphate, hydrogen peroxide for initiator, with unsaturated ester class or ethers polymeric monomer a, unsaturated carboxylic acid or its acid anhydrides b, unsaturated amides and derivative c thereof for reaction monomers, add chain-transfer agent d, carry out aqueous solution polymerization at 20 ~ 80 DEG C.Polymerization reaction time is 3 ~ 6 hours, reacts complete and is cooled to 45 DEG C, adds alkaline aqueous solution, trolamine or quadrol and is neutralized to pH=7 ~ 9, and obtaining massfraction is 40 ~ 60% finished products.Then spray-dried for polycarboxylic acid super-plasticizer solution method is obtained polycarboxylic acid super-plasticizer powder product, particle size range is at 20 ~ 160 μm, and water ratio is less than 4%.Spray drying parameters is: inlet temperature 150 DEG C ~ 230 DEG C, and air outlet temperature is 80 DEG C ~ 120 DEG C, centrifugal turntable rotating speed 12000 ~ 20000r/min.The feed postition of initiator and each reaction monomers be disposable add or drip add.
Wherein, the mol ratio of each reactant is a:b:c:d=1:2.0 ~ 5.0:0 ~ 5.0:0 ~ 2.0; The mol ratio of initiator amount and polymeric monomer a is 0.05 ~ 2:1, and is mixed with the aqueous solution and adds.
Example as unsaturated ester class polymeric monomer has: the Esterification obtained polymeric monomer of acrylic or methacrylic; Example as unsaturated ether polymeric monomer has: allyl ether series, iso-butylene beginning or primary isoamyl alcohol beginning polymeric monomer; And unsaturated ester class and ethers polymeric monomer remove outside its band double-key end group, long-chain is made up of the random or block polymer of oxyethane and propylene oxide.Its chemical formula is as follows:
formula (1)
In formula (1): R is ester class or the ethers end group of polymeric monomer.
The ratio m:(m+n of unsaturated ester class or ethers polymeric monomer ethylene oxide and propylene oxide)=0.1 ~ 0.95.
The oxyethane of unsaturated ester class or ethers polymeric monomer or polymerization degree m+n=10 ~ 112 of propylene oxide.
Example as unsaturated carboxylic acid or its acid anhydrides b has: vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, maleic anhydride.
Example as unsaturated amides and derivative c thereof has: acrylamide, 2-acrylamide-2-methylpro panesulfonic acid.
Example as chain-transfer agent has: methylpropene sodium sulfonate, sodium allylsulfonate, Thiovanic acid, thiohydracrylic acid, n-dodecyl mercaptan.
Beneficial effect of the present invention:
1. adjust its hydrophile-lipophile balance value from the molecular structure of polycarboxylate water-reducer, improve the dewatering of liquid water reducer, solve in pulverizing process and easily glue wall, coking and ignition issues.The powdery water-reducing agent water-absorbent made is little, trickling property is good, easy to use.
2. the Powdered polycarboxylic acid super-plasticizer active constituent content made can up to 95 ~ 98%, and not containing insoluble inorganic powder materials, invertible dissolution becomes liquid product.
3. the powdery polycarboxylic acid water reducer bleed of making is low, is particularly useful for making dry-mix, injection material, powder coating etc., also can be widely used in the various concrete of preparation.
4. solve polycarboxylate water-reducer long-distance transportation, packaging and storage inconvenience problem.Greatly reduce trucking costs and Packing Fee, there is the advantage of energy-saving low-carbon.
In order to technology contents of the present invention is described better, enumerate the following example.But the content of invention is not limited only to content listed by example.
Embodiment
formula 1
Note: m, n numerical value of the polymeric monomer mentioned in embodiment and comparative example is represented content in formula 1
Embodiment 1
In the four-hole boiling flask that stirring is housed, add m=1, the esters of acrylic acid polymeric monomer 28.07g of n=9, the propylene oxide of m=90, n=22 and oxyethane random copolymerization isobutene alcohol beginning ethers polymeric monomer 264.55g, and 185g distilled water fully stirs, and is warming up to 80 DEG C.Vinylformic acid 14.4g and methylpropene sodium sulfonate 31.6g is dissolved in 21.56g distilled water and is formulated as solution A, ammonium persulphate 1.14g is dissolved in 20.0g distilled water and is formulated as B solution.At 80 DEG C, A, B solution are dripped 2 hours respectively simultaneously, rear constant temperature is incubated 1 hour.Be cooled to 45 DEG C after insulation terminates, add 60%NaOH solution 10.0g and be neutralized to pH=7, obtained concentration is the polycarboxylic acid super-plasticizer sample 1 of 60%.By in the spray-dried method of polycarboxylic acid super-plasticizer solution of becoming reconciled obtain polycarboxylic acid super-plasticizer powder product, spray drying parameters is: inlet temperature 220 ° of C, and air outlet temperature is 110 ° of C, centrifugal turntable rotating speed 16000r/min.Powdered granule particle size range is at 40 ~ 150 μm, and water ratio is 2.1%.
Embodiment 2
M=95 is added in the four-hole boiling flask that stirring is housed, n=5 propylene oxide and ethylene oxide block copolymerization (its ethylene oxide and propylene oxide are 40-5-45 block arrangement) prenol beginning ethers polymeric monomer 700.0g, and 500.0g distilled water fully stirs, be warming up to 20 DEG C, in order every 5 ~ 10min by fumaric acid 58.1g, Thiovanic acid 5.0g, 30% concentration hydrogen peroxide 12.6g is all disposable joins in four-hole boiling flask.Xitix 8.71g is dissolved in 88.6g distilled water and is mixed with the aqueous solution.Adding in hydrogen peroxide 5 ~ 10min, at 20 DEG C, aqueous ascorbic acid is dripped 3 hours, rear constant temperature is incubated 3 hours.Insulation terminates directly to add 40%NaOH solution 20.0g afterwards, and trolamine 5 grams, is neutralized to pH=7.5, and obtained concentration is the polycarboxylic acid super-plasticizer sample 2 of 40%.By in the spray-dried method of polycarboxylic acid super-plasticizer solution of becoming reconciled obtain polycarboxylic acid super-plasticizer powder product, spray drying parameters is: inlet temperature 150 ° of C, and air outlet temperature is 80 ° of C, centrifugal turntable rotating speed 20000r/min.Powdered granule particle size range is at 20 ~ 80 μm, and water ratio is 2.5%.
Embodiment 3
Propylene oxide and the oxyethane random copolymerization prenol beginning ethers polymeric monomer 260.5g of m=n=25 is added in the four-hole boiling flask that stirring is housed, and 250g distilled water fully stirs, be warming up to 60 DEG C, join in four-hole boiling flask every 5 ~ 10min acrylamide 35.55g, n-dodecyl mercaptan 3.0g are all disposable in order, ammonium persulphate 3.6g is also disposable after being dissolved in and being made into homogeneous aqueous solution in 52.7g distilled water to be joined in four-hole boiling flask.At 60 DEG C, constant temperature is incubated 4 hours.Be cooled to 45 DEG C after insulation terminates, add 50%NaOH solution 5.0g and diethanolamine 2 grams, be neutralized to pH=8.0, obtained concentration is the polycarboxylic acid super-plasticizer sample 3 of 50%.By in the spray-dried method of polycarboxylic acid super-plasticizer solution of becoming reconciled obtain polycarboxylic acid super-plasticizer powder product, spray drying parameters is: inlet temperature 180 DEG C, and air outlet temperature is 120 DEG C, centrifugal turntable rotating speed 12000r/min.Powdered granule particle size range is at 30 ~ 100 μm, and water ratio is 1.8%.
Embodiment 4
M=15 is added in the four-hole boiling flask that stirring is housed, n=20 propylene oxide and ethylene oxide block copolymerization (its ethylene oxide and propylene oxide are alternately 5-10-5-10-5 block arrangement) prenol beginning ethers polymeric monomer 187.5g, and 40.0g distilled water fully stirs, be warming up to 70 DEG C.Methylene-succinic acid 8.6g, 2-acrylamide-2-methylpro panesulfonic acid 7.9g, thiohydracrylic acid 3.7g are dissolved in 21.0g distilled water and are formulated as solution A.Ammonium persulphate 6.1g is dissolved in the preparation of 21.0g distilled water and becomes solution B.At 70 DEG C, A, B solution are dripped 3 hours respectively simultaneously, rear constant temperature is incubated 2 hours.Be cooled to 45 DEG C after insulation terminates and add 60%NaOH solution 10.0g, 30%Na
2sO
3solution 3 grams, is neutralized to pH=9.0, and obtained concentration is the polycarboxylic acid super-plasticizer sample 4 of 80%.Then the spray-dried method of polycarboxylic acid super-plasticizer solution of neutralization is obtained polycarboxylic acid super-plasticizer powder product, particle size range is at 30 ~ 150 μm, and water ratio is 1.8%.Spray drying parameters is: inlet temperature 230 DEG C, and air outlet temperature is 90 DEG C, centrifugal turntable rotating speed 19000r/min, and water ratio is 1.5%.
Comparative example 5
In the four-hole boiling flask that stirring is housed, add m=26, n=0 prenol ethers polymeric monomer 100g and distilled water 150g fully stir, and are warming up to 70 DEG C, join in four-hole boiling flask every 5 ~ 10min by disposable for vinylformic acid 8.7g and MALEIC ANHYDRIDE 2.9g.The aqueous solution after 5 ~ 10min, 3.2g ammonium persulphate and 22.2g distilled water being mixed with water adds, and time for adding is 3 hours, dropwises rear insulation 2 hours.Then be cooled to 45 DEG C, add 40%NaOH solution 6.0g, be neutralized to pH=6.0, obtained concentration is the polycarboxylic acid super-plasticizer sample 5 of 40%.Then the spray-dried method of polycarboxylic acid super-plasticizer solution of neutralization is obtained polycarboxylic acid super-plasticizer powder product.Spray drying parameters is: inlet temperature 200 ° of C, and air outlet temperature is 90 DEG C, centrifugal turntable rotating speed 19000r/min.
Comparative example 6
In the four-hole boiling flask that stirring is housed, add m=53, n=0 isobutene alcohol ethers polymeric monomer 100g and distilled water 120g fully stir, and are warming up to 80 DEG C.Vinylformic acid 5.6g, methylene-succinic acid 2.9g, Thiovanic acid 0.9g and 22.0g distilled water are formulated as solution A; By 5.3g concentration be 30% hydrogen peroxide be dissolved in 22.0g distilled water and be formulated as solution B.Polymeric monomer be warming up to 80 DEG C and completely dissolve after start to drip solution A and B respectively simultaneously, time for adding is 2 hours, dropwises rear insulation 2 hours.Then be cooled to 45 DEG C, add 40%NaOH solution 6.0g, be neutralized to pH=6.0, obtained concentration is the polycarboxylic acid super-plasticizer sample 6 of 40%.By in the spray-dried method of polycarboxylic acid super-plasticizer solution of becoming reconciled obtain polycarboxylic acid super-plasticizer powder product, spray drying parameters is: inlet temperature 150 DEG C, and air outlet temperature is 80 DEG C, centrifugal turntable rotating speed 20000r/min.
Implementation result
1. rate of water loss experiment: laboratory sample is dripped skim in weighing bottle, and place in baking oven carry out drying, measure its rate of water loss and observe dehydration after state, experimental result is as table 1:
At table 1.80 DEG C, different sample rate of water loss compares
Can be drawn by table 1 result, the embodiment 3,4 containing propylene oxide component in polymeric monomer 1 hour at 80 DEG C can by moisture evaporation completely, and comparative example just can by water base evaporation completely at 3 hours.It can thus be appreciated that the present invention obtains the rate of water loss that sample accelerates polycarboxylic acid super-plasticizer, can significantly enhance productivity in process of production, and firmly crisp after drying, be easy to store and transport.
2. spray drying experiment
Table 2 spraying dry obtains the performance of powdery water-reducing agent
The polycarboxylate water-reducer of example of the present invention can make uniform powdered granule, and trickling property is good, without blocking in spray process, without block.
3. cement paste experiment: paste flowing degree experiment is tested according to GB8077-2000 " concrete admixture homogeneity experimental technique " relevant regulations, the results are shown in Table 3:
Table 3. starches experimental result only
Table 3 result shows, polycarboxylic acid super-plasticizer of the present invention has good initial dispersion and retention, can meet and exceed the comparative sample only containing oxyethane composition, under the prerequisite with better dehydration property, have good dispersing property simultaneously.
4. concrete experiments: concrete experiments is tested according to concrete GB8076-2008 " concrete admixture " relevant regulations, test each source material mixture ratio and experimental result in table 4:
Table 4. concrete proportioning and experimental result thereof
Note: in test, the solid volume of the folding of superplasticizer is 0.16%, and kg/m presses in each material mixture ratio unit
3calculate.
Table 4 result shows, in polycarboxylic acid super-plasticizer, introduce propylene oxide, hydrophilicly also improves the concrete slump and divergence and hold facility thereof simultaneously, ensure that concrete serviceability what change superplasticizer molecule.And the concrete intensity of this invention superplasticizer of admixture also makes moderate progress, its each age strength all can reach or higher than only containing the comparative sample of oxyethane composition.
Claims (6)
1. prepare a method for powder polycarboxylic acid superplasticizer, it is characterized in that, comprise the following steps:
With persulphate or, hydrogen peroxide or the redox system that formed for oxygenant with persulphate, hydrogen peroxide be for initiator, with unsaturated ester class or ethers polymeric monomer a, unsaturated carboxylic acid or its acid anhydrides b, unsaturated amides and derivative c thereof for reaction monomers, add chain-transfer agent d, carry out aqueous solution polymerization at 20 ~ 80 DEG C; Polymerization reaction time is 3 ~ 6 hours, and react complete and be cooled to not higher than 45 DEG C, add alkaline aqueous solution and be neutralized to pH=7 ~ 9, it is 40 ~ 80% finished products that discharging obtains massfraction, initiator and each reaction monomers disposable add or drip add;
Wherein, the mol ratio of each reactant is a:b:c:d=1:2.0 ~ 5.0:0 ~ 5.0:0 ~ 2.0; The mol ratio of initiator amount and polymeric monomer a is 0.05 ~ 2:1, and is mixed with the aqueous solution and adds;
Described unsaturated ester class polymeric monomer is the Esterification obtained polymeric monomer of acrylic or methacrylic, and described unsaturated ether polymeric monomer is allyl ether series, iso-butylene or prenol beginning polymeric monomer; And unsaturated ester class and ethers polymeric monomer are the random or block polymer comprising oxyethane, propylene oxide; Its chemical formula is as follows:
formula (1)
In formula (1): R is ester class or the ethers end group of polymeric monomer;
The ratio of described unsaturated ester class or ethers polymeric monomer oxypropylene and molar is m:(m+n)=0.1 ~ 0.95;
Described unsaturated ester class or the oxyethane of ethers polymeric monomer or polymerization degree m+n=10 ~ 112 of propylene oxide.
2. method according to claim 1, is characterized in that: described unsaturated carboxylic acid or its acid anhydrides b are vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, maleic anhydride.
3. method according to claim 1, is characterized in that: described unsaturated amides and derivative c thereof are acrylamide, 2-acrylamide-2-methylpro panesulfonic acid.
4. require described method according to right 1, it is characterized in that: described chain-transfer agent is methylpropene sodium sulfonate, propenyl sodium sulfonate, Thiovanic acid, thiohydracrylic acid, n-dodecyl mercaptan.
5. method according to claim 1, is characterized in that: alkaline aqueous solution used is the NaOH aqueous solution, the Na2SO3 aqueous solution, trolamine or quadrol.
6. method according to claim 1, it is characterized in that: after neutralization, obtain polycarboxylic acid super-plasticizer powder product in pH value spray-dried method of polycarboxylic acid super-plasticizer solution in 7 ~ 9 scopes, particle size range is at 20 ~ 160 μm, and water ratio is less than 4%; Spray drying parameters is: inlet temperature 150 DEG C ~ 250 DEG C, and air outlet temperature is 80 DEG C ~ 120 DEG C, centrifugal turntable rotating speed 12000 ~ 20000r/min.
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| CN103923276A (en) * | 2014-04-28 | 2014-07-16 | 中海油能源发展股份有限公司惠州石化分公司 | Method for synthesizing polyether-type polycarboxylate water reducer |
| CN105037646B (en) * | 2015-07-17 | 2018-05-29 | 清华大学 | A kind of polymer nanocomposite/micro particles additive and preparation method thereof |
| CN105036590B (en) * | 2015-07-20 | 2017-10-24 | 苏州市兴邦化学建材有限公司 | A kind of modified polycarboxylic acid powder water reducer being exclusively used in mobility mortar |
| CN105111387B (en) * | 2015-10-08 | 2017-09-15 | 南京瑞迪高新技术有限公司 | A kind of preparation method of low entraining type solid poly carboxylic acid series water reducer |
| CN105776937A (en) * | 2016-04-16 | 2016-07-20 | 南京友西科技股份有限公司 | Method for preparing dry powder polycarboxylate superplasticizer |
| MY197463A (en) * | 2017-11-27 | 2023-06-19 | Kzj New Mat Group Co Ltd | A method for preparing a dosage low-sensitive typed polycarboxylate superplasticizer at low temperature |
| CN108275941B (en) * | 2018-01-25 | 2020-07-14 | 龙南恒沣建材有限公司 | Fair-faced concrete composite additive and fair-faced concrete |
| CN111747671A (en) * | 2019-03-26 | 2020-10-09 | Sika技术股份公司 | High water-reducing powder formulation for dry mortar |
| CN112897929B (en) * | 2021-01-26 | 2022-04-26 | 山东同盛建材有限公司 | Slow-release polycarboxylate superplasticizer microsphere and preparation method thereof |
| CN113603840B (en) * | 2021-09-06 | 2023-09-19 | 抚顺东科精细化工有限公司 | Preparation method of rust-proof slow-release polycarboxylic acid superplasticizer |
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