CN105061689A - Preparation method of powdery polycarboxylic acid high-performance water reducing agent - Google Patents
Preparation method of powdery polycarboxylic acid high-performance water reducing agent Download PDFInfo
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- CN105061689A CN105061689A CN201510417460.9A CN201510417460A CN105061689A CN 105061689 A CN105061689 A CN 105061689A CN 201510417460 A CN201510417460 A CN 201510417460A CN 105061689 A CN105061689 A CN 105061689A
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Abstract
The invention provides a powdery polycarboxylic acid high-performance water reducing agent which can be quickly dissolved in water and further provides a polymerization method of the polycarboxylic acid high-performance water reducing agent. The polycarboxylic acid high-performance water reducing agent is obtained through free-radical bulk polymerization of small monomers and unsaturated polyoxyethylene ether in the absence of any solvent, the polymerization technology is simple, the gel effect which can occur during bulk polymerization production can be effectively avoided through polymerization technology design, and the method has the characteristics of controllable production process and stable product performance. Besides, the invention further provides a method for preparing powder, which can be quickly dissolved in water, from polymerization products. The powdery polycarboxylic acid high-performance water reducing agent prepared with the method has cement paste fluidity, retention capacity and concrete application performance similar to those of common liquid polycarboxylic acid water reducing agents, has the characteristic of capability of being quickly dissolved, can be widely applied to the concrete and mortar fields and contains no solvent, and the transportation cost is saved.
Description
Technical field
The present invention relates to chemical technology field, more specifically, relate to a kind of preparation method of powdery polycarboxylic acid high-performance water reducing agent.
Background technology
Concrete has become the basis of human lives, is the maximum material of construction of current consumption.Concrete admixture is the BSA in concrete except cement, sand, stone, water.It plays very important role in the application of high performance concrete.Polycarboxylate water-reducer is the good water reducer kind of a kind of over-all properties, and it has higher water-reducing rate and good slump-retaining.Present polycarboxylate water-reducer mostly is the liquid product about 40% mass concentration, due to the performance that it is superior, makes it more and more in various priority project.But sometimes because engineering construction place is comparatively far away, cause transportation cost constantly to increase, thus development high density or solid poly carboxylic acid product be reduce transportation cost and promote polycarboxylate water-reducer in various places widely used essential condition.
Current high-efficiency water-reducing agent of poly-carboxylic acid is generally carry out aqueous free radical polymerization under the existence of initiator.Polymerization reaction system increasing concentrations can cause system viscosity in reaction process to increase, and segment is reset and is hindered, reactive terminal even may be embedded, and double-basis stops difficulty.When reaction proceeds, when viscosity continues to increase, the activity level of reaction monomers can be hindered, cause partial polymerization transformation efficiency too high and badly influence the final performance of product.The concentration of polyreaction during synthesis is improved in commercial process, often cause the sharply decline of product performance, therefore poly carboxylic acid production concentration is generally 20% ~ 40%, should not store and transport, and the situation needing solid high-efficiency water reducer as dry-mixed mortar etc. can not be applicable to, limit it and apply widely.Therefore not solvent-laden solid high-performance polycarboxylate water-reducer is researched and developed, especially can rapidly-soluble powdery polycarboxylic acid high-performance water reducing agent, there is important effect for advancing the development of polycarboxylate water-reducer industry.
Patent CN102372828A reports a kind of preparation method of solid polycarboxylic acid water reducing agent.The method adopts the monomer containing unsaturated group to react in organic solvent, add alkaline matter neutralization after the completion of reaction and prepare polycarboxylate water-reducer through centrifuging treatment, more obtained poly carboxylic acid added water and obtains solid polycarboxylic acid water reducing agent through drying treatment.The method can obtain the polycarboxylate water-reducer of pure solid, but need to use organic solvent as one or more in alcohol, aromatic hydrocarbon, unsaturated aliphatic hydrocarbon, aliphatic saturated hydrocarbon, ester or ketone, and then need through the aftertreatment such as centrifugal, dry, process is more loaded down with trivial details, especially can produce more waste liquid and need process, add cost.
Patent CN102936349B discloses a kind of production method of solid polycarboxylic acid water reducing agent.The method uses microwave to carry out drying to the polycarboxylate water-reducer aqueous solution, solve the problem of spray dried prod performance loss, but the method needs before microwave treatment to carry out vacuum concentration to water reducer, does not have fundamentally workout cost problem.
Patent CN1844021A discloses a kind of concentrated method of polycarboxylate water-reducer, but due to polycarboxylate water-reducer be hydrophilic, this method concentrate the polycarboxylate water-reducer that obtains often concentration can only reach about 50%, still containing a large amount of water.
Patent CN101824125A reports a kind of preparation method of powdery polycarboxylic acid high-performance water reducer.This patent obtains powdery polycarboxylic acid high-performance water reducer by spray-dired method, but traditional powder injection process, that vertical or centrifugal technique is all undesirable, its major cause is the impact that water reducer is subject to high temperature in the process of dusting, continue to aggregate into the material of more macromolecule, cause losing water-reducing property, even lump, and the energy consumption of drying process with atomizing is high, adds cost.
Obtain numerous patent such as solid or powder polycarboxylic acids water reducing agent except above from the water of polycarboxylate water-reducer or the solution of organic solvent, also have patent to use the method for solvent-free preparation polycarboxylate water-reducer.
Patent CN102993387B and patent CN103012694B individually discloses the method using bulk polymerization to obtain ethers and ester class polycarboxylate water-reducer, although the two is of different types, but thinking is consistent: use mass polymerization to obtain the polycarboxylate water-reducer of the liquid state of solvent-free existence at a certain temperature, then cooling obtains solid polycarboxylic acid water reducing agent.But the initiator of aforementioned two patents and monomer are all once drop in reactor, rate of heat release is there is fast in reality amplification is produced, and then the probability causing gel effect to occur increases greatly, affect the stability of product performance, even cause production safety problem.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.
For this reason, the object of an aspect of of the present present invention there is provided a kind of powdery polycarboxylic acid high-performance water reducing agent.
The object of another aspect of the present invention there is provided that a kind of production technique is simple, low production cost, production process are controlled and the preparation method of the powdery polycarboxylic acid high-performance water reducing agent that product performance are stable.
For achieving the above object, The embodiment provides a kind of preparation method of powdery polycarboxylic acid high-performance water reducing agent.
The powdery polycarboxylic acid high-performance water reducing agent that embodiments of the invention provide, adopt bulk polymerization, designed by polymerization technique, realize initiator, temperature of reaction, the efficient combination of reaction monomers and polymerization technique, comprise and select suitable initiator, temperature of reaction, monomer, monomer participates in the mode of reaction system, reaction times and very important two-stage reaction method reduce the accumulation of polyreaction heat and heat, avoid gel effect to occur, ensure that polyreaction is stable to carry out, and obtain powdery polycarboxylic acid high-performance water reducing agent product by the mode of cutting into slices and pulverize.
In addition, the powdery polycarboxylic acid high-performance water reducing agent that embodiments of the invention provide also has following additional technical feature:
According to one embodiment of present invention, described powdery polycarboxylic acid high-performance water reducing agent has less particle diameter, can be dissolved in the water in 30 ~ 180 seconds.
The component that the powdery polycarboxylic acid high-performance water reducing agent preparation method that this enforcement provides comprises and mass ratio relation thereof, the performance of powdery polycarboxylic acid high-performance water reducing agent of the present invention can be played better, and make powdery polycarboxylic acid high-performance water reducing agent performance of the present invention have higher stability, solving the problems of the prior art better, is a preferred implementation.
Embodiments of the invention additionally provide a kind of preparation method of powdery polycarboxylic acid high-performance water reducing agent, and its polyreaction is divided into two sections to carry out, and comprise following step, wherein step 101-103 belongs to precondensation stage, and step 104 belongs to continuation step of reaction:
Step 101, adds in reactor by unsaturated Soxylat A 25-7, and intensification thawing becomes liquid;
Step 102, is adjusted to certain temperature by the reactor containing the unsaturated Soxylat A 25-7 be in a liquid state, and drops into initiator wherein;
Step 103, at the uniform velocity drips the mixing liquid of minor comonomer and molecular weight regulator within a certain period of time;
Step 104, after the mixing dropping liquid in described step 103 drips, adds initiator described in step 101, continues reaction certain hour;
Step 105, after described in step 104, insulation terminates, product is introduced slicing machine and is obtained certain thickness polycarboxylate water-reducer thin slice, then adds in pulverizer and pulverizes, obtain powdery polycarboxylic acid high-performance water reducing agent product.
Aforesaid method according to the present invention prepares powdery polycarboxylic acid high-performance water reducing agent, polymerization technique is simple, and designed by polymerization technique, realize the efficient combination of initiator, temperature of reaction, reaction monomers and polymerization technique, the gel effect that may run in can effectively avoiding mass polymerization to produce, has the advantages that production process is controlled, product performance are stable.And the powdery polycarboxylic acid high-performance water reducing agent prepared by the present invention not only has the flowing degree of net paste of cement close with common liq polycarboxylate water-reducer and hold facility, concrete application performance, there is rapidly-soluble feature simultaneously, concrete and field of mortar can be widely used in, and not containing solvent, save transportation cost.
According to one embodiment of present invention, in described step 101, the polymerization of described powdery polycarboxylic acid high-performance water reducing agent use raw material---the number-average molecular weight of unsaturated Soxylat A 25-7 is 1000-5000.
In described step 102, before dropping into initiator, the temperature of reactor containing the unsaturated Soxylat A 25-7 be in a liquid state is adjusted to 50-80 DEG C.And, in described step 102, initiator used is dibenzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, Diisopropyl azodicarboxylate, tert-Butyl peroxypivalate, azo-bis-isobutyrate hydrochloride, 2, 2-azo two (2-methylbutyronitrile), azo isobutyl cyano group methane amide, azo diisobutyl ether imidazole hydrochloride, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, one or more mixtures in 2,2'-Azobis(2,4-dimethylvaleronitrile), and the mass ratio of total monomer (comprising unsaturated Soxylat A 25-7 and minor comonomer) is 0.003-0.075: 1 described in consumption and step 101 and step 103.
According to one embodiment of present invention, in described step 103, described minor comonomer is a kind of vinyl monomer, as one or more mixtures in vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid, methylene-succinic acid styracin; And the more important thing is that the mixing liquid of minor comonomer and molecular weight regulator at the uniform velocity drips to participate in reaction, time for adding is 1.5-5 hour.
Adopt above-mentioned initiator of the present invention, temperature of reaction, monomer and the combination of polymerization technique that acrylic monomer and molecular weight regulator mixed solution at the uniform velocity dripped within the time extended effectively can reduce generation and the accumulation of the reaction heat in bulk polymerisation process, and then in suppression bulk polymerisation process, local temperature rise is too fast and then cause the appearance of gel effect, avoids having an impact to product performance and occurring industrial accident.
According to one embodiment of present invention, in described step 104, described in the initiator added be the initiator described in step 101, adding the initiator mass ratio dropped in initiator and step 101 is 0.025-0.5: 1.And the described time of continuing reaction is 0.5-3 hour.
Above-mentioned two sections of the present invention are adopted to answer method and step 101-step 103 to belong to first paragraph and the precondensation stage of reaction, and step 104 add the continuation step of reaction that initiator belongs to subordinate phase, this method can effectively regulate and control reaction heat and release stage by stage, and effectively can improve the transformation efficiency of monomer, actively impact is produced on the performance of powdery polycarboxylic acid water reducer.
According to one embodiment of present invention, in described step 105, the product after described insulation polymerization is without the direct import slices machine of cooling, and described slicing machine working temperature is 50-70 DEG C.The sheet thickness of the polycarboxylate water-reducer obtained after section is 0.5-5 millimeter.And, in described step 105, it is one or more couplings in crusher (product fineness is below 60 orders), pulverizer (product fineness is 60-120 order), ultrafine crusher (product fineness is 120-300 order), supper micron mill (product fineness is more than 300 orders) that described polycarboxylate water-reducer thin slice joins described pulverizer kind, and pulverizer operating temperature range is-10-30 DEG C.The described powdery polycarboxylic acid high-performance water reducing agent product cut size obtained is 0.05-1 millimeter, can be dissolved in the water in 30 ~ 180 seconds.
Above-mentioned section according to the present invention adds the method for pulverizing, can while the powdery polycarboxylic acid high-performance water reducing agent obtaining size tunable, prevent the phenomenons such as the caking caused due to local temperature rise in crushing process, sticky wall, so obtain demand can in water rapidly-soluble powdery polycarboxylic acid high-performance water reducing agent.
Additional aspect of the present invention and advantage become obvious by description part below, or are recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 is the schematic flow sheet of the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to one embodiment of the invention.
Embodiment
In order to more clearly understand above-mentioned purpose of the present invention, feature and advantage, below in conjunction with the drawings and specific embodiments, the present invention is further described in detail.It should be noted that, when not conflicting, the feature in the embodiment of the application and embodiment can combine mutually.
Set forth a lot of detail in the following description so that fully understand the present invention; but; the present invention can also adopt other to be different from mode described here to implement, and therefore, protection scope of the present invention is not by the restriction of following public specific embodiment.
The preparation method of powdery polycarboxylic acid high-performance water reducing agent is according to some embodiments of the invention described with reference to the accompanying drawings.
A kind of powdery polycarboxylic acid high-performance water reducing agent provided according to some embodiments of the invention has less particle diameter, can be soluble in water in 30 ~ 180 seconds.
The powdery polycarboxylic acid high-performance water reducing agent that the above embodiment of the present invention provides, employing bulk polymerization obtains, and what distinguish with the method in some patents is that the present invention is designed by polymerization technique, realize the efficient combination of initiator, temperature of reaction, reaction monomers and polymerization technique, comprise and select suitable initiator, temperature of reaction, monomer, monomer to participate in the mode of reaction system, reaction times and very important two-stage reaction method etc.First, bulk technique is adopted to have the advantage that technique is simple, energy consumption is little; Secondly, adopt and above-mentioned initiator, temperature of reaction, reaction monomers and polymerization technique are carried out efficient combination, comprise the heats that can effectively reduce in bulk polymerization such as selecting the mode of suitable initiator, temperature of reaction, monomer, monomer participation reaction system, reaction times and very important two-stage reaction method to produce and accumulation, and then suppress the appearance of gel effect; Again, the continuation step of reaction of above-mentioned two-stage method has an advantage namely effectively can improve the transformation efficiency of monomer, produces actively impact to the performance of powdery polycarboxylic acid water reducer.
Further, above-mentioned example of the present invention, have employed the method that section adds pulverizing, can while the powdery polycarboxylic acid high-performance water reducing agent obtaining size tunable, prevent the phenomenons such as the caking caused due to local temperature rise in crushing process, sticky wall, so obtain demand can in water rapidly-soluble powdery polycarboxylic acid high-performance water reducing agent.
It should be noted that, the mode of above-mentioned employing mass ratio represents the quantitative relationship between each component, be to weigh convenient in actual production process and weighing accurately, the mode such as volume ratio or mol ratio can certainly be adopted to represent quantitative relationship between each component.
It should be noted that, powdery polycarboxylic acid high-performance water reducing agent of the present invention can be widely used in the field such as concrete, mortar, has higher water-reducing rate, and saves transportation cost.
As shown in Figure 1, The embodiment provides a kind of preparation method of powdery polycarboxylic acid high-performance water reducing agent, it is characterized in that, polyreaction is divided into two sections to carry out, comprise following step, wherein step 101-103 belongs to precondensation stage, and step 104 belongs to continuation step of reaction:
Step 101, adds in reactor by unsaturated Soxylat A 25-7, and intensification thawing becomes liquid;
Step 102, is adjusted to certain temperature by the reactor containing the unsaturated Soxylat A 25-7 be in a liquid state, and drops into initiator wherein;
Step 103, at the uniform velocity drips the mixing liquid of minor comonomer and molecular weight regulator within a certain period of time;
Step 104, after the mixing dropping liquid in described step 103 drips, adds initiator described in step 101, continues reaction certain hour;
Step 105, after described in step 104, insulation terminates, product is introduced slicing machine and is obtained certain thickness polycarboxylate water-reducer thin slice, then adds in pulverizer and pulverizes, obtain powdery polycarboxylic acid high-performance water reducing agent product.
Aforesaid method according to the present invention prepares powdery polycarboxylic acid high-performance water reducing agent, polymerization technique is simple, and designed by polymerization technique, the gel effect that may run in can effectively avoiding mass polymerization to produce, has the advantages that production process is controlled, product performance are stable.And the powdery polycarboxylic acid high-performance water reducing agent prepared by the present invention not only has the flowing degree of net paste of cement close with common liq polycarboxylate water-reducer and hold facility, concrete application performance, there is rapidly-soluble feature simultaneously, concrete and field of mortar can be widely used in, and not containing solvent, save transportation cost.
Moreover, the powdery polycarboxylic acid high-performance water reducing agent that the above embodiment of the present invention provides, employing bulk polymerization obtains, and what distinguish with the method in some patents is that the present invention is designed by polymerization technique, realize the efficient combination of initiator, temperature of reaction, reaction monomers and polymerization technique, comprise and select suitable initiator, temperature of reaction, monomer, monomer to participate in the mode of reaction system, reaction times and very important two-stage reaction method etc.First, bulk technique is adopted to have the advantage that technique is simple, energy consumption is little; Secondly, adopt and above-mentioned initiator, temperature of reaction, reaction monomers and polymerization technique are carried out efficient combination, comprise the heats that can effectively reduce in bulk polymerization such as selecting the mode of suitable initiator, temperature of reaction, monomer, monomer participation reaction system, reaction times and very important two-stage reaction method to produce and accumulation, and then suppress the appearance of gel effect; Again, the continuation step of reaction of above-mentioned two-stage method has an advantage namely effectively can improve the transformation efficiency of monomer, produces actively impact to the performance of powdery polycarboxylic acid water reducer.
Further, above-mentioned example of the present invention, have employed the method that section adds pulverizing, can while the powdery polycarboxylic acid high-performance water reducing agent obtaining size tunable, prevent the phenomenons such as the caking caused due to local temperature rise in crushing process, sticky wall, so obtain demand can in water rapidly-soluble powdery polycarboxylic acid high-performance water reducing agent.
Particularly, in described step 101, the polymerization of described powdery polycarboxylic acid high-performance water reducing agent use raw material---the number-average molecular weight of unsaturated Soxylat A 25-7 is 1000-5000.
Further, in described step 102, before dropping into initiator, the temperature of reactor containing the unsaturated Soxylat A 25-7 be in a liquid state is adjusted to 50-80 DEG C.And, in described step 102, initiator used is dibenzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, Diisopropyl azodicarboxylate, tert-Butyl peroxypivalate, azo-bis-isobutyrate hydrochloride, 2, 2-azo two (2-methylbutyronitrile), azo isobutyl cyano group methane amide, azo diisobutyl ether imidazole hydrochloride, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, one or more mixtures in 2,2'-Azobis(2,4-dimethylvaleronitrile), and the mass ratio of total monomer (comprising unsaturated Soxylat A 25-7 and minor comonomer) is 0.003-0.075: 1 described in consumption and step 101 and step 103.
Further, in described step 103, described minor comonomer is a kind of vinyl monomer, as one or more mixtures in vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid, methylene-succinic acid styracin; And the more important thing is that the mixing liquid of minor comonomer and molecular weight regulator at the uniform velocity drips to participate in reaction, time for adding is 1.5-5 hour.
Adopt above-mentioned initiator of the present invention, temperature of reaction, monomer and the combination of polymerization technique that acrylic monomer and molecular weight regulator mixed solution at the uniform velocity dripped within the time extended effectively can reduce generation and the accumulation of the reaction heat in bulk polymerisation process, and then in suppression bulk polymerisation process, local temperature rise is too fast and then cause the appearance of gel effect, avoids having an impact to product performance and occurring industrial accident.
Further, in described step 104, described in the initiator added be the initiator described in step 101, adding the initiator mass ratio dropped in initiator and step 101 is 0.025-0.5: 1.And described soaking time is 0.5-3 hour.
Above-mentioned two sections of the present invention are adopted to answer method and step 101-step 103 to belong to first paragraph and the precondensation stage of reaction, and step 104 add the continuation step of reaction that initiator belongs to subordinate phase, this method can effectively regulate and control reaction heat and release stage by stage, and effectively can improve the transformation efficiency of monomer, actively impact is produced on the performance of powdery polycarboxylic acid water reducer.
Further, in described step 105, the product after described insulation polymerization is without the direct import slices machine of cooling, and described slicing machine working temperature is 50-70 DEG C.The sheet thickness of the polycarboxylate water-reducer obtained after section is 0.5-5 millimeter.And, in described step 105, it is one or more couplings in crusher (product fineness is below 60 orders), pulverizer (product fineness is 60-120 order), ultrafine crusher (product fineness is 120-300 order), supper micron mill (product fineness is more than 300 orders) that described polycarboxylate water-reducer thin slice joins described pulverizer kind, and pulverizer operating temperature range is-10-30 DEG C.The described powdery polycarboxylic acid high-performance water reducing agent product cut size obtained is 0.05-1 millimeter, can be dissolved in the water in 30 ~ 180 seconds.
Above-mentioned section according to the present invention adds the method for pulverizing, can while the powdery polycarboxylic acid high-performance water reducing agent obtaining size tunable, prevent the phenomenons such as the caking caused due to local temperature rise in crushing process, sticky wall, so obtain demand can in water rapidly-soluble powdery polycarboxylic acid high-performance water reducing agent.
Below in conjunction with embodiment, the present invention is described in detail further.
Embodiment one:
First 96g isobutenyl Soxylat A 25-7 (molecular weight is 2400) is added in reactor, be warming up to 65 DEG C, treat that isobutenyl Soxylat A 25-7 melts and be in a liquid state, be warming up to 70 DEG C, 1.09g benzoyl peroxide is dropped in still, after it dissolves, in 3h, drip the mixed solution of vinylformic acid and thiohydracrylic acid in reactor, wherein vinylformic acid is 12.96g, thiohydracrylic acid is 0.31g, after dropwising, add benzoyl peroxide 0.5g, after insulation 3h, reaction terminates.By reaction product import slices machine, slicing machine working temperature is 70 DEG C, obtain through section the polycarboxylate water-reducer thin slice that thickness is 1mm, then use supper micron mill to pulverize polycarboxylate water-reducer thin slice at-5 DEG C, obtain the powdery polycarboxylic acid water reducer that particle diameter is less than or equal to 0.05mm.
Embodiment two:
After the powdery polycarboxylic acid water reducer obtained in embodiment one is deposited 30 days at 30 DEG C, test its implementation result.
Embodiment three:
First 96g isopentene group Soxylat A 25-7 (molecular weight is 5000) is added in reactor, be warming up to 55 DEG C, treat that isopentene group Soxylat A 25-7 melts and be in a liquid state, be warming up to 80 DEG C, 0.32g Diisopropyl azodicarboxylate is dropped in still, after it dissolves, in 1.5h, drip the mixed solution of maleic anhydride and thiohydracrylic acid in reactor, wherein vinylformic acid is 6.91g, thiohydracrylic acid is 0.15g, after dropwising, add benzoyl peroxide 0.008g, after insulation 2h, reaction terminates.By reaction product import slices machine, slicing machine working temperature is 50 DEG C, obtain through section the polycarboxylate water-reducer thin slice that thickness is 5mm, then use ultrafine crusher to pulverize polycarboxylate water-reducer thin slice at-10 DEG C, obtain the powdery polycarboxylic acid water reducer that particle diameter is less than or equal to 0.1mm.
Embodiment four:
After the powdery polycarboxylic acid water reducer obtained in embodiment three is deposited 30 days at 5 DEG C, test its implementation result.
Embodiment five:
First 96g isobutenyl Soxylat A 25-7 (molecular weight is 1000) is added in reactor, be warming up to 50 DEG C, treat that isobutenyl Soxylat A 25-7 melts to be in a liquid state, fluid temperature in reactor is kept to be 50 DEG C, 9.53g azo dicyano valeric acid is dropped in still, after it dissolves, in reactor, the mixed solution of methylene-succinic acid and thiohydracrylic acid is dripped in 5h, wherein vinylformic acid is 31.10g, thiohydracrylic acid is 0.38g, after dropwising, add benzoyl peroxide 4.68g, after insulation 3h, reaction terminates.By reaction product import slices machine, slicing machine working temperature is 50 DEG C, obtain through section the polycarboxylate water-reducer thin slice that thickness is 0.5mm, then use crusher to pulverize polycarboxylate water-reducer thin slice at 30 DEG C, obtain the powdery polycarboxylic acid water reducer that particle diameter is less than or equal to 0.5mm.
Embodiment six:
After the powdery polycarboxylic acid water reducer obtained in embodiment five is deposited 30 days at 20 DEG C, test its implementation result.
Embodiment seven:
First 96g isopentene group Soxylat A 25-7 (molecular weight is 1500) is added in reactor, be warming up to 65 DEG C, treat that isopentene group Soxylat A 25-7 melts to be in a liquid state, fluid temperature in reactor is kept to be 65 DEG C, 2.50g 2,2'-Azobis(2,4-dimethylvaleronitrile) is dropped in still, after it dissolves, in reactor, the mixed solution of methacrylic acid and thiohydracrylic acid is dripped in 4h, wherein vinylformic acid is 20.74g, thiohydracrylic acid is 0.35g, after dropwising, add benzoyl peroxide 1.15g, after insulation 2h, reaction terminates.By reaction product import slices machine, slicing machine working temperature is 65 DEG C, obtain through section the polycarboxylate water-reducer thin slice that thickness is 2.5mm, then use crusher to pulverize polycarboxylate water-reducer thin slice at 15 DEG C, obtain the powdery polycarboxylic acid water reducer that particle diameter is less than or equal to 1mm.
Embodiment eight:
After the powdery polycarboxylic acid water reducer obtained in embodiment seven is deposited 30 days at 10 DEG C, test its implementation result.
Implementation result:
1. dissolution rate
For investigating the solubility property of the powdery polycarboxylic acid high-performance water reducing agent of the present invention's synthesis, in process of the test, the powdery polycarboxylic acid water reducer that the present invention synthesizes is mixed with 20% solution, the powdery polycarboxylic acid high-performance water reducing agent tested the present invention synthesizes adds in the water of metering until dissolve the required time completely.Adopt magnetic stirring apparatus to stir in process of the test, and keep often group test stir speed (S.S.) consistent, and the powder polycarboxylic acids water reducing agent (comparative example one) selecting existing commercially available employing spray drying process to prepare is as a comparison sample.Test-results is in table 1.
Table 1 dissolves required time when using each embodiment and comparative example 1 to prepare 20% solution
As can be seen from Table I, the present invention synthesizes the feature that the powdery polycarboxylic acid high-performance water reducing agent obtained has controllable dissolution rate.
2. flowing degree of net paste of cement
For investigating the performance of the powdery polycarboxylic acid high-performance water reducing agent of the present invention's synthesis, test is carried out according to GB/T8077-2012 " Methods for testing uniformity of concrete admixture ", test paste flowing degree and the hold facility thereof of each embodiment, comparative example 1 and existing commercially available polycarboxylate water-reducer (liquid, comparative example two).Use cement for east, Ji cement, water cement ratio is 0.29, and volume is 0.24%, for rolling over volume admittedly.Test-results is in table 2.
Table 2 flowing degree of net paste of cement result
As can be seen from Table II, the present invention synthesizes the powdery polycarboxylic acid high-performance water reducing agent that obtains compared with having higher water-reducing rate under low-dosage, and performance is better than comparative example one.
3. concrete slump and divergence
Divergence in concrete system of test determination each embodiment, comparative example one and comparative example two and slump retention performance.The concrete mix that test uses is: cement 2.4kg, flyash 1kg, breeze 0.6kg, sand 8.42kg, stone 9.88kg, water 1.8kg, and water reducer volume is 0.25%, for rolling over volume admittedly.Test-results is in table 3.
Table 3 concrete slump and divergence test-results
As can be seen from Table III, the present invention synthesizes the powdery polycarboxylic acid high-performance water reducing agent that obtains compared with having higher water-reducing rate under low-dosage, and performance is better than comparative example one and comparative example two.
In sum, the powdery polycarboxylic acid high-performance water reducing agent provided provided by the invention, polymerization technique is simple, and is designed by polymerization technique, the gel effect that may run in can effectively avoiding mass polymerization to produce, has the advantages that production process is controlled, product performance are stable.The powdery polycarboxylic acid high-performance water reducing agent prepared by the present invention not only has the flowing degree of net paste of cement close with common liq polycarboxylate water-reducer and hold facility, concrete application performance, there is rapidly-soluble feature simultaneously, concrete and field of mortar can be widely used in, and not containing solvent, save transportation cost.
In the description of this specification sheets, specific features, structure, material or feature that the description of term " embodiment ", " specific embodiment " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a preparation method for powdery polycarboxylic acid high-performance water reducing agent, is characterized in that, its polyreaction is divided into two sections to carry out, and comprise following step, wherein step 101-103 belongs to precondensation stage, and step 104 belongs to continuation step of reaction:
Step 101, adds in reactor by unsaturated Soxylat A 25-7, and intensification thawing becomes liquid;
Step 102, is adjusted to certain temperature by the reactor containing the unsaturated Soxylat A 25-7 be in a liquid state, and drops into initiator wherein;
Step 103, at the uniform velocity drips the mixing liquid of minor comonomer and molecular weight regulator within a certain period of time;
Step 104, after the mixing dropping liquid in described step 103 drips, adds initiator described in step 101, continues reaction certain hour;
Step 105, after described in step 104, insulation terminates, product is introduced slicing machine and is obtained certain thickness polycarboxylate water-reducer thin slice, then adds in pulverizer and pulverizes, obtain powdery polycarboxylic acid high-performance water reducing agent product.
2. the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to claim 1, is characterized in that,
In described step 101, the polymerization of described powdery polycarboxylic acid high-performance water reducing agent use raw material---the number-average molecular weight of unsaturated Soxylat A 25-7 is 1000-5000.
3. the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to claim 1, is characterized in that,
In described step 102, before dropping into initiator, the temperature of reactor containing the unsaturated Soxylat A 25-7 be in a liquid state is adjusted to 50-80 DEG C.And, in described step 102, initiator used is dibenzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, Diisopropyl azodicarboxylate, tert-Butyl peroxypivalate, azo-bis-isobutyrate hydrochloride, 2, 2-azo two (2-methylbutyronitrile), azo isobutyl cyano group methane amide, azo diisobutyl ether imidazole hydrochloride, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, one or more mixtures in 2,2'-Azobis(2,4-dimethylvaleronitrile), and the mass ratio of total monomer (comprising unsaturated Soxylat A 25-7 and minor comonomer) is 0.003-0.075: 1 described in consumption and step 101 and step 103.
4. the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to claim 1, is characterized in that,
In described step 103, described minor comonomer is a kind of vinyl monomer, as one or more mixtures in vinylformic acid, methacrylic acid, maleic anhydride, fumaric acid, methylene-succinic acid styracin; And the more important thing is that the mixing liquid of minor comonomer and molecular weight regulator at the uniform velocity drips to participate in reaction, time for adding is 1.5-5 hour.
5. the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to claim 1, is characterized in that,
In described step 104, described in the initiator added be the initiator described in step 101, adding the initiator mass ratio dropped in initiator and step 101 is 0.025-0.5: 1.And the described time of continuing reaction is 0.5-3 hour.
6. the preparation method of a kind of powdery polycarboxylic acid high-performance water reducing agent according to claim 1, is characterized in that,
In described step 105, the product after described insulation polymerization is without the direct import slices machine of cooling, and described slicing machine working temperature is 50-70 DEG C.The sheet thickness of the polycarboxylate water-reducer obtained after section is 0.5-5 millimeter.And, in described step 105, it is one or more couplings in crusher (product fineness is below 60 orders), pulverizer (product fineness is 60-120 order), ultrafine crusher (product fineness is 120-300 order), supper micron mill (product fineness is more than 300 orders) that described polycarboxylate water-reducer thin slice joins described pulverizer kind, and pulverizer operating temperature range is-10-30 DEG C.The described powdery polycarboxylic acid high-performance water reducing agent product cut size obtained is 0.05-1 millimeter, can be dissolved in the water in 30 ~ 180 seconds.
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| CN110642997A (en) * | 2019-10-18 | 2020-01-03 | 山东银泰化学技术有限公司 | High-adaptability powdery polycarboxylate superplasticizer and preparation method thereof |
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