CN108003301A - A kind of preparation method of viscosity reduction type polycarboxylate water-reducer - Google Patents
A kind of preparation method of viscosity reduction type polycarboxylate water-reducer Download PDFInfo
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- CN108003301A CN108003301A CN201711123413.9A CN201711123413A CN108003301A CN 108003301 A CN108003301 A CN 108003301A CN 201711123413 A CN201711123413 A CN 201711123413A CN 108003301 A CN108003301 A CN 108003301A
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- polycarboxylate water
- polyoxyethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The present invention provides a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, and viscosity reduction type polycarboxylate water-reducer is made by bulk polymerization, specifically includes following steps：(1) polyoxyethylene poly-oxygen propylene aether and polyoxyethylene ether are mixed, controlled at 40~60 DEG C, stirs evenly, then add initiator, and the mixture of unsaturated carboxylic acid, unsaturated carboxylic acid hydroxy alkyl ester and chain-transferring agent；(2) step (1) completes 1~1.5h of post curing, and cooling, is made viscosity reduction type polycarboxylate water-reducer.Bulk polymerization carries out at relatively low temperature, and workable, mild condition, energy consumption are low.Polycarboxylate water-reducer prepared by method described above is liquid at normal temperatures, and valid density is up to 100%, and shelf characteric is stablized, suitable for long-distance transportation and use；Water-reducing agent can effectively reduce concrete mix viscosity at the same time, be conducive to concrete stirring, transport and pumping, suitable for the popularization and application of high-rise engineering and high performance concrete.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to a kind of preparation side of viscosity reduction type polycarboxylate water-reducer
Method.
Background technology
Concrete has become the basis of human lives, is the construction material of current dosage maximum.Concrete admixture is
Fifth component in concrete in addition to cement, sand, stone, water, plays extremely important in the application of high performance concrete
Role.As one kind of concrete admixture, water-reducing agent (also known as super plasticizer, Superplasticizer) in concrete and
Under conditions of Yi Xing, cement consumption are constant, mixing water amount can be reduced, improve concrete strength, become concrete admixture
The hot spot of area research and the emphasis of exploitation.Water-reducing agent passes through surface-active action, complexing, electrostatic repulsion forces or three-dimensional row
Repulsion etc. is come the flocculent structure that hinders or destroy cement granules, so that while cement consumption is saved, ensures concrete and easily
Property and intensity.Polycarboxylate water-reducer has volume is low, water-reducing rate is high, the Molecular Design free degree is big and environmental-friendly etc.
Advantage, is known as third generation Concrete superplastizer, is widely used in the engineerings such as highway, bridge, tunnel, skyscraper.
In Concrete Industry, improve concrete intensity and durability become common recognition, especially high-strength concrete (>=
C60, C60 represent concrete under the conditions of standard curing, and the compression strength of 28 days is not less than 60MPa) and super high strength concrete (>=
C100, C100 represent concrete under the conditions of standard curing, the compression strength of 28 days is not less than 100MPa) wilderness demand, make
Concrete technology is obtained to quickly grow.It is guarantee concrete strength using low water binder ratio and improves the key measure of concrete durability
One of, but reduce water-cement ratio to also result in concrete viscosity larger, trigger concrete stirring, transport and pumping etc. are a series of to apply
Work problem, largely limits the popularization and application of high-strength shale ceramsite.Current adoptable viscosity reducing process master
If carry out in terms of organic admixture and admixture two.The organic admixture of addition is mainly air entraining agent, the incorporation of air entraining agent
Make to form a large amount of small spherical bubbles of closing in concrete mix, these microbubbles reduce aggregate as ball
The frictional resistance of intergranular, so that viscosity is reduced, but the effect of air entraining agent viscosity reduction is limited, the bubble of introducing is to the strong of high-strength concrete
Degree has a negative impact.In terms of admixture, presently mainly improve working performance of concrete by mixing a large amount of flyash, though
So incorporation flyash can reduce concrete viscosity, but for high-rise, high-strength or super high strength concrete its viscosity reducing effect very
It is limited.Therefore, how to solve to mix caused by preparing high-strength or super high strength concrete preparation process due to using low water binder ratio
Solidifying soil viscosity increase, has become the problem of concrete admixture field is in the urgent need to address.
The excellent water-reducing property of polycarboxylate water-reducer is widely recognized as by industry, however, substantial amounts of case history and research
Show, there are the problem of poor compatibility with concrete raw material for polycarboxylate water-reducer.Aggregate as concrete main composition into
Point, the clay in aggregate is due to that with huge specific surface area, can adsorb a large amount of mixing waters, reduce the flowing of cement concrete
Property；On the other hand, clay and cement granules competitive Adsorption polycarboxylate water-reducer, so as to influence the mobility of cement concrete, make
The viscosity of concrete mix dramatically increases, and is unfavorable for engineering pumping and high-rise engineering construction.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome can not effectively dropping for polycarboxylate water-reducer in the prior art
The problem of low concrete mixture viscosity.
For this reason, the present invention provides a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, by bulk polymerization system
The viscosity reduction type polycarboxylate water-reducer is obtained, specifically includes following steps：
(1) polyoxyethylene poly-oxygen propylene aether and polyoxyethylene ether are mixed, controlled at 40~60 DEG C, stirred evenly,
Then initiator, and the mixture of unsaturated carboxylic acid, unsaturated carboxylic acid hydroxy alkyl ester and chain-transferring agent are added；
In the step (1), the polyoxyethylene poly-oxygen propylene aether has the structure shown in Formulas I,
Wherein, R1For methyl or ethyl, R2For hydrogen or methyl, EO is oxyethylene group, and PO is oxypropylene group；M=30~
50, n=0~20；
(2) step (1) completes 1~1.5h of post curing, and cooling, is made viscosity reduction type polycarboxylate water-reducer.
Above-mentioned preparation method, the mixture are added dropwise in the form of single tube is added dropwise when 1.5~2 is small with constant speed
Complete.
Above-mentioned preparation method, further includes：After the viscosity reduction type polycarboxylate water-reducer is made, using in hydroxyethyl ethylenediamine
With the polycarboxylate water-reducer to pH value be 6~7 the step of.
Above-mentioned preparation method, in the step (1), polyoxyethylene poly-oxygen propylene aether：Polyoxyethylene ether：Initiator：Chain
The mass ratio of transfer agent is 1：(0.25~1):(0.01~0.03)：(0.01~0.03).
Above-mentioned preparation method, the polyoxyethylene poly-oxygen propylene aether are isobutenyl polyoxyethylene poly-oxygen propylene aether and different
At least one of pentenyl polyoxyethylene poly-oxygen propylene aether, the molecular weight of the polyoxyethylene poly-oxygen propylene aether for 1500~
2400。
Above-mentioned preparation method, the polyoxyethylene poly-oxygen propylene aether are prepared by the following method：
Mixed using unsaturated alcohol as initiator with base catalyst, ethylene oxide and epoxy third are added under oxygen-free environment
The mass ratio of alkane, the ethylene oxide and the propylene oxide is 1：(0.1~0.3)；The unsaturated alcohol and the epoxy second
With the propylene oxide polymerisation occurs for alkane, and controlling reaction temperature is 100 DEG C~130 DEG C, is made containing unsaturated polyoxyethylene
The reaction product of polyethenoxy ether；
Wherein, the unsaturated alcohol is at least one of isobutene alcohol and prenol.
Above-mentioned preparation method, the polyoxyethylene ether are isopentene group polyoxyethylene ether, and the polyoxyethylene ether is divided
Son amount is 500~1000.
Above-mentioned preparation method, the unsaturated carboxylic acid be acrylic acid, methacrylic acid, itaconic acid and maleic acid in extremely
Few one kind.
Above-mentioned preparation method, the unsaturated carboxylic acid hydroxy alkyl ester for hydroxy-ethyl acrylate, hydroxyethyl methacrylate,
At least one of hydroxypropyl acrylate and vinyl acetate.
Above-mentioned preparation method, the initiator are azo-bis-iso-dimethyl, azodiisobutyronitrile and peroxidating two
At least one of diisopropyl carbonate.
Above-mentioned preparation method, the chain-transferring agent are mercaptoethanol.
Above-mentioned preparation method, is cooled to temperature≤30 DEG C in the step (3).
The present invention has the following advantages that compared with the prior art：
1st, the preparation method of viscosity reduction type polycarboxylate water-reducer provided by the invention, can synthesize under room temperature for liquid and effectively
Polycarboxylate water-reducer of the concentration up to 100%.The molecular structure and molecular weight ranges of polyether macromonomer provided by the invention are on the one hand
With low melt temperature, the reaction temperature of bulk polymerization is reduced, synthetic reaction can be but carried out at 40~60 DEG C, avoid
Since phenomena such as local implode, reaction rate is controllable, not only solvent-free caused by high temperature during bulk polymerization
The polycarboxylate water-reducer that a kind of valid density is 100% is synthesized under environment, and the water-reducing agent synthesized has under aqueous environment
The performance of the product of synthesis.
On the other hand, polyoxyethylene poly-oxygen propylene aether makes the polycarboxylate water-reducer of synthesis introduce with terminal methyl and hold not
The polyoxyethylene poly-oxygen propylene aether side chain of saturation alkenyl, both polyoxyethylene poly-oxygen propylene aether and polyoxyethylene ether are collocated with each other,
To synthesize the polycarboxylate water-reducer stablized under room temperature for liquid and performance, there is the polycarboxylate water-reducer of synthesis length to take mutually
The polyether lateral chain matched somebody with somebody, forms good extended conformation, and water-reducing agent can play preferable space after being adsorbed onto on cement granules
Steric effect, persistently provides dispersibility.Due under water-reducer at normal temperature be liquid synthesis after can barrelling transport, it is not necessary to pass through
Cooling and solidifying and break process, simplify the process that product synthesizes, and reduce the production cost of product；The polycarboxylic acids diminishing of synthesis
Agent performance is stablized, and will not be separated out because of the rise of environment temperature and the growth of storage time, is adapted to long-distance transportation, greatly drop
Low cost of transportation.
The molecular structure of polyoxyethylene poly-oxygen propylene aether, introduces the hydrophobic group of terminal methyl, effectively in long polyether chains
The HLB value of the polycarboxylate water-reducer of synthesis is reduced, HLB value reduces the ability for the associated water that can reduce long polyether chains, so as to release
More Free waters are released, effectively reduce the viscosity of concrete.
Two kinds of polyether monomers are collocated with each other in preparation method provided by the invention, with unsaturated carboxylic acid, unsaturated carboxylic acid hydroxyl
Arrcostab forms the alkanes main chain with carboxylic acid group and hydrophilic polyether lateral chain under the action of initiator and chain-transferring agent
Pectination molecule structure.Unsaturated carboxylic acid hydroxyalkyl esters minor comonomer in synthesis material, can partly substitute unsaturated carboxylic acid,
Carboxylic acid hydroxyalkyl ester's class group is introduced at the same time on the main chain of polycarboxylate water-reducer, carboxylic acid hydroxyalkyl ester's class group is in cement alkalescence ring
The alcohol for discharging carboxylic group and small molecule can be slowly hydrolyzed in border, carboxylic group can be adsorbed on cement so as to ensure that diminishing
Agent is more firmly adsorbed on cement granules and is not easy to be adsorbed by soil, and improves the scattered of concrete by slowly discharging
Property, the alcohol of the small molecule in addition discharged, which can be intercalation into clay, to be gone so as to reduce absorption of the clay to water-reducing agent, effectively drop
Low concrete mixture viscosity.It is excellent with polycarboxylate water-reducer viscosity-reducing performance made from above-mentioned preparation method, it can effectively improve
The mobility of concrete mix, and be conducive to concrete stirring, transport and pumping, brought to concrete works good
Execution conditions, suitable for the popularization and application of high-rise engineering and high performance concrete.
The reaction process of polymerisation in bulk need not use water or organic solvent, avoid the toxic action of organic solvent,
Reaction process is environmentally protective, environmental friendliness is high.
2nd, unsaturated carboxylic acid hydroxy alkyl ester, unsaturated carboxylic acid are added dropwise with constant speed in preparation method provided by the invention
With the mixture of molecular weight regulator, and time for adding is controlled, be conducive to the reaction rate kept constant, improve the poly- carboxylic of synthesis
The molecular weight of sour water-reducing agent, reduces its distribution, and enhancing product improves polycarboxylate water-reducer to the applicability of concrete material
Viscosity reducing effect.
3rd, the mass ratio of polyoxyethylene poly-oxygen propylene aether provided by the invention, polyoxyethylene ether, initiator and chain-transferring agent
On the one hand it ensure that the high conversion of polymerisation, on the other hand can adjust the polyethers side of different length on polycarboxylate water-reducer
The blend proportion of chain, avoids being not easy mutually to wind between side chain, ensures that side chain forms good extended conformation, make polycarboxylic acids diminishing
The space steric effect of agent side chain and the electrostatic repulsion of the carboxylic acid group on polycarboxylate water-reducer main chain act synergistically, and hinder and break
The flocculent structure of bad cement granules, so that while cement consumption is saved, the easy property of work and intensity, raising that ensure concrete subtract
The application performance of aqua.
4th, the polyoxyethylene poly-oxygen propylene aether and the specific species of polyoxyethylene ether that the present invention selects have suitable space
Chemical constitution and polymerisation activation energy, both work in coordination, and effective reaction media can be used as to participate in polymerisation, reduced
The temperature of bulk polymerization, improve reactive polymeric rate, effectively control reaction efficiency, and synthesis is with high water-reducing property, room temperature
The polycarboxylate water-reducer for being liquid and effective content up to 100%.Polyoxyethylene ether and the high score that its middle-molecular-weihydroxyethyl is 500~1000
The polyoxyethylene ether of son amount ensure that bulk polymerization is completed in the environment of relative low temperature compared to having relatively low fusing point.
5th, unsaturated carboxylic acid, esters of unsaturated carboxylic acids, initiator and the chain-transferring agent and two kinds of polyether monomers that the present invention selects
Effectively coordinate, ensure the high polymerization efficiency of bulk polymerization, reaction of the unsaturated carboxylic acid under 40~60 DEG C of reaction temperature
Controllable-rate, reduces the autohemagglutination phenomenon of unsaturated carboxylic acid, avoids the long possibility of polycarboxylate water-reducer main chain.
The initiator that the present invention selects has suitable activation energy, can coordinate the melt temperature of polyether composition, 40
DEG C~60 DEG C at a temperature of trigger bulk polymerization, and reaction rate is suitable, can avoid caused by too fast reaction rate
Side reaction generation, ensure synthesis polycarboxylate water-reducer there is high water-reducing property.
Present invention selection mercaptoethanol advantageously forms the compact type with high sequence regularity as chain-transferring agent
Pectination polycarboxylic acids molecule, the range of molecular weight distributions of synthetic product is narrow, suitable size.In addition, mercaptoethanol is lived with chain tra nsfer
Property strong, advantage that toxicity is low and workable, under the volume requirement of same ratio, addition is few, can reduce reaction into
This.Compared with the chain-transferring agent such as mercaptopropionic acid and thioacetic acid, the chain transfer activity of mercaptoethanol is stronger, molecular weight controllability
By force, by the change of additive amount, system viscosity can be significantly adjusted, suitable for the polycarboxylate water-reducer of viscosity reduction type.
Embodiment
Illustrate embodiments of the present invention below by way of specific embodiment, unless otherwise stated, disclosed in this invention
Experimental method use the art routine techniques, used reagent and raw material can be bought by market in embodiment.
Embodiment 1
The present embodiment provides a kind of synthetic method of polycarboxylate water-reducer, following steps are specifically included：
1st, isopentene group polyoxyethylene poly-oxygen propylene aether is prepared
(1) prenol 85g and 0.15g KOH is added into reaction kettle, with air in nitrogen displacement kettle.
(2) treat that kettle temperature rises to 100~110 DEG C, start to be passed through ethylene oxide 1650g and propylene oxide 350g, keep poly-
It is 130 DEG C, reaction pressure 0.15Mpa to close reaction temperature, when curing 3 is small after, polyoxyethylene containing isopentene group polyoxy third is made
The reaction product of alkene ether.
(3) above-mentioned reaction product is neutralized, then degassing in reaction kettle, obtains m=15, n=20, average molecular weight
1892.38 isopentene group polyoxyethylene poly-oxygen propylene aether.
2nd, polycarboxylate water-reducer is prepared
(1) in four-hole boiling flask, isopentene group polyoxyethylene poly-oxygen propylene aether (m=15, the n=synthesized is added in step 1
20, average molecular weight 1892.38) 200g, isopentene group polyoxyethylene ether (average molecular weight 1000) 100g is added, is warming up to
40 DEG C, stirring and dissolving.
(2) temperature control adds azo-bis-iso-dimethyl 6g toward kettle is interior, stirs 10min at 60 DEG C, then interior with constant speed
Degree, the mixed solution (mass concentration for including 40g acrylic acid, 5g hydroxy-ethyl acrylates and 2g mercaptoethanols is added dropwise by single tube
98%), time for adding 2h.
(3) after completion of dropwise addition, continue to cure 1.5h, be then cooled to 30 DEG C, the viscosity reduction type polycarboxylic acids diminishing of liquid is made
Agent.
(4) add hydroxyethyl ethylenediamine into the viscosity reduction type polycarboxylate water-reducer of liquid to neutralize, it is 6 to adjust pH, is to obtain the final product had
Imitate the viscosity reduction type polycarboxylate water-reducer that concentration is 100%.
Embodiment 2
The present embodiment provides a kind of synthetic method of polycarboxylate water-reducer, following steps are specifically included：
1st, isobutenyl polyoxyethylene poly-oxygen propylene aether is prepared
(1) isobutene alcohol 90g and 0.20gKOH are added into reaction kettle, with air in nitrogen displacement kettle.
(2) treat that kettle temperature rises to 100 DEG C, start to be passed through ethylene oxide 1250g and propylene oxide 450g, keep polymerisation
Temperature is 130 DEG C, reaction pressure 0.20Mpa, when curing 3 is small after, the polyoxyethylene poly-oxygen propylene aether containing isobutenyl is made
Reaction product.
(3) above-mentioned reaction product is neutralized, then degassing in reaction kettle, obtains m=30, n=3, average molecular weight
1551.8 isobutenyl polyoxyethylene poly-oxygen propylene aether.
2nd, polycarboxylate water-reducer is prepared
(1) in four-hole boiling flask, isobutenyl polyoxyethylene poly-oxygen propylene aether (m=30, the n=synthesized is added in step 1
3, average molecular weight 1551.8) 150g, isopentene group polyoxyethylene ether (average molecular weight 500) 150g is added, is warming up to 45
DEG C, stirring and dissolving.
(2) temperature control adds azodiisobutyronitrile 3g toward kettle is interior, stirs 10min at 50 DEG C, then interior with constant speed, leads to
Cross single tube and the mixed solution (mass concentration for including 50g methacrylic acids, 2g hydroxy-ethyl acrylates and 4.5g mercaptoethanols is added dropwise
98%), time for adding 1.8h.
(3) after completion of dropwise addition, continue to cure 1h, be then cooled to 28 DEG C, the viscosity reduction type polycarboxylate water-reducer of liquid is made.
(4) add hydroxyethyl ethylenediamine into the viscosity reduction type polycarboxylate water-reducer of liquid to neutralize, it is 7 to adjust pH, is to obtain the final product had
Imitate the viscosity reduction type polycarboxylate water-reducer that concentration is 100%.
Embodiment 3
The present embodiment provides a kind of synthetic method of polycarboxylate water-reducer, following steps are specifically included：
1st, isopentene group polyoxyethylene poly-oxygen propylene aether is prepared
(1) prenol 100g and KOH 0.30g is added into reaction kettle, with air in nitrogen displacement kettle.
(2) treat that kettle temperature rises to 100~110 DEG C, start to be passed through ethylene oxide 1395g and propylene oxide 1300g, keep poly-
Close reaction temperature be 100~110 DEG C, reaction pressure 0.35Mpa, curing 3 it is small when after, be made polyoxyethylene containing isopentene group gather
The reaction product of oxypropylene ether.
(3) above-mentioned reaction product is neutralized, then degassing in reaction kettle, obtains m=35, n=10, average molecular weight
2192.62 isopentene group polyoxyethylene poly-oxygen propylene aether.
2nd, polycarboxylate water-reducer is prepared
(1) in four-hole boiling flask, isopentene group polyoxyethylene poly-oxygen propylene aether (m=35, the n=synthesized is added in step 1
10, average molecular weight 2192.62) 270g, isopentene group polyoxyethylene ether (average molecular weight 600) 67.5g is added, is warming up to
60 DEG C, stirring and dissolving.
(2) temperature control is total at 60 DEG C toward the interior addition azo-bis-iso-dimethyl of kettle and di-isopropyl peroxydicarbonate
2.7g, stirs 10min, and then interior with constant speed, being added dropwise by single tube includes 40g maleic acids, 5g hydroxyethyl methacrylates
With the mixed solution (mass concentration 98%) of 5.4g mercaptoethanols, time for adding 2h.
(3) after completion of dropwise addition, continue to cure 1.2h, be then cooled to 30 DEG C, the viscosity reduction type polycarboxylic acids diminishing of liquid is made
Agent.
(4) add hydroxyethyl ethylenediamine into the viscosity reduction type polycarboxylate water-reducer of liquid to neutralize, it is 6.5 to adjust pH, to obtain the final product
Valid density is 100% viscosity reduction type polycarboxylate water-reducer.
Embodiment 4
The present embodiment provides a kind of synthetic method of polycarboxylate water-reducer, following steps are specifically included：
1st, isobutenyl polyoxyethylene poly-oxygen propylene aether is prepared
(1) isobutene alcohol 100g and 0.25gKOH base catalyst is added into 2L reaction kettles, with air in nitrogen displacement kettle.
(2) treat that kettle temperature rises to 100~110 DEG C, start to be passed through ethylene oxide 1620g and propylene oxide 610g, keep poly-
It is 100 DEG C, reaction pressure 0.25Mpa to close reaction temperature, when curing 3 is small after, polyoxyethylene containing isobutenyl polyoxy third is made
The reaction product of alkene ether.
(3) above-mentioned reaction product is neutralized, then degassing in reaction kettle, obtains m=50, n=1, average molecular weight
2316.68 isobutenyl polyoxyethylene poly-oxygen propylene aether.
2nd, polycarboxylate water-reducer is prepared
(1) in four-hole boiling flask, isobutenyl polyoxyethylene poly-oxygen propylene aether (m=50, the n=synthesized is added in step 1
1, average molecular weight 2316.68) 180g, isopentene group polyoxyethylene ether (average molecular weight 600) 120g is added, is warming up to 40
DEG C, stirring and dissolving.
(2) temperature control adds azo-bis-iso-dimethyl 2g toward kettle is interior, stirs 10min at 40 DEG C, then interior with constant speed
Degree, the mixed solution (mass concentration for including 40g acrylic acid, 5g hydroxypropyl acrylates and 1.8g mercaptoethanols is added dropwise by single tube
98%), time for adding 2h.
(3) after completion of dropwise addition, continue to cure 1.5h, be then cooled to 30 DEG C, the viscosity reduction type polycarboxylic acids diminishing of liquid is made
Agent.
(4) add hydroxyethyl ethylenediamine into the viscosity reduction type polycarboxylate water-reducer of liquid to neutralize, it is 6 to adjust pH, is to obtain the final product had
Imitate the viscosity reduction type polycarboxylate water-reducer that concentration is 100%.
Detect example 1
High-strength concrete is prepared according to the C50 Concrete ratios shown in table 1, the air content of concrete is controlled 2.0
~2.5%, the divergence of concrete is controlled in 500~550mm；Reference《Standard for test methods of properties of ordinary concrete mixture standard》
(GB/T 50080-2016), tests the viscosity of concrete, slump is inverted in concrete outflow to be inverted the experiment of slump cylinder method
The used time of cylinder is smaller, represents that the viscosity of concrete is smaller.With commercially available water-reducing agent as a comparison, 1~embodiment of embodiment 4 is detected
The viscosity reducing effect of the polycarboxylate water-reducer of middle synthesis.Wherein, commercially available water-reducing agent as a comparison is the viscosity reduction type of 40% solid content
The viscosity reduction type polycarboxylate water-reducer PC415 of polycarboxylate water-reducer PJN and 56% solid content.
1 mix proportion of high-strength concrete of table (Kg/m3)
| C50 | Cement | Flyash (I grade) | Miberal powder | Sand (moisture content 5%) | Gravelstone | Great Shi | Water |
| 384 | 48 | 48 | 715 | 341 | 796 | 139 |
The application performance detection of 2 polycarboxylate water-reducer of table
As seen from the above table, in the case where controlling concrete initialization performance uniform condition, relative to commercially available polycarboxylic acids diminishing
Agent PCM and PC415, the used time that the lower concrete of water-reducing agent effect prepared by the method for the present invention flows out slump cylinder significantly subtract
It is small, illustrate the viscosity that concrete can be effectively reduced by polycarboxylate water-reducer prepared by the method for the present invention, and using the present invention
Water-reducing agent concrete mix encapsulation significantly better than the viscosity reduction mother liquor of commercially available different solid contents, mix and will not isolate even if crossing
Bleeding, working performance of concrete are greatly improved.Therefore, preparation method provided by the invention, effectively reduces polymerisation in bulk
Reaction temperature, reasonable control bulk polymerization speed, improve the conversion ratio of polymerisation, final synthesize under room temperature is liquid
State, valid density 100%, and it is capable of the polycarboxylate water-reducer of efficient viscosity-reducing performance.Polycarboxylate water-reducer solves the poly- carboxylic of tradition
The problem of sour water-reducing agent easily causes concrete mix viscosity excessive by adsorption by clay, the poor fluidity of cement concrete, favorably
Engineering pumping and high-rise engineering construction in concrete, suitable for large-scale commercial introduction and application.
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (12)
1. a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, it is characterised in that the drop is made by bulk polymerization
Viscous type polycarboxylate water-reducer, specifically includes following steps：
(1) polyoxyethylene poly-oxygen propylene aether and polyoxyethylene ether are mixed, controlled at 40~60 DEG C, stirred evenly, then
Add initiator, and the mixture of unsaturated carboxylic acid, unsaturated carboxylic acid hydroxy alkyl ester and chain-transferring agent；
In the step (1), the polyoxyethylene poly-oxygen propylene aether has the structure shown in Formulas I,
Wherein, R1For methyl or ethyl, R2For hydrogen or methyl, EO is oxyethylene group, and PO is oxypropylene group；M=30~50, n
=0~20；
(2) step (1) completes 1~1.5h of post curing, and cooling, is made viscosity reduction type polycarboxylate water-reducer.
2. preparation method according to claim 1, it is characterised in that the mixture is in the form of single tube is added dropwise, 1.5
~2 are added dropwise to complete when small with constant speed.
3. preparation method according to claim 1, it is characterised in that further include：The viscosity reduction type polycarboxylic acids diminishing is made
After agent, the step of viscosity reduction type polycarboxylate water-reducer to pH value is 6~7 is neutralized using hydroxyethyl ethylenediamine.
4. according to claim 1-3 any one of them preparation methods, it is characterised in that in the step (1), polyoxyethylene gathers
Oxypropylene ether：Polyoxyethylene ether：Initiator：The mass ratio of chain-transferring agent is 1：(0.25~1):(0.01~0.03)：(0.01~
0.03)。
5. according to claim 1-4 any one of them preparation methods, it is characterised in that the polyoxyethylene poly-oxygen propylene aether is
At least one of isobutenyl polyoxyethylene poly-oxygen propylene aether and isopentene group polyoxyethylene poly-oxygen propylene aether, the polyoxy second
The molecular weight of alkene polyethenoxy ether is 1500~2400.
6. preparation method according to claim 5, it is characterised in that the polyoxyethylene poly-oxygen propylene aether passes through with lower section
It is prepared by method：
Mixed using unsaturated alcohol as initiator with base catalyst, ethylene oxide and propylene oxide, institute are added under oxygen-free environment
The mass ratio for stating ethylene oxide and the propylene oxide is 1：(0.1~0.3)；The unsaturated alcohol and the ethylene oxide and institute
State propylene oxide and polymerisation occurs, controlling reaction temperature is 100 DEG C~130 DEG C, is made containing unsaturated polyoxyethylene polyoxy third
The reaction product of alkene ether；
Wherein, the unsaturated alcohol is at least one of isobutene alcohol and prenol.
7. according to claim 1-6 any one of them preparation methods, it is characterised in that the polyoxyethylene ether is isopentene group
Polyoxyethylene ether, the molecular weight of the polyoxyethylene ether is 500~1000.
8. according to claim 1-7 any one of them preparation methods, it is characterised in that the unsaturated carboxylic acid for acrylic acid,
At least one of methacrylic acid, itaconic acid and maleic acid.
9. according to claim 1-7 any one of them preparation methods, it is characterised in that the unsaturated carboxylic acid hydroxy alkyl ester is
At least one of hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and vinyl acetate.
10. according to claim 1-7 any one of them preparation methods, it is characterised in that the initiator is two isobutyl of azo
At least one of dimethyl phthalate, azodiisobutyronitrile and di-isopropyl peroxydicarbonate.
11. according to claim 1-7 any one of them preparation methods, it is characterised in that the chain-transferring agent is mercaptoethanol.
12. preparation method according to claim 1, it is characterised in that be cooled to temperature≤30 DEG C in the step (3).
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