CN107325236A - A kind of non-soil responsive type polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of non-soil responsive type polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
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Abstract
A kind of non-soil responsive type polycarboxylate water-reducer and preparation method thereof, water reducer is using 4 hydroxy butyl vinyl ether polymeric monomers, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer as comonomer, copolyreaction is carried out using initiator, chain-transferring agent as molecular regulation agent and is made, and the mass ratio of each component is：4 hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=(24~120):(4~8):(6~10):(10~20):(0.8~1.5):(0.4~2):(70~120).Present invention also offers the preparation method of water reducer.The water reducer of the present invention is insensitive to sandstone material clay content in concrete, applied in the high concrete of clay content, than traditional polycarboxylate water-reducer have higher water reducing ability and less slump-loss, solve traditional polycarboxylate water-reducer concrete application present in sandstone raw material soil sensitiveness the problem of.
Description
Technical field
The present invention relates to a kind of concrete admixture, more particularly to one kind are unwise to sandstone material clay content in concrete
The water reducer of sense, specifically a kind of non-soil responsive type polycarboxylate water-reducer, belongs to building material technical field.The present invention is also related to
And a kind of preparation method of polycarboxylate water-reducer, specifically a kind of preparation method of non-soil responsive type polycarboxylate water-reducer.
Background technology
Polycarboxylate water-reducer is as a kind of green, environment amenable concrete chemical admixture, because its function
Superiority is gradually widely used by industry.In many concrete workses, the tradition high-effective concrete such as naphthalene system is due to technical performance
Limitation, can not increasingly meet requirement of engineering.Polycarboxylate high performance water-reducing agent, according to scattered cement mechanism of action design
Effective molecular structure, with ultra-dispersed type, can prevent concrete slump loss without causing obvious slow setting, low-dosage is issued
Higher plasticizing effect is waved, mobility retentivity is good, cement adapts in wide, molecular configuration that the free degree is big, synthetic technology is more, Gao Xing
The leeway of energyization is very big, to concrete enhancing effect significantly, can reduce concrete shrinkage, and it is technical that harmful substance contents are extremely low etc.
Energy feature, is increasingly becoming the preferred additive for preparing high performance concrete.Especially since 21 century, country has been widely used in large-scale
Water conservancy, bridge, nuclear power, railway engineering.Soil sensitivity in sandstone is asked however, traditional polycarboxylate water-reducer generally faces
Topic, as China's sandstone material is increasingly deficient, material complexity is growing day by day, especially the high caused polycarboxylic acids diminishing of soil content
The problem of low loss of diminishing that agent occurs in application process is fast highlights increasingly.
Inventor retrieves following Patents documents：CN106008784A discloses a kind of concrete thinner and its system
Preparation Method, the thinner is formed by 4- hydroxy butyl vinyl ethers, unsaturated amides and unsaturated phosphate for polymerizable raw material.
It is the concrete thinner simple production process of preparation, good with polycarboxylate water-reducer adaptability, with the 0.01% of binder materials~
In 0.03% incorporation concrete, the workability of concrete can be obviously improved, low water binder ratio Under Concrete is effectively solved and glues
The problem of degree is big, pumping is difficult.CN103073687A discloses a kind of preparation method of high-dispersity polycarboxylic super plasticizer.Using
The synthetic method of Post functionalization is first esterified, using the methoxy poly (ethylene glycol) monomethyl ether and polypropylene glycol and methyl of different molecular weight
Acrylic acid is esterified, and introduces the different polyoxy alkyl alkene ethers side chain of length, then by radical polymerization introduce activity compared with
High (methyl) acrylate and sulfonate unsaturated monomer, and trimethoxy silane class unsaturated monomer is introduced, use
Trimethoxy silane substitutes part carboxyl, polymer is contained appropriate carboxyl and trimethoxy silane, so as to sulfate radical
Ion has stronger repellence, can have high dispersive property and dispersed holding capacity under low-dosage.
CN103450411A discloses a kind of preparation method of high-slump-retentionpolycarboxylate polycarboxylate water reducer, first by the poly- second of methoxyl group of different molecular weight
Glycol monomethyl ether and methacrylic acid, mix polymerization inhibitor, esterification a period of time, Ran Houyi are carried out under certain temperature and catalyst
Secondary property adds allyl alcohol, and the esterification that further esterification obtains the allyl methacrylate containing cross-linking monomer under the same conditions is single greatly
Body MP；Again by MP, unsaturated sulfonic acid salt, (methyl) esters of acrylic acid unsaturated monomer and chain-transferring agent, in Redox Initiator
Aqueous solution polymerization is carried out under system and cryogenic conditions, liquid caustic soda neutralization is eventually adding and obtains certain density polycarboxylate water-reducer.
CN101531747A discloses a kind of preparation method of polycarboxylic acid series high efficiency water reducing agent, with methoxy poly (ethylene glycol) monomethyl ether, third
Olefin(e) acid is the first synthesizing methoxy monomethyl polyethylene glycol acrylate ester polymeric monomer of raw material, is then esterified polymeric monomer and is total to acrylic acid
Combinate form is into high-efficiency water-reducing agent of poly-carboxylic acid.It is esterified in the synthesis of macromer methoxyl-polyethyleneglycol monomethyl ether acrylate and uses to benzene
Diphenol cooperates with inhibition with hydroquinone monomethyl ether, reduces the destructive rate of unsaturated double-bond, so makes the water reducer of synthesis effective
Content increase, improves concrete water-reducing ratio, function of slump protection enhancing.CN102181020A discloses a kind of amidatioon activated monomer
The method that copolyreaction synthesizes high performance water reducing agent of polyocarboxy acid, the method being polymerize again using first amidatioon prepares poly-carboxylic high-performance
Diminishing agent material, i.e., contain the methoxy polyoxyethylene ether of amino as reactant using (methyl) acrylic monomers and the other end,
A kind of polymerisable monomer is prepared by amidation process under catalyst action, then with (methyl) acrylic monomers, chain tra nsfer monomer
Use in alkaline solution and be made after copolymerization in the aqueous solution in the presence of initiator.CN102181062A discloses an a kind of step
Amidation process synthesizes the preparation method of high performance water reducing agent of polyocarboxy acid, and polycarboxylic acids is prepared using a direct reaction of step amidatioon method
High-performance water reducing agent material, i.e., contain the methoxy polyoxyethylene ether of amino as reaction using poly- (methyl) acrylic acid and the other end
Thing, is made in the presence of catalyst by amidation process.
How the above technology is for make water reducer turn into non-soil responsive type polycarboxylate water-reducer, to sand in concrete
Stone material clay content is insensitive, does not provide specific guidance program.
The content of the invention
Present invention aims at a kind of non-soil responsive type polycarboxylate water-reducer is provided, the water reducer is to sandstone in concrete
Material clay content is insensitive, is applied in the high concrete of clay content, with higher water reducing ability and less collapses
Degree of falling is lost, and sandstone raw material soil sensitiveness is asked present in concrete application with solving traditional polycarboxylate water-reducer
Topic.
Therefore, another technical problem to be solved by this invention is to provide a kind of non-soil responsive type polycarboxylic acids diminishing
The preparation method of agent.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of non-soil responsive type polycarboxylate water-reducer, its technical scheme is that it is with the big list of 4- hydroxy butyl vinyl ethers
Body, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, using initiator, chain-transferring agent as point
Sub- conditioning agent is made to carry out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic
Acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=(24~120):(4~8):
(6~10):(10~20):(0.8~1.5):(0.4~2):(70~120).
The unsaturated carboxylic acid is the one or more in acrylic acid, methacrylic acid, fumaric acid, maleic acid
Mixture (combination, its quality proportioning is arbitrary during combination)；The unsaturated sulfonic acid salt is sodium vinyl sulfonate, to benzene second
The mixture (combination, its quality proportioning is arbitrary during combination) of one or both of alkene sodium sulfonate；The unsaturated small list of esters
Body is one kind or one kind in hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate
Mixture above (combination, its quality proportioning is arbitrary during combination)；The initiator is hydrogen peroxide, ammonium persulfate, water
One or more kinds of mixture (combinations, group in dissolubility 4,4 '-azo double (4- cyanopentanoic acids sodium), benzoyl peroxides
Its quality proportioning is arbitrary during conjunction)；The chain-transferring agent is TGA, mercaptopropionic acid, 2 mercapto ethanol, metering system sulphur
One or more kinds of mixtures (combination, its quality proportioning is arbitrary during combination) in sour sodium.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than 4- hydroxy butyl vinyl ethers and 30~80 parts of deionized waters are added in 500ml three-necked flask, heat and start agitator
Heating, A liquid is configured to while initiator and chain-transferring agent are dissolved in 30~35 parts of deionized water；By unsaturated carboxylic acid, no
Saturation sulfonate and unsaturated esters minor comonomer are added in 5~10 parts of deionized water and are configured to B liquid；When reactor (i.e. institute
State three-necked flask) interior temperature is when rising to 45 DEG C~70 DEG C, while A liquid, B liquid is added dropwise, time for adding be respectively 150min,
1.5h~2.5h is incubated after 120min, completion of dropping, reaction terminates, it is 40% to add dilution water and be diluted to (theory) solid contain (amount)
Produce non-soil responsive type polycarboxylate water-reducer.
In above-mentioned technical proposal, the molecular weight of described 4- hydroxy butyl vinyl ethers is preferably 800~4000.Preparing
Cheng Zhong, when adding initiator and chain-transferring agent, first adds a small amount of initiator, and now the addition of initiator is its gross mass
5%~10%；Remaining initiator (such product is added whne when reactor temperature rises to 45 DEG C~70 DEG C, then to bottom
Performance is more preferable).
Currently preferred technical scheme can be found in the following examples 1~5.
Compared with prior art, the invention has the characteristics that (products characteristics advantage)：
Present invention introduces polymeric monomer 4- hydroxy butyl vinyl ethers, what 4- hydroxy butyl vinyl ether double bonds were linked below is ehter bond
And ' BDO ' this segmented structure, further reduce the space resistance of polyether lateral chain molecule swing so that polyethers side
The swing of chain is freer, and scope of activities is bigger so that the product is difficult intercalation easily and locked in soil, causes water reducer a large amount of
Absorbed, lose the performance of disperse cement particles.The structure suitably increases the lipophile of pfpe molecule chain one end simultaneously, in addition greatly
The addition of amount esters make it that absorption is slack-off, and the function of slump protection of whole product is more preferable.Especially in the case where clay content is high, absorption becomes
Slow whole loss situation is clearly better.The addition of unsaturated sulfonic acid salt monomer can be made with the reactivity ratio of effective coordination polymerisation
Copolymerization transformation efficiency is higher, while adding the diversity of absorption anchoring group, makes the adaptation of product stronger.
In summary, water reducer of the invention is insensitive to sandstone material clay content in concrete, is applied to contain mud
In the high concrete of amount, there is higher water reducing ability and less slump-loss, solution than traditional polycarboxylate water-reducer
Determined traditional polycarboxylate water-reducer concrete application present in sandstone raw material soil sensitiveness the problem of.The present invention is raw
The production cycle is short, and technique is simple, easy to operate, is conducive to industrialized production.
Embodiment
Embodiment 1：The non-soil responsive type polycarboxylate water-reducer of the present invention is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=72:4:6:16:1:1.5:80.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than 72 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 2400 and 40 parts of deionized waters are added in 500ml three-necked flask, plus
Heat simultaneously starts agitator heating, while being that ammonium persulfate and 1.5 parts of i.e. methylpropene sodium sulfonates of chain-transferring agent are molten by 1 part of initiator
A liquid is configured in 30 parts of deionized water；It is acrylic acid, 6 portions of unsaturated sulfonic acid salt i.e. to styrene by 4 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of sodium sulfonate and 16 parts are that hydroxy-ethyl acrylate is added in 10 parts of deionized water and is configured to B liquid；When
When reactor temperature rises to 70 DEG C, while A liquid, B liquid is added dropwise, after time for adding is respectively 150min, 120min, completion of dropping
1.5h is incubated, reaction terminates, adding dilution water, to be diluted to (theory) solid containing being 40% to produce non-soil responsive type polycarboxylic acids diminishing
Agent.
Embodiment 2：The non-soil responsive type polycarboxylate water-reducer of the present invention is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=120:4.5:8:20:1.5:2:95.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than being that 4000 4- hydroxy butyl vinyl ethers and 60 parts of deionized waters are added in 500ml three-necked flask by 120 parts, molecular weight,
Heat and start agitator heating, while being ammonium persulfate and 2 parts of chain-transferring agents i.e. methylpropene sodium sulfonate by 1.5 parts of initiators
A liquid is configured in the deionized water for being dissolved in 30 parts；By 4.5 parts of unsaturated carboxylic acids be maleic acid, 8 portions of unsaturated sulfonic acid salt i.e.
The unsaturated esters minor comonomers of sodium p styrene sulfonate and 20 parts are that hydroxypropyl acrylate is added in 5 parts of deionized water and is configured to
B liquid；When reactor temperature rises to 60 DEG C, while A liquid, B liquid is added dropwise, time for adding is respectively 150min, 120min, dropwise addition
2.5h is incubated after finishing, reaction terminates, addition dilution water is diluted to contain admittedly produces non-soil responsive type polycarboxylic acids diminishing for 40%
Agent.
Embodiment 3：The non-soil responsive type polycarboxylate water-reducer of the present invention is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=72:4:8:12:1.5:0.5:80.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than 72 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 2400 and 40 parts of deionized waters are added in 500ml three-necked flask, plus
Heat simultaneously starts agitator heating, while being that benzoyl peroxide and 0.5 part of i.e. TGA of chain-transferring agent are molten by 0.1 part of initiator
A liquid is configured in 30 parts of deionized water；It is fumaric acid, 8 portions of unsaturated sulfonic acid salt i.e. vinyl sulphur by 4 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of sour sodium and 12 parts are that hydroxypropyl acrylate is added in 10 parts of deionized water and is configured to B liquid；When anti-
When answering the temperature in the kettle to rise to 50 DEG C, 0.7 part of hydrogen peroxide, 0.7 part of ammonium persulfate are separately added into bottom, while A liquid, B is added dropwise
Liquid, time for adding is respectively to be incubated 1.5h after 150min, 120min, completion of dropping, and reaction terminates, add dilution water be diluted to it is solid
Containing producing non-soil responsive type polycarboxylate water-reducer for 40%.
Embodiment 4：The non-soil responsive type polycarboxylate water-reducer of the present invention is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=40:4:8:20:1.5:2:70.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than 40 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 1200 and 30 parts of deionized waters are added in 500ml three-necked flask, plus
Heat simultaneously starts agitator heating, while being that ammonium persulfate and 2 parts of i.e. methylpropene sodium sulfonates of chain-transferring agent are molten by 1.5 parts of initiators
A liquid is configured in 30 parts of deionized water；It is acrylic acid, 8 portions of unsaturated sulfonic acid salt i.e. to styrene by 4 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of sodium sulfonate and 20 parts are that hydroxypropyl acrylate is added in 10 parts of deionized water and is configured to B liquid；When
When reactor temperature rises to 70 DEG C, while A liquid, B liquid is added dropwise, after time for adding is respectively 150min, 120min, completion of dropping
2.5h is incubated, reaction terminates, addition dilution water is diluted to contain admittedly produces non-soil responsive type polycarboxylate water-reducer for 40%.
Embodiment 5：The non-soil responsive type polycarboxylate water-reducer of the present invention is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=120:5:7:18:1.2:1.8:120.
Described initiator is the group of 1 part of water solubility 4,4 '-azo double (4- cyanopentanoic acids sodium) and 0.2 part of ammonium persulfate
Close, chain-transferring agent is the combination of 1 part of 2 mercapto ethanol and 0.8 part of methylpropene sodium sulfonate, unsaturated esters minor comonomer is 10 parts
The combination of hydroxypropyl acrylate and 8 parts of hydroxyethyl methacrylates.
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Match somebody with somebody by above-mentioned quality
Than being that 4000 4- hydroxy butyl vinyl ethers and 80 parts of deionized waters are added in 500ml three-necked flask by 120 parts, molecular weight,
Heat and start agitator heating, configured while 1.2 parts of initiators and 1.8 parts of chain-transferring agents are dissolved in 30 parts of deionized water
Into A liquid；It is maleic acid, 7 portions of unsaturated sulfonic acid salt i.e. sodium vinyl sulfonate and 18 parts of beta-unsaturated esters by 5 parts of unsaturated carboxylic acids
Class minor comonomer, which is added in 10 parts of deionized water, is configured to B liquid；When reactor temperature rises to 70 DEG C, while dropwise addition A liquid,
B liquid, the time for adding of A liquid is 150min, and the time for adding of B liquid is to be incubated 2.5h after 120min, completion of dropping, and reaction terminates,
Addition dilution water is diluted to contain admittedly produces non-soil responsive type polycarboxylate water-reducer for 40%.
The effect that above-described embodiment 5 is produced is better than embodiment 1~4 (reference can be made to effect of embodiment 1~4).The present embodiment
The water reducer of preparation is insensitive to sandstone material clay content in concrete, is applied in the high concrete of clay content, than passing
The polycarboxylate water-reducer of system has higher water reducing ability and less slump-loss (damage of collapsing is without significant change).
It is below the implementation result (performance test) of the present invention：
Application example 1:According to GB/T8077-2012《Methods for testing uniformity of concrete admixture》, water-cement ratio is 0.29,
Volume is the solid volume of folding of binder materials, carries out flowing degree of net paste of cement and gradual loss experiment.Soil is bought on the market
Montmorillonite (test result indicates that being that montmorillonite influences maximum to additive), cement is high victory board Portland cement
(P.O42.5), result of the test such as table 1：
Table 1：Different water reducers paste flowing degree and gradual loss situation under the conditions of different clay contents
As it can be seen from table 1 embodiment 1,2,3 change pair soil content, needed for reaching identical initial extension degree
Admixture dosage change is smaller, and 1h gradual loss is slow；Common polycarboxylate water-reducer will reach identical with the change of clay content
Divergence, volume changes very greatly, and 1h gradual loss is also quickly.Embodiment 4 is very short due to side chain, steric hindrance itself compared with
It is small, without being lost in the case of soil also quickly.
Application example 2:Concrete experiments are in order to preferably verify the product in above-described embodiment to each department sand clay content
Sensitive question.In strict accordance with GB/T8077-2012《Methods for testing uniformity of concrete admixture》Serial coagulation is carried out
Soil experiment, is tested, C35 labels, match ratio cement using high victory P.O42.5 cement：Flyash：Miberal powder：Sand：Stone：
Water=260:60:60:765:1050:160.Experimental result such as table 2：
The variety classes additive of table 2 different clay content sand concrete slump and through when slump situation
From table 2 it can be seen that the water reducer water reducing ability of invention is almost consistent with common polycarboxylic acids diminishing, still
Application in the different clay content sand in different regions is substantially better than common polycarboxylate water-reducer, for the sand of different clay contents
Concrete is set to reach identical initial slump, the product of embodiment 1 increases with clay content, and volume increase is not obvious, clay content
Increase to 8.2 from 1.3, the solid volume of folding simply increases to 0.18 from 0.16, and damage of collapsing is not obvious.Show the non-of invention
Soil responsive type water reducer has extensive adaptability to the sand of different clay contents.
Water reducer prepared by the various embodiments above of the present invention is insensitive to sandstone material clay content in concrete, is transported
In the concrete high for clay content, there is higher water reducing ability and the less slump than traditional polycarboxylate water-reducer
Loss, solve traditional polycarboxylate water-reducer concrete application present in sandstone raw material soil sensitiveness the problem of.
The present invention is with short production cycle, and technique is simple, easy to operate, is conducive to industrialized production.
It is described above, only effect preferred embodiment, the present invention is not limited to the above embodiments, above-described embodiment and
Merely illustrating the principles of the invention described in specification, without departing from the spirit and scope of the present invention, the present invention is also
There are various changes and modifications, these changes and improvements are both fallen within the range of claimed invention.
Claims (9)
1. a kind of non-soil responsive type polycarboxylate water-reducer, it is characterised in that it is with 4- hydroxy butyl vinyl ethers polymeric monomer, no
Saturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are adjusted using initiator, chain-transferring agent as molecule
Section agent is made carrying out copolyreaction, and the mass ratio of each component is：4- hydroxy butyl vinyl ethers:Unsaturated carboxylic acid:No
Saturation sulfonate:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=(24~120):(4~8):(6~
10):(10~20):(0.8~1.5):(0.4~2):(70~120)；
The unsaturated carboxylic acid is one or more kinds of mixed in acrylic acid, methacrylic acid, fumaric acid, maleic acid
Compound；The unsaturated sulfonic acid salt is the mixture of one or both of sodium vinyl sulfonate, sodium p styrene sulfonate；Insatiable hunger
With esters minor comonomer in hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate
One or more kinds of mixtures；The initiator is hydrogen peroxide, ammonium persulfate, double (the 4- cyanopentanoic acids of 4,4 '-azo
Sodium), one or more kinds of mixtures in benzoyl peroxide；The chain-transferring agent is TGA, mercaptopropionic acid, 2-
One or more kinds of mixtures in mercaptoethanol, methylpropene sodium sulfonate；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：
4- hydroxy butyl vinyl ethers and 30~80 parts of deionized waters are added in 500ml three-necked flask by above-mentioned quality proportioning,
Heat and start agitator heating, A liquid is configured to while initiator and chain-transferring agent are dissolved in 30~35 parts of deionized water；
Unsaturated carboxylic acid, unsaturated sulfonic acid salt and unsaturated esters minor comonomer are added in 5~10 parts of deionized water and are configured to B
Liquid；When reactor temperature rises to 45 DEG C~70 DEG C, while A liquid, B liquid is added dropwise, time for adding be respectively 150min,
1.5h~2.5h is incubated after 120min, completion of dropping, reaction terminates, addition dilution water is diluted to contain admittedly produces non-soil for 40%
Responsive type polycarboxylate water-reducer.
2. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that above-mentioned 4- hydroxyls butylethylene
The molecular weight of base ether is 800~4000.
3. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that it is with 4- hydroxyl butyl second
Alkene ether polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are turned with initiator, chain
Move agent to carry out copolyreaction as molecular regulation agent and be made, the mass ratio of each component is：4- hydroxy butyl vinyl ethers:
Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=72:4:6:16:
1:1.5:80；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Will by above-mentioned quality proportioning
72 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 2400 and 40 parts of deionized waters are added in 500ml three-necked flask, and heating is simultaneously
Agitator heating is started, while being that ammonium persulfate and 1.5 parts of i.e. methylpropene sodium sulfonates of chain-transferring agent are dissolved in 30 by 1 part of initiator
A liquid is configured in the deionized water of part；It is acrylic acid, 6 portions of unsaturated sulfonic acid salt i.e. p styrene sulfonic acid by 4 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of sodium and 16 parts are that hydroxy-ethyl acrylate is added in 10 parts of deionized water and is configured to B liquid；Work as reaction
When temperature in the kettle rises to 70 DEG C, while A liquid, B liquid is added dropwise, time for adding is respectively insulation after 150min, 120min, completion of dropping
1.5h, reaction terminates, and addition dilution water is diluted to contain admittedly produces non-soil responsive type polycarboxylate water-reducer for 40%.
4. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that it is with 4- hydroxyl butyl second
Alkene ether polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are turned with initiator, chain
Move agent to carry out copolyreaction as molecular regulation agent and be made, the mass ratio of each component is：4- hydroxy butyl vinyl ethers:
Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=120:4.5:8:
20:1.5:2:95；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Will by above-mentioned quality proportioning
120 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 4000 and 60 parts of deionized waters are added in 500ml three-necked flask, heating
And agitator heating is started, while being that ammonium persulfate and 2 parts of i.e. methylpropene sodium sulfonates of chain-transferring agent are dissolved in by 1.5 parts of initiators
A liquid is configured in 30 parts of deionized water；It is maleic acid, 8 portions of unsaturated sulfonic acid salt i.e. to benzene by 4.5 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of vinyl sulfonic acid sodium and 20 parts are that hydroxypropyl acrylate is added in 5 parts of deionized water and is configured to B liquid；
When reactor temperature rises to 60 DEG C, while A liquid, B liquid is added dropwise, time for adding is respectively 150min, 120min, completion of dropping
After be incubated 2.5h, reaction terminates, add dilution water be diluted to it is solid contain produces non-soil responsive type polycarboxylate water-reducer for 40%.
5. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that it is with 4- hydroxyl butyl second
Alkene ether polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are turned with initiator, chain
Move agent to carry out copolyreaction as molecular regulation agent and be made, the mass ratio of each component is：4- hydroxy butyl vinyl ethers:
Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=72:4:8:12:
1.5:0.5:80；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Will by above-mentioned quality proportioning
72 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 2400 and 40 parts of deionized waters are added in 500ml three-necked flask, and heating is simultaneously
Agitator heating is started, while being that benzoyl peroxide and 0.5 part of i.e. TGA of chain-transferring agent are dissolved in 30 by 0.1 part of initiator
A liquid is configured in the deionized water of part；It is fumaric acid, 8 portions of unsaturated sulfonic acid salt i.e. sodium vinyl sulfonate by 4 parts of unsaturated carboxylic acids
And 12 parts of unsaturated esters minor comonomers are that hydroxypropyl acrylate is added in 10 parts of deionized water and is configured to B liquid；Work as reactor
When interior temperature rises to 50 DEG C, 0.7 part of hydrogen peroxide, 0.7 part of ammonium persulfate are separately added into bottom, while A liquid, B liquid is added dropwise, drop
Be respectively 150min, 120min between added-time, be incubated 1.5h after completion of dropping, reaction terminates, add dilution water be diluted to it is solid containing being
40% produces non-soil responsive type polycarboxylate water-reducer.
6. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that it is with 4- hydroxyl butyl second
Alkene ether polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are turned with initiator, chain
Move agent to carry out copolyreaction as molecular regulation agent and be made, the mass ratio of each component is：4- hydroxy butyl vinyl ethers:
Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=40:4:8:20:
1.5:2:70；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Will by above-mentioned quality proportioning
40 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 1200 and 30 parts of deionized waters are added in 500ml three-necked flask, and heating is simultaneously
Agitator heating is started, while being that ammonium persulfate and 2 parts of i.e. methylpropene sodium sulfonates of chain-transferring agent are dissolved in 30 by 1.5 parts of initiators
A liquid is configured in the deionized water of part；It is acrylic acid, 8 portions of unsaturated sulfonic acid salt i.e. p styrene sulfonic acid by 4 parts of unsaturated carboxylic acids
The unsaturated esters minor comonomers of sodium and 20 parts are that hydroxypropyl acrylate is added in 10 parts of deionized water and is configured to B liquid；Work as reaction
When temperature in the kettle rises to 70 DEG C, while A liquid, B liquid is added dropwise, time for adding is respectively insulation after 150min, 120min, completion of dropping
2.5h, reaction terminates, and addition dilution water is diluted to contain admittedly produces non-soil responsive type polycarboxylate water-reducer for 40%.
7. non-soil responsive type polycarboxylate water-reducer according to claim 1, it is characterised in that it is with 4- hydroxyl butyl second
Alkene ether polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, are turned with initiator, chain
Move agent to carry out copolyreaction as molecular regulation agent and be made, the mass ratio of each component is：4- hydroxy butyl vinyl ethers:
Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water=120:5:7:
18:1.2:1.8:120；
Described initiator is 1 part of water solubility 4, the combination of 4 '-azo double (4- cyanopentanoic acids sodium) and 0.2 part of ammonium persulfate, chain
Transfer agent is the combination of 1 part of 2 mercapto ethanol and 0.8 part of methylpropene sodium sulfonate, and unsaturated esters minor comonomer is 10 parts of acrylic acid
The combination of hydroxypropyl acrylate and 8 parts of hydroxyethyl methacrylates；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：Will by above-mentioned quality proportioning
120 parts, the 4- hydroxy butyl vinyl ethers that molecular weight is 4000 and 80 parts of deionized waters are added in 500ml three-necked flask, heating
And agitator heating is started, while being dissolved in 30 parts of deionized water by 1.2 parts of initiators and 1.8 parts of chain-transferring agents and being configured to A
Liquid；It is maleic acid, 7 portions of unsaturated sulfonic acid salt i.e. sodium vinyl sulfonate and 18 parts of unsaturated esters by 5 parts of unsaturated carboxylic acids
Minor comonomer, which is added in 10 parts of deionized water, is configured to B liquid；When reactor temperature rises to 70 DEG C, while A liquid, B is added dropwise
Liquid, the time for adding of A liquid is 150min, and the time for adding of B liquid is to be incubated 2.5h after 120min, completion of dropping, and reaction terminates, plus
Enter dilution water be diluted to it is solid contain produce non-soil responsive type polycarboxylate water-reducer for 40%.
8. a kind of preparation method of the non-soil responsive type polycarboxylate water-reducer described in claim 1, it is characterised in that it be with
4- hydroxy butyl vinyl ethers polymeric monomer, unsaturated carboxylic acid, unsaturated sulfonic acid salt, unsaturated esters minor comonomer are comonomer, with
Initiator, chain-transferring agent carry out copolyreaction as molecular regulation agent and are made, and the mass ratio of each component is：4- hydroxyl fourths
Base vinyl ethers:Unsaturated carboxylic acid:Unsaturated sulfonic acid salt:Unsaturated esters minor comonomer:Initiator:Chain-transferring agent:Deionized water
=(24~120):(4~8):(6~10):(10~20):(0.8~1.5):(0.4~2):(70~120)；
The unsaturated carboxylic acid is one or more kinds of mixed in acrylic acid, methacrylic acid, fumaric acid, maleic acid
Compound；The unsaturated sulfonic acid salt is the mixture of one or both of sodium vinyl sulfonate, sodium p styrene sulfonate；Insatiable hunger
With esters minor comonomer in hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate
One or more kinds of mixtures；The initiator is hydrogen peroxide, ammonium persulfate, double (the 4- cyanopentanoic acids of 4,4 '-azo
Sodium), one or more kinds of mixtures in benzoyl peroxide；The chain-transferring agent is TGA, mercaptopropionic acid, 2-
One or more kinds of mixtures in mercaptoethanol, methylpropene sodium sulfonate；
The preparation method of described non-soil responsive type polycarboxylate water-reducer is comprised the technical steps that：
4- hydroxy butyl vinyl ethers and 30~80 parts of deionized waters are added in 500ml three-necked flask by above-mentioned quality proportioning,
Heat and start agitator heating, A liquid is configured to while initiator and chain-transferring agent are dissolved in 30~35 parts of deionized water；
Unsaturated carboxylic acid, unsaturated sulfonic acid salt and unsaturated esters minor comonomer are added in 5~10 parts of deionized water and are configured to B
Liquid；When reactor temperature rises to 45 DEG C~70 DEG C, while A liquid, B liquid is added dropwise, time for adding be respectively 150min,
1.5h~2.5h is incubated after 120min, completion of dropping, reaction terminates, addition dilution water is diluted to contain admittedly produces non-soil for 40%
Responsive type polycarboxylate water-reducer.
9. the preparation method of non-soil responsive type polycarboxylate water-reducer according to claim 8, it is characterised in that preparing
During, when adding initiator and chain-transferring agent, a small amount of initiator is first added, now the addition of initiator is its gross mass
5%~10%；Remaining initiator is added whne when reactor temperature rises to 45 DEG C~70 DEG C, then to bottom.
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