CN107828027A - A kind of concrete workability conditioning agent with diminishing function and preparation method thereof - Google Patents
A kind of concrete workability conditioning agent with diminishing function and preparation method thereof Download PDFInfo
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- CN107828027A CN107828027A CN201711145151.6A CN201711145151A CN107828027A CN 107828027 A CN107828027 A CN 107828027A CN 201711145151 A CN201711145151 A CN 201711145151A CN 107828027 A CN107828027 A CN 107828027A
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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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Abstract
The invention provides a kind of workability conditioning agent with diminishing function, and it, which is formed, includes workability regulation macromolecular and water；The workability regulation macromolecular is obtained by copolyreaction, and its comonomer includes the micro- hydrophobically modified polyethers in polymerization activity end and α sodium olefin sulfonates；The workability conditioning agent with diminishing function can effectively introduce small and stable bubble, and Saline alkali tolerance is excellent.
Description
Technical field
The invention belongs to building material technical field, is related specifically to technical field of concrete additives, and in particular to arrives
A kind of concrete workability conditioning agent with diminishing function and preparation method thereof.
Background technology
High performance concrete (HPC) is proposed in nineteen ninety by United States Non-Provisional, refers to there is high durable, high intensity, high flowing
Property concrete, be the another major progress after high-strength concrete, be the dominant direction of current concrete development, one of them
Important content is that requirement fresh concrete has high workability.The workability for improving concrete is to improve fresh concrete work
The key point of property.In the various theoretical methods of proposition, additive is added to improve concrete mix workability
Can, it is considered to be an easy and effective feasible method.
It is well known that the additive for improving concrete mix workability energy now mainly has three kinds：Water reducer, air entraining agent
And thickener.Water reducer is that one kind can be on the premise of maintaining concrete slump constant, it is possible to reduce mixing water amount is mixed
Coagulate native additive.Air entraining agent is concrete mix is introduced air during mix and form a large amount of small, closings and steady
Determine the additive of bubble, these micro-bubbles have wetting, peptizaiton similar to ball, can improve the workability of concrete,
The bleeding of fresh concrete is effectively reduced, avoids isolating.Thickener is to improve concrete by the combination of a variety of mechanism of action
Workability, while its mobility (adding yield stress and plastic viscosity) can be reduced, main mechanism can be attributed to guarantor
Water acts on, the interaction between interaction and entanglement and polymer and cement granules between polymer molecule.
At present, it is difficult fundamentally to solve the problems, such as workability that certain additive, which is used alone, and more uses are more in practical application
The mode that kind composition of concrete admixture uses, such as water reducer and air entraining agent, water reducer and thickener or water reducer, air entraining agent and thickener
Three is used in conjunction with.
Patent CN201410208936.3 is disclosed " generating vinyl carboxylate base co-polymer concrete thickener and preparation method thereof ".
The patent uses polyether macromonomer, maleic acid double methyl esters, hydroxy-ethyl acrylate and styrene as comonomer, using one-step method
And disposably feed intake to obtain carboxyvinyl polymers' concrete thickener, concrete workability is can effectively improve, improves its bag
The property wrapped up in, but the styrene monomer introduced in the patent can dramatically increase the bleed performance of polymer, and foam stability is poor, Yi Zao
Intensity into concrete declines.
Patent GB2380504B uses 2- acrylamide-2-methyl propane sulfonics, maleic anhydride and unsaturated polyether polymeric monomer
Or (methyl) acrylate is prepared for a kind of polymeric retention agent based on vinyl sulfonic acid, utilized as comonomer
Water retention lifts the workability of polymer, but the maleic anhydride polymerization activity used in the patent is relatively low, is easy to get to 2- propylene
The homopolymer of acid amides -2- methyl propane sulfonic acids, thus obtained polymer under concrete high salt, high-alkali environment stability compared with
Difference.
Patent CN201310749293.9 discloses " a kind of water reducer and its conjunction with concrete workability regulatory function
Into method ".The patent uses the mixture of isoamyl alcohol polyoxyethylene ether, acrylic or methacrylic acid or both, maleic acid
Acid anhydride, sodium p styrene sulfonate, methylpropene sodium sulfonate are prepared for a kind of subtracting with workability regulatory function as comonomer
Aqua.While the water reducer has water holding capacity, there is the function of reducing concrete surface tension force so as to not influence concrete
Viscosity and mobility, while also ensure the normal condensation and strength development of concrete, but introduced in the patent to benzene second
Alkene sodium sulfonate and two kinds of monomer salt tolerances of methylpropene sodium sulfonate are poor, and polymerization is easily caused when being used in the hypersaline environment of concrete
The stability of thing declines, so as to influence its performance.
The content of the invention
It is sensitive for existing thickener volume to be present in the present invention, and it is excessive to easily cause slurry viscosity, poor fluidity, existing bleed
Bubble structure is improper causes intensity decreases due to introducing for agent, and existing water reducer molecular structure difference causes its workability adjustment effect
It is limited, the problems such as existing multi-functional water reducer Saline alkali tolerance difference, there is provided it is a kind of effectively to introduce small and stable bubble, it is resistance to
Saline alkali is excellent, and has concrete workability conditioning agent of diminishing function and preparation method thereof simultaneously.
The present invention is not on the premise of concrete strength is influenceed, first, a large amount of small, closings can be introduced into concrete
And stable bubble, second, there is certain receipts slurry ability, so as to reach the purpose of lifting concrete workability.
Concrete workability conditioning agent of the present invention with diminishing function, it, which is formed, includes big point of workability regulation
Son and water.
Workability regulation macromolecular is obtained by copolyreaction, and its comonomer includes that polymerization activity end is micro- hydrophobic to be changed
Property polyethers and α-sodium olefin sulfonate.
The structure of the micro- hydrophobically modified polyethers in polymerization activity end is：The polyether segment of unsaturated alcohols monomer end-blocking its one end,
The polyether segment is made up of propoxyl group construction unit and ethyoxyl construction unit, and polyether segment is connected to the-O- of unsaturated alcohol
On, propoxyl group construction unit is first connected, it is rear to connect ethyoxyl construction unit, form hydrophobic-hydrophilic-structure.Polymerization activity end is micro-
The molecular weight of hydrophobically modified polyethers is 500-3000.
The architectural feature of α-sodium olefin sulfonate is：One end is C=C double bonds, and the other end is-SO3Na, centre is-CH2-；
One of the structural formula of the α-sodium olefin sulfonate is as follows：
Wherein n represents 6~14 integer, and n values are too big or too small, influences final product and introduces the foam size of bubble, divides
Cloth and foam stability.
The structural formula of the micro- hydrophobically modified polyethers in polymerization activity end is as follows：
Wherein x represents 0~4 integer, and p is the average addition molal quantity of expoxy propane, and the integer for being 1~12, q is epoxy
The average addition molal quantity of ethane, for 10~65 integer, R5Represent hydrogen atom, methyl or ethyl.
P numerical value is too small, and hydrophily is strong, influences the bleed ability of final product；P numerical value is too big, and hydrophobicity is strong, influences final
The dispersive property of product.Molecular weight is too big or too small, influences the dispersive property of final product.
Preferably, the micro- hydrophobically modified polyethers in the polymerization activity end is polypropylene glycol polyethylene glycol vinyl ethers, poly- the third two
Alcohol polyethylene glycol allyl, polypropylene glycol polyethylene glycol methallyl ether, polypropylene glycol polyethylene glycol methyl butene base ether
In one kind, the preferable molecular weight of monomer C is 500-3000.
Preferably, the α-sodium olefin sulfonate is α-alkenyl sodium octyl, α-alkenyl nonyl sodium sulfonate, α-alkenyl decyl
One kind of sodium sulfonate, α-alkenyl undecyl sodium sulfonate or middle α-alkenyl dodecyl sodium sulfate.
Concrete workability conditioning agent of the present invention with diminishing function is existed by monomer A, monomer B, monomer C, monomer D
Under neutrality regulation, it is made by free radicals copolymerization reaction, the mol ratio of each component is A:B:C:D=1.0:0.5~2.0:0.2
~0.5:0.3~1.5
The monomer A is the material represented by formula (1)：
Wherein M1Represent hydrogen atom, monovalence alkali metal ion or ammonium ion；R1Represent hydrogen atom
Or methyl.
The monomer B is the material represented by formula (2a), (2b) or (2c)：
Wherein R1With the implication described in structural formula (1)；R2、R3It is separate for hydrogen atom or C1- to C4- alkyl
Or C1- to C4- hydroxyalkyl or C5- to C8- cycloalkyl or C6- to C14- aryl.
Wherein R1With the implication described in structural formula (1)；R4Represent hydrogen atom or C1- to C4- alkyl or-COOM1, its
Middle M1With the implication described in structural formula (1)；M represents 1~3 integer.
Wherein R1And R2Respectively with the implication described in structural formula (1) and (2a).
The monomer C is the micro- hydrophobically modified polyethers in aforementioned polymeric activity end；
The monomer D is foregoing α-sodium olefin sulfonate.
The molecular weight of the concrete workability conditioning agent with diminishing function is 3 × 104~12 × 104。
Preferably, the monomer A is acrylic or methacrylic acid.
Preferably, the monomer B is acrylamide, Methacrylamide, N methacrylamide, N- ethyl propylene acyls
Amine, N, N- DMAAs, N hydroxymethyl acrylamide, N, N- dicyclohexyls acrylamide, N- benzylacrylamides, N-
One kind in caprolactam, N- vinylpyridine networks alkanone, N- vinyl formamides, N- vinyl acetamides.
The hydroxy-acid group of absorption monomer A represented by structural formula (1) provides adsorption site in the copolymer so that copolymer is very
Cement particle surface is readily adsorbed in, forms absorption electric double layer, the attraction become between cement granules effectively prevents into electric repulsion
And the netted cohesion destroyed between cement granules, and make cement fully dispersed.
Amide groups or lactam group the regulation molecule hard and soft of amide-type monomer represented by structural formula (2).Utilize its position
Resistance group limitation main polymer chain rotates freely, the hard and soft of regulatory molecule chain, lifting polymer molecule high temperature with it is saline and alkaline
Under the conditions of stability.
Polymerization activity end hydrophobically modified unsaturated polyether polymeric monomer represented by structural formula (3) is necessary, and it not only may be used
To provide space steric effect so that polymer plays peptizaiton, while suitable length and parent in the fresh concrete stage
Hydrophobic performance effectively lifts the bleed ability of polymer.
α-sodium olefin sulfonate represented by structural formula (4) is necessary.Applicants have found that the foam of surfactant
Relevance rule between stability and concrete workability be present, i.e. foam stability is more excellent, and concrete workability is better.α-alkenyl
Sodium sulfonate is that a kind of bleed ability is moderate, but the surfactant that foam stability is superior, is incorporated into as comonomer
The foam stability of polymer can be effectively lifted in polymer.
A kind of preparation method of concrete workability conditioning agent with diminishing function of the present invention, specifically include with
Lower step：
(1) equipped with thermometer, agitator, dropping funel, nitrogen ingress pipe reactor in, add monomer A, monomer B,
Monomer C, monomer D and deionized water, mixture is neutralized to pH=7~8 with 32% liquid caustic soda solution；
(2) stirring is opened, is stirred while using nitrogen purge, and be warming up to 50 DEG C；
(3) initiator is configured to the solution that mass concentration is 1.0%~2.0%, it is dense that chain-transferring agent is configured to quality
The solution for 5.0%~10.0% is spent, the initiator prepared and chain-transferring agent solution are slowly dripped in 2h and 2.5h respectively
Add in reactor, after being added dropwise, be warming up to 70~80 DEG C, and continue 4~6h of reaction at this temperature, obtaining solid content is
25%~35% polymer, as described concrete workability conditioning agent macromolecular.
Described initiator is selected from water-soluble azo class initiator or persulfuric acid salt initiator；The water-soluble azo class
It is different that initiator is selected from azo diisobutyl amidine hydrochloride, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo two
One kind in propyl imidazole quinoline；The one kind of the persulfate initiator in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate.
The initiator amount accounts for the 0.5%~2.0% of reactant A+B+C+D gross weights.Initiator amount is excessive, can draw
Send out free radical more, accelerate reaction rate, the molecular weight of product reduces；Initiator amount very little, then the free radical triggered
Less, reaction speed is slack-off, even stops polymerization.
The time for adding of initiator solution is 2h, and the solvent of the initiator solution is water.The concentration of initiator solution
It is required that less, as long as control drips off can within preset time.Concentration height is then added dropwise slowly, and concentration is low, be added dropwise it is quicker, it is dense
Du Taigao amount of solution is less, the more difficult control of rate of addition, therefore controls in 1.0~2.0%.
Using the weight average molecular weight control of the concrete workability conditioning agent produced by the present invention with diminishing function 3 ×
104~12 × 104Between, molecular weight is too big or too small, and workability adjustment effect and water-reducing property can all be affected.The present invention
Effectively to control the molecular weight of polymer by using chain-transferring agent, 12 sulphur can be selected by being suitable for the chain-transferring agent of the present invention
Alcohol, 16 mercaptan, mercaptoethanol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids one or two kinds of or arbitrarily to compare
More kinds of chain-transferring agents are applied in combination in example.The dosage of chain-transferring agent is the 2.5%~5.0% of monomer (A+B+C+D) total mole number.
The time for adding of Chain transfer agent solution of the present invention is 2.5h, and the solvent of the chain-transferring agent solution is water.Chain turns
It is little to move the concentration requirement of the agent aqueous solution, as long as control drips off can within preset time.Concentration height is then added dropwise slowly, concentration
It is low, it is added dropwise quicker, the too high amount of solution of concentration is less, the more difficult control of rate of addition, therefore controls 5.0~10.0%.
4~6h is reacted in Raolical polymerizable selection at 70~80 DEG C in the present invention, before the reaction temperature is decided by
State the decomposition temperature of initiator.The half-life period too high or too low for temperature that initiator can all be changed, influence polymerization rate and gather
The relative molecular weight of product is closed, so as to change the combination property of polymerizate.
The present invention is by the reasonable control to synthesis material composition and proportioning and synthesis condition, by polymer A molecule
Amount control is 3 × 104~12 × 104, the obtained concrete workability conditioning agent with diminishing function is with such as under the molecular weight
Lower described beneficial effect：
(1) workability conditioning agent of the present invention is not on the premise of concrete strength is influenceed, first, can be to coagulation
Introduce a large amount of small, closings in soil and stable bubble, second, have certain receipts slurry ability, so as to reach lifting concrete and
The purpose of easy property.
(2) polymerization activity end hydrophobically modified polyethers is introduced in the present invention, can not only provides space steric effect, simultaneously
Suitable length and hydrophilicity and hydrophobicity effectively lift the bleed ability of the present invention；α-sodium olefin sulfonate is introduced in the present invention simultaneously
To lift the foam stability of the present invention.
(3) amide-type monomer is introduced in the present invention, not only improves Saline alkali tolerance, and the present invention is had necessarily
Receive slurry ability.
(4) the optimum mix amount of the invention is the 0.1%~0.3% of cement amount, and water-reducing rate can effectively change up to more than 25%
The workability of kind fresh concrete, does not isolate, not bleeding, does not settle, be a kind of functional form architectural chemistry additive.
Embodiment
The invention will be further elucidated with reference to specific embodiments.Following examples have been described in more detail according to this
The method of invention prepares the process of polymerizate, and these embodiments provide by way of illustration, familiar its object is to allow
The personage of technique can understand present disclosure and implement according to this, but these embodiments are in no way intended to limit the model of the present invention
Enclose.Any equivalent change or modification in accordance with the spirit of the invention, it should all be included within the scope of the present invention.
In synthetic example of the present invention, rheology modifier molecular weight is measured using aqueous gel permeation chromatography (GPC).
Condition determination is as follows：
Gel column：The root chromatogram columns of Shodex SB806+803 two are connected
Elutriant：0.1M NaNO3 solution
Flow phase velocity：1.0ml/min
Injection：The 20 μ l0.5% aqueous solution
Detector：Shodex RI-71 type differential refraction detectors
Reference material：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecular weight 263000,118000,44700,18600,
6690,1960,628,232)
Raw material in synthetic example of the present invention is purchased from Shanghai Aladdin biotech inc.
Raw materials used and code name in the synthetic example of table 1
Synthetic example 1
In the glass reactor equipped with thermometer, agitator, dropping funel, nitrogen ingress pipe and reflux condenser, add
Enter 36gA-1,17.8gB-1,54.2gC-1,40.5gD-2 and 62.2g deionized water, and be neutralized to solution with 62.5g liquid caustic soda
PH=7~8.Stirring is opened, is stirred while nitrogen purge is used, and be warming up to 50 DEG C, by 0.7g initiators Ia-1With
After 10.1g chain-transferring agents K-1 is each configured to the solution that mass concentration is 2.0% and 5.0%, respectively in 2h and 2.5h slowly
It is added dropwise in reactor, after being added dropwise, is warming up to 70~80 DEG C, and continue 4~6h of reaction at this temperature, obtains solid content
For 35% target product.
Synthetic example 2-16
The step of according to synthetic example 1, prepares the synthetic example 2-16 of the present invention, according to the ratio described by table 2, table 3
Fed intake.
Synthesize comparative example 1-2
The step of according to synthetic example 1, prepares the synthesis comparative example 1-2 of the present invention, according to the ratio described by table 2, table 3
Fed intake.
Table 2 prepares the ingredient proportion of synthetic example
Continued 2
Table 3 prepares synthetic example each monomer dosage, molecular weight of product and solid content
In Application Example of the present invention, except special instruction, used cement is the small wild cement of field 52.5R.P. II；Ore deposit
Powder is S95 levels, specific surface area 520m2/ kg, activity index 96%；Flyash is one-level flyash, water demand ratio 96%；Silicon ash
Specific surface area 18000m2/kg；Sand is river sand, sand in 2nd area, modulus of fineness 2.6；Stone is the lime stone of 5-20mm continuous gradings；
Water reducer is the homemade polycarboxylate water-reducer PCA I of Jiangsu Subotexin Material Co., Ltd.The slump and slump in experiment
Rheological parameters' change with time is spent with reference to GB/T 8076-2008《Concrete admixture》6.5.1 method described in is carried out；Water-reducing rate is with reference to GB/T
Method described in 8076-20086.5.2 calculates；Bleeding rate ratio method with reference to described in GB 8076-2008 6.5.3 calculates；Contain
Tolerance and air content the rheological parameters' change with time method with reference to described in GB/T 8076-2008 6.6.1 are carried out；Compression strength is with reference to GB/T
50081-2002《Standard for test methods of mechanical properties of ordinary concrete》Method described in 6 is carried out.T50For expansion rate, refer to
During measuring the slump, the timing since above carrying slump cylinder, when used when the extension diameter of concrete reaches 50cm
Between, this speed can embody the apparent viscosity of concrete to a certain extent.
Application Example 1
Comparative example 1 is anionic air entraining agent lauryl sodium sulfate (K12) and PCA I compound, and K12 is purchased from Nanjing
Card Neil science and technology Limited Liability Co., Ltd, PCA I volume are the 1% of gel material content；Comparative example 2 is commercially available macromolecule
It polymerize the compound of species thickener and PCA I, thickener is purchased from Yangtze BASF AG, and PCA I volume is glue
The 1% of gel material dosage；Comparative example 3,4,5 is respectively by A-1, B-2, C-4, and A-1, B-2, D-2, A-1, C-4, D-2 are according to synthesis
Method is prepared described in embodiment, and volume is identical with the volume of synthetic example 11.
Table 4 tests water-reducing rates of the synthetic example 1-16 under same volume, and normal concrete match ratio is with reference to GB/T
8076-2008, embodiment volume (being converted to solid) are the 0.12% of cement amount.
The embodiment 1-16 water-reducing rates of table 4
Table 5, table 6 test synthetic example 1-16 and comparative example 1-5 in low glue material concrete performance (0,
60min divergences, 0,60min air contents, 0,60min bleeding rates, T50And 28d compression strength), normal concrete is to mix 1.0%
PCA I concrete.The initial fluidity of volume concrete in experiment by adjusting synthetic example 1-16 is suitable.
The concrete mix of table 5
The influence of the synthetic example 1~16 of table 6 and the low glue material concrete properties of 1~5 pair of comparative example
Application Example 3
PCA I volume is the 2.0% of gel material content in comparative example 1；PCA I volume is gelling material in comparative example 2
Expect the 2.0% of dosage；Comparative example 3,4,5 is real according to synthesis by A-1, B-2, C-4, A-1, B-2, D-2, A-1, C-4, D-2 respectively
Apply method described in example to be prepared, volume is identical with the volume of synthetic example 11.
Table 7, table 8 test synthetic example 1-16 and comparative example 1-5 in high glue material concrete performance (0,
60min divergences, 0,60min air contents, 0,60min bleeding rates, T50And 28d compression strength), it is real by adjusting synthesis in experiment
The volume for applying a 1-16 make it that the initial fluidity of concrete is suitable.
The concrete mix of table 7
The influence of the synthetic example 1~16 of table 8 and 1~5 pair high glue material concrete properties of comparative example
Table 4, the data of table 6 show a kind of concrete workability conditioning agent with diminishing function prepared by the present invention, having
Isolation, the excreting water phenomenon of concrete are can effectively improve while having good dispersion.Embodiment 1-16 because reaction condition is different,
Products therefrom changes to the initial air content of concrete and 1h air contents, bleeding rate and T50All slightly distinguish, but be substantially better than conjunction
Paired ratio 1-2 and comparative example 1-5.The present invention is not on the premise of concrete strength is influenceed, first, by drawing into concrete
Enter a large amount of small, closings and stable bubble, second, make polymer that there are certain receipts to starch ability by introducing amide-type monomer,
So as to reach the purpose of lifting concrete workability.The concrete of incorporation synthesis comparative example 1, popularity occur instead increasing phenomenon,
0th, there is isolation, excreting water phenomenon in 60min, and 60min bleeding rate is more than 0min, and this is due to that monomer C structure is improper
It has impact on the scattered retentivity and bleed performance of final product.The concrete of incorporation synthesis comparative example 2,0,60min occurs
Isolation, excreting water phenomenon, this is due to that the improper final product that have impact on of monomer D structure introduces the foam size of bubble, distribution
And foam stability.Mix comparative example 1 concrete, 0,60min there is isolation, excreting water phenomenon, to concrete workability
Improvement is limited, and it is closely related that this is poor with its foam stability.Although incorporation comparative example 2 concrete do not occur from
Analysis, excreting water phenomenon, but concrete flowability is obviously reduced.The concrete of incorporation comparative example 3 (monomer-free D) shows and comparative example
There is isolation, bleeding in 1 similar phenomenon, concrete 0,60min, and this is due to that the foam stability of comparative example 3 is poor caused.Mix
Enter comparative example 4 (monomer-free C) although concrete do not occur isolation, excreting water phenomenon, without dispersive property.Mix (the nothing of comparative example 5
Monomer B) although concrete with excellent foam stability, receive that slurry is limited in one's ability, and it is existing that isolation, bleeding still occurs in concrete
As.
The data of table 8 show with the data identical rule of table 6, and as can be seen from Table 8, in high glue material concrete
In, comparative example 1-2 and comparative example 1-5 is compared with embodiment for synthesis, T50Time significantly increases.Comparative example 2 and comparative example 4 are due to
Liquidity value added to concrete viscosity increases, T50Time increases；Synthesize comparative example 1-2, comparative example 1, comparative example 3 and comparative example 5
It is due to that concrete isolation, excreting water phenomenon, T occurs50Time increases.
Claims (8)
1. a kind of concrete workability conditioning agent with diminishing function, it is characterised in that it, which is formed, includes workability regulation greatly
Molecule and water；
The workability regulation macromolecular is obtained by copolyreaction, and its comonomer gathers including the micro- hydrophobically modified in polymerization activity end
Ether and α-sodium olefin sulfonate；
The structure of the micro- hydrophobically modified polyethers in polymerization activity end is：The polyether segment of unsaturated alcohols monomer end-blocking its one end, it is described
Polyether segment is made up of propoxyl group construction unit and ethyoxyl construction unit, and polyether segment is connected on-the O- of unsaturated alcohol, first
Propoxyl group construction unit is connected, it is rear to connect ethyoxyl construction unit, form hydrophobic-hydrophilic-structure；Polymerization activity end is micro- hydrophobic to be changed
The molecular weight of property polyethers is 500-3000；
The architectural feature of α-sodium olefin sulfonate is：One end is C=C double bonds, and the other end is-SO3Na, centre is-CH2-；The α-
One of structural formula of sodium olefin sulfonate is as follows：
Wherein n represents 6~14 integer, and n values are too big or too small, influence final product introduce bubble foam size, distribution and
Foam stability.
2. the concrete workability conditioning agent according to claim 1 with diminishing function, it is characterised in that
The structural formula of the micro- hydrophobically modified polyethers in polymerization activity end is as follows：
Wherein x represents 0~4 integer, and p is the average addition molal quantity of expoxy propane, and the integer for being 1~12, q is oxirane
Average addition molal quantity, be 10~65 integer, R5Represent hydrogen atom, methyl or ethyl.
3. the concrete workability conditioning agent according to claim 2 with diminishing function, it is characterised in that the polymerization
The active micro- hydrophobically modified polyethers in end is polypropylene glycol polyethylene glycol vinyl ethers, polypropylene glycol polyethylene glycol allyl, poly- third
Glycol polyethylene glycol methallyl ether or polypropylene glycol polyethylene glycol methyl butene base ether.
4. the concrete workability conditioning agent with diminishing function according to any one of claim 1-3, its feature
It is, the α-sodium olefin sulfonate is α-alkenyl sodium octyl, α-alkenyl nonyl sodium sulfonate, α-alkenyl decyl sodium sulfonate, α-
Alkenyl undecyl sodium sulfonate or middle α-alkenyl dodecyl sodium sulfate.
5. the preparation side of the concrete workability conditioning agent with diminishing function described in any one in claim 1-4
Method, it is characterised in that the concrete workability conditioning agent with diminishing function is existed by monomer A, monomer B, monomer C, monomer D
Under neutral environment, it is made by free radicals copolymerization reaction, the mol ratio of each component is A:B:C:D=1.0:0.5~2.0:0.2
~0.5:0.3~1.5；
The monomer A is the material represented by formula (1)：
Wherein M1Represent hydrogen atom, monovalence alkali metal ion or ammonium ion；R1Represent hydrogen atom or methyl；
The monomer B is the material represented by formula (2a), (2b) or (2c)：
Wherein R1With the implication described in structural formula (1)；R2、R3It is separate for hydrogen atom or C1- to C4- alkyl or
C1- to C4- hydroxyalkyl or C5- to C8- cycloalkyl or C6- to C14- aryl；
Wherein R1With the implication described in structural formula (1)；R4Represent hydrogen atom or C1- to C4- alkyl or-COOM1, wherein M1
With the implication described in structural formula (1)；M represents 1~3 integer；
Wherein R1And R2Respectively with the implication described in structural formula (1) and (2a)；
The monomer C is the micro- hydrophobically modified polyethers in aforementioned polymeric activity end；
The monomer D is foregoing α-sodium olefin sulfonate；
The molecular weight of the concrete workability conditioning agent with diminishing function is 3 × 104~12 × 104。
6. according to the method for claim 5, and being characterised by, the monomer A is acrylic or methacrylic acid.
7. according to the method for claim 5, and being characterised by, the monomer B is acrylamide, Methacrylamide, N-
Methacrylamide, N- ethyl acrylamides, N, N- DMAAs, N hydroxymethyl acrylamide, N, N- dicyclohexyls
Acrylamide, N- benzylacrylamides, N- caprolactams, N- vinylpyridine networks alkanone, N- vinyl formamides, N- second
Any one in alkenyl acetamide.
8. according to the method described in any one of claim 5-7, it is characterised in that specifically include following steps：
(1) equipped with thermometer, agitator, dropping funel, nitrogen ingress pipe reactor in, add monomer A, monomer B, monomer
C, monomer D and deionized water, mixture is neutralized to pH=7~8 with 32% liquid caustic soda solution；
(2) stirring is opened, is stirred while using nitrogen purge, and be warming up to 50 DEG C；
(3) initiator is configured to the solution that mass concentration is 1.0%~2.0%, chain-transferring agent is configured into mass concentration is
5.0%~10.0% solution, by the initiator prepared and chain-transferring agent solution be slowly added dropwise respectively in 2h and 2.5h into
In reactor, after being added dropwise, 70~80 DEG C are warming up to, and continues 4~6h of reaction at this temperature, obtains solid content as 25%
~35% polymer, it is the concrete workability conditioning agent macromolecular with diminishing function；
Described initiator is selected from water-soluble azo class initiator or persulfuric acid salt initiator；The water-soluble azo class triggers
Agent is selected from azo diisobutyl amidine hydrochloride, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo diisopropyl
Any one in imidazoline；The persulfate initiator is any one in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate
Kind；The initiator amount accounts for the 0.5%~2.0% of reactant A+B+C+D gross weights；
Described chain-transferring agent is from lauryl mercaptan, 16 mercaptan, mercaptoethanol, TGA, 2 mercaptopropionic acid, 3- sulfydryls third
One or two kinds of any of the above ratio combination of acid；The dosage of chain-transferring agent is the 2.5% of monomer (A+B+C+D) total mole number
~5.0%.
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| CN109111556A (en) * | 2018-07-16 | 2019-01-01 | 山东高强建材有限公司 | A kind of ester ether cross-linking type polycarboxylic-acid workability regulator and preparation method thereof |
| CN113512156A (en) * | 2021-06-02 | 2021-10-19 | 甘肃新纪元建材有限公司 | Slow-setting slump-retaining water reducer and preparation method thereof |
| CN114163580A (en) * | 2021-12-22 | 2022-03-11 | 贵州乾鑫丰建材有限公司 | Thixotropic early-strength water reducing agent and preparation method and application thereof |
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