CN104628967B - A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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Abstract
It polymerize the copolymer formed the invention provides a kind of Early-strength polycarboxylate superplasticizer, including by four kinds of monomers.Present invention also offers a kind of preparation method of the Early-strength polycarboxylate superplasticizer.The sand material such as Early-strength polycarboxylate superplasticizer provided by the present invention and cement can preferably play its space steric effect when acting on, and concrete workability is good, and no bleeding, segregation phenomenon occur.
Description
Technical field
The present invention relates to concrete admixture, specially a kind of Early-strength polycarboxylate superplasticizer and preparation method thereof.
Background technology
With the development of China's concrete in recent years, the various aspects of performance of concrete is improved constantly, to cement water reducing agent
Requirement also more and more higher.Water reducer is a kind of more important concrete admixture, by its water-reducing rate size, can be divided into and commonly subtract
Aqua (using lignin sulfonate as representative), high efficiency water reducing agent (including naphthalene system, melamine system, sulfamate system, fatty family
Deng) and high-performance water reducing agent (using polycarboxylic acids high efficiency energy water reducer as representative).
Polycarboxylate water-reducer, it, based on the additive of carboxylic acids graft polymers, is usually by containing end alkenyl to be
Polyether macromonomer and unsaturated carboxylic acid（Salt）Minor comonomer precipitation from aqueous solution is formed, with volume is low, water-reducing rate is high, the slump is damaged
The advantages of small and cement adaptability is strong is lost, and the consumption of the mixing materials such as flyash in concrete, miberal powder can be improved, can be significantly
Cement is saved, high-strength, super high strength concrete is can also configure.Based on above-mentioned advantage, polycarboxylate water-reducer is widely used in high-speed iron
Road, bridge, water conservancy etc. are required in high intensity, high-durability, the engineering of high cement adaptability concrete.
The use of polycarboxylate water-reducer also exposes many problems while with above-mentioned advantage, for example, medium-sized
Polycarboxylate water-reducer can significantly delay the aquation of cement, especially at low ambient temperatures, and the early strength of concrete can be caused to develop
Slowly, its application in prefabricated components is also constrained in the use of cold environment which limits common polycarboxylate water-reducer.
At present, the concrete early strength agent more commonly used mainly has villaumite system, sulfate system, carbonate system, organic system, ore deposit
Species and complex accelerator.Existing early strength agent can only improve concrete 3 days, 7 days intensity 30%~60%, and be easily introduced chlorine from
Son or alkali metal, chlorion easily cause steel bar corrosion, and alkali metal content is too high easily to cause alkali, and both of which can cause knot
Structure is damaged.
Patent CN101205128B provides a kind of early strength type polycarboxylic acid series high-performance dehydragent and its manufacture method, the hair
It is bright to use the degree of polymerization to be gone back for 37 and 54 allyl polyethenoxy ether, acrylic acid, acrylamide, methylpropene sodium sulfonate in oxidation
It is penta-component copolymerized under the conditions of former initiation system to prepare.Due to active relatively low, the polymerisation completion of allyl polyethenoxy ether
Afterwards, there is part residual in polymeric solution, adverse effect can be brought to the water-reducing property and concrete performance of final polymer.
Patent CN101376576B provides a kind of early strength type polycarboxylic acid series high-performance dehydragent and its preparation technology, the hair
Bright polyethylene glycol monoether esters of acrylic acid polymeric monomer, (methyl) acrylic acid, ALS using two kinds of different chain numbers
Or methylpropene sodium sulfonate, polyoxyalkylene acrylate esters monomer take the mode once fed intake to be total under nitrogen protective condition
Poly- reaction, because the monomer reactivities such as (methyl) acrylic acid are stronger, easy autohemagglutination influences the copolymerization effect between monomer, and molecular weight is difficult
In control, so as to cause the hydraulic performance decline of product.
In summary, existing polycarboxylate water-reducer, or the building structure applied can be made because introducing corrosive substance
Into destruction, or the selection such as species, consumption because of polymerized monomer is improper, causes polycarboxylate water-reducer to be unable to reach in use
Good effect.
The content of the invention
To solve the above problems, the invention provides a kind of performance is stable, ultra early-strength strong to cement adaptability and to ring
The free of contamination Early-strength polycarboxylate superplasticizer in border.
Present invention also offers a kind of preparation method of the water reducer, this method technique is simple, workable, energy consumption
It is low, cheap.
A kind of Early-strength polycarboxylate superplasticizer, including it polymerize the copolymer formed, described four kinds by tetra- kinds of monomers of A, B, C, D
The structural formula of monomer is as follows：
1) monomer A：
Wherein, R1For-H or-CH3, R2For the alkylidene containing 2~4 carbon atoms, R3For-H or-CH3, n is 30~100；
2) monomer B：
Wherein, R4For-H or-CH3, m represents the average addition molal quantity of oxirane chain number, and m is 15~70；
3) monomer C：
R in formula5For-H ,-CH3, or-CH2COOH；
4) monomer D：
The percentage by weight of four kinds of monomers is respectively：A：70%~80%, B：10%~22%, C：3%~9%, D：3%~
5%；The percentage by weight is on the basis of the weight sum of four kinds of monomers.
According to an embodiment of the present invention, the weight average molecular weight of the copolymer is 10000~40000.
According to an embodiment of the present invention, the weight average molecular weight of the monomer A is 800~5000.
According to an embodiment of the present invention, the weight average molecular weight of the monomer B is 500~4000.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, including by four kinds of monomers, initiator and chain-transferring agent
Add in solvent, the copolymer is made by polymerisation in solution.
According to an embodiment of the present invention, the reaction temperature of the polymerisation in solution is 60 DEG C~80 DEG C.
According to another embodiment of the present invention, the reaction time of the polymerisation in solution is 4~6 hours.
According to another embodiment of the present invention, the initiator is selected from ammonium persulfate, potassium peroxydisulfate, the NSC 18620 of azo two
One or more in hydrochloride, the consumption of the initiator is the 0.1%~2% of four kinds of monomer gross mass.
According to another embodiment of the present invention, the chain-transferring agent is selected from TGA, 2 mercaptopropionic acid, 3- sulfydryls third
One or more in acid, the consumption of the chain-transferring agent is the 0.1%~0.6% of four kinds of monomer gross mass.
According to another embodiment of the present invention, including by four kinds of monomers add the solvent the step of；To described
The step of initiator is added dropwise in solvent；The step of chain-transferring agent is added dropwise into the solvent；Wherein, the initiator
Time for adding be 3~5 hours, be added dropwise within first 1~2 hour the 2/3 of the initiator amount, the initiator is added dropwise in remaining time
The 1/3 of consumption.
Early-strength type polycarboxylate water-reducer by introduced in the molecular structure of polymer a certain amount of sulfonic acid and
Amide group, while reducing the degree of polymerization of carboxyl-content and control polymer, to accelerate hydrated cementitious, reaches early stage enhancing effect
Really.
The sand material such as early-strength type polycarboxylate water-reducer and cement can preferably play its steric hindrance when acting on
Effect, concrete workability is good, and no bleeding, segregation phenomenon occur.
Embodiment
Below, early-strength type polycarboxylate water-reducer and preparation method thereof is done further with reference to embodiment
Explanation：
Early-strength type polycarboxylate water-reducer, including it polymerize the copolymer formed by tetra- kinds of monomers of A, B, C, D.
The structural formula of the monomer A is：
Wherein, R1For-H or-CH3, R2For the alkylidene containing 2~4 carbon atoms, R3For-H or-CH3, n is 30~100.
In one embodiment of the present invention, A is methoxy polyethylene glycol acrylate, n=52；In the another of the present invention
In embodiment, A is methoxypolyethylene glycol methacrylate, n=86；In the present invention, A weight average molecular weight can for 800~
5000, preferably 1000~4000, its quality accounts for the 70%~80% of monomer gross mass, in the above range value, obtained to subtract
Aqua makes the intensity of concrete substantially shift to an earlier date.
The monomer B is APEO, preferably methyl alkenyl APEO and/or alkylene alkenyl polyoxyethylene
Ether.Monomer B molecules amount is too small in reaction system, and whole polymerization rate can be made too fast, causes monomer B conversion ratio relatively low；
Monomer B molecules amount is excessive in system, can delay polymerization rate, it is impossible to reach good polymerization effect.In the present invention, monomer
B weight average molecular weight is 500~4000, and when quality accounts for the 10%~22% of monomer gross mass, polymerisation degree is optimal.
The preparation method of the Early-strength polycarboxylate superplasticizer, including by four kinds of monomers, initiator and chain-transferring agent
Add in solvent, the copolymer is made by polymerisation in solution.
In one embodiment of the present invention, the solvent is water；Temperature is a step of polymerisation most critical, and chain is drawn
Hair reaction plays the role of important.When temperature is relatively low, polymerisation is difficult to, and temperature is too high, easily produces side reaction.This hair
The temperature of bright selection between 60 DEG C~80 DEG C, should in the range of can preferably control the generation of reaction product.
Whether the copolymerization of polycarboxylate water-reducer structure is well relevant with feed way, and polymerization is that influence product structure is homogeneous
Property one of key factor, the copolymer structure that different polymerizations is obtained is different, so as to cause the difference in performance.Charging
Speed speed, directly affect the extent of polymerization of reactant, rate of addition is too fast, and material reaction is insufficient；Rate of addition is excessively slow,
Reaction is difficult to carry out, and the application performance of water reducer can be influenceed to a certain extent.
According to an embodiment of the present invention, the time for adding of the initiator is 4 hours, is added dropwise within preferably first 2 hours
The 2/3 of initiator amount, initiator amount is added dropwise in latter 2 hours 1/3.The present invention will be controlled at 4~6 hours in the reaction time, be made
Reaction raw materials give full play to its respective function, reach preferable polymerization effect, you can a kind of poly- carboxylic of early strong concrete is made
Sour water reducer.
In the present invention, the radical initiator can be in ammonium persulfate, potassium peroxydisulfate, azo-bis-isobutyrate hydrochloride
One or more, its consumption be monomer A, B, C, D gross mass 0.1%~2%, it is in one embodiment of the present invention, described
Initiator is ammonium persulfate；In another embodiment of the present invention, the initiator is potassium peroxydisulfate.
In the present invention, the chain-transferring agent is in mercaptoethanol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids
One or more, its consumption is the 0.1%~0.6% of monomer A, B, C, D gross mass；In one embodiment of the present invention, it is described
Chain-transferring agent is TGA；In another embodiment of the present invention, the chain-transferring agent is 2 mercaptopropionic acid；In the present invention
Another embodiment in, the chain-transferring agent be 3- mercaptopropionic acids.
Hereinafter, Early-strength polycarboxylate superplasticizer of the present invention and preparation method thereof is illustrated in conjunction with specific embodiments,
Wherein, tetra- kinds of monomers of A, B, C, D can be obtained by commercially available.
By the water reducer synthesized in following embodiments and cement, sand, stone, water and other additives with reference to certain cooperation
Than being designed by JGJ55；Various concrete test materials and environment temperature are held in (20 ± 3) DEG C；Compressive strength rate with
Fresh Concrete with Admixtures is mixed to represent with the ratio between age compression strength with normal concrete；By the resistance to compression of inspection concrete and normal concrete
Intensity is tested and calculated by GB/T50081, when test specimen makes, and is vibrated 15 seconds~20 seconds with shake table, test specimen precuring temperature
For (20 ± 3) DEG C, compressive strength rate is represented with the arithmetic mean of instantaneous value of three Specimen Determination values.
By GB/T50080 gas-water mixed type gas contents, and illustrate by instrument to be operated, but concrete mixing
Thing should be filled once and a little higher than container, with shake table jolt ramming 15 seconds~20 seconds.During experiment, air content is with three Specimen Determination values
Arithmetic mean of instantaneous value represent.
Other specification or detailed description refer to GB/8076-2008.
Embodiment 1
In the reactor, 190 grams of water and 270 grams of monomer A (methoxy polyethylene glycol acrylate, n=52), 40.5 are added
Gram monomer B (allyl polyethenoxy ether, m=28), 10.13 grams of monomer D (methyl propane sulfonic acid of 2- acrylamidos -2), stirring plus
Heat after after the dissolving of above-mentioned three kinds of monomers, adds 16.88 grams of monomer C (acrylic acid), (3.38 grams of initiator is then added dropwise to 65 DEG C
The mixture of ammonium persulfate and 40 grams of water), chain-transferring agent（The mixture of 0.68 gram of TGA and 68 grams of water), at the uniform velocity drip respectively
Plus 4 hours, ageing time is 2 hours, and system temperature is down to normal temperature by reaction after terminating, with the NaOH water that mass concentration is 30%
The pH value of solution regulation reaction gained mixture is to neutrality, and discharging produces high-performance polycarboxylic acids water reducing agent product ZPC-1, gained
Product solid content is 40%, and resulting polymers weight average molecular weight is 19800.
Embodiment 2
In the reactor, add 190 grams of water and 236.3 grams of monomer A (methoxy polyethylene glycol acrylate, n=30),
60.75 grams of monomer B (methyl allyl polyoxyethylene ether, m=28), 10.13 grams of monomer D (methyl-prop sulphurs of 2- acrylamidos -2
Acid), 60 DEG C are heated with stirring to, after adding 30.39 grams of monomer C (acrylic acid) after the dissolving of above-mentioned three kinds of monomers, is then added dropwise and triggers
Agent (4.05 grams of ammonium persulfates and 48 grams of aqueous mixtures), chain-transferring agent（1.01 grams of TGAs and 50.5 grams of aqueous mixtures), point
It is not added dropwise 3 hours at the uniform velocity, ageing time is 2 hours, and system temperature is down to normal temperature by reaction after terminating, is 30% with mass concentration
NaOH aqueous solution regulation reaction gained mixture pH value to neutrality, discharging produces high-performance polycarboxylic acids water reducing agent product
ZPC-2, products obtained therefrom solid content is 40%, and resulting polymers weight average molecular weight is 15600.
Embodiment 3
In the reactor, add 190 grams of water and 252.7 grams of monomer A (methoxy polyethylene glycol acrylate, n=50),
60.75 grams of monomer B (methyl allyl polyoxyethylene ether, m=20), 13.5 grams of monomer D (methyl-prop sulphurs of 2- acrylamidos -2
Acid), 70 DEG C are heated with stirring to, after adding 10.13 grams of monomer C (methacrylic acid) after the dissolving of above-mentioned three kinds of monomers, is then added dropwise
Initiator (3.04 grams of potassium peroxydisulfates and 30.4 grams of aqueous mixtures), chain-transferring agent（0.68 gram of 3- mercaptopropionic acid is mixed with 68 grams of water
Thing), at the uniform velocity it is added dropwise 3 hours respectively, ageing time is 3 hours, and system temperature is down to normal temperature by reaction after terminating, and uses mass concentration
The pH value of mixture is to neutrality obtained by 30% NaOH aqueous solution regulation reaction, and discharging produces high-performance polycarboxylic acids water reducing agent production
Product ZPC-3, products obtained therefrom solid content is 40%, and resulting polymers weight average molecular weight is 20560.
Embodiment 4
In the reactor, add 190 grams of water and 246 grams of monomer A (methoxypolyethylene glycol methacrylate, n=86),
70.88 grams of monomer B (allyl polyethenoxy ether, m=52), 10.13 grams of monomer D (methyl propane sulfonic acid of 2- acrylamidos -2) are stirred
Mix and be heated to 60 DEG C, 10.13 grams of monomer C (methacrylic acid) are added after dissolving, initiator (3.375 grams of persulfuric acid are then added dropwise
Ammonium and 33.8 grams of aqueous mixtures), time for adding is 4 hours, initiator amount is added dropwise in first 2 hours 2/3, and dropwise addition in latter 2 hours is drawn
The 1/3 of agent consumption is sent out, chain-transferring agent is finally added dropwise（0.34 gram of 2 mercaptopropionic acid and 34 grams of aqueous mixtures), at the uniform velocity it is added dropwise 3 hours,
Ageing time is 1 hour, and system temperature is down to normal temperature by reaction after terminating, and is adjusted with mass concentration for the 30% NaOH aqueous solution
The pH value of reaction gained mixture to neutrality, discharging produces high-performance polycarboxylic acids water reducing agent product ZPC-4, products obtained therefrom contains admittedly
Measure as 40%, resulting polymers weight average molecular weight is 24300.
Embodiment 5
In the reactor, 190 grams of water and 270 grams of monomer A (methoxy polyethylene glycol acrylate, n=69), 33.8 are added
Gram monomer B (methyl allyl polyoxyethylene ether, m=45), 13.5 grams of monomer D (methyl propane sulfonic acid of 2- acrylamidos -2), stirring
75 DEG C are heated to, 20.25 grams of monomer C (acrylic acid) are added after dissolving, initiator (2.7 grams of ammonium persulfates and 27 grams are then added dropwise
Aqueous mixtures), chain-transferring agent（0.73 gram of TGA and 73 grams of aqueous mixtures), at the uniform velocity it is added dropwise 3 hours respectively, ageing time is
1 hour, system temperature was down to normal temperature by reaction after terminating, mixed for 30% NaOH aqueous solution regulation reaction gained with mass concentration
The pH value of compound to neutrality, discharging produces high-performance polycarboxylic acids water reducing agent product ZPC-5, and products obtained therefrom solid content is 40%, institute
It is 19800 to obtain polymer average molecular weight.
Early-strength type polycarboxylate water-reducer (example 1~5) and the new of commercially available plain edition polycarboxylate water-reducer are mixed
Concrete crushing strength and air content compare.Test material and environment temperature are 5~10 DEG C, and other conditions shine GB8076-2008
Tested.Specific test result is shown in Table 1.
The Early-strength polycarboxylate superplasticizer concrete evaluating data of table 1
It is each in embodiment under the conditions of same volume it was found from the concrete evaluating data of the Early-strength polycarboxylate superplasticizer of table 1
Water reducer all has low gas content amount, and presetting period and final setting time shift to an earlier date compared with plain edition water reducer, and compressive strength rate substantially increases,
Later strength also increases, and the workability of concrete is good, and no bleeding, segregation phenomenon occur, and solve polycarboxylate water-reducer
Use in the problem of needing early strength during use, particularly solution prefabricated components, the exploitation of the concrete admixture,
By the more high intensity such as promotion high-speed railway, bridge, hydraulic engineering, the concrete works construction of high-durability.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is not used to limit the scope of the invention merely for exemplary purpose,
Those skilled in the art can make various other replacements, changes and improvements within the scope of the invention, thus, the invention is not restricted to
Above-mentioned embodiment, and be only defined by the claims.
Claims (9)
1. a kind of Early-strength polycarboxylate superplasticizer, including it polymerize the copolymer formed, four kinds of lists by tetra- kinds of monomers of A, B, C, D
The structural formula of body is as follows：
1) monomer A：
Wherein, R1For-H or-CH3, R2For the alkylidene containing 2~4 carbon atoms, R3For-H or-CH3, n is 30~100；
2) monomer B：
Wherein, R4For-H or-CH3, m is 15~70；
3) monomer C：
R in formula5For-H ,-CH3, or-CH2COOH；
4) monomer D：
The percentage by weight of four kinds of monomers is respectively：A：70%~80%, B：10%~22%, C：3%~9%, D：3%
~5%；The percentage by weight is on the basis of the weight sum of four kinds of monomers；The weight average molecular weight of the copolymer is
10000~40000.
2. Early-strength polycarboxylate superplasticizer according to claim 1, wherein, the weight average molecular weight of the monomer A for 800~
5000。
3. Early-strength polycarboxylate superplasticizer according to claim 1, wherein, the weight average molecular weight of the monomer B for 500~
4000。
4. a kind of preparation method of the Early-strength polycarboxylate superplasticizer of claim 1, including by four kinds of monomers, initiator and
Chain-transferring agent is added in solvent, and the copolymer is made by polymerisation in solution.
5. method according to claim 4, wherein, the reaction temperature of the polymerisation in solution is 60 DEG C~80 DEG C.
6. method according to claim 4, wherein, the reaction time of the polymerisation in solution is 4~6 hours.
7. method according to claim 4, wherein, the initiator is selected from ammonium persulfate, potassium peroxydisulfate, the NSC 18620 salt of azo two
One or more in hydrochlorate, the consumption of the initiator is the 0.1%~2% of four kinds of monomer gross mass.
8. method according to claim 4, wherein, the chain-transferring agent is selected from TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids
In one or more, the consumption of the chain-transferring agent is the 0.1%~0.6% of four kinds of monomer gross mass.
9. according to the method for any one of claim 4 to 8, including will four kinds of monomers addition solvent the step of；To institute
State the step of initiator is added dropwise in solvent；The step of chain-transferring agent is added dropwise into the solvent；Wherein, it is described to trigger
The time for adding of agent is 3~5 hours, is added dropwise within first 1~2 hour the 2/3 of the initiator amount, described trigger is added dropwise in remaining time
The 1/3 of agent consumption.
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| CN106146759A (en) * | 2015-04-09 | 2016-11-23 | 张耀忠 | A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof |
| CN105294004B (en) * | 2015-10-14 | 2018-01-12 | 广东红墙新材料股份有限公司 | A kind of preparation method of pile tube |
| CN105294950B (en) * | 2015-10-14 | 2017-12-05 | 广东红墙新材料股份有限公司 | A kind of pile tube and preparation method thereof |
| CN105330795B (en) * | 2015-10-14 | 2018-05-11 | 广东红墙新材料股份有限公司 | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
| CN105294949B (en) * | 2015-10-14 | 2017-12-05 | 广东红墙新材料股份有限公司 | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof |
| CN105271900B (en) * | 2015-10-14 | 2018-04-20 | 广东红墙新材料股份有限公司 | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
| CN105837765A (en) * | 2016-06-04 | 2016-08-10 | 石家庄市长安育才建材有限公司 | Ester-type high-early-strength water reducing agent and preparation method thereof |
| CN106397685B (en) * | 2016-09-21 | 2019-04-23 | 武汉奥克化学有限公司 | A kind of early-strength water-reducing agent and preparation method thereof |
| CN106632892B (en) * | 2016-12-28 | 2019-11-26 | 江苏奥克化学有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN110540621B (en) * | 2019-07-05 | 2022-05-13 | 广州市建筑科学研究院有限公司 | Polycarboxylate superplasticizer for prefabricated concrete structure and preparation method thereof |
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| WO2012083536A1 (en) * | 2010-12-22 | 2012-06-28 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant |
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