CN104649608A - Additive for improving early strength of cement based material as well as preparation method and application of additive - Google Patents
Additive for improving early strength of cement based material as well as preparation method and application of additive Download PDFInfo
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- CN104649608A CN104649608A CN201410536319.6A CN201410536319A CN104649608A CN 104649608 A CN104649608 A CN 104649608A CN 201410536319 A CN201410536319 A CN 201410536319A CN 104649608 A CN104649608 A CN 104649608A
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Abstract
The invention provides an additive for improving early strength of a cement based material. The additive is prepared by the reaction of an ionic copolymer and silane, wherein the ionic copolymer is prepared by the reaction of a monomer A, a monomer B, a monomer C and a monomer D. The invention further provides a preparation method of the additive for improving early strength of the cement based material and application of the additive in improvement of the early strength of the cement based material. The additive is simple in preparation process, convenient to use, low in cost and relatively high in water reduction rate, accelerates the hydration of the cement in the early stage, improves the early strength of the cement based material, particularly shows an obvious effect on improving the early strength of the cement based material at a low temperature environment, is relatively high in adaptability to the raw materials, has a good super early strength improving effect for different cement, and does not have any adverse effect on the future strength and durability.
Description
Technical field
The invention belongs to technical field of concrete additives, particularly a kind of admixture for improving cement-based material early strength and preparation method thereof.
Background technology
China all occupies first place in the world, for the application of cement-based material super hardening technology provides the huge market space in the great foundation works scale such as the high-speed railway built, subway and tunnel, large bridge, hydroelectric project, Highrise buildings, wind-power electricity generation and quantity.Fragment-free track slab for high ferro construction requires that concrete 16h ultimate compression strength is greater than 48MPa; Concrete shield pipe-plate for subway and tunnel construction even requires that 10h demoulding strength is greater than 20MPa; In addition, the senior engineer of water conservancy construction presses the high-strength annular prestressed concrete electric pole of the engineerings such as the large scale prefabricated concrete box girder of the static pressure of more than the C80 of heavy caliber steel cylinder concrete water transmission pipe (PCCP), Construction of highrise buildings high-strength prestressed (PHC) pile tube, bridge construction, two-channel filter banks and communication construction, concrete soil matrix wind-energy tower used for wind-energy power generation and the rush repair engineering such as airstrip, super highway also to have higher requirement to cement-based material early strength and weather resistance.
Improve the early strength of cement-based material, be conducive to accelerating the turnover of concrete template, improve construction speed and efficiency.Strong technology morning that tradition regulates and controls based on cement composition and fineness, as adopted superfine cement or adopting quick hardening Portland cement to improve the early strength of cement-based material, have that early water heat-transmission is high, contract with dry rate is large, easy to crack, and the deficiency such as later strength and degradation; Add the inorganic salts such as villaumite or vitriol small molecules hardening accelerator exist later strength retraction serious, accelerate steel bar corrosion and alkali-aggregate reaction, increase the series of defect such as concrete shrinkage; And adopting thermal curing technique to improve early strength, production power consumption is high, and the not only later strength decline of steamed concrete component, and weather resistance seriously reduces.
Polycarboxylic admixture is the multipolymer that a class has comb shaped structure, has that volume is low, water-reducing rate is high, function of slump protection is good, concrete contraction percentage is low, an outstanding advantages such as adjustability is strong on molecular structure.Increasing investigator, introduces functional type minor comonomer by copolyreaction or changes molecular structure, achieving the super hardening function of polycarboxylic admixture.Patent WO2011/076655A1 reports a kind of ultra high early strength poly-carboxylic superplasticizer and preparation method thereof, adopt the polyacrylic acid (PAA) of 4000 molecular weight and the poly glycol monomethyl ether (MPEG) of 5000 molecular weight, at 165 DEG C, carry out esterification, then obtain with sodium hydroxide neutralization.The method, in esterification process, adds a certain amount of polypropylene glycol and carries out esterification, can effectively reduce poly carboxylic acid air content; Prepared ultra early-strength polycarboxylic acid super-plasticizer, compared with the synthetic method of first esterification post polymerization, its 6h ultimate compression strength improves more than 50%.But the method needs first to synthesize polyacrylic acid, and due to PAA itself be polymkeric substance, viscosity is comparatively large, and during esterification with polymer MPEG, steric hindrance is comparatively large, and the transformation efficiency of esterification is influenced, and thus the volume of admixture is relatively high, and cost performance is low.Patent EP1547986 report adopts polyethylene glycol monomethyl ethermethacrylic acid esters and methacrylic acid to be polymerization single polymerization monomer, take polypropylene glycol dimethacrylate as cross-linking monomer, take thiohydracrylic acid as chain-transfer agent, by free-radical polymerized technology, prepared cross-linking type polycarboxylic admixture; Compared with uncrosslinked poly carboxylic acid, this admixture has significant super hardening effect in cement-based material.
Except to except the synthesis of the Molecular Structure Design of poly carboxylic acid itself, it is composite that many investigators also start to pay close attention to by polycarboxylate water-reducer and inorganic hardening accelerator.Patent CN101921083 reports a kind of ether-ether mixed ultra high early strength poly-carboxylic high-performance water reducer, the ether-ether mixed type high performance water reducing agent of polyocarboxy acid of 30 ~ 60%, the composite inorganic salt hardening accelerator of 0.1 ~ 5%, polyoxyethylene defoamer, the compound silicofluoride of 10 ~ 40%, the organic compound fast curing additives of 1 ~ 15% of 0.1 ~ 0.6% is adopted to carry out the composite of multicomponent mixture, early strong Be very effective.Patent CN103145368A provides a kind of early strength water-reducing agent, and the raw material of employing and the weight percent of each raw material are: polycarboxylate water-reducer 20 ~ 25%, tri-isopropanolamine 1 ~ 6%, trolamine 0.5 ~ 2%, Sodium Thiocyanate 99 5 ~ 15%, calcium formiate 3 ~ 10%, water 42 ~ 70.5%; This early strength water-reducing agent can improve the early strength of regenerative concrete products, improves the workability of regeneration concrete mixture.But, adopt the method for a large amount of inorganic salt of polycarboxylic acids water reducing agent compositional, add the ionic concn in poly carboxylic acid solution, easily cause polycarboxylate water-reducer flocculation sediment, and the admixture dosage of composite inorganic salt is relatively high, also there is impact to the weather resistance of later stage cement-based material.Such as, patent CN103979886 discloses a kind of preparation method mixing nano silica powder high performance concrete, its nano silica powder material volume used is higher, account for more than 1.5% of gelling material quality, and have no the impact on early stage hour intensity, only concrete seven d intensity is improved largely, due to employing is powder body material, particle agglomeration is serious, is difficult to good distribution, thus causes volume high and early strength does not promote.
Although the development and application of polycarboxylic acid series super hardening admixture makes the development of high-performance chemical admixture have qualitative leap, but just current effect, also have that the adaptability of admixture to cement is poor, early potent fruit fluctuation is comparatively large, be applied to low temperature environment under and the defect such as cement-based material early strength slower development of high adulterant, be difficult to the needs meeting modern project completely.Therefore develop high performance ultra early-strength admixture and certainly will will promote modern concrete further, the particularly concrete development of prefabricated components.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, for current cement-based material to improving the active demand of early strength and the existing early-strength admixture problem of early strong limited efficiency in cement-based material at low ambient temperatures, the object of the present invention is to provide a kind of admixture for improving cement-based material early strength and preparation method thereof, the admixture that the method obtains effectively can not only improve the early strength of cement-based material, there is higher water-reducing rate and cement adaptability, and do not affect later strength and the weather resistance of cement-based material.
Technical scheme: a kind of admixture improving cement-based material early strength provided by the invention is the nanoparticle dispersion liquid obtained by ionic copolymer and silane reaction; Described ionic copolymer reacts obtained by monomer A, monomers B, monomer C, monomer D, and its molecular weight is 50000 ~ 80000;
Monomer A is the vinyl monomer containing sulfonate radical, and its structural formula is such as formula shown in (I):
Wherein, R
1for H or-CH
3; X
1for-CH
2-,-C
6h
4-,-C (O) NHC (CH
3)
2cH
2-; M is H, Na, K;
Monomers B is the monomer containing primary amine, secondary amine or tertiary amine, and its structural formula is such as formula shown in (II) or formula (III):
Wherein, R
2for H or-CH
3; R
3, R
4for the alkyl of H or C1 ~ C5; R
5for H or CH
3; R
6, R
7for the alkyl of H or C1 ~ C5; N is the integer of 1 ~ 3.
Monomer C is double bond containing polyether macromonomer, and its structural formula is as shown in formula IV:
Wherein, R
8for H or-CH
3; R
9for the alkyl of H or C1 ~ C3; X
2for-C (O)-,-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or-C
6h
4-; M is polyoxyethylated average addition mole number, and m is the integer of 25 ~ 110;
Monomer D is the silane monomer containing vinyl, in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane any one or more than one with the mixture of arbitrary proportion mixing.
Present invention also offers the preparation method of the admixture of above-mentioned raising cement-based material early strength, comprise the following steps:
(1) preparation of ionic copolymer: under redox initiation system exists, monomer A, monomers B, monomer C and monomer D carry out free radicals copolymerization reaction, obtain ionic copolymer;
Monomer A is the vinyl monomer containing sulfonate radical, and its structural formula is such as formula shown in (I):
Wherein, R
1for H or-CH
3; X
1for-CH
2-,-C
6h
4-,-C (O) NHC (CH
3)
2cH
2-; M is H, Na, K;
Monomers B is the monomer containing primary amine, secondary amine or tertiary amine, and its structural formula is such as formula shown in (II) or formula (III):
Wherein, R
2for H or-CH
3; R
3, R
4for the alkyl of H or C1 ~ C5; R
5for H or CH
3; R
6, R
7for the alkyl of H or C1 ~ C5; N is the integer of 1 ~ 3.
Monomer C is double bond containing polyether macromonomer, and its structural formula is as shown in formula IV:
Wherein, R
8for H or-CH
3; R
9for the alkyl of H or C1 ~ C3; X
2for-C (O)-,-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or-C
6h
4-; M is polyoxyethylated average addition mole number, and m is the integer of 25 ~ 110;
Monomer D is the silane monomer containing vinyl, in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane any one or more than one with the mixture of arbitrary proportion mixing;
(2) preparation of nanoparticle dispersion liquid: the ionic copolymer aqueous solution that step (1) is obtained is diluted to mass concentration 5% ~ 10%, be warming up to 60 ~ 90 DEG C, add silane, adjust pH to 8 ~ 9, stirring reaction, obtained nanoparticle dispersion liquid, is the admixture improving cement-based material early strength.
In step (1), monomer A be in allyl sulphonic acid, methallylsulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, styrene sulfonic acid and their sodium, sylvite any one or more than one with arbitrary proportion mixing mixture.
In step (1), monomers B is acrylamide, Methacrylamide, N, N-DMAA, N, N-dimethylmethacryl amide, N methacrylamide, NIPA, N-isopropyl acrylamide, N tert butyl acrylamide, N-t-butylmethacrylamide, N-(2-dimethylaminoethyl) acrylamide, N-(2-dimethylaminoethyl) Methacrylamide, N-(3-dimethylamino-propyl) acrylamide, in N-(3-dimethylamino-propyl) Methacrylamide any one or more than one with arbitrary proportion mixing mixture.
In step (1), described monomer C is allyl polyethenoxy ether, methacrylic Soxylat A 25-7, butenyl Soxylat A 25-7, methyl butene base Soxylat A 25-7, vinyl Soxylat A 25-7, hydroxyl butyl vinyl Soxylat A 25-7, 4-ethenylphenyl Soxylat A 25-7, 4-pseudoallyl phenyl Soxylat A 25-7, monomethyl polyethylene glycol acrylate ester, polyethyleneglycol ethyl ether acrylate, polyoxyethylene glycol mono-n-butyl ether acrylate, polyethyleneglycol ethyl isobutyl ether acrylate, polyethylene glycol monomethyl ethermethacrylic acid esters, polyethyleneglycol ethyl ether methacrylate, polyoxyethylene glycol mono-n-butyl ether methacrylic ester, any one in polyethyleneglycol ethyl isobutyl ether methacrylic ester.
In step (1), the mol ratio of monomer A, monomers B, monomer C and monomer D is 1 ~ 10:0.5 ~ 5:1:0.1 ~ 1; Temperature of reaction is 5 ~ 50 DEG C, preferred 5-35 DEG C, adopts low-temp reaction can effectively reduce vinyl-based silane hydrolyzate; Reaction solvent is water, and reaction system pH is 6 ~ 7, and for maintaining this pH value, conventional bronsted lowry acids and bases bronsted lowry can be adopted to adjust system solution pH value, and under this pH value condition, vinyl-based silane is relatively stable;
Redox initiation system is water soluble, redox initiator system, to comprise oxidation component be persulphate and reduction components is the composition of hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, or the composition of oxidation component to be superoxide and reduction components be rongalite or L-AA; Wherein, the quality of oxidation component is 0.1% ~ 2% of monomer A, monomers B, monomer C and monomer D total mass, and the mass ratio of oxidation component and reduction components is 0.2 ~ 4:1;
In reaction system, the total concn of monomer A, monomers B, monomer C and monomer D is 40% ~ 60%.。The polymerization concentration of copolyreaction is formed with remarkably influenced to step (2) product nano particle: concentration is too low, and monomer polymerization transformation efficiency reduces, and water-reducing rate reduces, and in step (2), product nano particle dispersion is unstable; Concentration is too high, and system viscosity increases, and molecular weight increases, and easily causes product nano particle flocculation sediment in step (2), cannot stable dispersion.
In step (1), the molecular weight of ionic copolymer is 50000 ~ 80000; Molecular weight is too little or too large, and the dispersion liquid that step (2) all can be caused to prepare is unstable, occurs layering or flocculation, simultaneously in cement-based material time water-reducing effect obviously reduce.Adopt the method adding water-soluble chain transfer agent in copolyreaction to control the molecular weight of ionic copolymer, the quality of described water-soluble chain transfer agent is 0.1% ~ 1% of monomer A, monomers B, monomer C and monomer D total mass; Described water-soluble chain transfer agent is mercaptan type chain transfer agent, at least one in preferred 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol or the mixture of its arbitrary proportion.
In step (1), the feed way of copolyreaction adopts the mode dripped to carry out, be specially: the reduction components in monomer A, monomers B, initiator, chain-transfer agent and water compositing monomer solution mixture, adopt the mode at the uniform velocity dripped to feed intake after stirring; Monomer C, according to the difference of polymerization activity, drips together with after can mixing with the monomer solution mixture of monomer A, B, or directly before polymerization disposablely all to feed intake; Monomer D directly at the uniform velocity drips separately; Oxidation component in initiator can disposablely before polymerization all feed intake, or at the uniform velocity drips separately after being configured to the aqueous solution with water; Monomer solution mixture time for adding controls at 0.5 ~ 2 hour, and initiator oxidation component aqueous solution time for adding comparatively monomer solution mixture extends 5 ~ 10min, to improve monomer conversion.
In step (2), described silane is Trimethoxy silane, one or more in triethoxyl silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four n-butoxy silane, methyltrimethoxy silane, Union carbide A-162, dimethyldiethoxysilane mix with arbitrary proportion; The quality of described silane is 2 ~ 5:1 with the ratio of monomer A, monomers B, monomer C and monomer D total mass; Temperature of reaction is 60 ~ 90 DEG C.
The time adding silane in step (2) should will begin in a minute as early as possible after the material dropping of step (1).Interval time, the time was oversize no more than 30min, easily caused the silane monomer hydrolytic condensation of polymerization in step (1), unfavorable to subsequent reactions.Add the interval time with step (1) in order to what shorten silane in step (2) as far as possible, the dilution water of the ionic copolymer aqueous solution in step (1) is preferably adopted to the hot water being heated to design temperature in advance.In step (2), the feed postition of silane preferably slowly at the uniform velocity drips, and time for adding is 8 ~ 12h; After silane dropwises, adopt common liquid caustic soda that the pH value of solution is adjusted to 8 ~ 9, continue constant temperature and stir 6 ~ 8h.In constant temperature whipping process, reaction flask can be evacuated to tiny structure, negative pressure pressure is advisable to be no more than-0.03MPa, is more conducive to the by product of silane hydrolyzate in system to be taken out of fast.Constant temperature obtains admixture dispersion liquid after stirring and terminating.
Present invention also offers above-mentioned admixture and improve the application in cement-based material early strength, can according to engineering practice and test in place, selection is used alone, or add other admixtures such as a certain proportion of polycarboxylate water-reducer, defoamer, retardant, air entrapment agent and (or) thickening material, used by composite mode; By composite, the air content of cement-based material, time of coagulation and cohesiveness can be regulated, improve the over-all properties of cement-based material.This admixture conventional volume is in use 0.2% ~ 0.8% (the solid meter of admixture folding) of total gelling material weight; Volume is too low, then can not be satisfactory to the dispersion effect of cement, and super hardening effect reduces; Volume is too high, not only cause waste economically, and dispersion effect and super hardening performance does not increase further.It is preferred that engineering staff can carry out test according to practical situation.
Beneficial effect: the admixture preparation technology of raising cement-based material early strength provided by the invention is simple, easy to use, with low cost, not only there is higher water-reducing rate, accelerate cement early hydration process, be conducive to the early strength improving cement-based material, especially for the morning of cement-based material under low temperature environment, potent fruit was more remarkable, there is stronger starting material adaptability simultaneously, in different cement, all show good super hardening effect, and negative impact is not had to later strength and weather resistance.
Applicant finds, inorganic nano-particle mixes in cement-based material, can accelerate the formation of hydrolysis product of cement crystal, thus effectively improves the early strength of cement-based material.But, cause easy reunion, when using with solid state because inorganic nano-particle particle diameter is little, surface energy is high, be difficult to mix with cement-based material, and it be directly distributed in water, particle is reunited precipitation mutually, directly impact early potent fruit, also affects the mobility of cement-based material simultaneously.The present invention is by generating the obtained admixture of nanoparticle at ionic comb-shaped copolymer solution situ, achieve nanoparticle uniform and stable dispersion in aqueous, and this admixture has higher water-reducing rate and super hardening effect, especially cement-based material potent fruit morning for low temperature environment has more advantage, and does not have negative impact to later strength and weather resistance.
The preparation method of this admixture provided by the invention is by continuous two synthesis steps, first sulfonic acid monomer, amine monomers, polyether macromonomer and vinyl-based silane monomer is adopted to carry out free radicals copolymerization reaction, polymerization ratio between each monomer of conservative control and the molecular-weight average of multipolymer, prepare ionic copolymer, then prepare nanoparticle in this ionic copolymer solution situ hydrolytic condensation, obtain the nanoparticle dispersion liquid of high stability.This dispersion liquid is as the admixture of cement-based material, not only there is higher water-reducing rate, and cement early hydration process can be accelerated, be conducive to the early strength improving cement-based material, especially for the morning of cement-based material under low temperature environment, potent fruit was more remarkable, there is stronger starting material adaptability simultaneously, in different cement, all show good super hardening effect, and negative impact is not had to later strength and weather resistance.
Embodiment
Following examples describe in further detail the process that method preparation according to the present invention improves cement-based material early strength admixture, and these embodiments provide by way of illustration, its object is to person skilled in the art can be understood content of the present invention and implement according to this, but these embodiments never limit the scope of the invention.
Monomer code name in table 1 embodiment
Embodiment 1
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, adding 40g distilled water, 62.3g polyether macromonomer c-1 and 5.37g concentration is the hydrogen peroxide of 30%, stirs rising temperature for dissolving.Under nitrogen protection, pot temperature is maintained until 5 DEG C, then 8.22g monomer a-1,9.22g monomer b-1,0.41g 3-thiohydracrylic acid, 0.34g formaldehyde time sodium bisulfite and 80g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 1h; At the uniform velocity drip 0.92g monomer d-1, time for adding is 1h, and in dropping process, maintenance system pH value is 6 ~ 7 simultaneously.After monomer solution dropwises, obtain M
wthe Ionomer of=50345, and then in flask the disposable distilled water adding 1411.5g 60 DEG C, be warming up to 60 DEG C, then at the uniform velocity dropped in flask by 282.3g triethoxyl silane, time for adding 8h, after dropwising, system pH is adjusted between 8 ~ 9, then flask is evacuated to-0.03MPa, constant voltage constant temperature stirs 6h, obtains admixture dispersion liquid NP-1.
Embodiment 2
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 20g distilled water, 92.6g polyether macromonomer c-2, stir rising temperature for dissolving.Under nitrogen protection, pot temperature is maintained until 35 DEG C, then 29.26g monomer a-2,0.95g monomer b-2,0.14g Thiovanic acid, 0.51g sodium bisulfite and 30g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 0.5h; At the uniform velocity drip 3.45g monomer d-2, time for adding is 0.5h; At the uniform velocity drip the initiator solution mixed by 0.13g Sodium Persulfate and 34g distilled water, time for adding is 40min, and in dropping process, maintenance system pH value is 6 ~ 7 simultaneously.After initiator solution dropwises, obtain M
wthe Ionomer of=76408, and then in flask the disposable distilled water adding 1052.2g 90 DEG C, be warming up to 90 DEG C, then at the uniform velocity dropped in flask by 628.79g tetraethoxysilane, time for adding 12h, after dropwising, system pH is adjusted between 8 ~ 9, then flask is evacuated to-0.02MPa, constant voltage constant temperature stirs 8h, obtains admixture dispersion liquid NP-2.
Embodiment 3
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 37g distilled water, 84.2g polyether macromonomer c-3, stir rising temperature for dissolving.Under nitrogen protection, pot temperature is maintained until 20 DEG C, then 37.35g monomer a-3,3.26g monomer b-3,1.10g 2 mercaptopropionic acid, 2.86g S-WAT and 50g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 2h; At the uniform velocity drip 3.07g monomer d-3, time for adding is 2h; At the uniform velocity drip the initiator solution mixed by 1.02g Potassium Persulphate and 40g distilled water, time for adding is 125min, and in dropping process, maintenance system pH value is 6 ~ 7 simultaneously.After initiator solution dropwises, obtain M
wthe Ionomer of=79860, and then in flask the disposable distilled water adding 1342.7g 80 DEG C, be warming up to 80 DEG C, then at the uniform velocity dropped in flask by 345.28g tetramethoxy-silicane, time for adding 10h, after dropwising, system pH is adjusted between 8 ~ 9, then flask is evacuated to-0.01MPa, constant voltage constant temperature stirs 7h, obtains admixture dispersion liquid NP-3.
Embodiment 4
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 20g distilled water and 3.13g concentration is the hydrogen peroxide of 30%, stir and heat up.Under nitrogen protection, pot temperature is maintained until 30 DEG C, then 19.06g monomer a-4,3.75g monomer b-1,7.59g monomer b-2,42.3g polyether macromonomer c-4,0.77g mercaptoethanol, 0.8g L-AA and 44g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 0.5h; At the uniform velocity drip 5.57g monomer d-4, time for adding is 0.5h, and in dropping process, maintenance system pH value is 6 ~ 7 simultaneously.After monomer solution dropwises, obtain M
wthe Ionomer of=68225, and then in flask the disposable distilled water adding 1423.2g 65 DEG C, be warming up to 65 DEG C, then at the uniform velocity dropped in flask by the mixture of 102.3g tetraethoxysilane and 237.46g Union carbide A-162 composition, time for adding 9h, after dropwising, system pH is adjusted between 8 ~ 9, then flask is evacuated to-0.03MPa, constant voltage constant temperature stirs 8h, obtains admixture dispersion liquid NP-4.
Embodiment 5
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 50g distilled water and 1.81g ammonium persulphate, stirring and dissolving.Under nitrogen protection, pot temperature is maintained until 15 DEG C, then 6.75g monomer a-1,16.82g monomer a-3,12.36g monomer b-3,62.5g monomer c-5,0.25g 2-mercaprol, 2.72g sodium bisulfite and 73g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 1.5h; At the uniform velocity drip 2.38g monomer d-2, time for adding is 1.5h, and in dropping process, maintenance system pH value is 6 ~ 7.After monomer solution dropwises, obtain M
wthe Ionomer of=56210, and then in flask the disposable distilled water adding 1456.1g 85 DEG C, be warming up to 85 DEG C, then at the uniform velocity dropped in flask by 216.73g methyltrimethoxy silane, time for adding 11h, after dropwising, system pH is adjusted between 8 ~ 9, then flask is evacuated to-0.01MPa, constant voltage constant temperature stirs 6h, obtains admixture dispersion liquid NP-5.
Except above material, determine to adopt following material all can realize the object of the invention by simple experiment:
Monomer A be in allyl sulphonic acid, methallylsulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, styrene sulfonic acid and their sodium, sylvite any one or more than one with arbitrary proportion mixing mixture.
Monomers B is acrylamide, Methacrylamide, N, N-DMAA, N, N-dimethylmethacryl amide, N methacrylamide, NIPA, N-isopropyl acrylamide, N tert butyl acrylamide, N-t-butylmethacrylamide, N-(2-dimethylaminoethyl) acrylamide, N-(2-dimethylaminoethyl) Methacrylamide, N-(3-dimethylamino-propyl) acrylamide, in N-(3-dimethylamino-propyl) Methacrylamide any one or more than one with arbitrary proportion mixing mixture.
Monomer C is allyl polyethenoxy ether, methacrylic Soxylat A 25-7, butenyl Soxylat A 25-7, methyl butene base Soxylat A 25-7, vinyl Soxylat A 25-7, hydroxyl butyl vinyl Soxylat A 25-7, 4-ethenylphenyl Soxylat A 25-7, 4-pseudoallyl phenyl Soxylat A 25-7, monomethyl polyethylene glycol acrylate ester, polyethyleneglycol ethyl ether acrylate, polyoxyethylene glycol mono-n-butyl ether acrylate, polyethyleneglycol ethyl isobutyl ether acrylate, polyethylene glycol monomethyl ethermethacrylic acid esters, polyethyleneglycol ethyl ether methacrylate, polyoxyethylene glycol mono-n-butyl ether methacrylic ester, any one in polyethyleneglycol ethyl isobutyl ether methacrylic ester.
Comparative example 1
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, adding 40g distilled water, 62.3g polyether macromonomer c-1 and 5.37g concentration is the hydrogen peroxide of 30%, stirs rising temperature for dissolving.Under nitrogen protection, pot temperature is maintained until 5 DEG C, then 8.22g monomer a-1,9.22g monomer b-1,0.41g 3-thiohydracrylic acid, 0.34g formaldehyde time sodium bisulfite and 80g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 1h; At the uniform velocity drip 0.92g monomer d-1, time for adding is 1h simultaneously.After monomer solution dropwises, obtain M
wthe polymkeric substance of=65240, and then in flask the disposable distilled water adding 1411.5g60 DEG C, be warming up to 60 DEG C, constant temperature stir 6h, sample 1 must be contrasted.
Comparative example 2
In the 2L glass round bottom flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 24.5g distilled water, 121.4g polyether macromonomer c-2, stir rising temperature for dissolving.Under nitrogen protection, pot temperature is maintained until 50 DEG C, then 17.5g vinylformic acid, 1.32g Thiovanic acid, 0.69g sodium bisulfite and 38.1g distilled water mix and blend are made uniform monomer solution, it at the uniform velocity dropped in round-bottomed flask, time for adding is 2h; At the uniform velocity drip the initiator solution mixed by 0.18g Sodium Persulfate and 30g distilled water, time for adding is 2h10min, and in dropping process, maintenance system pH value is 6 ~ 7 simultaneously.After initiator solution dropwises, obtain M
wthe polymkeric substance of=34820, and then disposablely in flask add 1157.5g distilled water, be warming up to 90 DEG C, then 205.8g tetraethoxysilane is at the uniform velocity dropped in flask, time for adding 10h, after dropwising, is adjusted to system pH between 8 ~ 9, then constant temperature stirs 8h, must contrast sample 2.
Application Example 1
Prepared admixture is used for cement mortar strength test, cement joins PO 42.5 class g cement in using, and test sand adopts iso standard sand, and cement-sand ratio is 1:2.7, and water cement ratio is 0.4.Admixture dosage take cement quality as benchmark, and by the solid gauge of folding, adjusted by the volume of admixture, controlling mortar initial flow degree is 250 ± 10mm, adopts defoamer to control each group of mortar unit weight basically identical.After glue sand specimen molding, being placed in humidity is more than 95%, and temperature is carry out maintenance under the condition of 25 ± 2 DEG C.Contrast sample 1 and 2 is respectively the sample of comparative example's synthesis, and contrast sample 3 is the RHEOPLUS 411 ultra early-strength polycarboxylic admixture of commercially available BASF, and PCE is the polycarboxylate water-reducer of Su Bote companies market normal conventional
contrast sample 4 is commercially available Nano-meter SiO_2
2powder, particle diameter 10 ~ 100nm.
Table 2 cement mortar strength test-results
Find out from test-results, by admixture NP-1 ~ 5 of preparing described in embodiment, in middle PO 42.5 class g cement, all can increase substantially age strength morning of mortar.Under normal temperature 25 DEG C of conditions, compared with common poly carboxylic acid (PCE and contrast sample 1), 8h early strength obviously promotes, 10h ultimate compression strength raising about more than 150%; Compared with contrasting sample 3 with external ultra early-strength polycarboxylic admixture, the admixture prepared by the present invention improves about 50% in 8h and the 10h ultimate compression strength of mortar, does not have negative impact to the intensity of later stage 28d; Nano-meter SiO_2 is mixed with outer separately
2powder is compared, and admixture powder needs the volume increasing substantially water reducer, guarantee mortar initial fluidity, and Nano-meter SiO_2
2add with powder, and have no significant super hardening effect, improve Nano-meter SiO_2 further
2addition, then also need to improve the consumption of water reducer, and super hardening effect has no obvious lifting, this may be less due to diameter of particle, caused by the reason of difficult dispersion of easily reuniting.
Application Example 2
Prepared admixture is used for cement mortar strength test, cement uses little wild field P II 52.5 class g cement, and test sand adopts iso standard sand, and cement-sand ratio is 1:2.5, and water cement ratio is 0.36.Admixture dosage take cement quality as benchmark, by the solid gauge of folding, controls each group of mortar unit weight basically identical by defoamer.After glue sand specimen molding, being placed in humidity is more than 95%, and temperature is carry out maintenance under the condition of 5 ± 1 DEG C.Contrast sample 3 is the RHEOPLUS 411 ultra early-strength polycarboxylic admixture of commercially available BASF, and PCE is the polycarboxylate water-reducer of Su Bote companies market normal conventional
Table 3 cement mortar strength test-results
Find out from test-results, by admixture NP-1 ~ 5 of preparing described in embodiment, in little wild field P II 52.5 class g cement, all can increase substantially age strength morning of mortar, there is stronger cement adaptability.Under low temperature 5 DEG C of conditions, the super hardening admixture that 12h and 16h ultimate compression strength comparatively contrasts sample 3 significantly promotes, and lifting amplitude improves more than 50% more than 70%, 24h ultimate compression strength, and does not affect 28d later strength; Compared with the contrast sample 3 of composite trolamine, 12h and 16h ultimate compression strength still can improve about 50%.As can be seen here, even if at a lower temperature, the admixture dispersion liquid prepared described in this patent still has preferably super hardening action effect.
Claims (9)
1. improve an admixture for cement-based material early strength, it is characterized in that: the nanoparticle dispersion liquid obtained by ionic copolymer and silane reaction; Described ionic copolymer reacts obtained by monomer A, monomers B, monomer C, monomer D, and its molecular weight is 50000 ~ 80000;
Monomer A is the vinyl monomer containing sulfonate radical, and its structural formula is such as formula shown in (I):
Wherein, R
1for H or-CH
3; X
1for-CH
2-,-C
6h
4-,-C (O) NHC (CH
3)
2cH
2-; M is H, Na, K;
Monomers B is the monomer containing primary amine, secondary amine or tertiary amine, and its structural formula is such as formula shown in (II) or formula (III):
Wherein, R
2for H or-CH
3; R
3, R
4for the alkyl of H or C1 ~ C5; R
5for H or CH
3; R
6, R
7for the alkyl of H or C1 ~ C5; N is the integer of 1 ~ 3.
Monomer C is double bond containing polyether macromonomer, and its structural formula is as shown in formula IV:
Wherein, R
8for H or-CH
3; R
9for the alkyl of H or C1 ~ C3; X
2for-C (O)-,-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or-C
6h
4-; M is polyoxyethylated average addition mole number, and m is the integer of 25 ~ 110;
Monomer D is the silane monomer containing vinyl, in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane any one or more than one with the mixture of arbitrary proportion mixing.
2. a kind of preparation method improving the admixture of cement-based material early strength according to claim 1, is characterized in that: comprise the following steps:
(1) preparation of ionic copolymer: under redox initiation system exists, monomer A, monomers B, monomer C and monomer D carry out free radicals copolymerization reaction, obtain ionic copolymer;
Monomer A is the vinyl monomer containing sulfonate radical, and its structural formula is such as formula shown in (I):
Wherein, R
1for H or-CH
3; X
1for-CH
2-,-C
6h
4-,-C (O) NHC (CH
3)
2cH
2-; M is H, Na, K;
Monomers B is the monomer containing primary amine, secondary amine or tertiary amine, and its structural formula is such as formula shown in (II) or formula (III):
Wherein, R
2for H or-CH
3; R
3, R
4for the alkyl of H or C1 ~ C5; R
5for H or CH
3; R
6, R
7for the alkyl of H or C1 ~ C5; N is the integer of 1 ~ 3.
Monomer C is double bond containing polyether macromonomer, and its structural formula is as shown in formula IV:
Wherein, R
8for H or-CH
3; R
9for the alkyl of H or C1 ~ C3; X
2for-C (O)-,-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or-C
6h
4-; M is polyoxyethylated average addition mole number, and m is the integer of 25 ~ 110;
Monomer D is the silane monomer containing vinyl, in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane any one or more than one with the mixture of arbitrary proportion mixing;
(2) preparation of nanoparticle dispersion liquid: the ionic copolymer aqueous solution that step (1) is obtained is diluted to mass concentration 5% ~ 10%, be warming up to 60 ~ 90 DEG C, add silane, adjust pH to 8 ~ 9, stirring reaction, obtained nanoparticle dispersion liquid, is the admixture improving cement-based material early strength.
3. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, it is characterized in that: in step (1), monomer A be in allyl sulphonic acid, methallylsulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, styrene sulfonic acid and their sodium, sylvite any one or more than one with arbitrary proportion mixing mixture.
4. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, it is characterized in that: in step (1), monomers B is acrylamide, Methacrylamide, N, N-DMAA, N, N-dimethylmethacryl amide, N methacrylamide, NIPA, N-isopropyl acrylamide, N tert butyl acrylamide, N-t-butylmethacrylamide, N-(2-dimethylaminoethyl) acrylamide, N-(2-dimethylaminoethyl) Methacrylamide, N-(3-dimethylamino-propyl) acrylamide, in N-(3-dimethylamino-propyl) Methacrylamide any one or more than one with arbitrary proportion mixing mixture.
5. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, it is characterized in that: in step (1), described monomer C is allyl polyethenoxy ether, methacrylic Soxylat A 25-7, butenyl Soxylat A 25-7, methyl butene base Soxylat A 25-7, vinyl Soxylat A 25-7, hydroxyl butyl vinyl Soxylat A 25-7, 4-ethenylphenyl Soxylat A 25-7, 4-pseudoallyl phenyl Soxylat A 25-7, monomethyl polyethylene glycol acrylate ester, polyethyleneglycol ethyl ether acrylate, polyoxyethylene glycol mono-n-butyl ether acrylate, polyethyleneglycol ethyl isobutyl ether acrylate, polyethylene glycol monomethyl ethermethacrylic acid esters, polyethyleneglycol ethyl ether methacrylate, polyoxyethylene glycol mono-n-butyl ether methacrylic ester, any one in polyethyleneglycol ethyl isobutyl ether methacrylic ester.
6. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, is characterized in that: in step (1), the mol ratio of monomer A, monomers B, monomer C and monomer D is 1 ~ 10:0.5 ~ 5:1:0.1 ~ 1; Temperature of reaction is 5 ~ 50 DEG C, preferred 5-35 DEG C; Reaction solvent is water, and reaction system pH is 6 ~ 7; Redox initiation system is water soluble, redox initiator system, to comprise oxidation component be persulphate and reduction components is the composition of hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, or the composition of oxidation component to be superoxide and reduction components be rongalite or L-AA; Wherein, the quality of oxidation component is 0.1% ~ 2% of monomer A, monomers B, monomer C and monomer D total mass, and the mass ratio of oxidation component and reduction components is 0.2 ~ 4:1; In reaction system, the total concn of monomer A, monomers B, monomer C and monomer D is 40% ~ 60%.
7. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, is characterized in that: in step (1), the molecular weight of ionic copolymer is 50000 ~ 80000.
8. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, it is characterized in that: in step (1), add water-soluble chain transfer agent in reaction system, the quality of described water-soluble chain transfer agent is 0.1% ~ 1% of monomer A, monomers B, monomer C and monomer D total mass; Described water-soluble chain transfer agent is mercaptan type chain transfer agent, at least one in preferred 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol or the mixture of its arbitrary proportion.
9. a kind of preparation method improving the admixture of cement-based material early strength according to claim 2, it is characterized in that: in step (2), described silane is Trimethoxy silane, one or more in triethoxyl silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four n-butoxy silane, methyltrimethoxy silane, Union carbide A-162, dimethyldiethoxysilane mix with arbitrary proportion; The quality of described silane is 2 ~ 5:1 with the ratio of monomer A, monomers B, monomer C and monomer D total mass; Temperature of reaction is 60 ~ 90 DEG C; The feed postition of silane preferably slowly at the uniform velocity drips, and time for adding is 8 ~ 12h; After silane dropwises, adopt common liquid caustic soda that the pH value of solution is adjusted to 8 ~ 9, continue constant temperature and stir 6 ~ 8h.
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