CN105601825A - Preparation method for water reducer with relatively high clay tolerance - Google Patents
Preparation method for water reducer with relatively high clay tolerance Download PDFInfo
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- CN105601825A CN105601825A CN201510987981.8A CN201510987981A CN105601825A CN 105601825 A CN105601825 A CN 105601825A CN 201510987981 A CN201510987981 A CN 201510987981A CN 105601825 A CN105601825 A CN 105601825A
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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- Polymerisation Methods In General (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method for a water reducer with relatively high clay tolerance. The preparation method comprises the steps of performing thermal induced polymerization on unsaturated carboxylic acid monomers A, ultraviolet active special monomers C and initiation assistant monomers B in a toluene solution by adopting an initiator D to obtain macromolecules E with ultraviolet activities; and adding the prepared active macromolecules E into de-ionized water for dissolution, and under the ultraviolet irradiation, slowly dropwise adding N-vinyl pyrrolidone (N-VP) to perform a graft polymerization reaction to obtain final water reducer molecules. According to the preparation method, the water reducer has excellent clay tolerance while having better water reducing performance; when the mud content of aggregates is relatively high, the problems in water reduction and slump retention can be effectively solved; the excess blending does not need to be performed for improving the water reducing performance; an extra sacrificial agent does not need to be added; and the preparation method has relatively high economic benefits.
Description
Technical field
The present invention relates to one and do not contain polyethylene oxide side-chain, thereby there is the diminishing of good clay patienceAgent and preparation method thereof, belongs to technical field of concrete additives.
Background technology
Polycarboxylate water-reducer (being also referred to as cement dispersants) is important as the one in modern high performance concretePart, because it has that volume is low, diminishing is high, adaptability is good, adjustability of structure is strong and environmental protection etc.Advantage, obtains huge development and application widely in recent ten years. But academia and engineering practice all show,Clay in sand material, especially imvite have more significant shadow to the diminishing dispersive property of polycarboxylate water-reducerRing. The shared volume fraction of sandstone in concrete is 60～75%, and quality ratio 70～80%, is coagulationThe important component part of soil. In recent years, natural quality sand and stone resources growing tension, the use of low-grade aggregate is moreCome manyly, polycarboxylate water-reducer has spread in commerical ready-mixed concrete day by day in addition, the shadow of clay content to polycarboxylic acidsRing more and more outstanding.
In actual production, in the time that the clay content of aggregate exceeds standard and affect concrete work performance, general employing rinsedThe method of aggregate, but this method can cause environmental pollution, damages the grating of sand, has changed concrete match ratio,Especially at cold district, when flushing, cause and freeze, have a strong impact on project progress. In Practical Project, also find, whenWhen cement content is higher, improves merely polycarboxylic acids volume and can not solve diminishing and protect the problem of collapsing, polycarboxylic acids is super to be mixedNot only make cost increase, also can cause on the other hand the problems such as the initial segregation of concrete is serious, and setting time is long.
US Patent No. 6353952B1 has reported a kind of by optimizing ethylene oxide and oxidation in polycarboxylic acids side chainThe ratio of propylene, destroys compound with regular structure degree, reduces the hydrogen bond action of ethylene oxide and clay, reaches to reduce to gatherThe object of carboxylic acid and clay effect. Chinese patent CN201010119879.3 has reported a kind of polyethylene glycolsLittle molecule auxiliary agent, this auxiliary agent adds prior to polycarboxylic acids, is preferentially adsorbed in clay, plays the effect of sacrifice agent, soAfter mix again polycarboxylate water-reducer make its performance diminishing protect the effect of collapsing. Chinese patent CN201410075133.5 reportRoad one kind of multiple inorganic matters and the compound clay screener of organic matter, Chinese patent CN201310675751.9Report a kind of clay screener of cationic polymer. The diminishing that but these are composite or prepared by other technologiesAgent, has just suppressed the impact of clay on polycarboxylate water-reducer a little, can not tackle the problem at its root, andAdopt the method for sacrifice agent or screener, cause on the one hand the rising of cost, also make on the other hand efficiency of construction tightHeavily decline.
From the molecular structure of water reducer, improve its patience to clay especially imvite, become oneIndividual urgent problem.
Summary of the invention
When higher for aggregate clay content, polycarboxylic acids volume can not solve diminishing and protect the problem of collapsing, polycarboxylic acidsSuper mixing not only makes cost increase, and also can cause on the other hand the initial segregation of concrete serious, and setting time is long etc.Problem, the invention provides a kind of polycarboxylate water-reducer with polyvinylpyrrolidone side chain and preparation method thereof,Because it does not contain polyethylene oxide side-chain, clay is had to extraordinary patience.
From traditional polycarboxylic acids molecular structure, polycarboxylic acids is divided into main chain and side chain two parts, and main chain generally containsThere are the elecrtonegativity groups such as carboxyl, are adsorbed onto the cement particle surface of positive electricity; And side chain is generally and has certain lengthWith the large molecule of polyethylene glycol oxide of rigidity, form and there is certain thickness hydrophilic protective films, by sterically hinderedEffect stops the cohesion of cement granules, improves the mobility of cement slurry. Clay is such as imvite is a kind of multilayerLaminated structure, electronegative in its aspect, and positively charged on layer limit, from electrical angle, imvite is to poly-carboxylicIt is too many that the adsorption capacity of acid main chain should not exceed cement. But the interlayer of imvite very easily with polycarboxylic acids side chain inPolyethylene glycol oxide forms hydrogen bond action, and for polycarboxylic acids molecule, the shared quality ratio of side chain is far above main chain,Once and a side chain is adsorbed, whole polycarboxylic acids molecule just cannot be adsorbed onto on cement again, therefore from this angleDegree, imvite to the competitive Adsorption ability of traditional polycarboxylic acids molecule far above cement. United States Patent (USP)US6353952B1 attempts to destroy by introducing PPOX the hydrogen bond of ethylene oxide and imvite just,Reduce absorption, but it still contains a large amount of polyethylene glycol oxides, can only obtain the limited effect of improving.
The present invention first make a kind of by unsaturated carboxylic acid monomer and have ultraviolet activity particular monomers copolymerization andThe active large molecule of ultraviolet becoming, the large molecule of this activity under the irradiation of ultraviolet light, certain that can be on its strandA little avtive spots produce free radical, now drip vinylpyrrolidone monomer, be grafted on macromolecular main chain,Form the side chain of certain length. This polymer has the structure of similar traditional polycarboxylic acids, on its main chain, has carboxylicAcid adsorption group, side chain is by the large molecule of polyvinylpyrrolidone of certain length and rigidity, and formation has necessarily thickThe hydrophilic protective films of degree, stops cement granules cohesion by sterically hindered effect, improves cement thick liquid flowability.Because polyvinylpyrrolidone and imvite cannot form intercalation absorption, fundamentally solve clay to water reducerCompetitive Adsorption, there is extraordinary clay patience.
The invention provides a kind of preparation method of the water reducer with higher clay patience, comprise following stepRapid:
(1) preparation of active large molecule E: by the particular monomers C of unsaturated carboxylic acid monomer A and ultraviolet activityAnd help trigger monomer B in toluene solution, to adopt initator D to utilize thermal-initiated polymerization to make to there is ultraviolet activityLarge molecule E;
It is 10～25% that polymerization concentration should be controlled at mass concentration, and polymerization temperature is controlled at 60～70 DEG C, when polymerizationBetween be controlled at 5～10h, after polymerization completes, remove toluene by decompression distillation, obtain the large molecule E of activity of solid,By regulating and controlling polymerization concentration and its molecular weight of initiator amount control between 3000 to 8000;
Described initator D is azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO), consumption control0.5～2%; Wherein (B+C)/A quality ratio is between 0.5～1, B/C quality ratio 0.8～1.2 itBetween;
(2) preparation of water reducer: the large molecule E of activity of the solid that step (1) is made joins deionizationIn water, dissolve, under the irradiation of ultraviolet light, slowly splashing into NVP (N-VP), to carry out grafting poly-Close reaction and obtain final water reducer molecule;
It is 20～60% that the concentration of graft polymerization reaction should be controlled at mass concentration, NVP(N-VP) time for adding is controlled at 3～5h, and dropping finishes rear continuation reaction and obtains final subtracting after 0.5 hourAqua product, by regulating and controlling polymerization concentration and its molecular weight of time for adding control between 20000 to 80000;
The mass ratio of described NVP and active large molecule E is between 3～10, if higher than 10The follow-up water reducer main chain adsorption group obtaining is on the low side, causes the absorption of cement granules on the weak side; If lower than 3The follow-up water reducer side chain obtaining is on the low side, and sterically hindered effect is inadequate, is not enough to disperse cement granules;
The general formula of described monomer A is:
In formula, R1 represents H or COOM; R2 represents H or CH3, and in the time that R1 is COOM,R2 only represents H; M represents H, Na, K or NH4;
Described monomers B is the tertiary amines material that contains unsaturated double-bond, and described monomer C is for containing unsaturated double-bondBenzophenone material.
Above-mentioned three kinds of monomer A, B, C must meet certain ratio, and wherein (B+C)/A quality ratio is necessaryBetween 0.5～1, if on the low side higher than 1 follow-up water reducer main chain adsorption group obtaining, cause cementThe absorption of particle is on the weak side; If on the low side lower than 0.5 follow-up water reducer side chain obtaining, sterically hindered effect is inadequate,Be not enough to disperse cement granules. In addition, B/C quality ratio must be between 0.8～1.2, and the two could be maximumThe formation charge-transfer complex of limit, is conducive to improve the ultraviolet efficiency of initiation of subsequent step more.
In the present invention, monomer A mainly provides adsorption group. The monomer of general formula (1) representative comprises: acrylic acid,Sodium salt, sylvite or the ammonium salt of methacrylic acid, maleic acid or acrylic acid, methacrylic acid, maleic acid. TheseMonomer passes through commercially available, and uses separately or use with more than one arbitrary proportion form of mixtures.
Monomer C is the benzophenone material that contains unsaturated double-bond, and it has two keys, the bar that can cause in heatUnder part with monomer A polymerization. Benzophenone group can be used as potential active site simultaneously, in the irradiation of ultraviolet lightThe effect of Inducing Graft Polymerization is played in lower generation free radical site in next step reaction. Monomer C mainly wrapsDraw together following several material, these monomers are by commercially available, and use separately or with more than one arbitrary proportionsForm of mixtures is used.
Monomers B is the tertiary amines material that contains unsaturated double-bond, and it has two keys, under the condition that can cause in heatWith monomer A and monomer C polymerization. Simultaneously because tertiary amine group can be aggregated to same master with benzophenone groupOn chain, more easily form charge-transfer complex, reduced the activation energy that ultraviolet light causes, improved efficiency of initiation.α-C position by electric charge transferance tertiary amine group also can form free radical, in next step reaction, playsThe effect of Inducing Graft Polymerization. Monomers B mainly comprises following several material, and these monomers pass through commercially available,And use separately or use with more than one arbitrary proportion form of mixtures.
The water reducer with good clay patience of the present invention also can be selected from existing with at least oneKnown aminosulfonic water-reducing agent, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent phase in technologyMix. In addition, except known cement water reducing agent above-mentioned, wherein also can add air entraining agent, expansionAgent, set retarder, early strength agent, tackifier, economization agent and defoamer etc.
The invention has the beneficial effects as follows: water reducer of the present invention has good when having better water-reducing propertyClay patience, can be in the time that aggregate clay content be higher, effectively solves diminishing and protects the problem of collapsing, and does not need to lead toCross to surpass and mix to improve diminishing, also do not need to add extra sacrifice agent, there is good economic benefit.
Detailed description of the invention
Following examples have described in more detail the process that the method according to this invention is prepared polymerizate, and thisA little embodiment provide in the mode of explanation, and its object is to allow person skilled in the art can understand the present inventionContent and implement according to this, but these embodiment never limit the scope of the invention. All spiritual real according to the present inventionThe equivalence that matter is done changes or modifies, within all should being encompassed in protection scope of the present invention.
In synthetic example and comparative example, use the listed raw material code name of table 1:
Table 1 synthetic example and comparative example raw material code name
Synthetic example
Raw material and ratio that synthetic example and comparative example adopt are listed table 2 in.
The synthesis condition that the each embodiment of table 2 adopts
The molecular weight of sample adopts static light scattering to measure, and testing procedure is as follows: the polymer obtaining is configured toThe solution of 0.5mg/mL, with the water-based membrane filtration of 0.22 μ m, then adopts light scattering apparatus(ALV/CGS-3, ALV, Germany) carries out static light scattering test molecular weight analyte (SLS). Test specimensThe dn/dc of product adopts BI-DNDC (DNDC-2010, λ=620nm, WGE, Germany) to measure.
Synthetic example 1
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 52.98gA-1,12.25gB-1,14.76gC-1 and 719.58g toluene are heated to after 60 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.42gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-1,
Molecular weight is 5700. Get 38.46gE-1 and be dissolved in 325g water, stirring and dissolving is also led to nitrogen after 30 minutes,
Under the irradiation of ultraviolet light, in 3 hours, drip 136.54gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 65800.
Synthetic example 2
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 72.29gA-1,22.33gB-1,25.38gC-2 and 719.58g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-2,Molecular weight is 6900. Get 37.50gE-2 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 112.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 38300.
Synthetic example 3
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 90.57gA-1,26.31gB-2,27.12gC-1 and 654.43g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 1.57gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-3,Molecular weight is 5900. Get 34.78gE-3 and be dissolved in 300g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 165.22gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 56700.
Synthetic example 4
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 83.72gA-2,30.14gB-3,30.14gC-2 and 655.21g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.79gD-2 insulation reaction after 8 hours, decompression steams toluene, obtains intermediate product E-4,Molecular weight is 7200. Get 15.27gE-4 and be dissolved in 400g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 4 hours, drip 84.73gN-VP, dropwise rear continuation and irradiate reaction 30Minute, obtaining the water reducer aqueous solution, molecular weight is 52700.
Synthetic example 5
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 48.48gA-2,22.37gB-4,25.14gC-3 and 703.28g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.72gD-2 insulation reaction after 8 hours, decompression steams toluene, obtains intermediate product E-5,Molecular weight is 3600. Get 22.58gE-5 and be dissolved in 325g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 4 hours, drip 152.42gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 22800.
Synthetic example 6
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 64.86gA-3,26.86gB-4,28.27gC-4 and 678.84g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 1.16gD-2 insulation reaction after 10 hours, decompression steams toluene, obtains intermediate product E-6,Molecular weight is 4900. Get 20.20gE-6 and be dissolved in 300g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 4 hours, drip 179.80gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 77600.
Synthetic example 7
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 91.43gA-3,35.12gB-2,33.45gC-5 and 637.58g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 2.42gD-2 insulation reaction after 10 hours, decompression steams toluene, obtains intermediate product E-7,Molecular weight is 5000. Get 22.83gE-7 and be dissolved in 250g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 5 hours, drip 227.17gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 20700.
Synthetic example 8
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 129.03gA-1,37.96GB-3,33.01gC-1 and 596.52g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir30 minutes. Add 3.48gD-1 insulation reaction after 8 hours, decompression steams toluene, obtains intermediate product E-8,Molecular weight is 5800. Get 27.27gE-8 and be dissolved in 200g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 5 hours, drip 272.73gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 31800.
Synthetic example 9
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 106.67gA-1,37.53GB-1,31.80gC-2 and 621.75g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir30 minutes. Add 2.25gD-1 insulation reaction after 8 hours, decompression steams toluene, obtains intermediate product E-9,Molecular weight is 3900. Get 17.50gE-9 and be dissolved in 325g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 5 hours, drip 157.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 35900.
Synthetic example 10
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 64.17gA-1,28.86gB-1,26.97gC-1 and 677.60g toluene are heated to after 70 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 2.40gD-1 insulation reaction after 8 hours, decompression steams toluene, obtains intermediate product E-10,Molecular weight is 7400. Get 21.79gE-10 and be dissolved in 300g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 5 hours, drip 178.21gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 23100.
Comparative example 1
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 92.31gA-1,12.96gB-1,14.73gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-11,Molecular weight is 7200. Get 37.50gE-11 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 112.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 40400.
Comparative example 2
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 48.00gA-1,33.70gB-1,38.30gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-12,Molecular weight is 5200. Get 37.50gE-12 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 112.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 37900.
Comparative example 3
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 72.29gA-1,15.90gB-1,31.81gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-13,Molecular weight is 7900. Get 37.50gE-13 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 112.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 27300.
Comparative example 4
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 72.29gA-1,28.63gB-1,19.08gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-14,Molecular weight is 5400. Get 37.50gE-14 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 112.50gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 63700.
Comparative example 5
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 72.29gA-1,22.33gB-1,25.38gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-15,Molecular weight is 6900. Get 50.00gE-15 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 100.00gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 30300.
Comparative example 6
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 72.29gA-1,22.33gB-1,25.38gC-2 and 679.08g toluene are heated to after 65 DEG C under the condition that is connected with nitrogen, stir 30Minute. Add 0.92gD-1 insulation reaction after 5 hours, decompression steams toluene, obtains intermediate product E-16,Molecular weight is 6900. Get 11.54gE-15 and be dissolved in 350g water, stirring and dissolving is also led to nitrogen after 30 minutes,Under the irradiation of ultraviolet light, in 3 hours, drip 138.46gN-VP, dropwise rear continuation and irradiate reaction30 minutes, obtain the water reducer aqueous solution, molecular weight is 91500.
Application Example
Application Example 1
For evaluating diminishing and the function of slump protection of the water reducer prepared of the present invention, enter with reference to GB/T8077-2012 standardGo flowing degree of net paste of cement test, cement 300g, amount of water is 87g, stirs after 4 minutes at plate glassUpper mensuration flowing degree of net paste of cement, and test the clean slurry fluidity after 1 hour, experimental result is in table 3.
Table 3 embodiment and comparative example flowing degree of net paste of cement
Water-reducing Admixtures To Cements prepared by the present invention of table 3 data declaration has good dispersibility and disperses to keep energyPower. By comparative example 2 and comparative example 1,2, illustrate (B+C)/A quality ratio must 0.5～1 itBetween, if on the low side lower than 0.5 follow-up water reducer side chain obtaining, sterically hindered effect is inadequate, is not enough to disperseCement granules, if on the low side higher than 1 follow-up water reducer main chain adsorption group obtaining, causes cement granulesAdsorb on the weak sidely, also weakened the dispersion effect of water reducer. By comparative example 2 and comparative example 3,4, sayBright B/C quality ratio must be between 0.8～1.2, and the two could form to greatest extent electric charge and shift cooperationThing, otherwise affect the efficiency of initiation of subsequent reactions, and then affect the dispersion effect of gained water reducer. By contrastEmbodiment 2 and comparative example 5,6, illustrate that NVP is necessary with the mass ratio of active large molecule EBe controlled between 3～10, if on the low side higher than 10 follow-up water reducer main chain adsorption groups that obtain, it is right to causeThe absorption of cement granules is on the weak side; If on the low side lower than 3 follow-up water reducer side chains that obtain, sterically hindered effect is notEnough, be not enough to disperse cement granules.
Application Example 2
For evaluating the clay adaptability of the water reducer prepared of the present invention, with reference to GB/T8077-2012 standard (differencePart is to mix a small amount of imvite) to embodiment 1 and two kind of commercially available commodity polycarboxylate water-reducer (manufacturerFor Jiangsu Bo Te new material limited company) carry out flowing degree of net paste of cement test, and test 30 minutesAnd clean slurry fluidity after 1 hour, experimental result is in table 4.
Table 4 embodiment 1 and the two kind of commercially available commodity polycarboxylate water-reducer adaptability to clay
The above results shows: two kinds of commercially available commodity polycarboxylate water-reducers are increasing after 1% imvite, cement mortarBody fluidity declines and exceedes 55%; And the water reducer that embodiment 1 makes is increasing after 1% imvite, cement mortarIt is only 12% left and right that body fluidity declines; All can improve fluidity by the volume that increases the said goods, 1%Under imvite content, the volume that commercially available sample need increase more than 30% just can reach original flow effect, and realExecuting water reducer that example 1 makes only needs to increase and can reach former producing effect less than 10% volume, and embodiment 1 makesWater reducer compare commercial goods volume in the time reaching similar fluidity and reduce by 30%, and function of slump protection is more excellentDifferent. The volume that simultaneously further increases imvite, we find that synthetic water reducer is very good to its patience.
All embodiment and commercial goods are carried out to clay compatibility test, the results are shown in Table 5.
The all embodiment of table 5 and the commercial goods adaptability to clay
The above results shows: mix after 1% imvite, (embodiment 1 is to enforcement for the water reducer of gained of the present inventionExample 10) by improving the volume of approximately 10% left and right, all can make cement mortar mobility and the situation class without imviteSeemingly; And traditional comb-type structure water reducer (commodity sample 1 and commodity sample 2) needs to increase by 20～40% volumeCan reach original effect, and function of slump protection obviously reduces. These results suggest that the water reducer phase that the present invention makesTraditional comb-type structure polycarboxylate water-reducer is had to very excellent clay patience.
Application Example 3
For investigating the clay adsorption of all synthetic samples and commercial goods, take respectively 1 gram of powder (cement,Imvite), in the water reducer solution of the pure water preparation that the concentration that joins 50ml is 1g/L, stir 4 minutesRear high speed centrifugation obtains supernatant, gets after 20 times of 2mL supernatant dilutions, adopts toc total organic carbon analyzerTest organic carbon content, the organic carbon content deducting in supernatant from the water reducer total amount of admixture is water reducerBy the amount of solid absorption. The adsorpting data of sample in cement and imvite is in table 6.
The all embodiment of table 6 and the commercial goods adsorptivity to cement and clay
| Sample | Cement mg/g | Imvite mg/g |
| Commodity sample 1 (ether type) | 7.8 | 40.8 |
| Commodity sample 2 (ester type) | 9.6 | 45.1 |
| Embodiment 1 | 8.2 | 16.1 |
| Embodiment 2 | 7.8 | 16.1 |
| Embodiment 3 | 7.2 | 17.1 |
| Embodiment 4 | 7 | 15.3 |
| Embodiment 5 | 7.9 | 17.1 |
| Embodiment 6 | 8.8 | 15.9 |
| Embodiment 7 | 7.7 | 17 |
| Embodiment 8 | 7.9 | 15.4 |
| Embodiment 9 | 8.3 | 14.1 |
Find by contrasting above-mentioned data, the adsorption capacity of commercial goods water reducer in imvite is about at cement5 times of left and right of upper adsorption capacity, even if the imvite amount therefore containing in cement is little, still have the poly-of a great deal ofCarboxylic acid water reducer is adsorbed in imvite, thereby the polycarboxylate water-reducer of cement particle absorption is reduced, stableEffect declines.
And the water reducer that the present invention makes, although do not improve its absorption on cement, greatly reducesIts absorption in imvite, on the whole the adsorption capacity of water reducer in imvite be on cement 2Doubly left and right, under the condition of same imvite content, the diminishing dosage that is adsorbed in imvite greatly reduces, to cementThe impact of fluidity is less, and the sample that therefore the present invention makes improves greatly to the patience of clay.
Claims (4)
1. a preparation method with the water reducer of higher clay patience, is characterized in that, comprises following stepRapid:
(1) preparation of active large molecule E: by the particular monomers C of unsaturated carboxylic acid monomer A and ultraviolet activityAnd help trigger monomer B in toluene solution, to adopt initator D to utilize thermal-initiated polymerization to make to there is ultraviolet activityLarge molecule E;
It is 10～25% that polymerization concentration should be controlled at mass concentration, and polymerization temperature is controlled at 60～70 DEG C, when polymerizationBetween be controlled at 5～10h, after polymerization completes, remove toluene by decompression distillation, obtain the large molecule E of activity of solid,By regulating and controlling polymerization concentration and its molecular weight of initiator amount control between 3000 to 8000;
Described initator D is azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO), consumption control0.5～2%; Wherein (B+C)/A quality ratio is between 0.5～1, B/C quality ratio 0.8～1.2 itBetween;
(2) preparation of water reducer: the large molecule E of activity of the solid that step (1) is made joins deionizationIn water, dissolve, under the irradiation of ultraviolet light, slowly splashing into NVP (N-VP), to carry out grafting poly-Close reaction and obtain final water reducer molecule;
It is 20～60% that the concentration of graft polymerization reaction should be controlled at mass concentration, NVP(N-VP) time for adding is controlled at 3～5h, and dropping finishes rear continuation reaction and obtains final subtracting after 0.5 hourAqua product, by regulating and controlling polymerization concentration and its molecular weight of time for adding control between 20000 to 80000;
The mass ratio of described NVP and active large molecule E is between 3～10;
The general formula of described monomer A is:
In formula, R1 represents H or COOM; R2 represents H or CH3, and in the time that R1 is COOM,R2 only represents H; M represents H, Na, K or NH4;
Described monomers B is the tertiary amines material that contains unsaturated double-bond, and described monomer C is for containing unsaturated double-bondBenzophenone material.
2. the preparation method of a kind of water reducer with higher clay patience according to claim 1, itsBe characterised in that, the monomer A of general formula (1) representative comprises: acrylic acid, methacrylic acid, maleic acid or propyleneSodium salt, sylvite or the ammonium salt of acid, methacrylic acid, maleic acid, can be used alone or any with more than oneRatio form of mixtures is used.
3. the preparation method of a kind of water reducer with higher clay patience according to claim 1, itsBe characterised in that, described monomer C mainly comprises following several material, can be used alone or with more than oneMeaning ratio form of mixtures is used:
4. the preparation method of a kind of water reducer with higher clay patience according to claim 1, itsBe characterised in that, described monomers B mainly comprises following several material, can be used alone or with more than oneMeaning ratio form of mixtures is used:
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| CN107778384A (en) * | 2017-10-17 | 2018-03-09 | 江苏苏博特新材料股份有限公司 | A kind of building materials emulsifies free microemulsion and preparation method thereof |
| WO2018090354A1 (en) * | 2016-11-21 | 2018-05-24 | 北京英力科技发展有限公司 | Photocurable composition without benzene release |
| CN113831071A (en) * | 2021-10-22 | 2021-12-24 | 福建省闽宏建材实业有限公司 | Durable concrete |
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| CN102849978A (en) * | 2012-09-10 | 2013-01-02 | 重庆健杰科技有限公司 | Sustained-release polycarboxylic high-performance water reducing agent and preparation method thereof |
| CN102993430A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Intermediate of high strength water reducer, preparation method thereof and high strength water reducer prepared by intermediate |
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| CN102849978A (en) * | 2012-09-10 | 2013-01-02 | 重庆健杰科技有限公司 | Sustained-release polycarboxylic high-performance water reducing agent and preparation method thereof |
| CN102993430A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Intermediate of high strength water reducer, preparation method thereof and high strength water reducer prepared by intermediate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018090354A1 (en) * | 2016-11-21 | 2018-05-24 | 北京英力科技发展有限公司 | Photocurable composition without benzene release |
| CN107778384A (en) * | 2017-10-17 | 2018-03-09 | 江苏苏博特新材料股份有限公司 | A kind of building materials emulsifies free microemulsion and preparation method thereof |
| CN107778384B (en) * | 2017-10-17 | 2020-05-26 | 江苏苏博特新材料股份有限公司 | Soap-free microemulsion for building materials and preparation method thereof |
| CN113831071A (en) * | 2021-10-22 | 2021-12-24 | 福建省闽宏建材实业有限公司 | Durable concrete |
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