CN105601825B - A kind of preparation method of the water reducer with higher clay patience - Google Patents
A kind of preparation method of the water reducer with higher clay patience Download PDFInfo
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- CN105601825B CN105601825B CN201510987981.8A CN201510987981A CN105601825B CN 105601825 B CN105601825 B CN 105601825B CN 201510987981 A CN201510987981 A CN 201510987981A CN 105601825 B CN105601825 B CN 105601825B
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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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Abstract
The invention discloses a kind of preparation method of the water reducer with higher clay patience, including by unsaturated carboxylic acid monomer A and UV active particular monomers C and help and trigger monomer B that the macromolecular E with UV active is made using thermal-initiated polymerization using initiator D in toluene solution；Obtained active macromolecules E is added in deionized water and dissolved, under the irradiation of ultraviolet light, N vinyl pyrrolidones (N VP) progress graft polymerization reaction is slowly instilled and obtains final diminishing agent molecule.With excellent clay patience while the water reducer of the present invention is with preferable water-reducing property, diminishing can be efficiently solved when aggregate clay content is higher and the problem of guarantor is collapsed, it is not necessary to mix to improve diminishing by super, also without extra sacrifice agent is added, there is preferable economic benefit.
Description
Technical field
Not to contain polyethylene oxide side-chain the present invention relates to one kind, thus the water reducer with good clay patience and
Its preparation method, belong to technical field of concrete additives.
Background technology
Polycarboxylate water-reducer (also referred to as cement dispersants) is as a kind of important composition in modern high performance concrete
Part, because it has the advantages that volume is low, diminishing is high, adaptability is good, adjustability of structure is strong and green, in recent ten years
Obtain huge development and be widely applied.But academia and engineering practice show, the clay in sand material, especially cover
De- soil has more significant influence to the diminishing dispersive property of polycarboxylate water-reducer.Shared volume fraction of the sandstone in concrete
For 60~75%, quality ratio 70~80%, be concrete important component.In recent years, natural quality sand and stone resources day
Beneficial nervous, the use of low-grade aggregate is more and more, and polycarboxylate water-reducer has been become increasingly popular in commerical ready-mixed concrete in addition, contains
Influence of the mud amount to polycarboxylic acids is more and more prominent.
It is general using flushing aggregate when the clay content of aggregate is exceeded and influences working performance of concrete in actual production
Method, but the method can cause environmental pollution, damage the grading of sand, change the match ratio of concrete, especially in cold district,
Cause to freeze during flushing, have a strong impact on project progress.In Practical Project it has also been found that, when cement content is higher, poly- carboxylic is improved merely
Sour volume can not solve the problems, such as that diminishing and guarantor are collapsed, and super mix of polycarboxylic acids not only increases cost, on the other hand can also cause to mix
Coagulate the problems such as native initial isolation is serious, and setting time is long.
United States Patent (USP) US6353952B1 reports a kind of by optimizing ethylene oxide and propylene oxide in polycarboxylic acids side chain
Ratio, to destroy structural integrity, the hydrogen bond action of ethylene oxide and clay is reduced, reach and reduce polycarboxylic acids and clay effect
Purpose.Chinese patent CN201010119879.3 reports a kind of small molecule auxiliary agent of polyethylene glycols, and the auxiliary agent is prior to poly- carboxylic
Acid adds, and Preferential adsorption plays a part of sacrifice agent, then mixing polycarboxylate water-reducer again makes its performance diminishing guarantor collapse in clay
Effect.Chinese patent CN201410075133.5 reports the compound clay screener of one kind of multiple inorganic matters and organic matter, in
State patent CN201310675751.9 reports a kind of clay screener of cationic polymer.But these compoundings or other skills
Water reducer prepared by art, simply somewhat inhibits influence of the clay to polycarboxylate water-reducer, can not tackle the problem at its root,
And the method for using sacrifice agent or screener, the rising of cost is on the one hand caused, on the other hand also makes efficiency of construction degradation.
From the molecular structure of water reducer, its patience to clay especially montmorillonite is improved, it has also become a urgency
Need to solve the problems, such as.
The content of the invention
For aggregate clay content it is higher when, polycarboxylic acids volume can not solve the problems, such as that diminishing and guarantor are collapsed, and polycarboxylic acids is super to be mixed
Not only increase cost, on the other hand can also cause the problems such as concrete initial isolation is serious, and setting time is long, the present invention carries
For a kind of polycarboxylate water-reducer with polyvinylpyrrolidone side chain and preparation method thereof, because it does not contain polyethylene glycol oxide
Side chain, there is extraordinary patience to clay.
For traditional polycarboxylic acids molecular structure, polycarboxylic acids is divided into main chain and side chain two parts, and main chain typically contains carboxylic
The electronegative groups such as base, it is adsorbed onto the cement particle surface of positive electricity；And side chain is typically certain length and rigid polyoxy
Change ethene macromolecular, formation has certain thickness hydrophilic protective films, is acted on by steric hindrance and prevents the solidifying of cement granules
It is poly-, improve the mobility of cement slurry.Clay such as montmorillonite is a kind of multilayer chip structure, negatively charged in its aspect, and layer
Positively charged on side, for electrical angle, it is too many that montmorillonite should not exceed cement to the adsorption capacity of polycarboxylic acids main chain.But cover
The interlayer for taking off soil easily forms hydrogen bond action, for polycarboxylic acids molecule, side chain institute with the polyethylene glycol oxide in polycarboxylic acids side chain
The quality ratio accounted for is far above main chain, and once a side chain is adsorbed, and whole polycarboxylic acids molecule just can not be adsorbed onto cement again
On, therefore for this angle, montmorillonite is far above cement to the competitive Adsorption ability of traditional polycarboxylic acids molecule.United States Patent (USP)
US6353952B1 is just being attempt to destroy the hydrogen bond of ethylene oxide and montmorillonite by introducing PPOX, reduces absorption, but
It still contains a large amount of polyethylene glycol oxides, can only obtain limited improvement.
The present invention is made a kind of and is copolymerized what is formed by unsaturated carboxylic acid monomer and the particular monomers with UV active first
UV active macromolecular, this active macromolecules can produce under the irradiation of ultraviolet light in some avtive spots on its strand
Raw free radical, is now added dropwise vinyl-pyrrolidone monomers, is grafted on macromolecular main chain, form the side chain of certain length.
This polymer has the structure of similar traditional polycarboxylic acids, has carboxylic acid adsorption group on its main chain, side chain by certain length with
Rigid polyvinylpyrrolidone macromolecular, formation have certain thickness hydrophilic protective films, are acted on and hindered by steric hindrance
Sealing mud particle aggregation, improve cement thick liquid flowability.Because polyvinylpyrrolidone and montmorillonite can not form intercalation absorption,
Fundamentally solve competitive Adsorption of the clay to water reducer, there is extraordinary clay patience.
The invention provides a kind of preparation method of the water reducer with higher clay patience, comprise the following steps：
(1) active macromolecules E preparation：By unsaturated carboxylic acid monomer A and UV active particular monomers C and help initiation single
The macromolecular E with UV active is made using thermal-initiated polymerization using initiator D in toluene solution in body B；
It is 10~25% that polymerization concentration, which should be controlled in mass concentration, and polymerization temperature control is at 60~70 DEG C, polymerization time control
System removes toluene after the completion of 5~10h, polymerization by being evaporated under reduced pressure, and obtains the active macromolecules E of solid, by regulating and controlling to polymerize
Concentration and initiator amount control its molecular weight between 3000 to 8000；
The initiator D is azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO), dosage control 0.5~
2%；Wherein (B+C)/A quality ratios are between 0.5~1, and B/C quality ratios are between 0.8~1.2；
(2) preparation of water reducer：The active macromolecules E of solid made from step (1) is added in deionized water and dissolved,
Under the irradiation of ultraviolet light, slowly instill NVP (N-VP) progress graft polymerization reaction and obtain final diminishing
Agent molecule；
It is 20~60% that the concentration of graft polymerization reaction, which should be controlled in mass concentration, NVP (N-VP)
Time for adding control obtains final water reducer product after continuing reaction after 3~5h, completion of dropwise addition 0.5 hour, passes through regulation and control
Polymerization concentration and time for adding control its molecular weight between 20000 to 80000；
The mass ratio of NVP and the active macromolecules E is follow-up if higher than 10 to obtain between 3~10
The water reducer main chain adsorption group arrived is relatively low, causes the absorption to cement granules on the weak side；The water reducer subsequently obtained if less than 3
Side chain is on the low side, and steric hindrance effect is inadequate, is not enough to disperse cement particles；
The formula of the monomer A is：
R1 represents H or COOM in formula；R2 represents H or CH3, and when R1 is COOM, R2 only represents H；M represent H,
Na, K or NH4；
The monomer B is the tertiary amines material containing unsaturated double-bond, and the monomer C is the hexichol containing unsaturated double-bond
First letones.
Above-mentioned three kinds of monomers A, B, C must are fulfilled for certain ratio, wherein (B+C)/A quality ratios must 0.5~1 it
Between, the water reducer main chain adsorption group subsequently obtained if higher than 1 is relatively low, causes the absorption to cement granules on the weak side；If it is less than
0.5 water reducer side chain subsequently obtained is on the low side, and steric hindrance effect is inadequate, is not enough to disperse cement particles.In addition, B/C matter
Measuring ratio must be between 0.8~1.2, and the two could form charge-transfer complex to greatest extent, advantageously in raising
The ultraviolet efficiency of initiation of subsequent step.
In the present invention, monomer A mainly provide adsorption group.The monomer that formula (1) represents includes：Acrylic acid, metering system
Acid, maleic acid or acrylic acid, methacrylic acid, the sodium salt of maleic acid, sylvite or ammonium salt.These monomers by commercially available, and
It is used alone or is used with more than one arbitrary proportion form of mixtures.
Monomer C is the benzophenone material containing unsaturated double-bond, and it has double bond, can under conditions of thermal initiation with
Monomer A polymerize.Benzophenone group can be used as potential active site simultaneously, and free radical site is produced under the irradiation of ultraviolet light,
Play a part of initiation grafting polymerization in next step is reacted.Monomer C mainly includes following several materials, and these monomers pass through business
Purchase obtains, and is used alone or is used with more than one arbitrary proportion form of mixtures.
Monomer B is the tertiary amines material containing unsaturated double-bond, and it has double bond, can under conditions of thermal initiation with monomer
A and monomer C polymerizations.Simultaneously because tertiary amine group can be aggregated on same main chain with benzophenone group, electric charge is more likely formed
Complex is shifted, ultraviolet light-initiated activation energy is reduced, improves efficiency of initiation.Tertiary amine group is acted on by electric charge transfer
α-location of C can also form free radical, play a part of initiation grafting polymerization in next step is reacted.Monomer B mainly include with
Under several materials, these monomers by commercially available, and be used alone or made with more than one arbitrary proportion form of mixtures
With.
Water reducer of the present invention with good clay patience can also be selected from prior art with least one
In known aminosulfonic water-reducing agent, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent mix.In addition, remove
Outside known cement water reducing agent above-mentioned, wherein air entraining agent, swelling agent, retarder, early strength agent, thickening can also be added
Agent, economization agent and defoamer etc..
The beneficial effects of the invention are as follows：With excellent clay while the water reducer of the present invention is with preferable water-reducing property
Patience, diminishing can be efficiently solved and the problem of guarantor is collapsed, it is not necessary to subtract to improve by super mix when aggregate clay content is higher
Water, it is not required that add extra sacrifice agent, there is preferable economic benefit.
Embodiment
Following examples have described in more detail the process that the method according to the invention prepares polymerizate, and these realities
Apply example to provide by way of illustration, its object is to allow person skilled in the art to understand present disclosure and according to this
Implement, but these embodiments are in no way intended to limit the scope of the present invention.All equivalence changes made according to spirit of the invention are repaiied
Decorations, should all be included within the scope of the present invention.
The raw material code name listed by table 1 is used in synthetic example and comparative example：
The synthetic example of table 1 and comparative example raw material code name
Synthetic example
Raw material and ratio are included in table 2 used by synthetic example and comparative example.
The synthesis condition that 2 each embodiment of table uses
The molecular weight of sample is determined using static light scattering, and testing procedure is as follows：Obtained polymer is configured to
0.5mg/mL solution, with 0.22 μm of water-based membrane filtration, then using light scattering apparatus (ALV/CGS-3, ALV, Germany)
Carry out static light scattering test sample molecular weight (SLS).The dn/dc of test sample using BI-DNDC (DNDC-2010, λ=
620nm, WGE, Germany) measure.
Synthetic example 1
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 52.98g A-1,12.25g B-1,
14.76g C-1 and 719.58g toluene, after being connected with conditions of nitrogen and being heated to 60 DEG C, stir 30 minutes.Add 0.42g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-1,
Molecular weight is 5700.38.46g E-1 are taken to be dissolved in 325g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes,
Under the irradiation of ultraviolet light, 136.54g N-VP were added dropwise in 3 hours, continue 30 points of irradiation reaction after being added dropwise
Clock, obtain the water reducer aqueous solution, molecular weight 65800.
Synthetic example 2
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 72.29g A-1,22.33g B-1,
25.38g C-2 and 719.58g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-2, molecular weight 6900.37.50g E-2 are taken to be dissolved in
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 112.50g N-VP were added dropwise in 3 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 38300.
Synthetic example 3
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 90.57g A-1,26.31g B-2,
27.12g C-1 and 654.43g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 1.57g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-3, molecular weight 5900.34.78g E-3 are taken to be dissolved in
In 300g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 165.22g N-VP were added dropwise in 3 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 56700.
Synthetic example 4
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 83.72g A-2,30.14g B-3,
30.14g C-2 and 655.21g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.79g
After D-2 insulation reactions 8 hours, decompression steams toluene, obtains intermediate product E-4, molecular weight 7200.15.27g E-4 are taken to be dissolved in
In 400g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 84.73g N-VP were added dropwise in 4 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 52700.
Synthetic example 5
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.48g A-2,22.37g B-4,
25.14g C-3 and 703.28g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.72g
After D-2 insulation reactions 8 hours, decompression steams toluene, obtains intermediate product E-5, molecular weight 3600.22.58g E-5 are taken to be dissolved in
In 325g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 152.42g N-VP were added dropwise in 4 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 22800.
Synthetic example 6
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 64.86g A-3,26.86g B-4,
28.27g C-4 and 678.84g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 1.16g
After D-2 insulation reactions 10 hours, decompression steams toluene, obtains intermediate product E-6, molecular weight 4900.Take 20.20g E-6 molten
In 300g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 179.80g N- were added dropwise in 4 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 77600.
Synthetic example 7
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 91.43g A-3,35.12g B-2,
33.45g C-5 and 637.58g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 2.42g
After D-2 insulation reactions 10 hours, decompression steams toluene, obtains intermediate product E-7, molecular weight 5000.Take 22.83g E-7 molten
In 250g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 227.17g N- were added dropwise in 5 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 20700.
Synthetic example 8
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 129.03g A-1,37.96g B-3,
33.01g C-1 and 596.52g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 3.48g
After D-1 insulation reactions 8 hours, decompression steams toluene, obtains intermediate product E-8, molecular weight 5800.27.27g E-8 are taken to be dissolved in
In 200g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 272.73g N-VP were added dropwise in 5 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 31800.
Synthetic example 9
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 106.67g A-1,37.53g B-1,
31.80g C-2 and 621.75g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 2.25g
After D-1 insulation reactions 8 hours, decompression steams toluene, obtains intermediate product E-9, molecular weight 3900.17.50g E-9 are taken to be dissolved in
In 325g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 157.50g N-VP were added dropwise in 5 hours,
Continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 35900.
Synthetic example 10
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 64.17g A-1,28.86g B-1,
26.97g C-1 and 677.60g toluene, after being connected with conditions of nitrogen and being heated to 70 DEG C, stir 30 minutes.Add 2.40g
After D-1 insulation reactions 8 hours, decompression steams toluene, obtains intermediate product E-10, molecular weight 7400.Take 21.79g E-10 molten
In 300g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 178.21g N- were added dropwise in 5 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 23100.
Comparative example 1
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 92.31g A-1,12.96g B-1,
14.73g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-11, molecular weight 7200.Take 37.50g E-11 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 112.50g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 40400.
Comparative example 2
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.00g A-1,33.70g B-1,
38.30g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-12, molecular weight 5200.Take 37.50g E-12 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 112.50g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 37900.
Comparative example 3
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 72.29g A-1,15.90g B-1,
31.81g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-13, molecular weight 7900.Take 37.50g E-13 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 112.50g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 27300.
Comparative example 4
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 72.29g A-1,28.63g B-1,
19.08g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-14, molecular weight 5400.Take 37.50g E-14 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 112.50g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 63700.
Comparative example 5
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 72.29g A-1,22.33g B-1,
25.38g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-15, molecular weight 6900.Take 50.00g E-15 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 100.00g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 30300.
Comparative example 6
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 72.29g A-1,22.33g B-1,
25.38g C-2 and 679.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.92g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-16, molecular weight 6900.Take 11.54g E-15 molten
In 350g water, stirring and dissolving simultaneously leads to nitrogen after 30 minutes, and under the irradiation of ultraviolet light, 138.46g N- were added dropwise in 3 hours
VP, continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution, molecular weight 91500.
Application Example
Application Example 1
The diminishing and function of slump protection of the water reducer prepared for the evaluation present invention, are carried out with reference to GB/T8077-2012 standards
Flowing degree of net paste of cement is tested, cement 300g, amount of water 87g, and stirring determines cement paste stream after 4 minutes on plate glass
Dynamic degree, and the paste flowing degree after testing 1 hour, experimental result are shown in Table 3.
The embodiment of table 3 and comparative example flowing degree of net paste of cement
The data of table 3 illustrate that Water-reducing Admixtures To Cements prepared by the present invention have preferable dispersibility and dispersion holding capacity.
By comparative example 2 and comparative example 1,2, illustrate that (B+C)/A quality ratios must be between 0.5~1, after being less than if 0.5
It is on the low side to continue obtained water reducer side chain, steric hindrance effect is inadequate, is not enough to disperse cement particles, is subsequently obtained if higher than 1
Water reducer main chain adsorption group it is relatively low, cause the absorption to cement granules on the weak side, also weaken the dispersion effect of water reducer.It is logical
Comparative example 2 and comparative example 3,4 are crossed, illustrates that B/C quality ratios must be between 0.8~1.2, the two could to greatest extent
Charge-transfer complex is formed, otherwise influences the efficiency of initiation of subsequent reactions, and then influence the dispersion effect of gained water reducer.It is logical
Comparative example 2 and comparative example 5,6 are crossed, illustrates that NVP and active macromolecules E mass ratio must be controlled 3
Between~10, the water reducer main chain adsorption group subsequently obtained if higher than 10 is relatively low, causes the absorption to cement granules on the weak side；
The water reducer side chain subsequently obtained if less than 3 is on the low side, and steric hindrance effect is inadequate, is not enough to disperse cement particles.
Application Example 2
The clay adaptability of the water reducer prepared for the evaluation present invention, with reference to GB/T 8077-2012 standard (differences
It is to mix a small amount of montmorillonite) (manufacturer is Jiangsu Bo Te green woods to the commodity polycarboxylate water-reducer commercially available to embodiment 1 and two kind
Material limited company) carry out flowing degree of net paste of cement test, and the paste flowing degree after testing 30 minutes and 1 hour, it is real
Test and the results are shown in Table 4.
The adaptability of the embodiment 1 of table 4 and two kind of commercially available commodity polycarboxylate water-reducer to clay
The above results are shown：Two kinds of commercially available commodity polycarboxylate water-reducers are after increasing by 1% montmorillonite, cement slurry flowing
Degree decrease beyond 55%；And water reducer made from embodiment 1 is after increasing by 1% montmorillonite, cement slurry fluidity, which declines, is only
12% or so；Fluidity can be improved by the volume for increasing the said goods, under 1% montmorillonite content, commercial samples need to increase
More than 30% volume is added to can be only achieved original flow effect, and water reducer made from embodiment 1 only needs increase less than 10%
Volume can reach original effect, the volume when reaching similar fluidity compared to commercial goods of water reducer made from embodiment 1
30% is reduced, and function of slump protection is more excellent.Further increase the volume of montmorillonite simultaneously, it has been found that the water reducer of synthesis
It is very good to its patience.
Clay compatibility test is carried out to all embodiments and commercial goods, the results are shown in Table 5.
The adaptability of 5 all embodiments of table and commercial goods to clay
The above results are shown：After mixing 1% montmorillonite, the water reducer (embodiment 1 to embodiment 10) of present invention gained is logical
The volume of raising about 10% or so is crossed, can all make cement mortar mobility similar with the situation without montmorillonite；And traditional combed knot
The volume that structure water reducer (commodity sample 1 and commodity sample 2) need to increase by 20~40% can be only achieved original effect, and function of slump protection is bright
It is aobvious to reduce.These results suggest that for the relatively conventional comb-type structure polycarboxylate water-reducer of water reducer produced by the present invention have it is non-
Chang Youyi clay patience.
Application Example 3
To investigate the clay adsorption of all synthetic samples and commercial goods, weighing 1 gram of powder respectively, (cement, illiteracy are de-
Soil), it is added in diminishing agent solution of the 50ml concentration for 1g/L pure water preparation, high speed centrifugation obtains after stirring 4 minutes
Clear liquid, after taking 2mL supernatants to dilute 20 times, organic carbon content is tested using toc total organic carbon analyzers, from the water reducer of admixture
It is water reducer by the amount of solid absorption that the organic carbon content in supernatant is subtracted in total amount.Sample is on cement and montmorillonite
Adsorpting data is shown in Table 6.
The adsorptivity of 6 all embodiments of table and commercial goods to cement and clay
| Sample | Cement mg/g | Montmorillonite 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 |
By contrasting above-mentioned number it has been found that adsorption capacity of the commercial goods water reducer in montmorillonite is about inhaled on cement
5 times or so of attached ability, therefore even if the montmorillonite amount contained in cement is seldom, still there is considerable amount of polycarboxylate water-reducer to adsorb
In montmorillonite, so that the polycarboxylate water-reducer of cement particle absorption is reduced, stabilization declines.
And water reducer produced by the present invention, although not improving its absorption on cement, greatly reduce its
Absorption in montmorillonite, adsorption capacity of the water reducer in montmorillonite is 2 times or so on cement on the whole, and same cover takes off
Under conditions of native content, the diminishing dosage for being adsorbed in montmorillonite greatly reduces, and the influence to cement fluidity is smaller, therefore this hair
Bright obtained sample greatly improves to the patience of clay.
Claims (4)
1. a kind of preparation method of the water reducer with higher clay patience, it is characterised in that comprise the following steps：
(1) active macromolecules E preparation：By unsaturated carboxylic acid monomer A and UV active particular monomers C and help and trigger monomer B
The macromolecular E with UV active is made using thermal-initiated polymerization using initiator D in toluene solution；
It is 10~25% that polymerization concentration, which should be controlled in mass concentration, and at 60~70 DEG C, polymerization time is controlled 5 for polymerization temperature control
~10h, after the completion of polymerization by be evaporated under reduced pressure remove toluene, obtain the active macromolecules E of solid, by regulate and control polymerization concentration and
Initiator amount controls its molecular weight between 3000 to 8000；
The initiator D is azo-bis-isobutyl cyanide (AIBN) or benzoyl peroxide (BPO), and dosage is controlled 0.5~2%；Its
In (B+C)/A quality ratios between 0.5~1, B/C quality ratios are between 0.8~1.2；
(2) preparation of water reducer：The active macromolecules E of solid made from step (1) is added in deionized water and dissolved, in purple
Under the irradiation of outer light, slowly instill NVP (N-VP) progress graft polymerization reaction and obtain final water reducer point
Son；
It is 20~60% that the concentration of graft polymerization reaction, which should be controlled in mass concentration, the dropwise addition of NVP (N-VP)
Time control obtains final water reducer product after continuing reaction after 3~5h, completion of dropwise addition 0.5 hour, by regulating and controlling to polymerize
Concentration and time for adding control its molecular weight between 20000 to 80000；
The mass ratio of NVP and the active macromolecules E is between 3~10；
The formula of the monomer A is：
R1 represents H or COOM in formula；R2 represents H or CH3, and when R1 is COOM, R2 only represents H；M represents H, Na, K
Or NH4；
The monomer B is the tertiary amines material containing unsaturated double-bond, and the monomer C is the benzophenone containing unsaturated double-bond
Class material.
A kind of 2. preparation method of water reducer with higher clay patience according to claim 1, it is characterised in that
The monomer A that formula (1) represents includes：Acrylic acid, methacrylic acid, maleic acid or acrylic acid, methacrylic acid, the sodium of maleic acid
Salt, sylvite or ammonium salt, it can be used alone or used with more than one arbitrary proportion form of mixtures.
A kind of 3. preparation method of water reducer with higher clay patience according to claim 1, it is characterised in that
The monomer C includes following several materials, can be used alone or is used with more than one arbitrary proportion form of mixtures：
A kind of 4. preparation method of water reducer with higher clay patience according to claim 1, it is characterised in that
The monomer B includes following several materials, can be used alone or is used with more than one arbitrary proportion form of mixtures：
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| 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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| 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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