CN105601826B - A kind of preparation method of viscosity reduction type water reducer - Google Patents
A kind of preparation method of viscosity reduction type water reducer Download PDFInfo
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- CN105601826B CN105601826B CN201510979227.XA CN201510979227A CN105601826B CN 105601826 B CN105601826 B CN 105601826B CN 201510979227 A CN201510979227 A CN 201510979227A CN 105601826 B CN105601826 B CN 105601826B
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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
- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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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
- C04B24/2688—Copolymers containing at least three different monomers
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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
- C04B2103/302—Water reducers
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Abstract
The macromolecular E with UV active is obtained using thermal-initiated polymerization using initiator D in toluene the invention discloses a kind of preparation method of viscosity reduction type water reducer, including by unsaturated carboxylic acid monomer A, unsaturated phosphonate monomers B and UV active particular monomers C；The active macromolecules E of obtained solid is added in deionized water and dissolved, under the irradiation of ultraviolet light, slowly instill acrylamide (AM) and the cationic quaternary ammonium salt monomer F containing unsaturated double-bond carries out graft polymerization reaction and obtains final diminishing agent molecule.With excellent viscosity reducing effect, remarkable in economical benefits while water reducer prepared by the inventive method is with high water reducing rate.
Description
Technical field
The present invention relates to a kind of preparation method of the copolymer concrete water reducer with viscosity reducing effect, belong to outside concrete
Add agent technical field.
Background technology
With flourishing for China's building cause, high-rise and Super High concrete structure continuously emerges, to engineering coagulation
The intensity requirement also more and more higher of soil, occur high-strength (C60~C100), even superelevation it is strong (>C100) concrete.It is general next
Say, strong concrete can be improved by reducing the ratio of mud, increase gel material content, improving the methods of mineral admixture ratio
Degree, but these measures will also result in concrete viscosity increase simultaneously, mobility declines, and have impact on the workability of concrete.
Just because of this, the research of viscosity reduction type polycarboxylate water-reducer has obtained huge concern at present, and TW200424145 is adopted
Reach viscosity reduction purpose with methacrylic polyethers, allyl polyether, maleic acid, hydroxy-ethyl acrylate copolymerization, but effect is also not
It is enough abundant；No. 2004-43280 bulletin of JP improves slurry viscosity using short-side chain reactive polyether polymeric monomer, but because it subtracts
Water poor performance is, it is necessary to compared with high additive competence exertion effect；CN20091077550.2 on the basis of polycarboxylic acids mother liquor, early strength agent,
Compound polyethylene glycol and be used as viscosity reduction component, to reach the purpose for reducing concrete viscosity raising workability, but additionally add
Polyethylene glycol does not obviously work to diminishing, and economic benefit is relatively low.
The content of the invention
It is an object of the invention to provide a kind of preparation method of viscosity reduction type water reducer, while possessing high diminishing, Ke Yi great
The viscosity of amplitude reduction concrete (especially high-strength concrete), improves its service behaviour.
The present invention is made a kind of by unsaturated carboxylic acid monomer, unsaturated phosphonate monomers and special with UV active first
The UV active macromolecular that monomer is copolymerized by a certain percentage, this active macromolecules, can be at them under the irradiation of ultraviolet light
Some avtive spots on strand produce free radical, be now added dropwise a certain proportion of acrylamide and unsaturated quaternary ammonium salt sun from
Sub- monomer, by their graft copolymerizations to macromolecular main chain, form the side chain of certain length.
This polymer has the structure of similar traditional polycarboxylic acids, and its main chain is carboxylic acid and phosphonic acids adsorption group, side chain are
Acrylamide with positive charge-quaternary ammonium salt cationic monomer copolymerization macromolecular, pass through the dual of Coulomb repulsion and steric hindrance
Coupling prevents cement granules from condensing, and water-reducing property is greatly improved.Meanwhile the side chain of water reducer of the present invention carries positive electricity
Lotus, side chain itself more stretch, and hydration shell is thicker, can effectively reduce the viscosity of concrete.In addition, point of water reducer of the present invention
There is negative electrical charge main chain and positive charge side chain simultaneously, this amphiphatic molecule structure can effectively improve the work of its surface in minor structure
Property, the further viscosity for reducing concrete.
The invention provides a kind of preparation method of viscosity reduction type water reducer, comprise the following steps：
(1) active macromolecules E preparation：By unsaturated carboxylic acid monomer A, unsaturated phosphonate monomers B and UV active spy
Different monomer C obtains the macromolecular E with UV active using initiator D in toluene using thermal-initiated polymerization；
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 C/ (A+B) molar ratio must be between 0.13~0.3, and B/A molar ratios must be between 0.05~0.2；
(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 acrylamide (AM) and monomer F carries out graft polymerization reaction and obtains final water reducer
Molecule；
It is 30~50% that the concentration of graft polymerization reaction, which should be controlled in mass concentration, acrylamide (AM) and monomer F drop
Time control is added to obtain final water reducer product after continuing reaction after 3~5h, completion of dropwise addition 0.5 hour, it is poly- by regulating and controlling
Close concentration and time for adding controls its molecular weight between 25000 to 100000；
For wherein (AM+F)/E mass ratio between 3~10, the water reducer main chain subsequently obtained if higher than 10 adsorbs base
Group's amount is on the low side, causes the absorption to cement granules on the weak side, influences initial water-reducing property；The water reducer subsequently obtained if less than 3
Side chain is partially short, is not enough to disperse cement particles, and viscosity reducing effect is also poor；
AM/F molar ratio should be controlled between 5~20, and the positively charged amount of side chain institute is on the low side if higher than 20, and electric charge is steady
It is set for using and viscosity reducing effect unobvious；If higher less than the positively charged amount of 5 side chains institute, the repulsive force of side chain and cement granules is caused
It is higher, the absorption of water reducer is influenceed, and too high positive charge amount has broken the balance of zwitterion, influences diminishing agent molecule
Surface-active, there is detrimental effect to viscosity reducing effect；
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 monomer containing carbon-carbon double bond and phosphate group；The monomer C is the peace containing unsaturated double-bond
Cease fragrant ether material；The monomer F is the cationic quaternary ammonium salt monomer containing unsaturated double-bond.
Above-mentioned three kinds of monomers A, B, C must are fulfilled for certain ratio, wherein C/ (A+B) molar ratio must 0.13~
Between 0.3, the water reducer main chain adsorption group density subsequently obtained if monomer C content is too high is relatively low, causes to cement granules
Absorption it is on the weak side, influence water-reducing effect；Monomer C content is too low, and the water reducer side chains number subsequently obtained is on the low side, dispersibility
It is weaker with viscosity reducing effect.
B/A molar ratios must must assure that certain phosphate group between 0.05~0.2, in main chain, just can guarantee that
Obtain preferably adsorbing conformation, be advantageous to dispersibility raising.But be possible to if phosphate group too high levels influence negative and positive from
The charge ratio of son, so as to influence the surface-active of diminishing agent molecule, has detrimental effect to viscosity reducing effect.
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 B is the monomer containing carbon-carbon double bond and phosphate group, including methylacryoyloxyethyl phosphate, acryloyl
Oxygen ethyl phosphonic acid ester, methacryloxypropyl phosphate and methacryloxypropyl butyl phosphoric acid ester.These monomers pass through commercially available
Obtain, and be used alone or used with more than one arbitrary proportion form of mixtures.
Monomer C is the styrax ether material containing unsaturated double-bond, and it has double bond, can under conditions of thermal initiation with
Other monomers polymerize.At the same time as potential active site, produced freely under the irradiation of ultraviolet light and in the presence of catalytic materials
Base site, play a part of initiation grafting polymerization in next step is reacted.Monomer C mainly includes following several materials, these lists
Body is used alone or used with more than one arbitrary proportion form of mixtures by commercially available.
Monomer F is the cationic quaternary ammonium salt monomer containing unsaturated double-bond, and monomer F can be carried out free-radical polymerized merge with AM
It is grafted on active macromolecules E and is formed with certain electropositive side chain, plays a part of diminishing and viscosity reduction.Monomer F includes first
Base acrylyl oxy-ethyl-trimethyl salmiac (DMC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), dimethyl diallyl
Ammonium chloride (DMDAAC) and diethyl diallyl ammonium chloride (DEDAAC), these monomers are used alone by commercially available
Or used with more than one arbitrary proportion form of mixtures.
Water reducer of the present invention can also be with least one selected from aminosulfonic water-reducing agent known in the state of the art, wood
Quality system ordinary water-reducing agent and existing polycarboxylate dehydragent mix.In addition, except known concrete diminishing above-mentioned
Outside agent, wherein air entraining agent, swelling agent, retarder, early strength agent, tackifier, economization agent and defoamer etc. can also be added.
The beneficial effects of the invention are as follows：With excellent while water reducer prepared by the inventive method is with high water reducing rate
Viscosity reducing effect, remarkable in economical benefits.
Embodiment
The process that the method according to the invention prepares polymerizate, and these realities are described in further detail in following examples
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 molecular weight of sample uses static light
Scattering measure, testing procedure are as follows：Obtained polymer is configured to 0.5mg/mL solution, with 0.22 μm of water-based filter membrane mistake
Filter, static light scattering test sample molecular weight (SLS) is then carried out using light scattering apparatus (ALV/CGS-3, ALV, Germany).
The dn/dc of test sample is determined using BI-DNDC (DNDC-2010, λ=620nm, WGE, Germany).
The synthesis condition that 2 each embodiment of table uses
Synthetic example 1
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.67g A-1,18.49gB-1,
28.84g C-1 and 703.47g toluene, after being connected with conditions of nitrogen and being heated to 60 DEG C, stir 30 minutes.Add 0.53g
After D-1 insulation reactions 10 hours, decompression steams toluene, obtains intermediate product E-1.Take 37.5g E-1 to be dissolved in 150g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, dropwise addition 87.06g AM and 25.44g F-1 (is dissolved in 3 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 2
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.89g A-1,23.22gB-1,
23.89g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-2.Take 20.0g E-2 to be dissolved in 100g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 131.85g AM and 48.15g F-1 were added dropwise in 5 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 3
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 36.90g A-1,14.26g B-2,
28.84g C-1 and 718.76g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 1.24g
After D-1 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-3.Take 32.14g E-3 to be dissolved in 75g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 161.42g AM and 31.44g F-1 were added dropwise in 4 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 4
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 50.85g A-2,28.62g B-3,
40.53g C-2 and 678.02g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 1.98g
After D-2 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-4.Take 27.78g E-4 to be dissolved in 50g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 143.84g AM and 78.38g F-2 were added dropwise in 5 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 5
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 103.14g A-2,35.09g B-4,
61.77g C-3 and 596.90g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 3.10g
After D-2 insulation reactions 5 hours, decompression steams toluene, obtains intermediate product E-5.Take 35.00g E-5 to be dissolved in 125g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 114.06g AM and 25.94g F-3 were added dropwise in 3 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 6
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 113.84g A-3,10.50g B-2,
51.66g C-4 and 620.57g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 3.43g
After D-2 insulation reactions 10 hours, decompression steams toluene, obtains intermediate product E-6.Take 20.00g E-6 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 152.82g AM and 27.18g F-4 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 7
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 52.41g A-3,13.39g B-1,
30.20g C-2 and 702.08g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 1.92g
After D-2 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-7.Take 25.00g E-7 to be dissolved in 100g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 152.69g AM and 22.31g F-1 were added dropwise in 4 hours
In 200g deionized waters) (being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain water reducer
The aqueous solution.
Synthetic example 8
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 81.48g A-1,38.70g B-1,
39.82g C-2 and 639.20g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.80g
After D-1 insulation reactions 10 hours, decompression steams toluene, obtains intermediate product E-8.Take 18.18g E-8 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 153.87g AM and 27.95g F-2 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 9
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 50.74g A-1,20.89g B-1,
24.37g C-2 and 703.23g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.77g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-9.Take 33.33g E-9 to be dissolved in 100g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 144.72g AM and 21.94g F-3 were added dropwise in 3 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Synthetic example 10
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 61.35g A-1,25.26g B-1,
33.39g C-2 and 678.92g toluene, after being connected with conditions of nitrogen and being heated to 70 DEG C, stir 30 minutes.Add 1.08g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-10.Take 28.57g E-10 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 132.67g AM and 38.76g F-1 were added dropwise in 4 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 1
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 58.61g A-1,27.84g B-1,
9.55g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g D-
After 1 insulation reaction 7 hours, decompression steams toluene, obtains intermediate product E-11.Take 20.0g E-11 to be dissolved in 100g water, stir
After dissolving and leading to nitrogen 30 minutes, under the irradiation of ultraviolet light, it is (molten that 131.85g AM and 48.15g F-1 were added dropwise in 5 hours
In 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 2
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 34.55g A-1,16.41g B-1,
45.03g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-12.Take 20.0g E-12 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 131.85g AM and 48.15g F-1 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 3
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.89g A-1,23.22g B-1,
23.89g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-13.Take 20.0g E-13 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 73.15g AM and 106.85g F-1 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 4
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.89g A-1,23.22g B-1,
23.89g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-14.Take 20.0g E-14 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 161.17g AM and 18.83g F-1 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 5
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.89g A-1,23.22g B-1,
23.89g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-15.Take 57.14g E-15 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 104.64g AM and 38.22g F-1 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Comparative example 6
Equipped with thermometer, agitator, nitrogen inlet pipe glass flask in add 48.89g A-1,23.22g B-1,
23.89g C-2 and 703.09g toluene, after being connected with conditions of nitrogen and being heated to 65 DEG C, stir 30 minutes.Add 0.91g
After D-1 insulation reactions 7 hours, decompression steams toluene, obtains intermediate product E-15.Take 15.38g E-15 to be dissolved in 100g water, stir
Mix and dissolve and lead to nitrogen after 30 minutes, under the irradiation of ultraviolet light, 135.23g AM and 49.39g F-1 were added dropwise in 5 hours
(being dissolved in 200g deionized waters), continue irradiation reaction 30 minutes after being added dropwise, obtain the water reducer aqueous solution.
Application Example
Application Example 1
(manufacturer is Jiangsu Bo Te to the water reducer and two kinds of commercially available commodity polycarboxylate water-reducers prepared for the contrast present invention
New material limited company) dispersive property and dispersion holding performance, it is net to have carried out cement with reference to GB/T8077-2012 standards
Fluidity test, cement 300g, amount of water 87g are starched, stirring determines flowing degree of net paste of cement after 4 minutes on plate glass,
And the paste flowing degree of different time is tested, experimental result is shown in Table 3.
3 each embodiment of table and the flowing degree of net paste of cement of commercial goods
The data of table 3 illustrate that Water-reducing Admixtures To Cements prepared by the present invention have extraordinary dispersibility and scattered holding energy
Power, it is only the 80~90% of presently commercially available sample with volume under fluidity.Pass through comparative example 2 and comparative example 1,2, instruction sheet
Body C content is extremely important, and the water reducer main chain adsorption group density that too high levels (comparative example 2) then subsequently obtain is relatively low, makes
The absorption of paired cement granules is on the weak side, influences water-reducing effect；The water reducer that monomer C content too low (comparative example 1) then subsequently obtains
Side chains number is on the low side, and dispersibility and viscosity reducing effect are weaker.By comparative example 2 and comparative example 3,4, illustrate propylene on side chain
The ratio of acid amides and cationic monomer is particularly significant, if cationic monomer is too low (comparative example 3), the charge stable effect of side chain
It is weaker；If cationic monomer is too high (comparative example 4), side-chain charges density is too high, causes the repulsive force of side chain and cement granules
It is higher, influence the absorption of water reducer.By comparative example 2 and comparative example 5,6, illustrate that the ratio of side chain and main chain is very heavy
Will, the water reducer main chain adsorption group amount subsequently obtained if 10 (comparative examples 6) are higher than is on the low side, causes the absorption to cement granules
It is on the weak side；The water reducer side chain subsequently obtained if 3 (comparative examples 5) are less than is partially short, is not enough to disperse cement particles.
Application Example 2
To investigate the surface charge after the absorption of the absorption property and cement particle of all synthetic samples and commercial goods, weigh
1 gram of cement, it is added in diminishing agent solution of the 50ml concentration for 1g/L pure water preparation, its surface is tested with zeta potential instrument
Electric charge.1 gram of cement is weighed, it is high after stirring 4 minutes in the diminishing agent solution that the pure water that the concentration for being added to 50ml is 1g/L is prepared
Speed centrifugation obtains supernatant, and after taking 2mL supernatants to dilute 20 times, organic carbon content is tested using toc total organic carbon analyzers, from
The organic carbon content subtracted in the water reducer total amount of admixture in supernatant is water reducer by the amount of solid absorption.Sample is in cement
On adsorpting data and zeta potential datas be shown in Table 4.
Cement particle zeta current potentials after adsorbance and absorption of the sample of table 4 on cement
| Sample | Adsorbance mg/g | Zeta potential mV |
| Commodity sample 1 (ether type) | 7.8 | -6.9 |
| Commodity sample 2 (ester type) | 9.6 | -8.3 |
| Embodiment 1 | 10.2 | 20.9 |
| Embodiment 2 | 9.5 | 24 |
| Embodiment 3 | 10.5 | 19.6 |
| Embodiment 4 | 10.1 | 22.4 |
| Embodiment 5 | 11 | 20.7 |
| Embodiment 6 | 10.1 | 18.7 |
| Embodiment 7 | 9.7 | 18.7 |
| Embodiment 8 | 9.9 | 23.6 |
| Embodiment 9 | 10.6 | 24.9 |
| Embodiment 10 | 9.5 | 23.8 |
Upper table data show that cement particle is slightly above commodity sample, but cement particle absorption business to the adsorbance of inventive samples
Surface charge after product sample is relatively low for negative and absolute value, and sample produced by the present invention, the electricity on cement particle surface after absorption
Lotus is just and absolute value is higher, and this illustrates that the peptizaiton of sample produced by the present invention comes not only from the steric hindrance of side chain,
The also stronger charge stable effect of side chain, while the surface-active of inventive samples and commodity sample are also different, therefore have
Preferable viscosity reducing effect.
Application Example 3
The drop of water reducer prepared by invention is evaluated using net slurry apparent viscosity and concrete inverted slump test tube flow time
Sticky energy.Specific method is：Only apparent fluidity is starched, cement paste proportioning is cement：Ground slag：Water=150：150：87,
SNB intelligence rotors viscosimeter test cement slurry viscosity is moistened using Buddhist nun；Concrete inverted slump test tube is tested, cement：400Kg/m3, powder
Coal ash：40Kg/m3, miberal powder：50Kg/m3, sand：684Kg/m3, stone：1116Kg/m3, water：140Kg/m3, slump cone is fallen
Put, bottom seal cap, fill concrete and floating, slip off bottom rapidly, the concrete stream empty time is measured with stopwatch.Using water
Mud is the cement of south of the River little Ye fields 52.5R.P. II, and sand is modulus of fineness Mx=2.6 middle sand, and stone is that particle diameter is that 5~20mm connects
The rubble of continuous grading.Only starch apparent fluidity experimental result and be shown in Table 5, concrete inverted slump test tube experiment flow time experimental result
It is shown in Table 6.
The viscosity-reducing performance of the water reducer of table 5-starch apparent fluidity only
| Numbering | Volume (%) | Paste flowing degree/mm | Net slurry apparent viscosity/mPaS |
| Embodiment 1 | 0.090 | 266 | 143 |
| Embodiment 2 | 0.090 | 269 | 128 |
| Embodiment 3 | 0.095 | 260 | 129 |
| Embodiment 4 | 0.085 | 277 | 149 |
| Embodiment 5 | 0.090 | 268 | 144 |
| Embodiment 6 | 0.095 | 261 | 148 |
| Embodiment 7 | 0.085 | 278 | 126 |
| Embodiment 8 | 0.095 | 260 | 137 |
| Embodiment 9 | 0.095 | 263 | 145 |
| Embodiment 10 | 0.095 | 261 | 138 |
| Comparative example 1 | 0.115 | 276 | 358 |
| Comparative example 2 | 0.115 | 275 | 420 |
| Comparative example 3 | 0.120 | 267 | 279 |
| Comparative example 4 | 0.125 | 270 | 268 |
| Comparative example 5 | 0.115 | 280 | 315 |
| Comparative example 6 | 0.110 | 260 | 372 |
| Commodity (ether type) | 0.105 | 274 | 305 |
| Commodity (ester type) | 0.115 | 263 | 257 |
The data of table 5 illustrate that the cement paste apparent viscosity that is obtained using the water reducer for preparing of the present invention is smaller, and contrast is real
Apply example and commodity sample, it is seen that the cement paste apparent viscosity that simple comb polymer obtains is led in addition apparently higher than embodiment
Cross comparative example 2 and comparative example, it is seen that change synthesis condition and not only diminishing is had a great influence, viscosity is also adversely affected,
Although the paste flowing degree that can reach same by increasing volume, cement paste apparent viscosity substantially increase.
The viscosity-reducing performance of the water reducer of table 6-concrete inverted slump test tube experiment
It is equal that the concrete inverted slump test tube that the data of table 6 illustrate to obtain using water reducer prepared by the present invention tests flow time
It is shorter, comparative example and commodity sample, it is seen that the concrete flow time that simple comb polymer obtains is apparently higher than implementation
Example, passes through comparative example 2 and comparative example in addition, it is seen that changes synthesis condition and not only diminishing is had a great influence, also have to viscosity
Adverse effect, although can reach the same slump by increasing volume, concrete flow time substantially increases, and illustrates that it is viscous
The obvious increase of degree, is unfavorable for its construction.
Data above absolutely proves that water reducer prepared by the present invention can obtain same concrete flowing under more low-dosage
Property, while concrete viscosity is smaller, has obvious viscosity reducing effect.
Claims (4)
1. a kind of preparation method of viscosity reduction type water reducer, it is characterised in that comprise the following steps：
(1) active macromolecules E preparation：By unsaturated carboxylic acid monomer A, unsaturated phosphonate monomers B and UV active special list
Body C obtains the macromolecular E with UV active using initiator D in toluene using thermal-initiated polymerization；
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 azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO), and dosage is controlled 0.5~2%；Its
Middle C/ (A+B) molar ratio must be between 0.13~0.3, and B/A molar ratios must be between 0.05~0.2；
(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 acrylamide (AM) and monomer F carries out graft polymerization reaction and obtains final diminishing agent molecule；
It is 30~50% that the concentration of graft polymerization reaction, which should be controlled in mass concentration, when acrylamide (AM) and monomer F dropwise addition
Between control continue after 3~5h, completion of dropwise addition reaction 0.5 hour after obtain final water reducer product, by regulate and control polymerization it is dense
Degree and time for adding control its molecular weight between 25000 to 100000；Wherein (AM+F)/E mass ratio between 3~10,
AM/F molar ratio should be controlled between 5~20；
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 monomer containing carbon-carbon double bond and phosphate group；The monomer F is the cation containing unsaturated double-bond
Quaternary ammonium salt monomer；The monomer C includes following several materials, can be used alone or with more than one arbitrary proportion mixture shapes
Formula uses：
2. the preparation method of a kind of viscosity reduction type water reducer according to claim 1, it is characterised in that what formula (1) represented
Monomer A includes：Acrylic acid, methacrylic acid, maleic acid or acrylic acid, methacrylic acid, the sodium salt of maleic acid, sylvite or ammonium
Salt, it can be used alone or used with more than one arbitrary proportion form of mixtures.
3. the preparation method of a kind of viscosity reduction type water reducer according to claim 1, it is characterised in that the monomer B includes
Methylacryoyloxyethyl phosphate, acrylyl oxy-ethyl phosphate, methacryloxypropyl phosphate and methacryl
Oxygen-butyl phosphate, it can be used alone or used with more than one arbitrary proportion form of mixtures.
4. the preparation method of a kind of viscosity reduction type water reducer according to claim 1, it is characterised in that the monomer F includes
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), the allyl of dimethyl two
Ammonium chloride (DMDAAC) and diethyl diallyl ammonium chloride (DEDAAC), it can be used alone or with more than one any ratios
Example form of mixtures uses.
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| CN104136571A (en) * | 2012-02-13 | 2014-11-05 | 巴斯夫欧洲公司 | Use of terpolymers as fluid loss additives in well cementing |
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