CN108373523A - Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof - Google Patents
Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof Download PDFInfo
- Publication number
- CN108373523A CN108373523A CN201810149061.2A CN201810149061A CN108373523A CN 108373523 A CN108373523 A CN 108373523A CN 201810149061 A CN201810149061 A CN 201810149061A CN 108373523 A CN108373523 A CN 108373523A
- Authority
- CN
- China
- Prior art keywords
- reducer
- polycarboxylate water
- inorganic hybridization
- solution
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of polycarboxylate water-reducer of organic inorganic hybridization, general structure is：Wherein, R1For H or CH3, R2For CH2Or COOCH2CH2CH2, a, b, c, d, m and n are the degree of polymerization and are positive integer, a=5~12, b=1~5, c=40~80, d=1~3, m=135~225, n=40~55.The invention also discloses the preparation methods of the polycarboxylate water-reducer of organic inorganic hybridization.Inorganic nano-silicon dioxide particle is carried in the polycarboxylate water-reducer molecule that the present invention synthesizes, compares pure organic polycarboxylic acids molecule, not only the characteristic with organic polycarboxylic acid water-reducing agent, it may have the dimensional effect of inorganic particulate, including：Steric hindrance effect, " ball " effect and " filling " effect；Water conservation, function of slump protection are good after addition concrete, and paste flowing degree variation is small after 120min, are more advantageous to early strength of concrete growth.
Description
Technical field
The present invention relates to technical field of concrete, in particular to the polycarboxylate water-reducer of organic inorganic hybridization and its preparation side
Method.
Background technology
For polycarboxylate water-reducer as third generation water-reducing agent product, the designability of molecular structure is strong, and high performance is dived
Power is big, can prepare the product of multifunction by selecting the monomer of different function to be copolymerized.However, in recent years, cement,
Mineral blend, coarse aggregate, fine aggregate and other issues are serious, in addition China's cement type is various, Engineering Mixed Proportions are a variety of more
Sample often causes polycarboxylate water-reducer incompatible with concrete, fresh concrete easily occur bleeding, isolate, collapse damage it is too fast
The problems such as.Therefore, pass through Molecular Design, synthesis technology and Study on mechanism, the work(of constantly improve polycarboxylate water-reducer
Can property, make it from different cement and mineral admixture, sand material inferior etc. have good adaptability to have become to study both at home and abroad
Emphasis.
104530325 A of patent CN add using allyl polyethenoxy base ether as bottom material when temperature is increased to set point of temperature
Enter a certain amount of and concentration oxidant, acrylic acid aqueous solution and the adjusting-reduction of high concentration is added dropwise in stirring simultaneously after a certain period of time
Mixed liquor, addition programs are simple, and reaction condition is easily controllable, and product cost is high.By controlling process conditions, it is made to have and fits
With the ethers polycarboxylic acid water reducing agent that property is strong, water-reducing rate is high, function of slump protection is good.
106380551 A of patent CN provide a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereof.Its pH
It is 6.0~6.5, solid content is 45~55%, and raw material is grouped as by the group of following parts by weight：Molecular weight is 2000~5000
90~130 parts by weight of 4- hydroxyl butyl vinyls polyoxyethylene ether, 6~10 parts by weight of unsaturated monocarboxylic acid, unsaturated carboxylic acid
3~6 parts by weight of esters monomer, unsaturated 1~5 parts by weight of both sexes quaternary alkylphosphonium salt, 0.2~0.8 parts by weight of oxidant, reducing agent 0.2
~1.0 parts by weight, 0.02~0.06 parts by weight of catalyst, 0.2~0.6 parts by weight of chain-transferring agent, appropriate potassium hydroxide aqueous solution,
Appropriate sodium hydrate aqueous solution and appropriate amount of deionized water.The side chain distribution of thus obtained polycarboxylate water-reducer is more uniform, protects
Effect of collapsing is good, has excellent hyposensitivity energy to the volume variation of polycarboxylate water-reducer, high with the adaptability of concrete.
107189026 A of patent CN first by be added poly glycol monomethyl ether 1000, poly glycol monomethyl ether 2000,
Methacrylic acid, p-methyl benzenesulfonic acid, hydroquinone are reacted 8 hours at -0.08MPa in 110 DEG C, vacuum degree, are then cooled to
60 DEG C of dischargings, obtain esters polymeric monomer.Then in four-hole boiling flask, soft water is added, then stirring and heating water bath is to temperature 81
~83 DEG C, under this temperature, mix monomer was added dropwise with 180 minutes, and (wherein mix monomer is esters polymeric monomer/ethers polymeric monomer
=0~10/10~0 monomer), thioacetic acid, soft water composition mixed liquor, while be added dropwise 2.87% ammonium persulfate aqueous solution,
It drips off within 210 minutes, 1 hour is kept the temperature after dripping off, be then cooled to 50 DEG C, 30% sodium hydroxide solution is added and is copolymerized to get ether-ether
Type high-adaptability polycarboxylate water-reducer.
These patents are successfully prepared for the functional more and higher polycarboxylate water-reducer of concrete adaptability,
Molecular structure belongs to a kind of organic chemical constitution, and concrete is as a kind of inorganic material, includes mainly cement, mine
Polymer blends material and sand material etc., are the entities of a variety of inorganic particulates, embodiment be inorganic particulate characteristic.Therefore, organically
Even if polycarboxylate water-reducer still lacks the characteristic of some inorganic particulates, with inorganic coagulation by Molecular Designs more again
The compatibility of soil is difficult to further perfect, is also difficult to reach breakthrough raising in terms of adaptability.
Invention content
The object of the present invention is to provide a kind of polycarboxylate water-reducers of organic inorganic hybridization, and gained polycarboxylate water-reducer is not only
Characteristic with organic polycarboxylic acid molecule, it may have the characteristic of inorganic particulate in diminishing, protects the property for collapsing, being retained, enhancing etc.
It can better, the adaptability higher with concrete；It is a further object of the present invention to provide a kind of polycarboxylic acids of organic inorganic hybridization
The preparation method of water-reducing agent, condition is easy to control when preparation, and synthesis step is few.
To achieve the above object, the technical solution adopted by the present invention is：A kind of polycarboxylate water-reducer of organic inorganic hybridization,
Its general structure is：
Wherein, R1For H or-CH3, R2For-CH2Or-COOCH2CH2CH2, a, b, c, d, m and n are the degree of polymerization and are just
Integer, a=5~12, b=1~5, c=40~80, d=1~3, m=135~225, n=40~55.
Further, the molecular weight of the polycarboxylate water-reducer of the organic inorganic hybridization is 30000~80000.
A kind of preparation method of the polycarboxylate water-reducer of organic inorganic hybridization of the present invention, includes the following steps：
1) methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester and deionized water are added anti-
It answers in kettle, heating for dissolving obtains solution A；
2) deionized water solution and acrylic acid, unsaturated nano-silica of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of SiClx monomer, insulation reaction simultaneously are cooled to room temperature to obtain B solution；
3) liquid caustic soda of mass fraction 30~32% is added in B solution, it is 6~8 to adjust pH value, obtains mass fraction 40%
Organic inorganic hybridization polycarboxylate water-reducer.
Further, the methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, propylene
Acid, unsaturated nano-silica monomer, ammonium persulfate molar ratio be 1.0: (0.1~0.3): (6.0~8.5): (0.05~
0.15): (0.22~0.55).
Specifically, the molecular weight of methacrylic polyoxyethylene ether is 6000~10000 in the step 1), methyl-prop
The molecular weight of olefin(e) acid poly glycol monomethyl ether ester is 1800~2400.
Specifically, the temperature of insulation reaction is 60~80 DEG C in the step 2), and the time of reaction is 1.0~2.0h.
Further, the unsaturated nano-silica monomer is prepared as follows method and is made：To be screened out through 3A molecules
The toluene of water makees dispersant, and unsaturated silane monomer, nano silicon dioxide are carried out ultrasound point for 1: 1 with molar ratio in toluene
10~20min is dissipated, then 3~4h of back flow reaction at 80~90 DEG C, is centrifuged through 11000~13000rpm after being cooled to room temperature,
Precipitation is washed for several times repeatedly with absolute ethyl alcohol, the unsaturated silica monomer finished product of vacuum dried acquisition.
Specifically, unsaturated silane monomer is allyltrimethoxysilanis, allyl triethoxy in the step 2)
Silane, three isopropoxy silane of allyl, acryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane,
One kind in methyl allyl acyloxypropyl trimethoxysilane and methacryloxypropyl triethoxysilane.
Preferably, the grain size of the nano silicon dioxide be 30 ± 5nm, content 99.5%, specific surface area 150~
300m2The surface of/g, the nano silicon dioxide carry alcoholic extract hydroxyl group, and the mass fraction of alcoholic extract hydroxyl group is 10~15%.
1) inorganic nano-silicon dioxide particle is carried in polycarboxylate water-reducer molecule of the invention, is that a kind of organic-inorganic is miscellaneous
The molecular structure of change compares pure organic polycarboxylic acids molecular structure, and not only the characteristic with organic polycarboxylic acid water-reducing agent, also has
There is the dimensional effect of inorganic particulate, including：Steric hindrance effect, " ball " effect and " filling " effect；2) after concrete being added
It is retained, function of slump protection is good, and diminishing and enhancing effect performance are better, and paste flowing degree variation is small after 120min；3) side
Chain long-chain containing there are many, can provide more steric hindrances, increase the dispersibility and mobility of concrete, while the side of overlength
Chain is more advantageous to the growth of early strength of concrete.
Specific implementation mode
With reference to preferred embodiment, invention is further described in detail, convenient for more clearly understanding this
Invention, but the present invention is not limited to following specific implementation modes.
The present invention cardinal principle be：Using organic inorganic hybridization technology, make the activity hydroxy of nano-silica surface
Condensation reaction is carried out with unsaturated silane monomer, to which inorganic nano-silicon dioxide particle is introduced into organic polycarboxylic acids point
In the organic side chain of minor structure, polycarboxylate water-reducer is made not only to have the steric hindrance effect of captain side chain, organic group
Absorption and electrostatic repulsion effect, and the entire specific wetting lubricating action of organic polycarboxylic acid molecule etc., it may have inorganic grain
Steric hindrance effect, " ball " effect and " filling " effect of son, improve the function of polycarboxylate water-reducer, make it breakthroughly
Performance is more perfect, the adaptability higher with concrete；In addition, the C-C main chains and carboxyl short-side chain in molecule are adsorbed on concrete
Or cement particle surface, certain polymer adsorbed layers are formed, a variety of different long side chain interactions then provide enough skies
Between steric hindrance so that the dispersibility of concrete or cement that polycarboxylate water-reducer is added is excellent, it is good to protect effect of collapsing；At the same time,
The molecular side chain of overlength is more favorable to the growth of early strength of concrete.
A kind of polycarboxylate water-reducer of organic inorganic hybridization of the present invention, general structure are：
Wherein, R1For H or-CH3, R2For-CH2Or-COOCH2CH2CH2, a, b, c, d, m and n are the degree of polymerization and are just
Integer, a=5~12, b=1~5, c=40~80, d=1~3, m=135~225, n=40~55；Organic inorganic hybridization
The molecular weight of polycarboxylate water-reducer is 30000~80000.
A kind of preparation method of the polycarboxylate water-reducer of organic inorganic hybridization of the present invention, includes the following steps：
1) methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester and deionized water are added anti-
It answers in kettle, is dissolved by heating at being 20~80 DEG C in temperature and obtain solution A；
2) deionized water solution and acrylic acid, unsaturated nano-silica of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of SiClx monomer carries out 1.0~2.0h of insulation reaction at being 60~80 DEG C in temperature and is cooled to room
Temperature obtains B solution；
3) liquid caustic soda of mass fraction 30~32% is added in B solution, it is 6~8 to adjust pH value, obtains mass fraction 40%
Organic inorganic hybridization polycarboxylate water-reducer；Methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether
Ester, acrylic acid, unsaturated nano-silica monomer, ammonium persulfate molar ratio be 1.0: (0.1~0.3): (6.0~8.5):
(0.05~0.15): (0.22~0.55)；The molecular weight of methacrylic polyoxyethylene ether is 6000~10000, methyl-prop
The molecular weight of olefin(e) acid poly glycol monomethyl ether ester is 1800~2400；Used unsaturated nano-silica monomer is by following
Preparation method is made：Make dispersant with the toluene removed water through 3A molecular sieves, by unsaturated silane monomer, nano silicon dioxide to rub
You in toluene for 1: 1 than carrying out 10~20min of ultrasonic disperse, and then 3~4h of back flow reaction at 80~90 DEG C, is cooled to room
It is centrifuged through 11000~13000rpm after temperature, precipitation is washed for several times repeatedly with absolute ethyl alcohol, vacuum dried acquisition finished product；Wherein
Unsaturated silane monomer be allyltrimethoxysilanis, allyltriethoxysilane, three isopropoxy silane of allyl,
Acryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane, methacryloxypropyl trimethoxy silicon
One kind in alkane and methacryloxypropyl triethoxysilane.
The grain size of used nano silicon dioxide is 30 ± 5nm, content 99.5%, specific surface area in following embodiments
150~300m2/ g, the surface of nano silicon dioxide carry alcoholic extract hydroxyl group, and the mass fraction of alcoholic extract hydroxyl group is 10~15%, can be with
The commercially available nanometer titanium dioxide of the nano silicon dioxide of vapor phase method production or the nano silicon dioxide of liquid phase method production after purification
Silicon product, molecular forms indicate as follows：
Embodiment 1
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by allyl
Base trimethoxy silane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 10min, the back flow reaction 4h at 80 DEG C, instead
It is cooled to room temperature after answering, is centrifuged through 13000rpm, precipitation is washed for several times repeatedly with absolute ethyl alcohol, vacuum dried up to white
The powdered unsaturated nano-silica monomer of color.Wherein, allyltrimethoxysilanis, the molar ratio of nano silicon dioxide
It is 1: 1；(2) polymerisation：The methyl-prop for being 1816 by methacrylic polyoxyethylene ether that molecular weight is 6026, molecular weight
Olefin(e) acid poly glycol monomethyl ether ester and deionized water are added in reaction kettle, are obtained after being dissolved by heating completely at a temperature of 20~80 DEG C
Solution A；The deionized water solution and acrylic acid, unsaturated nano silicon dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of monomer, 3.0h is added dropwise at 60 DEG C, insulation reaction 1.0h, reaction at a temperature of 60 DEG C after dripping off
After be cooled to room temperature to obtain B solution；The liquid caustic soda of mass fraction 30% is added into B solution again, it is 6~8 to adjust pH value, is obtained
It is the polycarboxylate water-reducer of the organic inorganic hybridization of mass fraction 40% to product, is denoted as Z1, the molecular weight of Z1 is 30864；
Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, unsaturated nano-silica
The molar ratio of SiClx monomer and ammonium persulfate is 1.0: 0.1: 6.0: 0.05: 0.22.
Embodiment 2
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by allyl
Ethyl triethoxy silicane alkane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 10min, the back flow reaction 4h at 80 DEG C, instead
It is cooled to room temperature after answering, is centrifuged through 13000rpm, precipitation is washed for several times repeatedly with absolute ethyl alcohol, vacuum dried up to white
The powdered unsaturated nano-silica monomer of color.Wherein, the molar ratio of allyltriethoxysilane, nano silicon dioxide
It is 1: 1；
(2) polymerisation：The methyl for being 2036 by methacrylic polyoxyethylene ether that molecular weight is 6026, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 70 DEG C, after dripping off at a temperature of 70 DEG C insulation reaction 1.5h, instead
It is cooled to room temperature to obtain B solution after answering；The liquid caustic soda of mass fraction 31% is added into B solution again, it is 6~8 to adjust pH value,
The polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40% is obtained, Z2 is denoted as, the molecular weight of Z2 is
36975；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, unsaturation are received
The molar ratio of rice silica monomer and ammonium persulfate is 1.0: 0.12: 6.4: 0.08: 0.25.
Embodiment 3
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by allyl
Three isopropoxy silane of base, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 10min, the back flow reaction 4h at 80 DEG C,
Be cooled to room temperature, centrifuged through 13000rpm after completion of the reaction, precipitation is washed for several times repeatedly with absolute ethyl alcohol, it is vacuum dried to obtain the final product
The unsaturated nano-silica monomer of white powder.Wherein, allyl three isopropoxy silane, nano silicon dioxide rub
You are than being 1: 1；
(2) polymerisation：The methyl for being 1816 by methacrylic polyoxyethylene ether that molecular weight is 7038, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 80 DEG C insulation reaction 2.0h, instead
It is cooled to room temperature to obtain B solution after answering；The liquid caustic soda of mass fraction 31% is added into B solution again, it is 6~8 to adjust pH value,
The polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40% is obtained, Z3 is denoted as, the molecular weight of Z3 is
44262；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, unsaturation are received
The molar ratio of rice silica monomer and ammonium persulfate is 1.0: 0.15: 6.8: 0.08：0.3.
Embodiment 4
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by propylene
Monomethacryloxypropyl trimethoxy silane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 10min, flow back at 80 DEG C anti-
4h is answered, is cooled to room temperature after completion of the reaction, is centrifuged through 13000rpm, precipitation is washed for several times repeatedly with absolute ethyl alcohol, dry through vacuum
The dry unsaturated nano-silica monomer up to white powder.Wherein, acryloxypropyl trimethoxy silane, nanometer two
The molar ratio of silica is 1: 1；
(2) polymerisation：The methyl for being 2036 by methacrylic polyoxyethylene ether that molecular weight is 7038, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 60~80 DEG C insulation reaction 1.0
~2.0h is cooled to room temperature to obtain B solution after reaction；The liquid caustic soda of mass fraction 32% is added into B solution again, adjusts pH
Value is 6~8, obtains the polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40%, is denoted as Z4, the molecule of Z4
Amount is 50894；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, insatiable hunger
It is 1.0: 0.18: 7.2: 0.1: 0.35 with the molar ratio of nano-silica monomer and ammonium persulfate.
Embodiment 5
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by propylene
Monomethacryloxypropyl triethoxysilane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 10min, flow back at 85 DEG C anti-
3h is answered, is cooled to room temperature after completion of the reaction, is centrifuged through 11000rpm, precipitation is washed for several times repeatedly with absolute ethyl alcohol, dry through vacuum
The dry unsaturated nano-silica monomer up to white powder.Wherein, acryloxypropyl triethoxysilane, nanometer two
The molar ratio of silica is 1: 1；
(2) polymerisation：The methyl for being 2036 by methacrylic polyoxyethylene ether that molecular weight is 8006, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 60~80 DEG C insulation reaction 1.0
~2.0h is cooled to room temperature to obtain B solution after reaction；The liquid caustic soda of mass fraction 30% is added into B solution again, adjusts pH
Value is 6~8, obtains the polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40%, is denoted as Z5, the molecule of Z5
Amount is 58723；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, insatiable hunger
It is 1.0: 0.22: 7.5: 0.12: 0.4 with the molar ratio of nano-silica monomer and ammonium persulfate.
Embodiment 6
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by methyl
Acryloxypropyl trimethoxy silane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 15min, next time at 85 DEG C
Stream reaction 4h, is cooled to room temperature, is centrifuged through 12000rpm, precipitation is washed repeatedly with absolute ethyl alcohol for several times, through true after completion of the reaction
Sky is drying to obtain the unsaturated nano-silica monomer of white powder.Wherein, methacryloxypropyl trimethoxy silicon
Alkane, nano silicon dioxide molar ratio be 1: 1；
(2) polymerisation：The methyl for being 2388 by methacrylic polyoxyethylene ether that molecular weight is 8006, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 60~80 DEG C insulation reaction 1.0
~2.0h is cooled to room temperature to obtain B solution after reaction；The liquid caustic soda of mass fraction 30% is added into B solution again, adjusts pH
Value is 6~8, obtains the polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40%, is denoted as Z6, the molecule of Z6
Amount is 64682；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, insatiable hunger
It is 1.0: 0.25: 7.8: 0.12: 0.45 with the molar ratio of nano-silica monomer and ammonium persulfate.
Embodiment 7
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by methyl
Acryloxypropyl triethoxysilane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 15min, next time at 90 DEG C
Stream reaction 3h, is cooled to room temperature, is centrifuged through 13000rpm, precipitation is washed repeatedly with absolute ethyl alcohol for several times, through true after completion of the reaction
Sky is drying to obtain the unsaturated nano-silica monomer of white powder.Wherein, methacryloxypropyl triethoxysilicane
Alkane, nano silicon dioxide molar ratio be 1: 1；
(2) polymerisation：The methyl for being 2036 by methacrylic polyoxyethylene ether that molecular weight is 9986, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 60~80 DEG C insulation reaction 1.0
~2.0h is cooled to room temperature to obtain B solution after reaction；The liquid caustic soda of mass fraction 32% is added into B solution again, adjusts pH
Value is 6~8, obtains the polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40%, is denoted as Z7, the molecule of Z7
Amount is 73258；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, insatiable hunger
It is 1.0: 0.28: 8.2: 0.15: 0.5 with the molar ratio of nano-silica monomer and ammonium persulfate.
Embodiment 8
(1) synthesis of unsaturated nano-silica monomer：Make dispersant with the toluene removed water through 3A molecular sieves, by methyl
Acryloxypropyl triethoxysilane, nano silicon dioxide are added in reaction kettle, after ultrasonic disperse 20min, next time at 90 DEG C
Stream reaction 4h, is cooled to room temperature, is centrifuged through 13000rpm, precipitation is washed repeatedly with absolute ethyl alcohol for several times, through true after completion of the reaction
Sky is drying to obtain the unsaturated nano-silica monomer of white powder.Wherein, methacryloxypropyl triethoxysilicane
Alkane, nano silicon dioxide molar ratio be 1: 1；
(2) polymerisation：The methyl for being 2388 by methacrylic polyoxyethylene ether that molecular weight is 9986, molecular weight
Polyalkylene glycol acrylate monomethyl ether ester and deionized water are added in reaction kettle, after being dissolved by heating completely at a temperature of 20~80 DEG C
To solution A；The deionized water solution and acrylic acid, unsaturated nanometer titanium dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of silicon monomer, 3.0h is added dropwise at 80 DEG C, after dripping off at a temperature of 60~80 DEG C insulation reaction 1.0
~2.0h is cooled to room temperature to obtain B solution after reaction；The liquid caustic soda of mass fraction 32% is added into B solution again, adjusts pH
Value is 6~8, obtains the polycarboxylate water-reducer that product is the organic inorganic hybridization of mass fraction 40%, is denoted as Z8, the molecule of Z8
Amount is 79841；Wherein, methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, insatiable hunger
It is 1.0: 0.3: 8.5: 0.15: 0.55 with the molar ratio of nano-silica monomer and ammonium persulfate.
Comparative example 1
With reference to the method for the polymerisation of embodiment 1, the difference is that unsaturated nano-silica monomer is not used.Specifically
Polymerisation be：The methacrylic acid for being 1816 by methacrylic polyoxyethylene ether that molecular weight is 6026, molecular weight
Poly glycol monomethyl ether ester and deionized water are added in reaction kettle, and it is molten to obtain A after being dissolved by heating completely at a temperature of 20~80 DEG C
Liquid；The deionized water solution of ammonium persulfate and the deionized water mixed solution of acrylic acid is added dropwise simultaneously respectively in solution A, 60
3.0h is added dropwise at DEG C, after dripping off at a temperature of 60 DEG C insulation reaction 1.0h, be cooled to room temperature to obtain B solution after reaction；
The liquid caustic soda of mass fraction 30% is added into B solution again, it is 6~8 to adjust pH value, and it is having for mass fraction 40% to obtain product
The polycarboxylate water-reducer of machine inorganic hybridization is denoted as A1, and the molecular weight of A1 is 32154；Wherein, methacrylic polyoxyethylene groups
Ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid and ammonium persulfate molar ratio be 1.0: 0.1: 6.0: 0.22.
Comparative example 2
Commercially available polycarboxylate water-reducer, is denoted as A2.
Embodiment 9
Implementation result is verified：
By the pure organic structure of the polycarboxylate water-reducer of the organic inorganic hybridization of the embodiment of the present invention 1~8 and comparative example 1
Polycarboxylate water-reducer and the commercially available polycarboxylate water-reducer of comparative example 2 are according to GB/T 8077-2012《Concrete admixture is equal
Matter test method》Paste flowing degree is measured, cement on the basis of cement, experimental result is shown in Table 1：
1 each sample flowing degree of net paste of cement test result of table
As seen from the results in Table 1, compare comparative example 1 and comparative example 2, the embodiment of the present invention 1~8 in initial paste flowing degree and
It is substantially better than comparative example 1 and comparative example 2 in terms of the gradual loss of 60min, 120min paste flowing degree.It can be seen that organic nothing
The molecular structure of machine hydridization compare pure organic polycarboxylic acids molecular structure, be more advantageous to improve polycarboxylate water-reducer water-reducing rate and
Slump retaining has superior dispersibility and fluidity retentivity especially compared with the commercial product in comparative example 2.
Embodiment 10
Implementation result is verified：
By the pure organic structure of the polycarboxylate water-reducer of the organic inorganic hybridization of the embodiment of the present invention 1~8 and comparative example 1
Polycarboxylate water-reducer and the commercially available polycarboxylate water-reducer of comparative example 2 are according to GB/T 50081-2002《Normal concrete mechanics
Method for testing performance standard》Test its compression strength, experiment use the match ratio of concrete for：Reference cement 360Kg/m3, sand
792Kg/m3, gravelstone 290Kg/m3(5~10mm), great Shi 678Kg/m3(10~20mm), water-cement ratio 0.4.Experimental result is shown in Table
2：
2 each sample concrete crushing strength test result of table
As shown in Table 2, comparative example 1 and comparative example 2, resistance to compression of the embodiment of the present invention 1~8 in concrete different larval instar are compared
It is above comparative example 1 and comparative example 2 in terms of intensity.It can be seen that the molecular structure of organic inorganic hybridization is organically poly- compared to pure
Carboxylic acid molecules structure, steric hindrance act on higher, and dispersibility is more preferable, and have filling density to concrete, are more advantageous to mixed
The growth of solidifying soil intensity, especially compared with the commercial product in comparative example 2, early epistasis is better.
Unspecified content is the prior art known to a person of ordinary skill in the art in this specification.
Above-described specific implementation mode is only schematical, and used technical term is limited in the present invention
Only for convenience of description of the invention, those skilled in the art subtract qualifier in the polycarboxylic acids of organic inorganic hybridization of the present invention
Under the enlightenment of aqua and preparation method thereof, without breaking away from the scope protected by the purposes and claims of the present invention, may be used also
Many forms are derived, these are within protection scope of the present invention.
Claims (9)
1. a kind of polycarboxylate water-reducer of organic inorganic hybridization, which is characterized in that its general structure is：
Wherein, R1For H or-CH3, R2For-CH2Or-COOCH2CH2CH2, a, b, c, d, m and n is the degree of polymerization and are positive integer,
A=5~12, b=1~5, c=40~80, d=1~3, m=135~225, n=40~55.
2. the polycarboxylate water-reducer of organic inorganic hybridization according to claim 1, it is characterised in that：The organic-inorganic is miscellaneous
The molecular weight of the polycarboxylate water-reducer of change is 30000~80000.
3. a kind of preparation method of the polycarboxylate water-reducer of organic inorganic hybridization as claimed in claim 1 or 2, feature exist
In including the following steps：
1) reaction kettle is added in methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester and deionized water
In, heating for dissolving obtains solution A；
2) deionized water solution and acrylic acid, unsaturated nano silicon dioxide of ammonium persulfate is added dropwise simultaneously respectively in solution A
The deionized water mixed solution of monomer, insulation reaction simultaneously are cooled to room temperature to obtain B solution；
3) liquid caustic soda of mass fraction 30~32% is added in B solution, it is 6~8 to adjust pH value, obtains having for mass fraction 40%
The polycarboxylate water-reducer of machine inorganic hybridization.
4. the preparation method of the polycarboxylate water-reducer of organic inorganic hybridization according to claim 3, it is characterised in that：It is described
Methacrylic polyoxyethylene ether, Methylacrylic acid polyethylene glycol single armor ether ester, acrylic acid, unsaturated nano silicon dioxide list
Body, ammonium persulfate molar ratio be 1.0: (0.1~0.3): (6.0~8.5): (0.05~0.15): (0.22~0.55).
5. the preparation method of the polycarboxylate water-reducer of organic inorganic hybridization according to claim 4, it is characterised in that：It is described
Methacrylic polyoxyethylene ether molecular weight in step 1) is 6000~10000, Methylacrylic acid polyethylene glycol single armor ether
The molecular weight of ester is 1800~2400.
6. the preparation method of the polycarboxylate water-reducer of organic inorganic hybridization according to claim 5, it is characterised in that：It is described
The temperature of insulation reaction is 60~80 DEG C in step 2), and the time of reaction is 1.0~2.0h.
7. the preparation method of the polycarboxylate water-reducer of the organic inorganic hybridization according to any one of claim 4~6, special
Sign is：The unsaturation nano-silica monomer is prepared as follows method and is made, and is made with the toluene removed water through 3A molecular sieves
Dispersant, by unsaturated silane monomer, nano silicon dioxide with molar ratio be 1: 1 in toluene carry out ultrasonic disperse 10~
20min, then 3~4h of back flow reaction at 80~90 DEG C, centrifuges after being cooled to room temperature through 11000~13000rpm, and precipitation is used
Absolute ethyl alcohol washs for several times repeatedly, the unsaturated silica monomer finished product of vacuum dried acquisition.
8. the preparation method of the polycarboxylate water-reducer of organic inorganic hybridization according to claim 7, it is characterised in that：It is described
Unsaturated silane monomer is allyltrimethoxysilanis, allyltriethoxysilane, three isopropoxy silane of allyl, third
Alkene monomethacryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane, methyl allyl acyloxypropyl trimethoxysilane
With one kind in methacryloxypropyl triethoxysilane.
9. the preparation method of the polycarboxylate water-reducer of organic inorganic hybridization according to claim 7, it is characterised in that：It is described
The grain size of nano silicon dioxide is 30 ± 5nm, content 99.5%, 150~300m of specific surface area2/ g, the nanometer titanium dioxide
The surface of silicon carries alcoholic extract hydroxyl group, and the mass fraction of alcoholic extract hydroxyl group is 10~15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149061.2A CN108373523B (en) | 2018-02-12 | 2018-02-12 | Organic-inorganic hybrid polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149061.2A CN108373523B (en) | 2018-02-12 | 2018-02-12 | Organic-inorganic hybrid polycarboxylate superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108373523A true CN108373523A (en) | 2018-08-07 |
| CN108373523B CN108373523B (en) | 2020-07-03 |
Family
ID=63017954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810149061.2A Active CN108373523B (en) | 2018-02-12 | 2018-02-12 | Organic-inorganic hybrid polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108373523B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606695A (en) * | 2019-10-17 | 2019-12-24 | 江苏兆佳建材科技有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
| CN113045718A (en) * | 2021-04-07 | 2021-06-29 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer, preparation method and application |
| CN113248171A (en) * | 2021-05-12 | 2021-08-13 | 安徽建筑大学 | Preparation method of high-performance polycarboxylate superplasticizer |
| CN113387607A (en) * | 2021-06-07 | 2021-09-14 | 广西交建工程检测咨询有限公司 | Novel retarding high-performance water reducing agent and preparation method thereof |
| CN113413643A (en) * | 2021-07-26 | 2021-09-21 | 中建西部建设建材科学研究院有限公司 | Efficient settling method for waste slurry of concrete mixing plant |
| CN114380955A (en) * | 2021-12-31 | 2022-04-22 | 苏州弗克技术股份有限公司 | Silicon modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
| CN118005863A (en) * | 2024-04-10 | 2024-05-10 | 中铁上海工程局集团有限公司 | Super-early-strength shrinkage-reducing polycarboxylate-type water reducer and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
| WO2017113990A1 (en) * | 2015-12-31 | 2017-07-06 | 江苏苏博特新材料股份有限公司 | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof |
| CN107312132A (en) * | 2017-07-19 | 2017-11-03 | 中交二航武汉港湾新材料有限公司 | Polycarboxylate water-reducer of modified sugars side-chain structure and preparation method thereof |
-
2018
- 2018-02-12 CN CN201810149061.2A patent/CN108373523B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
| WO2017113990A1 (en) * | 2015-12-31 | 2017-07-06 | 江苏苏博特新材料股份有限公司 | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof |
| CN107312132A (en) * | 2017-07-19 | 2017-11-03 | 中交二航武汉港湾新材料有限公司 | Polycarboxylate water-reducer of modified sugars side-chain structure and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606695A (en) * | 2019-10-17 | 2019-12-24 | 江苏兆佳建材科技有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
| CN113045718A (en) * | 2021-04-07 | 2021-06-29 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer, preparation method and application |
| CN113248171A (en) * | 2021-05-12 | 2021-08-13 | 安徽建筑大学 | Preparation method of high-performance polycarboxylate superplasticizer |
| CN113387607A (en) * | 2021-06-07 | 2021-09-14 | 广西交建工程检测咨询有限公司 | Novel retarding high-performance water reducing agent and preparation method thereof |
| CN113413643A (en) * | 2021-07-26 | 2021-09-21 | 中建西部建设建材科学研究院有限公司 | Efficient settling method for waste slurry of concrete mixing plant |
| CN114380955A (en) * | 2021-12-31 | 2022-04-22 | 苏州弗克技术股份有限公司 | Silicon modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
| CN114380955B (en) * | 2021-12-31 | 2023-08-22 | 苏州弗克技术股份有限公司 | Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
| CN118005863A (en) * | 2024-04-10 | 2024-05-10 | 中铁上海工程局集团有限公司 | Super-early-strength shrinkage-reducing polycarboxylate-type water reducer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108373523B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108373523A (en) | Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof | |
| CN107337766B (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| CN110172128B (en) | Brush-type polycarboxylic acid high-efficiency viscosity-reducing water reducer and preparation method thereof | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN104725573B (en) | It is a kind of to promote super plasticizer of hydrated cementitious and preparation method and application | |
| CN111484582A (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| Yang et al. | Synthesis and performance of an environmentally friendly polycarboxylate superplasticizer based on modified poly (aspartic acid) | |
| CN107629177A (en) | A kind of preparation method of anti-mud polycarboxylate water-reducer | |
| CN109734833A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain and preparation method thereof | |
| Feng et al. | Comparison of ester-based slow-release polycarboxylate superplasticizers with their polycarboxylate counterparts | |
| CN110713573A (en) | Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor | |
| CN108484840A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of ester ether mixed structure and preparation method thereof | |
| CN116622034A (en) | Slow-release viscosity-reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof | |
| CN105199060B (en) | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof | |
| CN108948283B (en) | Phthalic anhydride modified polycarboxylate superplasticizer and preparation method thereof | |
| CN110294825A (en) | A kind of hud typed tertiary carbon redispersable latex powder and preparation method thereof | |
| CN112608424B (en) | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof | |
| CN105271902B (en) | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof | |
| CN108003302A (en) | A kind of amidogen ether class ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof | |
| CN111087552A (en) | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance | |
| WO2024139523A1 (en) | Polycarboxylate superplasticizer prepared from viscosity-reducing macromonomer and preparation method therefor | |
| CN108191289B (en) | Carbon black modified polycarboxylate superplasticizer and preparation method and application thereof | |
| CN107057003B (en) | Self-curing type poly carboxylic acid series water reducer and preparation method thereof | |
| CN106905493B (en) | Defoaming polycarboxylic acid cement dispersant and preparation method thereof | |
| CN112250799B (en) | Organic silicon modified polycarboxylate dispersant, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |