CN109970931A - A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications - Google Patents
A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications Download PDFInfo
- Publication number
- CN109970931A CN109970931A CN201910089432.7A CN201910089432A CN109970931A CN 109970931 A CN109970931 A CN 109970931A CN 201910089432 A CN201910089432 A CN 201910089432A CN 109970931 A CN109970931 A CN 109970931A
- Authority
- CN
- China
- Prior art keywords
- monomer
- carboxylic acid
- super plasticizer
- poly carboxylic
- integer
- 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.)
- Pending
Links
Classifications
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/128—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to reaction products of polysiloxanes having at least one Si-H bond and compounds having carbon-to-carbon double bonds
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C04B2103/32—Superplasticisers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of shrinkage type poly carboxylic acid series super plasticizers, preparation method and applications, by monomer A (5~50 parts), monomer B (1~60 part), monomer C (20~100), monomer D (10~60 parts) and monomer E (1~20 part), free radicals copolymerization reaction is carried out under the conditions of existing for the initiator and chain-transferring agent, finally plus alkali neutralization makes PH=7~8；Monomer A is acrylic acid, acrylate, acrylates or acrylate salt；Monomer B is methacrylic sulfonic acid or methacrylic sulfonic acid salt；Monomer C is polyether monoacrylates or alkoxy polyether mono acrylic ester；Monomer D is maleic anhydride polyether ester, maleic anhydride half-ester, maleic anhydride polyether ester salt or maleic anhydride half-ester salt；Monomer E is polysiloxanes and acrylic acid modified copolyether.Raw material sources of the present invention are wide, and production technology is mature, and water-reducing rate is high, and reinforcing effect is obvious, and bleed excellent effect, function of slump protection is good, and anti-shrink resists dry and cracked.
Description
Technical field
The invention belongs to concrete structures and concrete works technical field, are related to concrete admixture synthetic technology neck
Domain belongs to the synthesis of polycarboxylic acid series high efficiency water reducing agent activity organic monomer and the synthetic technology neck of poly carboxylic acid series super plasticizer
Domain, and in particular to arrive a kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications.
Background technique
In recent decades, concrete has developed into the present age most important Structural Engineering material, according to State Statistics Bureau's public affairs
The data of cloth show that 2,400,000,000 tons of national cement yield in 2016 increases by 2.5% on a year-on-year basis, cement consumed by capital construction
With concrete amount all in rank first.With quickly propelling for China's urbanization, Asia infrastructure investment bank
Set up, the modernization development of infrastructural project certainly will be promoted.Due to varying environment, different infrastructural projects mostly with
For concrete as structural timber, this certainly will will accelerate the progress of concrete technology.
Basic material of the concrete as architectural engineering, concrete cracking have become the common fault of civil engineering.?
Fracture width is less than 0.5mm when relative humidity (RH) < 65%, and in RH > 65%, fracture width is less than 0.3mm, although this is right
After concrete structure will not bring big harm, but concrete structure is acted on by load, crack will broaden, harmless or few evil
Crack will will become harmful cracks.Harmful cracks not only influence concrete structure using safe, while can also shorten coagulation
The service life of native structures brings huge economic loss.
It improves concrete durability and guarantees that the major measure of its service life can be divided into terms of two: first, guarantee mixed
Solidifying soil is closely knit enough, reduces and permeates and delay steel bar corrosion；Second: reducing various cracks, especially early crack.Concrete one
There is crack in denier, just considerably increases the permeability of concrete, aggravates the corrosion of reinforcing bar and the freeze-thaw damage degree of concrete, such as
What, which takes effective measures, reduces or even eliminates various contractions, is always that engineer makes great efforts the problem of exploring.The most commonly used is
Compensate contraction using the swelling agent of entringite class, but volume is big (10-the 15% of cement consumption), when production pollutes environment；
And maintenance difficulty is big；In addition, adding swelling agent in the concrete of high water-cement ratio, to reduce early expansion bigger, after concrete
Phase shrinks but more greatly, and expansion effect is poor in low water binder ratio concrete, cannot substantially compensate contraction.BENTZ D P,
The contraction of concrete can be effectively reduced in the novel economization agent that HANSEN K K and ENGSTRAND J. is developed, but its volume is higher
(the 2%~3% of cementitious material quality), at high cost, no diminishing function are difficult to promote in the middle low-strength concrete of big dosage.
Further, since the water-reducing rate of poly carboxylic acid series water reducer is much higher compared to traditional naphthalene water reducer and flows retention property more
Well, and there is certain reducing function, is suitable for preparing flyash in great mixed amount or large dosage slag concrete, sprays super plasticized mix
Solidifying soil, fiber reinforcement fluidity concrete and high-strength high-flowing concrete, the successive development and application of new special concrete make
Poly carboxylic acid series water reducer receives an acclaim very much, becomes especially noticeable.Meanwhile many new concretes are in high-rise, big
The engineerings such as span bridge, marine drilling platform, tunnel obtain large-scale popularization application.The research and development of poly carboxylic acid series water reducer are more next
More paid attention to both at home and abroad, research polycarboxylate high performance water-reducing agent has represented the main of concrete chemical admixture research
Direction.
CN200510037872.6 reports a kind of with the super modeling of multifunctional carboxylic-acid comb graft copolymer slow setting soil
Agent there is dispersion, guarantor to collapse, enhance, reducing function, but effect is far from enough.
JP8268741 report it is a kind of using allyl alcohol ether-copolymer-maleic anhydride as the Mobyneb additive of principal component,
With diminishing and reducing function, when mixing 0.2%, water-reducing rate 18%, the dry shrinkage ratio reference cement of 28d reduces 35% left side
The right side, there are also a certain distance compared with the effect of economization agent.Furthermore this analog copolymer price is higher and dispersion performance to cement
It is poor.
US2005/0096413 reports a kind of Mobyneb additive, main component α-allyl alcohol-ω-methyl polyethers-
The copolymer of maleic anhydride dries the common poly carboxylic acid series water reducer of shrinkage ratio using ordinary portland cement (W/C=0.3) for 24 hours
Chupol HP-11 is compared to 15%-25% is reduced, and there are also certain differences compared with the effect of economization agent.
CN200610040089.X disclose it is a kind of decrement, crack resistance type grafted copolymer as concrete super-plasticizing agent, volume
When 0.2%, water-reducing rate reaches dry shrink of 25% or more, 28d reduces 40-50% compared with naphthalene water reducer, than benchmark coagulation
Soil reduces 30-50%；But oleaginous system used in synthesis, pollution is easily caused, and it also requires rising temperature reclamation is organic molten
Agent causes energy waste, does not meet the modernization development of environmental protection and energy saving.
In conclusion Mobyneb additive is there are still clearly disadvantageous at present, including primary raw material price is high, dispersibility
Can be poor, water-reducing rate is inadequate, pollutes environment, the consumption energy etc..
The above retrieval discovery, above technical solution do not influence novelty of the invention；And mutual group of the above patent
Conjunction cannot destroy creativeness of the invention.
Summary of the invention
For the defects in the prior art and insufficient, the first purpose of the invention is to provide a kind of shrinkage type polycarboxylic-acids
Super plasticizer, the super plasticizer have that good high water reducing rate, reinforcing effect, bleed excellent effect, function of slump protection is good, anti-shrink is anti-dry
The advantages that splitting and be cheap.
Second object of the present invention is to provide the preparation method of shrinkage type poly carboxylic acid series super plasticizer, provides a variety of use
Used raw material sources are abundant when the organic monomer of synthesizing polycarboxylic acid high-performance water reducing agent, preparation, cheap, preparation
Simple process.
Third object of the present invention is the application that shrinkage type poly carboxylic acid series super plasticizer is used to prepare concrete, is prepared into
To concrete have that good high water reducing rate, reinforcing effect, bleed excellent effect, function of slump protection be good, anti-shrink resists dry and cracked and price
The advantages that cheap.
Three above-mentioned purposes of the present invention are deferred to, technical solution of the present invention is as follows:
To reach the first purpose of this invention, a kind of shrinkage type poly carboxylic acid series super plasticizer, the super plasticizer
Chemical structural formula are as follows:
In formula, EO represents ethylene oxide unit, and PO represents propylene oxide units, R1And R4Respectively alkoxy or hydroxyl,
R2、R3And R5Respectively hydrogen, monovalent metal or ammonium, a and c are respectively 0~50 integer, b and d be respectively 0~150 it is whole
Number, the integer that e is 0~30, x and y are respectively 0~50 integer, and m and n are respectively 0~50 integer；
And the shrinkage type poly carboxylic acid series super plasticizer molecular weight is 5000~50000.
Optionally, by monomer A (5~50 parts), monomer B (1~60 part), monomer C (20~100), monomer D (10~60
Part) and monomer E (1~20 part), free radicals copolymerization reaction is carried out under the conditions of existing for the initiator and chain-transferring agent, finally plus alkali
Neutralization makes PH=7~8；
Monomer A is acrylic acid, acrylate, acrylates or acrylate salt；Monomer B is methacrylic sulfonic acid or methyl
Sodium allyl sulphonate；Monomer C is polyether monoacrylates or alkoxy polyether mono acrylic ester；Monomer D be maleic anhydride polyether ester,
Maleic anhydride half-ester, maleic anhydride polyether ester salt or maleic anhydride half-ester salt；Monomer E is polysiloxanes and acrylic acid modified polyethers
Copolymer.
Optionally, the initiator is water-soluble radical initiator, the water-soluble radical initiator
Selected from potassium peroxydisulfate K2S2O8, ammonium persulfate (NH4)2S2O8, sodium peroxydisulfate Na2S2O8, hydrogen peroxide H2O2, ferrous salt, sulfurous acid
One of salt and thiosulfate or more than one mixture；
The dosage of initiator accounts for the 0.1%~10.0% of reaction monomers gross mass；
The reaction temperature of the free radicals copolymerization reaction is 70~130 DEG C；
The chain-transferring agent includes but is not limited to isopropanol, mercaptoethanol, mercaprol, thioacetic acid and mercaptopropionic acid
One of or more than one mixture；
The dosage of chain-transferring agent is the 0.1%~5% of each monomer gross mass.
Optionally, the monomer A can be indicated with following general formula (1):
R in formula (1)5Indicate hydrogen, monovalent metal or ammonium.
Optionally, the monomer B can be indicated with following general formula (2):
R in formula (2)2Indicate hydrogen, monovalent metal or ammonium.
Optionally, the monomer C can be indicated with following general formula (3):
R in formula (3)1It is the alkyl, allyl or hydroxyl of 1~4 carbon atom, x and y are respectively 0~50 integer；
The preparation method of the monomer C: by acrylic acid and following (4) polyethers by the molar ratio of 1:1.0~4.5 solvent-free
Under the conditions of, polymerization inhibitor is added and esterification occurs for catalyst；
In its (4), x, y are respectively 0~50 integer, R1For the alkyl or hydroxyl of 1~5 carbon atom；
The catalyst be selected from the concentrated sulfuric acid, p-methyl benzenesulfonic acid, phosphorous acid with, solid super-strong acid, boron trifluoride, tri-chlorination
One of aluminium, lewis acid and amine substance or more than one mixture, the dosage of catalyst are polyether quality
0.1%~5.0%；
The polymerization inhibitor is in hydroquinone, phenthazine, hydroquinone-methyl ether and di-t-butyl-paracresol
One or more kinds of mixtures, dosage are the 0.01%~5.0% of acrylic acid quality；
The temperature of esterification is 75~140 DEG C, and the reaction time is 3~15h.
Optionally, the monomer D can be indicated with following general formula (5):
R in formula (5)3Indicate hydrogen, monovalent metal or ammonium；R4For the alkyl or allyl or hydroxyl of 1~4 carbon atom； x
It is respectively 0~10 integer with y；
The monomer D preparation method: by maleic anhydride and following (6) polyethers by the molar ratio of 1:1.0~5.0 in catalyst
Catalysis under esterification occurs；
X and y is respectively 0~10 integer in formula (6)；R4For the alkyl or allyl or hydroxyl of 1~4 carbon atom.
Catalyst is selected from one of the concentrated sulfuric acid, p-methyl benzenesulfonic acid, phosphoric acid and solid super-strong acid or more than one is mixed
Object is closed, the dosage of catalyst is the 0.01%~5.0% of polyether quality；
The temperature of its esterification is 80~150 DEG C, and the reaction time is 3~15h.
Optionally, the monomer E can be indicated with following general formula (7):
X, y, m and n are respectively 0~50 integer in formula (7)；
The monomer E preparation method: by following (9) the Si-H base dimethyl silicone polymer of silicon oil of low hydrogen content PHMS and poly- second two
Addition reaction is obtained for 1:0.1~4.0 and under the effect of the catalyst in molar ratio for alcohol diacrylate following (8)；
X and y is respectively 0~50 integer in formula；M and n is respectively 0~30 integer and m >=1；
Catalyst is selected from H2PtCl6、(Ph3P)4Pd、[RhCl(CO)2]2(Ph3P)2NiCl2One of or more than one
Mixture, the dosage of catalyst is 1~100ppm of PHMS and allyl polyether gross mass；
The temperature of its addition reaction is 70~140 DEG C, and the reaction time is 3~15h.
To reach second object of the present invention, the preparation side of shrinkage type poly carboxylic acid series super plasticizer of the present invention
The synthesis technology process of method, poly carboxylic acid series super plasticizer includes:
Step 1: monomer C and monomer E are hybridly prepared into the first monomer solution, the quality of the first monomer solution is accounted for instead
The 20%~40% of total mass of raw material is answered, mass percent of the monomer C in the first monomer solution is 10%~40%, monomer
Mass percent of the E in the first monomer solution is 0~10%；
Step 2: monomer A, monomer B and monomer D are hybridly prepared into second comonomer aqueous solution, second comonomer aqueous solution is accounted for instead
Answer the 10%~40% of total mass of raw material, the mass percent difference of monomer A, monomer B and monomer D in second comonomer aqueous solution
It is 20%~50%, 5%~20% and 0%~10%；Initiator and chain-transferring agent are hybridly prepared into initiator mixed aqueous solution,
It is water-soluble in initiator mixing that initiator mixed aqueous solution accounts for the 20%~40% of reaction raw materials gross mass, initiator and chain-transferring agent
Mass percent in liquid is respectively 0%~10% and 0%~10%；Second comonomer aqueous solution and initiator mixed aqueous solution point
It is not added drop-wise in 3~5h and 1-2h is reacted and kept the temperature in the first monomer solution obtains reactant；
Third step neutralizes the reactant that step 2 obtains with alkaline solution, and the mass concentration for obtaining solids is
20%~30%.
Shrinkage type poly carboxylic acid series super plasticizer of the present invention is used to prepare the application of concrete, shrinkage type polycarboxylic-acid
Super plasticizer accounts for the 0.1%~0.3% of concrete gross mass.
Advantages of the present invention are as follows:
The present invention provides shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications, and production technology is mature simply simultaneously
With high water reducing rate, reinforcing effect is good, and bleed excellent effect, function of slump protection is good, anti-shrink resist it is dry and cracked, it is cheap.In addition, mentioning
For a variety of organic monomers for synthesizing polycarboxylic acid high-performance water reducing agent, when preparation, used raw material sources were abundant, price
Cheaply, preparation process is simple.
Specific embodiment
Applicant has found that for concrete in its hydration process, dehydration is to cause the dry main original shunk when investigating document
Cause.Applicant also found that reducing interfacial tension mechanism is the most important reason of reducing and anti-cracking type super plasticizer (Ran when investigating document
Thousand flat, Miao Changwen et al. research achievement).Applicant also found that the chemical composition of agent on crack resistance of concrete contracting agent can divide when investigating document
For three categories, they are small molecule aliph polyols, alkyl ether polyethylene glycol oxide or polypropylene oxide monohydric alcohol and polyoxy respectively
Change ethylene or polypropylene oxide polycarboxylic acids graft copolymer.Therefore, by the polyether grafting and polycarboxylic-acid of certain molecular weight size
Contraction can be not only reduced in super plasticizer main chain, and also there is water retention property and dispersibility.
In formula, EO represents ethylene oxide unit, and PO represents propylene oxide units, R1、R4Represent alkoxy or hydroxyl, R2、
R3、R5Represent hydrogen or monovalent metal or ammonium.Monovalent metal is Na+,K+Deng a, b, c, d and e represent in main chain Bu Tong single in formula
First chain link number and be integer, wherein a and c is respectively 0~50 integer, and b and d are respectively 0~150 integer, and e is 0~30
Integer；X and y represents side chain ethylene oxide and propylene oxide number and is integer, and x and y are respectively 0~50 integer；m
Siloxane unit number in side chain is represented with n and is integer, and m and n are respectively 0~50 integer；And the shrinkage type polycarboxylic-acid
Super plasticizer molecular weight is about 5000~50000.
The present invention is by monomer A: acrylic acid or acrylate or 5~50 parts of its salt, monomer B: methacrylic sulfonic acid its salt 1~
60 parts, monomer C: polyether monoacrylates or 20~100 parts of alkoxy polyether mono acrylic ester, monomer D: maleic anhydride polyether ester
Or maleic anhydride half-ester or 10~60 parts of its salt, monomer E: polysiloxanes passes through for 1~20 part with acrylic acid modified copolyether
After Raolical polymerizable, and it is prepared after adding alkali neutralization that it is made to be converted into the form of salt.
In above-mentioned monomer A, B, C, D and E, monomer A, B are known substance, in which:
Monomer A can be indicated with following general formula (1):
R in formula5Indicate hydrogen, monovalent metal (Na+,K+Deng) or ammonium etc..Carboxylate radical is conducive to improve water-reducing property, and guarantor is collapsed
Performance, meanwhile, can also have certain deferred action.It is main that absorption point and electric repulsion are provided.
Monomer B can be indicated with following general formula (2):
R in formula2Indicate hydrogen, monovalent metal (Na+,K+Deng) or ammonium etc..Sulfonate radical is conducive to generate high efficiency dispersion performance,
Improve water-reducing rate.It is main that absorption point and electric repulsion are provided.
Monomer C can be indicated with following general formula (3):
R in formula1It is the alkyl of 1~4 carbon atom or allyl or hydroxyl, x, y are respectively 0~50 integer；
The preparation method of monomer C: by acrylic acid and following (4) polyethers by the molar ratio of 1:1.0~4.5 in condition of no solvent
Under, and esterification directly occurs under conditions of polymerization inhibitor and catalyst is added；
In formula (4), x, y are respectively 0~50 integer, R1For the alkyl or hydroxyl of 1~5 carbon atom；EO represents ring
Oxirane unit, PO represent propylene oxide units, can be linear or branching polymer, homopolymer, block copolymer
Deng.The grafting of these polyether groups provides certain dispersibility and water retention property, while providing certain space with copolymer
Steric hindrance ability.
Catalyst noted earlier can be the concentrated sulfuric acid, p-methyl benzenesulfonic acid, and phosphorous acid and solid super-strong acid etc. can also be used
The amine substances such as the lewis acids such as boron trifluoride, alchlor and ferric sulfate and ethylenediamine, triethylamine make catalyst, they
Can be used alone or it is a variety of be used in combination, the dosage of catalyst is the 0.1%~5.0% of polyether quality；
Aforementioned polymerization inhibitor is selected from hydroquinone, phenthazine, hydroquinone-methyl ether, di-t-butyl-paracresol etc., uses
Amount is the 0.01%~4.0% of acrylic acid quality；The effect of polymerization inhibitor mainly prevents acrylic acid autohemagglutination or acrylic acid and life
At the premature polymerization of beta-unsaturated esters；
The temperature of its esterification is 80~85 DEG C, and the reaction time can achieve required esterification yield in 5~7h, obtain
Brownish red transparency liquid, that is, monomer C after esterification, is sealed, and excessive acrylic acid does not need separation removal, can be with
It participates directly in and polymerize in next step.
Monomer D can be indicated with following general formula (5):
R in formula (5)3Indicate hydrogen, monovalent metal (Na+,K+Deng) or ammonium；R4For the alkyl or allyl of 1~4 carbon atom
Base or hydroxyl；X and y is respectively 0~10 integer.
Monomer D preparation method: it is urged by the molar ratio of 1:1.0~5.0 solvent-free by maleic anhydride and following (6) polyethers
Esterification generation directly occurs under the conditions of agent is existing.It is grafted in polymer superplasticizer, can not only reduce
The contraction of concrete also has certain steric hindrance, while improving dispersion performance.
X and y is respectively 0~10 integer in formula (6)；R4For the alkyl or allyl or hydroxyl of 1~4 carbon atom.
Aforementioned catalytic agent is selected from the concentrated sulfuric acid, and p-methyl benzenesulfonic acid, phosphoric acid and solid super-strong acid etc., they can be used alone
Or be used in mixed way, the dosage of catalyst is the 0.1%~5.0% of polyether quality；
The temperature of its esterification is 130~140 DEG C, and temperature is too high, and side reaction increases, and influences the generation of half ester, finally
Influence the performance of product；Reaction time can achieve required esterification yield in 4~7h, obtain rufous clear solution i.e. monomer
D after esterification, is sealed, and excessive maleic anhydride does not need separation removal, can be participated directly in poly- in next step
It closes.
Monomer E can be indicated with following general formula (7):
X, y, m and n are respectively 0~50 integer in formula (7)；
Monomer E preparation method: by silicon oil of low hydrogen content PHMS following (9) (Si-H base dimethyl silicone polymer) and polyethylene glycol
Addition reaction is obtained for 1:0.1~4.0 and under the effect of the catalyst in molar ratio for diacrylate following (8)；
X and y is respectively 0~50 integer in formula (8) and (9)；M and n is respectively 0~30 integer and m >=1；
Aforementioned catalytic agent is selected from H2PtCl6·6H2O, (Ph3P)4Pd, [RhCl (CO)2]2, (Ph3P)2NiCl2Deng they can
To be used alone or be used in mixed way, the dosage of catalyst is 1~100ppm of PHMS and allyl polyether gross mass；
The temperature of its addition reaction is 70~100 DEG C, and the reaction time can achieve required conversion ratio in 3~8h, obtain
To yellow or weak yellow liquid, that is, monomer E, it is sealed.
By monomer A, monomer B, monomer C, monomer D, monomer E according to mass ratio be (5~50): (1~60): (20~
100): (10~60): (1~20) carries out free radical polymerization at 70-90 DEG C and under the action of initiator chain-transferring agent, and adds
Alkali neutralization, PH adjust to 7-8 (PH excessively high or too low can influence its storage stability) polycarboxylic-acid for obtaining rufous
Super plasticizer finished product, solid content 20%-30%.
The initiator is water-soluble radical initiator and its mixture, including potassium peroxydisulfate K2S2O8, ammonium persulfate
(NH4) 2S2O8, sodium peroxydisulfate Na2S2O8, hydrogen peroxide H2O2And ferrous salt, sulphite, thiosulfate etc..Its dosage
Account for the 0.1%~10.0% of reaction monomers gross mass.
The reaction synthesizer of the poly carboxylic acid series super plasticizer include heater, magnetic stirring apparatus, thermometer, peristaltic pump and
The parts such as 500ml three-necked flask.
Polycarboxylic acid super-plasticizer molecular weight of copolymer controls strand size, the chain-transferring agent using alcohol acids chain-transferring agent
Including but not limited to isopropanol, mercaptoethanol, mercaprol, thioacetic acid and mercaptopropionic acid etc., dosage are the total matter of each monomer
The 0.1%~5% of amount.
The synthesis technology process of poly carboxylic acid series super plasticizer, which generally synthesizes, to be carried out in three steps:
Step 1: monomer C and monomer E are hybridly prepared into the first monomer solution, the quality of the first monomer solution is accounted for instead
The 20%~40% of total mass of raw material is answered, mass percent of the monomer C in the first monomer solution is 10%~40%, monomer
Mass percent of the E in the first monomer solution is 0~10%；
Step 2: monomer A, monomer B and monomer D are hybridly prepared into second comonomer aqueous solution, second comonomer aqueous solution is accounted for instead
Answer the 10%~40% of total mass of raw material, the mass percent difference of monomer A, monomer B and monomer D in second comonomer aqueous solution
It is 20%~50%, 5%~20% and 0%~10%；Initiator and chain-transferring agent are hybridly prepared into initiator mixed aqueous solution,
It is water-soluble in initiator mixing that initiator mixed aqueous solution accounts for the 20%~40% of reaction raw materials gross mass, initiator and chain-transferring agent
Mass percent in liquid is respectively 0%~10% and 0%~10%；Second comonomer aqueous solution and initiator mixed aqueous solution point
It is not added drop-wise in 3~5h and 1-2h is reacted and kept the temperature in the first monomer solution obtains reactant；
Third step neutralizes the reactant that step 2 obtains with alkaline solution, and the mass concentration for obtaining solids is
20%~30%.
Embodiment 1: super plasticizer preparation process
Monomer C preparation process:
In the 500ml glass reactor equipped with thermometer, blender, nitrogen ingress pipe and the condenser that flows back, without molten
Under conditions of agent, appropriate polyethers (such as following formula, wherein x=23, y=0, R is added1For hydroxyl), temperature is promoted to 50 DEG C, to polyethers
After being completely melt, add acrylic acid (wherein acrylic acid and polyethers molar ratio are 3:1), polymerization inhibitor (hydroquinone, and to benzene
Diphenol accounts for the 2% of acrylic acid gross mass) and catalyst (concentrated sulfuric acid, and the concentrated sulfuric acid accounts for the 1.0% of polyethers gross mass), gradually rise
Temperature is to 80-85 DEG C and monomer C crude product can be obtained in successive reaction 5h, which can be directly used for synthesis shrinkage type polycarboxylic-acid
Super plasticizer；
Monomer D preparation process:
When not adding any catalyst, equipped with thermometer, blender, nitrogen ingress pipe and reflux condenser
In 500ml glass reactor, appropriate maleic anhydride is added, temperature is promoted to 55 DEG C, after maleic anhydride is completely melt, then plus
Enter diethylene glycol monobutyl ether (such as following formula, wherein x=2, y=0, R1For butyl ,-C4H9) (wherein maleic anhydride and diethylene glycol mono butyl
Ether molar ratio is 3:1), 130 DEG C are gradually warming up to, and keep constant temperature, is esterified after 4.5h to get decrement activated monomer diglycol monotertiary
Butyl ether maleic anhydride monoesters, i.e. monomer D.
Monomer E preparation process:
In the 500ml glass reactor equipped with thermometer, blender, nitrogen ingress pipe and the condenser that flows back, it is added suitable
Measure containing hydrogen silicone oil PHMS (following Si-H base dimethyl silicone polymer (wherein m=1, n=10~20)) and two propylene of polyethylene glycol
Acid esters (such as following formula (wherein x=20~30, y=0)) is 1:1 by containing hydrogen silicone oil and polyethyleneglycol diacrylate molar ratio,
Catalyst H2PtCl6(dosage of catalyst is the 20ppm of PHMS and allyl polyether gross mass；), temperature is gradually risen to 80-
85 DEG C of successive reaction 7h obtain yellow or weak yellow liquid i.e. monomer E.
Super plasticizer preparation process:
90g is added in the 500ml glass reactor equipped with thermometer, blender, nitrogen ingress pipe and the condenser that flows back
Water uses nitrogen purge while stirring, and increases temperature to 75 DEG C, by 25g monomer C (wherein, x=23, y=
0,R1For hydroxyl) and 3g monomer E (wherein, x=20~30, y=0, m=1, n=10~20) addition there-necked flask, and stir into
Even monomer solution；Again by 40g monomer A (wherein, R5For hydrogen), 12g monomer B (wherein, R2For sodium), 5g monomer D (wherein, R3
For hydrogen, x=2, y=0, R4For butyl) and 60g water be hybridly prepared into uniform activity monomer solution；Then, 4.5g initiator
Ammonium persulfate and 2.0g mercaptopropionic acid chain-transferring agent are added in 90g water and are configured to uniform initiator mixed solution；Finally,
Initiator mixed solution and activated monomer aqueous solution are added drop-wise to there-necked flask reactor according to certain speed by peristaltic pump
In, time for adding 3h keeps the temperature 2h after being added dropwise, is cooled to room temperature, and the use of concentration is that 30%NaOH solution is neutralized to pH value
It is 7.5 or so, obtaining solid content is 25.5% brownish red clear solution, molecular weight ranges 5000-20000.
Embodiment 2: the concrete of super plasticizer is mixed
The super plasticizer that the present embodiment uses is the super plasticizer being prepared in embodiment 1.According in super plasticizer
Solids carries out Mass Calculation:
By mass percentage, cement 15.119%, sand 35.067%, 5~10mm cobble 17.135%, 10~20mm
Cobble 25.702%, water 6.929%, super plasticizer 0.048%；By the method for SL352-2006 " concrete for hydraulic structure testing regulations "
Cooperation stirring (slump is controlled in 21 ± 1cm) is carried out, puts and is formed after vibrating 30s on a vibration table, smeared before concrete initial set
Face, for 24 hours rear demoulding, is sent into fog room and carries out standard curing.
It is standardized according to GB8076-2008 " concrete admixture ", which has reached standard type high-performance water reducing agent
It is required that performance indicator meets code requirement.When super plasticizer volume is the 0.32% of cement quality, product index reaches
It arrives: water-reducing rate 25%, slump 21.5cm, 1h slump-loss 3cm, 2h slump-loss 7cm, air content 4.5%, bleeding
Rate ratio is 10%.
When volume is 0.32%, influence of the super plasticizer to concrete shrinkage is as shown in table 1, mixes super plasticizer concrete
Shrinking percentage is 0.044043%, and normal concrete shrinking percentage is 0.051915%, according to GB8076-2008 " concrete admixture "
Specification, 28d shrinkage ratio are 85%, meet the requirement of 28d shrinkage ratio≤110%；When volume is 0.32%, super plasticizer
Influence to concrete strength is as shown in table 2, and mixing super plasticizer concrete 28d compression strength is 43.35MPa, normal concrete
28d compression strength is 28.02MPa, and 28d compressive strength rate is 155%, meets the requirement of 28d compressive strength rate >=140%.
Table 1
Table 2
Embodiment 3: the concrete of super plasticizer is mixed
The super plasticizer that the present embodiment uses is the super plasticizer being prepared in embodiment 1.According in super plasticizer
Solids carries out Mass Calculation:
By mass percentage, cement 15.121%, sand 35.072%, 5~10mm cobble 17.137%, 10~20mm
Cobble 25.706%, water 6.930%, super plasticizer 0.033%；By the method for SL352-2006 " concrete for hydraulic structure testing regulations "
Cooperation stirring (slump is controlled in 21 ± 1cm) is carried out, puts and is formed after vibrating 30s on a vibration table, smeared before concrete initial set
Face, for 24 hours rear demoulding, is sent into fog room and carries out standard curing.
It is standardized according to GB8076-2008 " concrete admixture ", performance indicator meets code requirement.Work as super plasticizer
When volume is the 0.22% of cement quality, product index reaches: water-reducing rate 25%, slump 21cm, 1h slump-loss 6cm,
2h slump-loss 8cm, air content 4%, bleeding rate ratio are 25%.
When volume is 0.22%, influence of the super plasticizer to concrete shrinkage is as shown in table 3, mixes super plasticizer concrete
Shrinking percentage is 0.049362%, and normal concrete shrinking percentage is 0.051915%, according to GB8076-2008 " concrete admixture "
Specification, 28d shrinkage ratio are 95%, meet the requirement of 28d shrinkage ratio≤110%；When volume is 0.22%, super plasticizer
Influence to concrete strength is as shown in table 4, and mixing super plasticizer concrete 28d compression strength is 39.39MPa, normal concrete
28d compression strength is 28.02MPa, and 28d compressive strength rate is 141%, meets the requirement of 28d compressive strength rate >=140%.
Table 3
Table 4
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure,
These simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (10)
1. a kind of shrinkage type poly carboxylic acid series super plasticizer, which is characterized in that the chemical structural formula of the super plasticizer are as follows:
In formula, EO represents ethylene oxide unit, and PO represents propylene oxide units, R1And R4Respectively alkoxy or hydroxyl, R2、R3With
R5Respectively hydrogen, monovalent metal or ammonium, a and c are respectively 0~50 integer, and b and d are respectively 0~150 integer, and e is 0~
30 integer, x and y are respectively 0~50 integer, and m and n are respectively 0~50 integer；
And the shrinkage type poly carboxylic acid series super plasticizer molecular weight is 5000~50000.
2. shrinkage type poly carboxylic acid series super plasticizer according to claim 1, which is characterized in that by monomer A (5~50 parts),
Monomer B (1~60 part), monomer C (20~100), monomer D (10~60 parts) and monomer E (1~20 part) turn in initiator and chain
Free radicals copolymerization reaction is carried out under the conditions of moving existing for agent, finally plus alkali neutralization makes PH=7~8；
Monomer A is acrylic acid, acrylate, acrylates or acrylate salt；Monomer B is methacrylic sulfonic acid or metering system
Sulfonate；Monomer C is polyether monoacrylates or alkoxy polyether mono acrylic ester；Monomer D is maleic anhydride polyether ester, Malaysia
Acid anhydrides half ester, maleic anhydride polyether ester salt or maleic anhydride half-ester salt；Monomer E is that polysiloxanes and acrylic acid modified polyethers are copolymerized
Object.
3. shrinkage type poly carboxylic acid series super plasticizer according to claim 2, which is characterized in that the initiator is water-soluble
Property radical initiator, the water-soluble radical initiator be selected from potassium peroxydisulfate K2S2O8, ammonium persulfate (NH4)2S2O8, sodium peroxydisulfate Na2S2O8, hydrogen peroxide H2O2, ferrous salt, one of sulphite and thiosulfate or more than one
Mixture；
The dosage of initiator accounts for the 0.1%~10.0% of reaction monomers gross mass；
The reaction temperature of the free radicals copolymerization reaction is 70~130 DEG C；
The chain-transferring agent includes but is not limited in isopropanol, mercaptoethanol, mercaprol, thioacetic acid and mercaptopropionic acid
One or more kinds of mixtures；
The dosage of chain-transferring agent is the 0.1%~5% of each monomer gross mass.
4. shrinkage type poly carboxylic acid series super plasticizer according to claim 2 or 3, which is characterized in that the monomer A can be used
Following general formula (1) indicates:
R in formula (1)5Indicate hydrogen, monovalent metal or ammonium.
5. shrinkage type poly carboxylic acid series super plasticizer according to claim 2 or 3, which is characterized in that the monomer B can be used
Following general formula (2) indicates:
R in formula (2)2Indicate hydrogen, monovalent metal or ammonium.
6. shrinkage type poly carboxylic acid series super plasticizer according to claim 2 or 3, which is characterized in that the monomer C can be used
Following general formula (3) indicates:
R in formula (3)1It is the alkyl, allyl or hydroxyl of 1~4 carbon atom, x and y are respectively 0~50 integer；
The preparation method of the monomer C: by acrylic acid and following (4) polyethers by the molar ratio of 1:1.0~4.5 in condition of no solvent
Under, polymerization inhibitor is added and esterification occurs for catalyst；
In its (4), x, y are respectively 0~50 integer, R1For the alkyl or hydroxyl of 1~5 carbon atom；
The catalyst be selected from the concentrated sulfuric acid, p-methyl benzenesulfonic acid, phosphorous acid with, solid super-strong acid, boron trifluoride, alchlor, road
One of Lewis acid and amine substance or more than one mixture, the dosage of catalyst be polyether quality 0.1%~
5.0%；
The polymerization inhibitor is selected from one of hydroquinone, phenthazine, hydroquinone-methyl ether and di-t-butyl-paracresol
Or more than one mixture, dosage are the 0.01%~5.0% of acrylic acid quality；
The temperature of esterification is 75~140 DEG C, and the reaction time is 3~15h.
7. shrinkage type poly carboxylic acid series super plasticizer according to claim 2 or 3, which is characterized in that the monomer D can be used
Following general formula (5) indicates:
R in formula (5)3Indicate hydrogen, monovalent metal or ammonium；R4For the alkyl or allyl or hydroxyl of 1~4 carbon atom；X and y points
Not Wei 0~10 integer；
The monomer D preparation method: by maleic anhydride with following (6) polyethers by molar ratio the urging in catalyst of 1:1.0~5.0
Change lower generation esterification；
X and y is respectively 0~10 integer in formula (6)；R4For the alkyl or allyl or hydroxyl of 1~4 carbon atom.
Catalyst is selected from one of the concentrated sulfuric acid, p-methyl benzenesulfonic acid, phosphoric acid and solid super-strong acid or more than one mixture,
The dosage of catalyst is the 0.01%~5.0% of polyether quality；
The temperature of its esterification is 80~150 DEG C, and the reaction time is 3~15h.
8. shrinkage type poly carboxylic acid series super plasticizer according to claim 2 or 3, which is characterized in that the monomer E can be used
Following general formula (7) indicates:
X, y, m and n are respectively 0~50 integer in formula (7)；
The monomer E preparation method: by following (9) the Si-H base dimethyl silicone polymer of silicon oil of low hydrogen content PHMS and polyethylene glycol two
Addition reaction is obtained for 1:0.1~4.0 and under the effect of the catalyst in molar ratio for acrylate following (8)；
X and y is respectively 0~50 integer in formula；M and n is respectively 0~30 integer and m >=1；
Catalyst is selected from H2PtCl6、(Ph3P)4Pd、[RhCl(CO)2]2(Ph3P)2NiCl2One of or more than one mixed
Object is closed, the dosage of catalyst is 1~100ppm of PHMS and allyl polyether gross mass；
The temperature of its addition reaction is 70~140 DEG C, and the reaction time is 3~15h.
9. the preparation method of shrinkage type poly carboxylic acid series super plasticizer described in claim 1-8 any claim, feature exist
In the synthesis technology process of poly carboxylic acid series super plasticizer includes:
Step 1: monomer C and monomer E are hybridly prepared into the first monomer solution, it is former that the quality of the first monomer solution accounts for reaction
Expect the 20%~40% of gross mass, mass percent of the monomer C in the first monomer solution is 10%~40%, and monomer E exists
Mass percent in first monomer solution is 0~10%；
Step 2: monomer A, monomer B and monomer D are hybridly prepared into second comonomer aqueous solution, it is former that second comonomer aqueous solution accounts for reaction
Expect the 10%~40% of gross mass, the mass percent of monomer A, monomer B and monomer D in second comonomer aqueous solution is respectively
20%~50%, 5%~20% and 0%~10%；Initiator and chain-transferring agent are hybridly prepared into initiator mixed aqueous solution, draw
Hair agent mixed aqueous solution accounts for the 20%~40% of reaction raw materials gross mass, and initiator and chain-transferring agent are in initiator mixed aqueous solution
In mass percent be respectively 0%~10% and 0%~10%；Second comonomer aqueous solution and initiator mixed aqueous solution difference
It is added drop-wise in 3~5h and 1-2h is reacted and kept the temperature in the first monomer solution obtains reactant；
Third step neutralizes the reactant that step 2 obtains with alkaline solution, and the mass concentration for obtaining solids is 20%
~30%.
10. shrinkage type poly carboxylic acid series super plasticizer described in claim 1-8 any claim is used to prepare answering for concrete
With shrinkage type poly carboxylic acid series super plasticizer accounts for the 0.1%~0.3% of concrete gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089432.7A CN109970931A (en) | 2019-01-30 | 2019-01-30 | A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089432.7A CN109970931A (en) | 2019-01-30 | 2019-01-30 | A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109970931A true CN109970931A (en) | 2019-07-05 |
Family
ID=67076824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910089432.7A Pending CN109970931A (en) | 2019-01-30 | 2019-01-30 | A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970931A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608479A (en) * | 2019-11-14 | 2021-04-06 | 科之杰新材料集团(贵州)有限公司 | Low-viscosity modifier |
| WO2022033588A1 (en) * | 2020-08-14 | 2022-02-17 | 中国石油化工股份有限公司 | Polymer having dispersing function, oil well cement dispersant, and preparation method therefor and use thereof |
| CN118580436A (en) * | 2024-08-05 | 2024-09-03 | 浙江天造环保科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193410A (en) * | 2013-03-27 | 2013-07-10 | 华南理工大学 | Shrinkage-reducing poly carboxylic acid water reducing agent and preparation method |
| CN107540795A (en) * | 2017-09-12 | 2018-01-05 | 上海三瑞高分子材料股份有限公司 | A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof |
-
2019
- 2019-01-30 CN CN201910089432.7A patent/CN109970931A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193410A (en) * | 2013-03-27 | 2013-07-10 | 华南理工大学 | Shrinkage-reducing poly carboxylic acid water reducing agent and preparation method |
| CN107540795A (en) * | 2017-09-12 | 2018-01-05 | 上海三瑞高分子材料股份有限公司 | A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 陈宝璠: "高性能聚羧酸减缩材料对混凝土性能的综合评价", 《江南大学学报（自然科学版）》 * |
| 陈宝璠: "高性能聚羧酸减缩材料的研发(Ⅱ)———高分子聚合物(HP-SRA)的合成与表征", 《精细化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608479A (en) * | 2019-11-14 | 2021-04-06 | 科之杰新材料集团(贵州)有限公司 | Low-viscosity modifier |
| CN112608479B (en) * | 2019-11-14 | 2022-04-15 | 科之杰新材料集团(贵州)有限公司 | Low-viscosity modifier |
| WO2022033588A1 (en) * | 2020-08-14 | 2022-02-17 | 中国石油化工股份有限公司 | Polymer having dispersing function, oil well cement dispersant, and preparation method therefor and use thereof |
| CN118580436A (en) * | 2024-08-05 | 2024-09-03 | 浙江天造环保科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110938176B (en) | Super-long slump loss resistant cement-based polycarboxylate superplasticizer mother liquor and application thereof | |
| CN105418857A (en) | Preparation method and application of polycarboxylate water reducer containing phosphate group | |
| CN102910855B (en) | Super plasticizer for precast concrete component | |
| CN104761689A (en) | Preparation method of super high-early-strength polycarboxylate superplasticizer | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN106519139A (en) | Early-strength admixture and preparation method and application thereof | |
| CN103359971B (en) | Nuclear-power concrete air-entraining polycarboxylic acid additive | |
| CN103450415B (en) | A kind of multifunctional type concrete additive and preparation method thereof | |
| JP6359772B2 (en) | Cement additive, cement composition, and raw material for cement additive | |
| CN107652404A (en) | A kind of normal temperature synthesizing polyester polyether type of poly carboxylic acid and preparation method thereof | |
| CN109776021A (en) | A kind of low entraining type clear-water concrete additive and preparation method thereof | |
| CN108250448A (en) | The preparation method and application of the low molecule cement water reducing agent of phosphorous acid groups | |
| JP2003221266A (en) | Cement admixture | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN109970931A (en) | A kind of shrinkage type poly carboxylic acid series super plasticizer, preparation method and applications | |
| CN104496253A (en) | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| US11505496B2 (en) | Phosphonato block polymer, preparation method therefor and application thereof | |
| WO2023184785A1 (en) | Crosslinked polycarboxylic acid water reducer and preparation method therefor | |
| CN105713154B (en) | A kind of preparation method of Early-strength polycarboxylate superplasticizer | |
| CN114656600A (en) | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer | |
| CN101407386A (en) | High dispersing plasticizing adulterating agent for cement concrete | |
| CN109485323A (en) | Early strong viscosity reduction type polycarboxylate water-reducer is preparing the purposes in prefabricated components concrete | |
| JP2020023422A (en) | Additive for recycled aggregate-containing cement composition | |
| CN109320714A (en) | A kind of dedicated small molecule super plasticizer of middle low-slump concrete and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190705 |