CN109053971A - A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density - Google Patents
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density Download PDFInfo
- Publication number
- CN109053971A CN109053971A CN201810743833.5A CN201810743833A CN109053971A CN 109053971 A CN109053971 A CN 109053971A CN 201810743833 A CN201810743833 A CN 201810743833A CN 109053971 A CN109053971 A CN 109053971A
- Authority
- CN
- China
- Prior art keywords
- solution
- water
- parts
- molecular weight
- reducer
- 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
- 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
- C04B24/16—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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of polycarboxylate water-reducer preparation method of high long short-chain branch of carboxyl density, the following steps are included: 1) a certain proportion of 3000 molecular weight polyether polymeric monomer, 1200 molecular weight polyether polymeric monomers and water are added in reaction kettle, agitating and heating waits for its dissolution；2) control temperature is initially added into a certain amount of hydrogen peroxide at 45-50 DEG C；3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A starts to be added dropwise in the 10min after hydrogen peroxide addition；Solution A time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution A is made of a certain proportion of acrylic acid, unsaturated sulfonic acid salt and water, and solution B is made of ascorbic acid, phosphate ester monomer, chain-transferring agent and water；4) it after completion of dropwise addition, keeps temperature constant, cures b hours, when reaction solution temperature is lower than 30 DEG C, be slowly added to a certain amount of neutralizer, moisturizing to 1000 parts of polycarboxylate water-reducers to get a kind of high long short-chain branch of carboxyl density.
Description
Technical field
The invention belongs to building material technical fields, are related to concrete admixture field, and specifically a kind of high carboxyl is close
Spend the polycarboxylate water-reducer preparation method of long short-chain branch.
Background technique
Water-reducing agent is one of the indispensable component for preparing high performance concrete, and use is more and more extensive.Currently, most poly-
The molecular weight for the polyether macromonomer that carboxylic acid water reducer uses has arrived at a bottleneck 2400 or so in development degree, needs
Research is increased to the polyethers of other different molecular weights and uses dynamics, and a variety of different molecular weight polyethers also have with the use of problem
It is to be excavated.
Using two kinds of biggish polyether macromonomers of molecular weight difference, the alternatively distributed side-chain structure of long short-chain branch is obtained.Subtract
After aqua molecule is adsorbed, the steric hindrance effect that long side chain plays is bigger, has stronger dispersibility and preferably protects
It collapses effect；Although the steric hindrance effect of short-side chain is smaller, its activity side chain significantly greater than long in copolymerization, polymerization
Shi Rongyi separates long side chain, keeps long side chain distribution uniform, reduces the problem of interfering with each other influence between long side chain, improves
Stability.Compared with common polycarboxylate water-reducer, which has works fine when cement sandstone material quality is preferable
Can, there is more stable dispersion effect.
Side chain is longer to bring side chain degree of disturbing larger to make up, and causes two cement granules because of the intermolecular mutual space of water-reducing agent
Steric hindrance it is unobvious and too close to the problem of, prepare longer main chain and peracid ether than design, obtain and be higher than general poly- carboxylic
Two cement granules are separated into long side using the powerful electrostatic repulsion of high carboxyl density bring by the carboxyl density of sour water-reducing agent
Chain can play the position of steric hindrance effect；Sulfonic group, phosphate etc. are introduced compared with the stronger group of carboxylic acid group's adsorption capacity, enhancing
Adsorption capacity and sticking probability of the anchoring group to positively charged cement granules.
Patent CN106277899A discloses a kind of polycarboxylate water-reducer preparation method, the invention polycarboxylate water-reducer
It is that unsaturated polyether polymeric monomer first is prepared for initiator by ethylene glycol monovinyl ether, then by unsaturated polyether polymeric monomer
(EPEG) it carries out polymerizeing with minor comonomer acrylic acid and be made.Hydrophilic radical in polycarboxylate water-reducer molecule structure made from the invention
More, water-reducing rate is high, and fluidity retentivity is remarkably reinforced, and anti-mud is remarkably reinforced, therefore can meet higher construction requirement.
Patent CN106349435A discloses a kind of synthetic method of polycarboxylate water-reducer, which is specifically by reducing agent
Vitamin C and chain-transferring agent are configured to aqueous solution, are denoted as A material；Acrylic acid is configured to aqueous solution, is denoted as B material；By water and polymeric monomer
It is added in reaction kettle, photochemical catalyst is added in reaction kettle, introduce ultraviolet source prolonged exposure in reaction system；It heats up to system
When to 25-30 DEG C, A material and B material is added dropwise；To the end of A expects, the reaction was continued after B material is added dropwise to reaction；Cooling after reaction,
Neutralize, both the polycarboxylate water-reducer.
Patent CN106632890A discloses a kind of collapse protective poly-carboxylic acid water reducing agent preparation method, especially by unsaturated first
Base cyclobutenyl polyethylene glycol ethers monomer, unsaturated carboxylic acid class monomer, sealing end phosphate and unsaturated acids hydroxy ester are in initiator
After being copolymerized under the action of molecular weight regulator, adds in alkaline solution and obtained after pH value to 6-7.The invention
Collapse protective poly-carboxylic acid water reducing agent have the advantages that low-dosage, high water reduction, high-thin arch dam and cement adaptability are good, and production cycle
Short, low energy consumption, and production cost is low, has very high application value.
It is different from the above patent, the present invention is big using the polyether macromonomer of 3000 molecular weight and the polyethers of 1200 molecular weight
Monomer is used in combination, and the formula using peracid ether than, low chain-transferring agent dosage designs, and the final backbone length that obtains is longer, carboxyl
Density is big, and electrostatic repulsion is stronger, and side-chain structure synergistic effect is obvious, the strong polycarboxylate water-reducer of stability.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of polycarboxylate water-reducer of high long short-chain branch of carboxyl density
Preparation method.
A part of longer side chain is obtained using the polyether macromonomer of 3000 molecular weight, the polyethers using 1200 molecular weight is big
Monomer brings shorter a part of side chain；The steric hindrance effect that long side chain plays is bigger, have stronger dispersibility and
It is preferable to protect effect of collapsing；Although the steric hindrance effect of short-side chain is smaller, its activity is significantly greater than in copolymerization to be grown
Side chain is easy when polymerization to separate long side chain, keeps long side chain distribution uniform, reduces and interferes with each other influence between long side chain
Problem；Meanwhile short-chain branch can reduce the steric hindrance that diminishing agent molecule is subject in cement particle surface absorption, be conducive to diminishing
Agent molecule improves the stability that water-reducing agent uses in the adsorption capacity and absorption stability of cement particle surface.It is inhaled by force in stratiform
In the case that attached matter is more, the steric hindrance that the long side chain of the water-reducing agent will not completely lose into adsorbate interlayer is made
With longer side chain can also promote main chain is longer to promote to form thicker hydrated sheath, and diminishing agent molecule is made to play good dispersion
Property.In the longer situation of side chain, the short-side chain of introducing can reduce the degree of disturbing of long side chain, cause even if there is side chain to be adsorbed on clay
When interlayer, into interlayer side chain can because detent be caused there are differential seat angle in approach axis and interlayer direction, make adsorbate without
Method further influences entire diminishing agent molecule；Meanwhile short-side chain can also be resisted in strong adsorbate layer structure end face, prevent diminishing
Agent molecule is further adsorbed.
Side chain is longer to bring side chain degree of disturbing larger to further compensate for, and causes two cement granules because of the intermolecular phase of water-reducing agent
Mutual steric hindrance effect it is unobvious and too close to the problem of, prepare longer main chain and peracid ether than design, obtain and be higher than one
As polycarboxylate water-reducer carboxyl density, it is using the powerful electrostatic repulsion of high carboxyl density bring that two water-reducing agents are intermolecular
Long side chain intersect, commissure state repulsion to chain end of drawing money on credit contradicts state, this conflict state energy can preferably play water-reducing agent
The steric hindrance of molecule acts on；In addition, the carboxyl density design point of the diminishing agent molecule is normality water-reducing agent carboxyl density
1.5-2 times, match sulfonic group, the strong anchoring group of phosphate, adsorption energy of the enhancing diminishing agent molecule to positively charged cement granules
Power and sticking probability.On the basis of electrostatic repulsion arranges cement granules, the polyethers bring short-side chain of low molecular weight plays empty
Between steric hindrance, continue to arrange cement granules, long side chain finally allowed to play steric hindrance effect.
Technical scheme is as follows:
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) by 290-310 parts of high molecular weight polyether polymeric monomers, 30-45 parts of low molecular polyether polymeric monomers and 180-220 parts
Water is added in reaction kettle, and agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 0.9-1.8 parts of dioxygens at 45-50 DEG C
Water；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is a hours, and a value is 2-4, and solution B time for adding is that a+0.5 is small
When；Solution B is by 0.32-0.5 parts of ascorbic acid, 0.4-0.8 parts of phosphate ester monomers, 0.5-0.9 parts of chain-transferring agents and 80-100 parts
Water composition, solution A are made of 44-53 parts of acrylic acid, 2-5 portions of unsaturated sulfonic acid salt and 50-70 parts of water；
4) it after completion of dropwise addition, keeps temperature constant, cures b hours, b value is 1-3, is lower than 30 DEG C to reaction solution temperature
When, be slowly added to 7-14 parts of neutralizers, moisturizing to 1000 parts be 40% to get mass fraction the high long short-chain branch of carboxyl density
Polycarboxylate water-reducer.
Allyl polyethenoxy ether, methacrylic polyoxy of the 3000 molecular weight polyether polymeric monomer by molecular weight 3000
One or more of vinethene, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether composition；Preferably by dividing
The first of the isoamyl alcohol polyoxyethylene ether of son amount 3000, the methyl allyl polyoxyethylene ether of molecular weight 3000, molecular weight 3000
One or more of base allyl polyethenoxy ether composition；The preferably methyl allyl polyoxyethylene ether of molecular weight 3000.
Allyl polyethenoxy ether, methacrylic polyoxy of the 1200 molecular weight polyether polymeric monomer by molecular weight 1200
One or more of vinethene, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether composition；Preferably by dividing
Son measures the allyl alcohol of 1200 methyl allyl polyoxyethylene ether, the poly glycol monomethyl ether of molecular weight 1200, molecular weight 1200
One or more of polyoxyethylene ether composition；The preferably methyl allyl polyoxyethylene ether of molecular weight 1200.
The unsaturated sulfonic acid salt is by sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate, styrene sulfonic acid
One or more of sodium, 2- acrylamide-2-methyl propane sulfonic composition；Preferred mass than for 1:1 acrylic sodium sulfonate and
The composition of methylpropene sodium sulfonate.
The phosphate function monomer is by methylacryoyloxyethyl phosphate, glycolmethacrylate phosphate
One or two kinds of compositions；Preferred mass is than the methylacryoyloxyethyl phosphate and glycolmethacrylate for 3:1
The composition of phosphate.
The chain-transferring agent is made of one or more of thioacetic acid, mercaptopropionic acid, mercaptoethanol, mercaprol；
Composition of the preferred mass than thioacetic acid and mercaptopropionic acid for 1:2.
The neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, second
One or more of hydramine, diethanol amine, triethanolamine, triisopropanolamine composition；Preferred mass than for 1:1 sodium methoxide and
The composition of ethanol amine.
The hydrogen peroxide is that mass percent is 27.5% industrial grade hydrogen peroxide.
The preferred 2.5h of the solution A time for adding a.
The preferred 1.5h of curing time b.
The beneficial effects of the present invention are:
1, a part of longer side chain is obtained using the polyether macromonomer of 3000 molecular weight, using the polyethers of 1200 molecular weight
Polymeric monomer brings shorter a part of side chain；The steric hindrance effect that long side chain plays is bigger, has stronger dispersibility
Effect of collapsing is protected with preferable；Although the steric hindrance effect of short-side chain is smaller, its activity is significantly greater than in copolymerization
Long side chain is easy when polymerization to separate long side chain, keeps long side chain distribution uniform, reduces and interferes with each other influence between long side chain
The problem of；Meanwhile short-chain branch can reduce the steric hindrance that diminishing agent molecule is subject in cement particle surface absorption, be conducive to subtract
Aqua molecule improves the stability that water-reducing agent uses in the adsorption capacity and absorption stability of cement particle surface.
2, in the case where the strong adsorbate of stratiform is more, the long side chain of the water-reducing agent will not into adsorbate interlayer
The steric hindrance effect completely lost, longer side chain can also promote main chain is longer to promote to form thicker hydrated sheath, make diminishing
Agent molecule plays good dispersibility.In the longer situation of side chain, the short-side chain of introducing can reduce the degree of disturbing of long side chain, cause i.e.
When making to there is side chain to be adsorbed on clay interlayer, into interlayer side chain can because approach axis and interlayer direction there are differential seat angle and
Detent is caused, makes adsorbate that can not further influence entire diminishing agent molecule；Meanwhile short-side chain can also be resisted in strong adsorbate layer
Shape structure end face prevents diminishing agent molecule from further being adsorbed.
3, side chain is longer to bring side chain degree of disturbing larger to make up, and causes two cement granules because of the intermolecular mutual sky of water-reducing agent
Between steric hindrance it is unobvious and too close to the problem of, prepare longer main chain and peracid ether than design, obtain be higher than it is general poly-
Two cement granules are separated into length using the powerful electrostatic repulsion of high carboxyl density bring by the carboxyl density of carboxylic acid water reducer
Side chain can play the position of steric hindrance effect；The carboxyl density of the invention is greater than ordinary water-reducing agent, can reach 1.5-2 times of number
Value difference brings stronger anchoring ability, and the electrostatic repulsion between the carboxyl being adsorbed between different cement granules is also stronger, performance
Stronger dispersibility out；Sulfonic group, phosphate etc. are introduced compared with the stronger group of carboxylic acid group's adsorption capacity, enhances anchoring group to band
The adsorption capacity and sticking probability of the cement granules of positive electricity.On the basis of electrostatic repulsion arranges cement granules, low molecular weight
Polyethers bring short-side chain plays steric hindrance effect, continues to arrange cement granules, and long side chain is finally allowed to play steric hindrance
Effect.
Specific embodiment
For the ease of those of ordinary skill in the art understand and implement the present invention, below with reference to embodiment to the present invention make into
The detailed description of one step, it should be appreciated that embodiment described herein is merely to illustrate and explain the present invention, and is not used to limit
The fixed present invention.
It should be noted that Losec 702 is the isoamyl alcohol polyoxyethylene ether of molecular weight 3000, Losec 703 in embodiment
The specially methyl allyl polyoxyethylene ether of molecular weight 3000 joins the methacrylic that deep WR6251 is specially molecular weight 3000
Polyoxyethylene ether；
Losec chemistry TPEG1200 is specially the methyl allyl polyoxyethylene ether of molecular weight 1200, Losec chemistry
MPEG1200 is specially the poly glycol monomethyl ether of molecular weight 1200, and goodization chemistry APEG1200 is specially the alkene of molecular weight 1200
Propyl alcohol polyoxyethylene ether.
Embodiment 1
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) 290 parts of 702 monomers of Losec, 40 parts of Losec chemistry TPEG1200 monomers and 180 parts of water are added in reaction kettle,
Agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 45 DEG C, and after temperature is stablized, being added at one time 0.9 part of mass percent is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 2 hours, and solution B time for adding is 2.5 hours；Solution B is by 0.32
Part ascorbic acid, the methylacryoyloxyethyl phosphate of 0.4 part of mass ratio 3:1 and glycolmethacrylate phosphate
Composition, 0.9 part of mercaprol and 80 parts of water compositions, solution A is by 53 parts of acrylic acid, 2 parts of sodium vinyl sulfonates and 70 parts of water groups
At；
4) it after completion of dropwise addition, keeps temperature constant, cures 1 hour, when reaction solution temperature is lower than 30 DEG C, be slowly added to
14 parts of triisopropanolamines, moisturizing to 1000 parts of polycarboxylic acids to get mass fraction for the 40% high long short-chain branch of carboxyl density subtract
Aqua.
Embodiment 2
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) the deep WR6251 monomer of 303 parts of connection, 30 parts of Losec chemistry MPEG1200 monomers and 185 parts of water are added to reaction kettle
In, agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 46 DEG C, and after temperature is stablized, being added at one time 1 part of mass percent is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 2.3 hours, and solution B time for adding is 2.8 hours；Solution B by
The methylacryoyloxyethyl phosphate and glycolmethacrylate phosphoric acid of 0.35 part of ascorbic acid, 0.5 part of mass ratio 1:1
The composition of ester, 0.8 part of thioacetic acid and 85 parts of water compositions, solution A is by 50 parts of acrylic acid, 2.5 parts of acrylic sodium sulfonates and 68
Part water composition；
4) it after completion of dropwise addition, keeps temperature constant, cures 1.5 hours, when reaction solution temperature is lower than 30 DEG C, slowly add
Enter 13 parts of sodium methoxides, the polycarboxylic acids diminishing for the high long short-chain branch of carboxyl density that moisturizing is 40% to get mass fraction to 1000 parts
Agent.
Embodiment 3
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) 310 parts of 703 monomers of Losec, 34 parts of Losec chemistry MPEG1200 monomers and 200 parts of water are added in reaction kettle,
Agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 48 DEG C, and after temperature is stablized, being added at one time 1.4 parts of mass percents is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 3 hours, and solution B time for adding is 3.5 hours；Solution B is by 0.45
The thioacetic acid and mercaptopropionic acid that part ascorbic acid, 0.55 part of methylacryoyloxyethyl phosphate, 0.65 part of mass ratio are 1:2
Composition, 95 parts of water composition, solution A is made of 44 parts of acrylic acid, 2.5 parts of methylpropene sodium sulfonates and 57 parts of water；
4) it after completion of dropwise addition, keeps temperature constant, cures 1.8 hours, when reaction solution temperature is lower than 30 DEG C, slowly add
Enter 8 parts of sodium bicarbonates, the polycarboxylic acids diminishing for the high long short-chain branch of carboxyl density that moisturizing is 40% to get mass fraction to 1000 parts
Agent.
Embodiment 4
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) the deep WR6251 monomer of 294 parts of connection, 45 parts of Losec chemistry TPEG1200 monomers and 190 parts of water are added to reaction kettle
In, agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 47 DEG C, and after temperature is stablized, being added at one time 1.2 parts of mass percents is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 2.7 hours, and solution B time for adding is 3.2 hours；Solution B by
0.4 part of ascorbic acid, 0.6 part of glycolmethacrylate phosphate, 0.7 part of mercaptopropionic acid and 90 parts of water composition, solution A by
49 parts of acrylic acid, 3.5 parts of sodium styrene sulfonate and 70 parts of water compositions；
4) it after completion of dropwise addition, keeps temperature constant, cures 2 hours, when reaction solution temperature is lower than 30 DEG C, be slowly added to
The sodium methoxide of 7 parts of mass ratio 1:1 and the composition of ethanol amine, moisturizing to 1000 parts be 40% to get mass fraction high carboxyl
The polycarboxylate water-reducer of the long short-chain branch of density.
Embodiment 5
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer；Total matter
Amount 1000 parts, after preparation final product quality score be 40%, preparation method the following steps are included:
1) 300 parts of 702 monomers of Losec, 42 parts of goodization chemistry APEG1200 monomers and 210 parts of water are added in reaction kettle,
Agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 49 DEG C, and after temperature is stablized, being added at one time 1.6 parts of mass percents is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 3.5 hours, and solution B time for adding is 4 hours；Solution B is by 0.48
The methylacryoyloxyethyl phosphate and glycolmethacrylate phosphate of part ascorbic acid, 0.42 part of mass ratio 1:1
Composition, 0.55 part of mercaptoethanol and 84 parts of water composition, solution A is by 45 parts of acrylic acid, 2.2 parts of 2- acrylamide -2- methyl
Propane sulfonic acid and 66 parts of water compositions；
4) it after completion of dropwise addition, keeps temperature constant, cures 2.5 hours, when reaction solution temperature is lower than 30 DEG C, slowly add
Enter 9 parts of ethanol amines, the polycarboxylic acids diminishing for the high long short-chain branch of carboxyl density that moisturizing is 40% to get mass fraction to 1000 parts
Agent.
Embodiment 6
A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl is close
The polycarboxylate water-reducer for spending long short-chain branch is mainly prepared from the following components: high molecular weight polyether polymeric monomer, low molecular weight are poly-
Ether polymeric monomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；Always
1000 parts of quality, after preparation final product quality score be 40%, preparation method the following steps are included:
1) 298 parts of 703 monomers of Losec, 38 parts of Losec chemistry TPEG1200 monomers and 220 parts of water are added in reaction kettle,
Agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature is at 50 DEG C, and after temperature is stablized, being added at one time 1.8 parts of mass percents is
27.5% industrial grade hydrogen peroxide；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A adds in hydrogen peroxide
Start to be added dropwise in 10min after entering；Solution A time for adding is 4 hours, and solution B time for adding is 4.5 hours；Solution B is by 0.5
Part ascorbic acid, the methylacryoyloxyethyl phosphate of 0.4 part of mass ratio 2:3 and glycolmethacrylate phosphate
Composition, 0.5 part of thioacetic acid and 93 parts of water composition, solution A is by 48 parts of acrylic acid, the acrylic sodium sulfonate of 5 parts of mass ratio 1:1
Composition, 68 parts of water compositions with methylpropene sodium sulfonate；
4) it after completion of dropwise addition, keeps temperature constant, cures 3 hours, when reaction solution temperature is lower than 30 DEG C, be slowly added to
10 parts of triethanolamines, the polycarboxylic acids diminishing for the high long short-chain branch of carboxyl density that moisturizing is 40% to get mass fraction to 1000 parts
Agent.
A kind of polycarboxylic acids diminishing for high long short-chain branch of carboxyl density that respectively prepared by test above-described embodiment 1,2,3,4,5,6
The cement paste initial fluidity and 1h mobility of agent and ordinary water-reducing agent under comparable sodium.Testing cement used is Hua Xin
42.5 ordinary portland cements, 42.5 ordinary portland cement of Ge Zhou Ba, blue 42.5 ordinary portland cements in capital, with reference to GB/8076-2008, " concrete is additional
Agent " testing standard.
The different Water-reducing Admixtures To Cements net slurry flow effects of table 1 (new 42.5 ordinary portland cement of China)
| Water-reducing agent type | Initial fluidity/mm | 1h mobility/mm |
| Ordinary water-reducing agent | 235 | 225 |
| Embodiment 1 | 245 | 235 |
| Embodiment 2 | 235 | 220 |
| Embodiment 3 | 235 | 225 |
| Embodiment 4 | 250 | 230 |
| Embodiment 5 | 240 | 220 |
| Embodiment 6 | 240 | 230 |
The different Water-reducing Admixtures To Cements net slurry flow effects (42.5 ordinary portland cement of Ge Zhou Ba) of table 2
| Water-reducing agent type | Initial fluidity/mm | 1h mobility/mm |
| Ordinary water-reducing agent | 180 | 150 |
| Embodiment 1 | 230 | 230 |
| Embodiment 2 | 235 | 225 |
| Embodiment 3 | 230 | 235 |
| Embodiment 4 | 240 | 220 |
| Embodiment 5 | 230 | 225 |
| Embodiment 6 | 225 | 230 |
The different Water-reducing Admixtures To Cements net slurry flow effects of table 3 (capital 42.5 ordinary portland cements of orchid)
| Water-reducing agent type | Initial fluidity mm | 1h mobility mm |
| Ordinary water-reducing agent | - | - |
| Embodiment 1 | 230 | 210 |
| Embodiment 2 | 235 | 230 |
| Embodiment 3 | 220 | 235 |
| Embodiment 4 | 235 | 225 |
| Embodiment 5 | 230 | 230 |
| Embodiment 6 | 225 | 215 |
According to above-mentioned cement paste initial fluidity, the data comparison of 1h mobility, embodiment 1,2,3,4,5,6 is for China
New cement, Ge Zhou Ba cement show highly stable water-reducing property, are almost able to maintain in the application of different cement same
Initial fluidity and 1h mobility.For ordinary water-reducing agent, the initial fluidity and embodiment of net slurry when acting on magnificent new cement
1,2,3,4,5,6 substantially quite, but when acting on Ge Zhou Ba cement, and initial fluidity and 1h mobility all greatly reduce, and makees
When for capital orchid cement, or even the mobility of cement is not measured, it is very bright with the gap of embodiment 1,2,3,4,5,6
It is aobvious.In conclusion the polycarboxylate water-reducer of the high long short-chain branch of carboxyl density can be shown very in the cement of different qualities
Stable performance is suitable for various cement.
Claims (8)
1. a kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density, it is characterised in that: the high carboxyl density
The polycarboxylate water-reducer of long short-chain branch is mainly prepared from the following components: 3000 molecular weight polyether polymeric monomers, 1200 molecular weight
Polyether macromonomer, hydrogen peroxide, ascorbic acid, phosphate ester monomer, chain-transferring agent, acrylic acid, unsaturated sulfonic acid salt, neutralizer, water；
1000 parts of gross mass, after preparation final product quality score be 40%, preparation method the following steps are included:
1) by 3000 molecular weight polyether polymeric monomer of 290-310 part, 1200 molecular weight polyether polymeric monomer of 30-45 part and 180-220 parts
Water is added in reaction kettle, and agitating and heating waits for its dissolution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 0.9-1.8 parts of hydrogen peroxide at 45-50 DEG C；
3) after the 5min after hydrogen peroxide addition, successively start that solution B, solution A is added dropwise, wherein solution A is after hydrogen peroxide addition
10min in start to be added dropwise；Solution A time for adding is a hours, and a value is 2-4, and solution B time for adding is a+0.5 hours；It is molten
Liquid B is by 0.32-0.5 parts of ascorbic acid, 0.4-0.8 parts of phosphate ester monomers, 0.5-0.9 parts of chain-transferring agents and 80-100 parts of water groups
At solution A is made of 44-53 parts of acrylic acid, 2-5 portions of unsaturated sulfonic acid salt and 50-70 parts of water；
4) it after completion of dropwise addition, keeping temperature constant, cures b hours, b value is 1-3, when reaction solution temperature is lower than 30 DEG C,
Be slowly added to 7-14 parts of neutralizers, moisturizing to 1000 parts to get mass fraction be 40% the high long short-chain branch of carboxyl density it is poly-
Carboxylic acid water reducer.
2. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: described
3000 molecular weight polyether polymeric monomers by molecular weight 3000 allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl
One or more of enol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether composition.
3. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: described
1200 molecular weight polyether polymeric monomers by molecular weight 1200 allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl
One or more of enol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether composition.
4. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: it is described not
Sulfonate is saturated by sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate, sodium styrene sulfonate, 2- acrylamide-
One or more of 2- methyl propane sulfonic acid composition.
5. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: the phosphorus
Acid esters function monomer is by one or both of methylacryoyloxyethyl phosphate, glycolmethacrylate phosphate group
At.
6. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: the chain
Transfer agent is made of one or more of thioacetic acid, mercaptopropionic acid, mercaptoethanol, mercaprol.
7. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: in described
With agent by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanol amine, diethanol amine,
One or more of triethanolamine, triisopropanolamine composition.
8. a kind of polycarboxylate water-reducer of the high long short-chain branch of carboxyl density according to claim 1, it is characterised in that: described double
Oxygen water is that mass percent is 27.5% industrial grade hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810743833.5A CN109053971A (en) | 2018-07-09 | 2018-07-09 | A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810743833.5A CN109053971A (en) | 2018-07-09 | 2018-07-09 | A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109053971A true CN109053971A (en) | 2018-12-21 |
Family
ID=64819595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810743833.5A Pending CN109053971A (en) | 2018-07-09 | 2018-07-09 | A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109053971A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072870A (en) * | 2019-12-31 | 2020-04-28 | 广东奥克化学有限公司 | High-adaptability polycarboxylate superplasticizer and preparation method thereof |
| CN111333788A (en) * | 2020-04-23 | 2020-06-26 | 重庆牧野实业有限公司 | Preparation method of polycarboxylic acid water reducing agent containing multiple layers of side chain lengths |
| CN111875754A (en) * | 2020-08-28 | 2020-11-03 | 马清萍 | Polycarboxylate superplasticizer with excellent water reducing property and preparation method thereof |
| CN112694573A (en) * | 2020-12-31 | 2021-04-23 | 浙江衢州鼎盛建材有限公司 | Cement slump loss resistant water reducer with early strength function |
| WO2022056975A1 (en) * | 2020-09-17 | 2022-03-24 | 江苏尼高科技有限公司 | Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584093A (en) * | 2012-02-28 | 2012-07-18 | 昆明理工大学 | Main chain carboxy-density-adjustable high-efficiency polycarboxylic acid water reducing agent |
| CN103897116A (en) * | 2014-02-28 | 2014-07-02 | 北京东方雨虹防水技术股份有限公司 | Mud-resistant polycarboxylic acid water reducer and preparation method thereof |
| CN105061692A (en) * | 2015-08-03 | 2015-11-18 | 中国建筑材料科学研究总院 | Polyether polycarboxylic acid water reducing agent and preparation method therefor |
| CN107987224A (en) * | 2017-11-30 | 2018-05-04 | 湖北工业大学 | A kind of short-chain branch crosslinking water conservation solvent layer control release type polycarboxylic acid slump retaining agent and preparation method |
-
2018
- 2018-07-09 CN CN201810743833.5A patent/CN109053971A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584093A (en) * | 2012-02-28 | 2012-07-18 | 昆明理工大学 | Main chain carboxy-density-adjustable high-efficiency polycarboxylic acid water reducing agent |
| CN103897116A (en) * | 2014-02-28 | 2014-07-02 | 北京东方雨虹防水技术股份有限公司 | Mud-resistant polycarboxylic acid water reducer and preparation method thereof |
| CN105061692A (en) * | 2015-08-03 | 2015-11-18 | 中国建筑材料科学研究总院 | Polyether polycarboxylic acid water reducing agent and preparation method therefor |
| CN107987224A (en) * | 2017-11-30 | 2018-05-04 | 湖北工业大学 | A kind of short-chain branch crosslinking water conservation solvent layer control release type polycarboxylic acid slump retaining agent and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072870A (en) * | 2019-12-31 | 2020-04-28 | 广东奥克化学有限公司 | High-adaptability polycarboxylate superplasticizer and preparation method thereof |
| CN111333788A (en) * | 2020-04-23 | 2020-06-26 | 重庆牧野实业有限公司 | Preparation method of polycarboxylic acid water reducing agent containing multiple layers of side chain lengths |
| CN111875754A (en) * | 2020-08-28 | 2020-11-03 | 马清萍 | Polycarboxylate superplasticizer with excellent water reducing property and preparation method thereof |
| CN111875754B (en) * | 2020-08-28 | 2022-07-22 | 马清萍 | Polycarboxylate superplasticizer with excellent water reducing property and preparation method thereof |
| WO2022056975A1 (en) * | 2020-09-17 | 2022-03-24 | 江苏尼高科技有限公司 | Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete |
| CN112694573A (en) * | 2020-12-31 | 2021-04-23 | 浙江衢州鼎盛建材有限公司 | Cement slump loss resistant water reducer with early strength function |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109053971A (en) | A kind of polycarboxylate water-reducer preparation method of the high long short-chain branch of carboxyl density | |
| CN104261721B (en) | A kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof | |
| CN102976655B (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN109111551A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer preparation method of 3000 molecular weight polyethers | |
| JP6074517B2 (en) | Method for producing slump retention type polycarboxylate-based high performance fluidizing agent | |
| CN108948288A (en) | A kind of cross-linking type polycarboxylate water-reducer preparation method using carboxyl function monomer | |
| CN106496445A (en) | A kind of hydrophobic minor comonomer modification viscosity reduction type polycarboxylate water-reducer masterbatch | |
| CN106749972B (en) | A kind of prefabricated components low slump Early-strength polycarboxylate superplasticizer masterbatch | |
| CN109053972A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer preparation method of barrier intercalation | |
| CN105367721A (en) | Method for preparing viscosity-reduction-type polycarboxylic acid superplasticizer and application of viscosity-reduction-type polycarboxylic acid superplasticizer | |
| CN106749970B (en) | A kind of sheet polycarboxylic acid slump retaining agent and preparation method thereof admittedly | |
| CN102976654B (en) | Polycarboxylic superplasticizer and application thereof | |
| CN108585594A (en) | A kind of high and easy retentivity polycarboxylate water-reducer of 1800 molecular weight polyethers and preparation method | |
| CN105754047A (en) | Phosphate containing high-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| CN110105504A (en) | A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application | |
| CN101575403A (en) | Polymerization method for preparing polycarboxylic high-efficiency water-reducing agent | |
| CN105037658A (en) | Preparation method of polycarboxylate water reducer with intensively-distributed carboxyl groups and high water reduction performance, product thereof, and application of product | |
| CN105036596B (en) | Low-temperature synthesis polycarboxylate superplasticizer and preparation method thereof | |
| CN106380552A (en) | High-adaptability polycarboxylic acid water reducing agent master batch | |
| CN106519137A (en) | Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof | |
| CN107987223A (en) | A kind of ester modified high-adaptability polycarboxylate water-reducer of alkyl acrylic and preparation method | |
| CN109593167A (en) | A kind of citric acid-modified polycarboxylate water-reducer of sorbierite acrylate and preparation method thereof | |
| CN108948287B (en) | Preparation method of polycarboxylic acid slump retaining agent based on 3000 molecular weight polyether | |
| CN112708041B (en) | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108822262A (en) | 1200 molecular weight polyether polycarboxylate water-reducers of one kind and preparation method |
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: 20181221 |