CN106279702A - A kind of froth breaking type function monomer, polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of froth breaking type function monomer, polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—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
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- 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
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention provides a kind of froth breaking type function monomer, polycarboxylate water-reducer and preparation method thereof, the preparation method of described defoaming function monomer is that the siloxanes segment with defoaming function is introduced froth breaking type function monomer molecular structure, prepares defoaming function monomer；The preparation method of the described polycarboxylate water-reducer with defoaming function is to be introduced in polycarboxylate water-reducer molecular structure to obtain the polycarboxylate water-reducer with defoaming function by the way of polymerization by the siloxanes segment with defoaming function.Froth breaking type function monomer prepared in the present invention introduces siloxane structure, has more excellent defoaming function, and without Si O C-structure in structure, thus avoid the stability problem occurred because of the hydrolysis of Si O C-structure.The polycarboxylate water-reducer of the present invention, on the premise of not affecting water-reducing effect, gives the function of water reducer froth breaking, makes polycarboxylate water-reducer have diminishing, the function of froth breaking one, it is to avoid the problems such as the compounding compatibility occurred and stability.
Description
Technical field
The invention belongs to concrete additives in building materials technical field, it relates in particular to one has froth breaking merit
The froth breaking type function monomer of energy, polycarboxylate water-reducer and preparation method thereof.
Background technology
Bubble to be introduced in concrete configuration and construction, wherein diameter is remarkably improved in 50nm bubbles below
Freeze proof, impervious, the durability of concrete, also can improve mobility and the application property of concrete, thus improve concrete quality.With
Concrete Industry development, the raising of performance requirements various to concrete, polycarboxylate water-reducer obtains application the most rapidly, but
Polycarboxylate water-reducer, due to its own molecular structure feature, causes its bleed ability strong, introduces size in concrete preparation process
The bubble differed, air content is too high, has a strong impact on concrete strength, outward appearance and resistance to performance of waiting so long.
For this problem, many is researched and proposed addition proper quantity of defoaming agent in polycarboxylate water-reducer and is carried out compounding to reach control
Air content processed, but due to defoamer and the polycarboxylate water-reducer compatibility and less stable, the method is controlling air content problem
Upper less effective.Therefore research is had to attempt being modified solving the compatibility by defoamer.
Polyoxyethylene polyoxypropylene is carried out amido end-blocking by patent US6803396, and increase is mutual with polycarboxylate water-reducer
Active force, this kind of polyethers price is costly；Document " the regulation and control method of polycarboxylate water-reducer and concrete 's air-containing " is reported in system
During standby esters polymeric monomer, polyoxyethylene poly-oxygen propylene aether is introduced system, the ratio of regulation polyoxypropylene and polyoxyethylene segment with
Control the bleed of polycarboxylate water-reducer.In prior art all by polyether-modified to improve the gassiness of polycarboxylate water-reducer
Amount.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to solve present in above-mentioned prior art
One or more problems.Such as, an object of the present invention is provide a kind of water-reducing property excellent and have excellent disappearing simultaneously
The polycarboxylate water-reducer of bubble function.
To achieve these goals, an aspect of of the present present invention provides the preparation method of a kind of froth breaking type function monomer.Institute
The siloxanes segment and polyether segment structure with defoaming function are introduced froth breaking type by the preparation method stating froth breaking type function monomer
Function monomer molecular structure.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, described froth breaking type function monomer
Preparation method may comprise steps of: heating polyether modified silicon oil, and by the unsaturated carboxylic acid containing acid catalyst or acyl
Chlorine drops to carry out in described polyether modified silicon oil esterification, or anhydride drops to dispersing and dissolving in polyether modified silicon oil
And heating carries out esterification, obtain the froth breaking type function monomer of silicone-containing and polyether lateral chain.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, described polyether modified silicon oil with not
The mol ratio of saturated carboxylic acid is 1:1.05～1:1.10, and described acid catalyst accounts for described polyether modified silicon oil and unsaturated carboxylic acid
The 0.5%～3.0% of total mole number, described polyether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of acyl chlorides, described poly-
Ether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of anhydride.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, heats described polyether modified silicon oil
To 60～100 DEG C.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, described unsaturated carboxylic acid is propylene
At least one in acid, methacrylic acid, butenoic acid, 2-butylene acid, described acyl chlorides is in acryloyl chloride, methacrylic chloride
At least one, described anhydride is maleic anhydride, and described acid catalyst is concentrated sulphuric acid and/or p-methyl benzenesulfonic acid.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, passed through constant voltage in 1～2 hour
Dropping funnel drips acyl chlorides or the unsaturated carboxylic acid containing acid catalyst in described polyether modified silicon oil.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, in described polyether modified silicon oil
Dropping acyl chlorides or containing the unsaturated carboxylic acid of acid catalyst after, continue esterification 1～2 hours, or be directly added into
Anhydride dispersing and dissolving carries out esterification 1～2 hours.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, described preparation method also include by
Unsaturated carboxylic acid and acid catalyst or acyl chlorides are stirred when dropping in described polyether modified silicon oil.
The preparation method of froth breaking type function monomer according to an exemplary embodiment of the present invention, described froth breaking type function monomer is used
There is the polycarboxylate water-reducer of defoaming function in preparation.
Another aspect of the present invention provides a kind of froth breaking type function monomer.Described froth breaking type function monomer silicone-containing and polyethers
Side chain and without Si-O-C structure, the molecular structure of described froth breaking type function monomer is:
Froth breaking type function monomer according to an exemplary embodiment of the present invention, described froth breaking type function monomer is by above-mentioned froth breaking type
The preparation method of function monomer is prepared from.
The preparation method of a kind of polycarboxylate water-reducer with defoaming function of further aspect of the present invention.Described have froth breaking merit
The preparation method of the polycarboxylate water-reducer of energy includes: a, the siloxanes segment will with defoaming function and polyether segment structure introduce
Froth breaking type function monomer molecular structure, to prepare froth breaking type function monomer；B, by described froth breaking type function monomer introduce polymer
In system, obtain the polycarboxylate water-reducer with defoaming function.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described step according to an exemplary embodiment of the present invention
B make under the effect of initiator and chain-transferring agent described froth breaking type function monomer, polyether macromonomer and unsaturated carboxylic acid and/or its
Derivant (i.e. the derivant of unsaturated carboxylic acid) carries out aqueous free radical polyreaction, obtains the polycarboxylic acids with defoaming function
Water reducer.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described step according to an exemplary embodiment of the present invention
B may include that and described froth breaking type function monomer, polyether macromonomer and water is mixed and heated, and obtains solution A；By unsaturation carboxylic
Acid and/or its derivant and initiator, chain-transferring agent and water wiring solution-forming B；Described solution B is dropped in described solution A, complete
Become aqueous free radical polyreaction, obtain the polycarboxylate water-reducer with defoaming function.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, by 4.0～
The described froth breaking type function monomer of 24.4 weight portions, 300～400 weight portion polyether macromonomer and the water of 200～260 weight portions
It is mixed and heated, obtains described solution A.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, by 40～60
The initiator of the unsaturated carboxylic acid of weight portion and/or its derivant and 0.3～3.0 weight portions, 1.0～4.0 the chain of weight portion turn
Move agent and the water wiring solution-forming B of 180～240 weight portions.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, described water-soluble
Liquid Raolical polymerizable is carried out under the temperature conditions of 40～60 DEG C.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, disappear described
Alveolitoid function monomer, polyether macromonomer and water are heated to 40～60 DEG C.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described solution according to an exemplary embodiment of the present invention
B was dropped in described solution A by constant pressure funnel within 1.5～3.5 hours.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described side's system according to an exemplary embodiment of the present invention
Standby method be additionally may included in described aqueous free radical polyreaction complete after be cooled to less than 40 DEG C, and regulate pH to neutral.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, use alkalescence
Material enters the step that described regulation pH is the most neutral, and described alkaline matter can be in sodium hydroxide, potassium hydroxide and calcium hydroxide
At least one.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described polyethers according to an exemplary embodiment of the present invention
Polymeric monomer can be the prenol polyoxyethylene poly-oxygen propylene aether of molecular weight 2200～2800, methacrylic polyoxyethylene gather
At least one in oxypropylene ether and 4-hydroxyl butyl vinyl polyoxyethylene poly-oxygen propylene aether.
Having the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, described chain turns
Moving agent can be at least one in mercaptopropionic acid, TGA, methylpropene sodium sulfonate and Sodium styrene sulfonate.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described initiation according to an exemplary embodiment of the present invention
Agent can be Ammonium persulfate., potassium peroxydisulfate, ascorbic acid and Ammonium persulfate., ascorbic acid and potassium peroxydisulfate or ascorbic acid
With hydrogen peroxide.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described step according to an exemplary embodiment of the present invention
A includes: heating polyether modified silicon oil, and the unsaturated carboxylic acid containing acid catalyst or acyl chlorides is dropped to described polyether-modified
Silicone oil carries out esterification, or anhydride is dropped to dispersing and dissolving heating in polyether modified silicon oil carries out esterification,
Obtain the froth breaking type function monomer of silicone-containing and polyether lateral chain.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described polyethers according to an exemplary embodiment of the present invention
Modified silicon oil is 1:1.05～1:1.10 with the mol ratio of unsaturated carboxylic acid, and described acid catalyst accounts for described polyether modified silicon oil
With the 0.5%～3.0% of unsaturated carboxylic acid total mole number, described polyether modified silicon oil is 1:1.05～1 with the mol ratio of acyl chlorides:
1.10, described polyether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of anhydride.
Having the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, heating is described
Polyether modified silicon oil is to 60～100 DEG C.
There is the preparation method of the polycarboxylate water-reducer of defoaming function, described insatiable hunger according to an exemplary embodiment of the present invention
Being at least one in acrylic acid, methacrylic acid, butenoic acid, 2-butylene acid with carboxylic acid, described acyl chlorides is acryloyl chloride, methyl
At least one in acryloyl chloride, described anhydride is maleic anhydride, and described acid catalyst is concentrated sulphuric acid and/or to toluene
Sulfonic acid.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, little in 1～2
Time interior in described polyether modified silicon oil, dripped acyl chlorides by constant pressure funnel or containing the unsaturated carboxylic acid of acid catalyst.
There is the preparation method of the polycarboxylate water-reducer of defoaming function according to an exemplary embodiment of the present invention, to described poly-
Ether modified silicon oil drips acyl chlorides or containing the unsaturated carboxylic acid of acid catalyst after, continue esterification 1～2 hours,
Or it is directly added into anhydride dispersing and dissolving and carries out esterification 1～2 hours.
Further aspect of the present invention provides a kind of polycarboxylate water-reducer with defoaming function.Described polycarboxylate water-reducer is by upper
The preparation method stating the polycarboxylate water-reducer with defoaming function is prepared from.
Compared with prior art, the polycarboxylate water-reducer of the application, on the premise of not affecting water-reducing effect, gives diminishing
The function of agent froth breaking, on the basis of i.e. ensureing the concrete flowability of preparation, application property, eliminates residual bubble in concrete.This
Froth breaking type function monomer prepared in application introduces siloxane structure, has more excellent froth breaking compared with polyethers froth breaking monomer
Without Si-O-C structure in function, and structure, structural behaviour is stable.It is introduced into polymerization system, prepared polycarboxylic acids diminishing
Agent has diminishing, the function of froth breaking one, it is to avoid the problems such as the compounding compatibility occurred and stability.
Detailed description of the invention
Hereinafter, describe the froth breaking type function monomer according to the present invention in detail by combining exemplary embodiment, have
Defoaming function polycarboxylate water-reducer and preparation method thereof.
The present invention by by have the siloxanes segment of defoaming function and polyether segment structure by polymerization by the way of introduce
To give the function of polycarboxylate water-reducer froth breaking in polycarboxylate water-reducer molecular structure.First silicone-containing and polyethers side are prepared
The froth breaking type function monomer of chain, then makes froth breaking type function monomer, polyether macromonomer under the effect of initiator and chain-transferring agent
Carrying out aqueous free radical polyreaction with unsaturated carboxylic acid and/or its derivant, the polycarboxylic acids obtaining having defoaming function subtracts
Water preparation.
The preparation method of the polycarboxylate water-reducer according to an exemplary embodiment of the present invention with defoaming function includes following
Step:
1) preparation of froth breaking type function monomer: add in the there-necked flask equipped with puddler, constant pressure funnel and thermometer
Enter polyether modified silicon oil, described polyether modified silicon oil is heated to 60～100 DEG C, in 1～2 hour, pass through constant pressure funnel
In described polyether modified silicon oil, dropping contains unsaturated carboxylic acid or the acyl chlorides of acid catalyst, and dropping is stirred simultaneously, drips
Continue esterification 1～2 hours after Biing, or anhydride adds dispersing and dissolving heating in polyether modified silicon oil, and to carry out esterification anti-
Answer 1～2 hour, after reaction, obtain the froth breaking type function monomer of silicone-containing and polyether lateral chain.
2) preparation of polycarboxylate water-reducer: add in the four-hole bottle equipped with puddler, constant pressure funnel and thermometer
Described froth breaking type function monomer, polyether macromonomer and water, be heated to 40～60 DEG C, stirring and dissolving, forms solution A；1.5～
Dripped in solution A by constant pressure funnel within 3.5 hours and turned by unsaturated carboxylic acid and/or its derivant, initiator, chain
The mixed solution B that shifting agent and water are made into, continues reaction 1.5～2.0 hours at 40～60 DEG C after dropping, and reaction is dropped after terminating
Warm to less than 40 DEG C, neutralize with alkaline substance solution, regulation pH value of solution is to neutral, and the prepared polycarboxylic acids with defoaming function subtracts
Water preparation.
Above, if two reactants of esterification are acid and alcohol, it is necessary to add acid catalyst, and need higher temperatures
Degree, generally at about 100 DEG C.If reactant is activity higher anhydride or acyl chlorides, course of reaction need not catalyst, and
Lower temperature just can react.Such as, acyl chlorides directly drops in polyether modified silicon oil.
Unsaturated carboxylic acid and acid catalyst or acyl chlorides are dropped to the reason in described polyether modified silicon oil and be because rubbing
You than close to when, polyether silicone oil molecular weight is big, and quality is the biggest, operates for convenience, be that a small amount of liquid drips the when of dropping
Enter in big quantity of fluid.Another aspect is a small amount of sour or acyl chlorides contacts with a large amount of polyether silicone oils, is in " hungry " state, it is to avoid ester
Change the hydroxyl on more polyether silicone oil segment, in order to avoid forming cross-linked structure.
" dripped in described polyether modified silicon oil containing acid catalyst by constant pressure funnel in 1～2 hour
Unsaturated carboxylic acid or acyl chlorides ", here, about time for adding, on the premise of not affecting product structure and performance the time the shortest more
Good, shorten flow process, cost-effective.But it is uneven to drip too fast easily dispersion, or reacts too fast, with multiple hydroxyl reactions.
Drip complete follow-up continuous esterification 1～2 hours, on the premise of time-consuming, ensure conversion ratio.
Wherein, described unsaturated carboxylic acid is at least one in acrylic acid, methacrylic acid, butenoic acid, 2-butylene acid, institute
Stating acyl chlorides is at least one in acryloyl chloride, methacrylic chloride, and described anhydride is maleic anhydride, described acid based catalyst
Agent is concentrated sulphuric acid and/or p-methyl benzenesulfonic acid.
Because derivant has a variety of, including esters, amide-type, such as, methyl methacrylate, acrylamide, its with
The reaction of alcohols is complex, and general esterification monomer selects acid, anhydride or acyl chlorides.Therefore, when step (1) prepares monomer
Wait, the when of using unsaturated carboxylic acid, anhydride or acyl chlorides, acyl chlorides and anhydride esterifying reaction, catalyst need not be added, in step (2)
The when of preparing water reducer, owing to being radical polymerization, solution B can be unsaturated carboxylic acid and/or its derivant (includes acid
Acid anhydride).
Described polyether modified silicon oil is Si--C type structure, and has certain defoaming function.
Described initiator be Ammonium persulfate., potassium peroxydisulfate, ascorbic acid and Ammonium persulfate., ascorbic acid and potassium peroxydisulfate,
Or ascorbic acid and hydrogen peroxide.I.e. Ammonium persulfate., potassium peroxydisulfate can individually do initiator, self can carry out oxidation also
Former reaction, now reaction temperature is higher, it is possible to being used together with reducing agent ascorbic acid, now temperature is relatively low.Hydrogen peroxide can only
It is used together with ascorbic acid.After polyether macromonomer dissolves completely, in its solution, add oxidant hydrogen peroxide, Ammonium persulfate.
Or potassium peroxydisulfate continues stirring, reducing agent ascorbic acid is dissolved in unsaturated carboxylic acid and/or its derivative solution.
Described chain-transferring agent be in mercaptopropionic acid, TGA, methylpropene sodium sulfonate and Sodium styrene sulfonate at least
A kind of.
Described alkaline matter is at least one in sodium hydroxide, potassium hydroxide and calcium hydroxide.
Described polyether macromonomer is the prenol polyoxyethylene poly-oxygen propylene aether of molecular weight 2200～2800, methallyl
At least one in base polyoxyethylene poly-oxygen propylene aether and 4-hydroxyl butyl vinyl polyoxyethylene poly-oxygen propylene aether.
Polyether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of unsaturated carboxylic acid, and described acid catalyst accounts for described
Polyether modified silicon oil and the 0.5%～3.0% of unsaturated carboxylic acid total mole number, described polyether modified silicon oil and the mol ratio of acyl chlorides
For 1:1.05～1:1.10, described polyether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of anhydride.
Parts by weight of raw materials in described step (2) is: froth breaking type function monomer 4.0～24.4 parts, polyether macromonomer 300～
400 parts, water 200～260 parts；Unsaturated carboxylic acid and/or its derivant 40～60 parts, initiator 0.3～3.0 parts, chain-transferring agent
1.0～4.0 parts, water 180～240 parts.
The preparation method of froth breaking type function monomer i.e. uses above-mentioned steps 1 according to an exemplary embodiment of the present invention).This
Froth breaking type function monomer prepared in bright introduces siloxanes and polyether segment structure, has more excellent defoaming function, and knot
Without Si-O-C structure in structure, structural behaviour is stable.The molecular structural formula of froth breaking type function monomer prepared in the present invention is:
By froth breaking type function monomer introduce polymerization system, prepared polycarboxylate water-reducer have diminishing, froth breaking one
Function, it is to avoid the problems such as the compounding compatibility occurred and stability.
In order to be more fully understood that the above-mentioned exemplary embodiment of the present invention, below in conjunction with concrete example, it is carried out further
Explanation.
Example 1
1) silicone-containing and the preparation of polyether lateral chain froth breaking type function monomer: equipped with puddler, constant pressure funnel and
The there-necked flask of thermometer adds the polyether modified silicon oil of 500 weight portions, is heated to 90 DEG C.7.9 parts by weight of acrylic acid add
Enter the concentrated sulphuric acid of the 98wt% of 0.1 weight portion and dripped in polyether modified silicon oil by constant pressure funnel at 2 hours, stirring
Mix, drip complete follow-up continuous reaction 2 hours, obtain the froth breaking type function monomer SPA-1 of silicone-containing and polyether lateral chain.
2) there is the preparation of the polycarboxylate water-reducer of defoaming function: equipped with puddler, constant pressure funnel and thermometer
Four-hole bottle in add the froth breaking type function monomer SPA-1 of 4.0 weight portions, 300 weight portion prenol polyoxyethylene polyoxies third
Alkene ether and 200 weight parts waters, be warming up to 60 DEG C, stirring and dissolving；By 40 parts by weight of acrylic acid, 0.3 weight portion Ammonium persulfate., 1.0
Weight portion methylpropene sodium sulfonate and 180 weight parts waters are made into mixed solution, are dripped by constant pressure funnel within 1.5 hours
Complete, then continue reaction 1.5 hours at 60 DEG C；Reaction is cooled to less than 40 DEG C after terminating, and neutralizes with sodium hydrate aqueous solution, adjusts
Joint pH value of solution, to neutral, prepares the polycarboxylate water-reducer with defoaming function.
Example 2
1) silicone-containing and the preparation of polyether lateral chain froth breaking type function monomer: equipped with puddler, constant pressure funnel and
The there-necked flask of thermometer adds the polyether modified silicon oil of 500 weight portions, weighs 10.3 weight portion maleic anhydrides and add poly-
Dispersing and dissolving in ether modified silicon oil, is heated to 60 DEG C, stirring, reacts 1 hour, obtains the froth breaking type of silicone-containing and polyether lateral chain
Function monomer SPA-2.
2) there is the preparation of the polycarboxylate water-reducer of defoaming function: equipped with puddler, constant pressure funnel and thermometer
Four-hole bottle in add the froth breaking type function monomer SPA-2 of 6.5 weight portions, 360 weight portion methacrylic polyoxyethylene polyoxies
Propylene ether and 240 weight parts waters, be warming up to 45 DEG C, stirring and dissolving；By 45 weight parts of methacrylic acid, 15 weight portion metering systems
Acid methyl ester, 0.5 weight portion ascorbic acid, 3.5 weight portion TGAs and 220 weight parts waters were made into mixed solution, at 2.5 hours
Within by constant pressure funnel drip off (before dropping in large monomer solution add 2.5 parts of potassium peroxydisulfates, stirring and dissolving 10 points
Clock), and continue reaction 1.5 hours at 45 DEG C；Reaction is cooled to less than 40 DEG C after terminating, and neutralizes with potassium hydroxide aqueous solution, adjusts
Joint pH value of solution, to neutral, prepares the polycarboxylate water-reducer with defoaming function.
Example 3
1) silicone-containing and the preparation of polyether lateral chain froth breaking type function monomer: equipped with puddler, constant pressure funnel and
The there-necked flask of thermometer adds the polyether modified silicon oil of 500 weight portions, is heated to 100 DEG C.At 9.5 weight parts of methacrylic acid
The concentrated sulphuric acid of the 98wt% of middle addition 0.6 weight portion was also dripped by constant pressure funnel at 2 hours in polyether modified silicon oil,
Stirring, drips complete follow-up continuous reaction 2 hours, obtains the froth breaking type function monomer SPA-3 of silicone-containing and polyether lateral chain.
2) there is the preparation of the polycarboxylate water-reducer of defoaming function: equipped with puddler, constant pressure funnel and thermometer
Four-hole bottle in add the froth breaking type function monomer SPA-3 of 24.4 weight portions, 400 weight portion 4-hydroxyl butyl vinyl polyoxyethylene
With 260 weight parts waters in polyethenoxy ether, it is warming up to 40 DEG C, stirring and dissolving；By 52 weight parts of methacrylic acid, 0.7 weight portion
Ascorbic acid, 3.0 weight portion mercaptopropionic acids and 220 weight parts waters are made into mixed solution, pass through constant pressure addition within 3.5 hours
Funnel drips off (adding the hydrogen peroxide of 3.0 part of 30% mass concentration before dropping in large monomer solution, stir 10 minutes), and
40 DEG C are continued reaction 2.0 hours；Reaction is cooled to less than 40 DEG C after terminating, and neutralizes with calcium hydroxide aqueous solution, regulates pH value of solution
To neutral, prepare the polycarboxylate water-reducer with defoaming function.
Example 4
1) silicone-containing and the preparation of polyether lateral chain froth breaking type function monomer: equipped with puddler, constant pressure funnel and
The there-necked flask of thermometer adds the polyether modified silicon oil of 500 weight portions, is heated to 60 DEG C.By 9.9 parts by weight propylene acyl chlorides 2
Hour drip in polyether modified silicon oil by constant pressure funnel, stir, drip complete follow-up continuous reaction 1 hour, contained
The froth breaking type function monomer SPA-4 of siloxanes and polyether lateral chain.
2) there is the preparation of the polycarboxylate water-reducer of defoaming function: equipped with puddler, constant pressure funnel and thermometer
Four-hole bottle in add the froth breaking type function monomer SPA-4 of 8.1 weight portions, 390 weight portion 4-hydroxyl butyl vinyl polyoxyethylene
With 240 weight parts waters in polyethenoxy ether, it is warming up to 40 DEG C, stirring and dissolving；By 50 parts by weight of acrylic acid, 0.6 weight portion is anti-bad
Hematic acid, 2.3 weight portion mercaptopropionic acids and 220 weight parts waters are made into mixed solution, pass through constant pressure funnel within 3.0 hours
Drip off (in large monomer solution, adding the hydrogen peroxide of 2.8 part of 30% mass concentration before dropping, stir 10 minutes), and at 40 DEG C
Continue reaction 1.5 hours；Reaction terminate after be cooled to less than 40 DEG C, with calcium hydroxide aqueous solution neutralize, regulation pH value of solution in
Property, prepare the polycarboxylate water-reducer with defoaming function.
The experimental data of the polycarboxylate water-reducer prepared by above example 1-4 with defoaming function is as shown in the table.Table 1 is
The paste flowing degree test result of example 1-4 gained polycarboxylate water-reducer, homogeneous according to GB/T8077-2012 concrete admixture
Property test method, water-cement ratio is 0.29.Table 2 is concrete mix, and table 3 is concrete experiments data.More than diminishing in experiment
Agent volume (calculating by effective solid) is all the 0.2% of Binder Materials.
The paste flowing degree of table 1 example 1-4 gained polycarboxylate water-reducer
Table 2 concrete mix
Table 3 concrete experiments data
As it can be seen from table 1 initial paste flowing degree >=300 of the polycarboxylate water-reducer of the application, after 1 hour, it starches stream only
Dynamic degree >=270.
From table 3 it can be seen that after using the water reducer of the application, water-reducing rate >=31% of concrete, air content≤
2.6%, compressive strength rate >=224 of 3 days, compressive strength rate >=190 of 7 days, compressive strength rate >=133 of 3 days.
In sum, the polycarboxylate water-reducer of the present invention, on the premise of not affecting water-reducing effect, gives water reducer froth breaking
Function, i.e. ensure the concrete flowability of preparation, on the basis of application property, eliminate residual bubble in concrete.In the present invention
Prepared froth breaking type function monomer introduces siloxane structure, has more excellent defoaming function, and without Si-O-C in structure
Structure, thus avoid the stability problem occurred because of Si-O-C constitution water solution.It is introduced into polymerization system, prepared containing silica-based
Group have defoaming function polycarboxylate water-reducer there is diminishing, the function of froth breaking one, it is to avoid compounding occurred compatible
The problem such as property and stability.
Although the most describing the present invention by combining exemplary embodiment, but those skilled in the art should be clear
Chu, in the case of the spirit and scope limited without departing from claim, can be carried out respectively the exemplary embodiment of the present invention
Plant modifications and changes.
Claims (10)
1. the preparation method of a froth breaking type function monomer, it is characterised in that the preparation method of described froth breaking type function monomer will
Siloxanes segment and the polyether segment structure with defoaming function introduce froth breaking type function monomer molecular structure.
The preparation method of froth breaking type function monomer the most according to claim 1, it is characterised in that described froth breaking type function list
The preparation method of body comprises the following steps: heating polyether modified silicon oil, and by the unsaturated carboxylic acid containing acid catalyst or
Acyl chlorides drops to carry out in described polyether modified silicon oil esterification, or anhydride adds dispersing and dissolving in polyether modified silicon oil
And heating carries out esterification, obtain the froth breaking type function monomer of silicone-containing and polyether lateral chain.
The preparation method of froth breaking type function monomer the most according to claim 2, it is characterised in that described polyether modified silicon oil
Being 1:1.05～1:1.10 with the mol ratio of unsaturated carboxylic acid, described acid catalyst accounts for described polyether modified silicon oil with unsaturated
The 0.5%～3.0% of carboxylic acid total mole number, described polyether modified silicon oil is 1:1.05～1:1.10 with the mol ratio of acyl chlorides, institute
The mol ratio stating polyether modified silicon oil and anhydride is 1:1.05～1:1.10.
The preparation method of froth breaking type function monomer the most according to claim 2, it is characterised in that heat described polyether-modified
Silicone oil is to 60～100 DEG C.
5. a froth breaking type function monomer, it is characterised in that the molecular structure of described froth breaking type function monomer is:
Froth breaking type function monomer the most according to claim 5, it is characterised in that described froth breaking type function monomer is wanted by right
The preparation method seeking in 1 to 4 the froth breaking type function monomer described in any one is prepared from.
7. the preparation method of a polycarboxylate water-reducer with defoaming function, it is characterised in that described in there is defoaming function
The preparation method of polycarboxylate water-reducer includes:
A, the preparation method of employing froth breaking type function monomer as described in any one in Claims 1-4 prepare froth breaking type merit
Can monomer；
B, described froth breaking type function monomer is introduced in polymerization system, obtain the polycarboxylate water-reducer with defoaming function.
The preparation method of the polycarboxylate water-reducer with defoaming function the most according to claim 7, it is characterised in that described
Step b includes:
Described froth breaking type function monomer, polyether macromonomer and water are mixed and heated, obtain solution A；
By the derivant of unsaturated carboxylic acid and/or unsaturated carboxylic acid and initiator, chain-transferring agent and water wiring solution-forming B；
Drop to described solution B, in described solution A, complete aqueous free radical polyreaction, obtain that there is defoaming function
Polycarboxylate water-reducer.
The preparation method of the polycarboxylate water-reducer with defoaming function the most according to claim 8, it is characterised in that will
The described froth breaking type function monomer of 4.0～24.4 weight portions, 300～400 weight portion polyether macromonomer and 200～260 weight
The water of part is mixed and heated, and obtains described solution A；
Initiator, 1.0～4.0 by the unsaturated carboxylic acid of 40～60 weight portions and/or its derivant with 0.3～3.0 weight portions
The water wiring solution-forming B of the chain-transferring agent of weight portion and 180～240 weight portions.
10. a polycarboxylate water-reducer with defoaming function, it is characterised in that described polycarboxylate water-reducer is by claim 7
In 9, the preparation method of the polycarboxylate water-reducer with defoaming function described in any one is prepared from.
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| CN111019054A (en) * | 2019-11-25 | 2020-04-17 | 中建西部建设股份有限公司 | Low-air-entraining polycarboxylate superplasticizer and preparation method thereof |
| CN112159151A (en) * | 2020-10-16 | 2021-01-01 | 吉安市金羧科技有限公司 | Pumping agent and preparation method thereof |
| CN113501918A (en) * | 2021-09-08 | 2021-10-15 | 江苏福吉利亚建材有限公司 | Easily-stored high-performance polycarboxylate superplasticizer and preparation method thereof |
| CN114276550A (en) * | 2021-12-22 | 2022-04-05 | 东南大学 | Organic-inorganic composite additive for fair-faced concrete and preparation method and application thereof |
| CN115368517A (en) * | 2022-09-30 | 2022-11-22 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylic acid water reducing agent |
| CN115611565A (en) * | 2022-09-07 | 2023-01-17 | 云南筑辉建材有限公司 | Formula and preparation method of novel nano composite material UHPC |
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Cited By (9)
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| CN111019054A (en) * | 2019-11-25 | 2020-04-17 | 中建西部建设股份有限公司 | Low-air-entraining polycarboxylate superplasticizer and preparation method thereof |
| CN111019054B (en) * | 2019-11-25 | 2023-02-28 | 中建西部建设股份有限公司 | Low-air-entraining polycarboxylate superplasticizer and preparation method thereof |
| CN112159151A (en) * | 2020-10-16 | 2021-01-01 | 吉安市金羧科技有限公司 | Pumping agent and preparation method thereof |
| CN113501918A (en) * | 2021-09-08 | 2021-10-15 | 江苏福吉利亚建材有限公司 | Easily-stored high-performance polycarboxylate superplasticizer and preparation method thereof |
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| CN114276550A (en) * | 2021-12-22 | 2022-04-05 | 东南大学 | Organic-inorganic composite additive for fair-faced concrete and preparation method and application thereof |
| CN115611565A (en) * | 2022-09-07 | 2023-01-17 | 云南筑辉建材有限公司 | Formula and preparation method of novel nano composite material UHPC |
| CN115368517A (en) * | 2022-09-30 | 2022-11-22 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylic acid water reducing agent |
| CN115368517B (en) * | 2022-09-30 | 2024-10-15 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylate superplasticizer |
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