CN109354654A - A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN109354654A CN109354654A CN201811000732.5A CN201811000732A CN109354654A CN 109354654 A CN109354654 A CN 109354654A CN 201811000732 A CN201811000732 A CN 201811000732A CN 109354654 A CN109354654 A CN 109354654A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention discloses a kind of Early-strength polycarboxylate superplasticizers and preparation method thereof, the water-reducing agent be the compound of unsaturated polyether, unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group in redox system and under chain-transferring agent effect as made from Raolical polymerizable, preparation process is not necessarily to heat source, environmentally protective.Gained water-reducing agent takes the unsaturated polyether with long side chain, there is certain humidification to the early strength of cement and concrete component；The compound of the beta-unsaturated esters and unsaturated phosphinylidyne-containing amine group that select alcohol-containing amine groups is unsaturated early strong monomer, and alcohol amine groups therein and amide group can promote C3A aquation generates entringite, accelerates to enter hydrated cementitious accelerated period, shortens cement setting time, to improve early strength, improves the production efficiency of cement and concrete component.Meanwhile carboxylic acid group in diminishing agent molecule and ester group can make it have good dispersibility and dispersion retentivity.
Description
Technical field
The present invention relates to a kind of Early-strength polycarboxylate superplasticizers and preparation method thereof, and in particular to arrives a kind of alcohol-containing amine groups
Beta-unsaturated esters and unsaturated phosphinylidyne-containing amine group compound be unsaturated early strong monomer Early-strength polycarboxylate superplasticizer and
Preparation method belongs to building material technical field.
Background technique
In building engineering field, concrete is a kind of maximum civil engineering material of dosage, build house, repair the dykes and build dams with
And railway construction is both needed to using concrete.With the development of the times, requirements at the higher level are proposed to the performance of concrete, also to poly- carboxylic
The functionality of sour water-reducing agent has higher requirement.Polycarboxylate water-reducer have volume is low, water-reducing rate is high, concrete mix and
The features such as easy property and good durability, have a vast market application prospect.
At low ambient temperatures, polycarboxylate water-reducer is unfavorable for hydrated cementitious, extends setting time, generates to early strength
Certain influence when preparing prefabricated components, if can be improved early strength, can greatly increase production efficiency.Therefore, needle
The problem weak to polycarboxylate water-reducer addition bring early strength, someone develops with early powerful poly- carboxylic at present
Sour water-reducing agent is conducive to improve the concrete slow problem of hydration rate and quickening construction and manufacture tubular pole system at low ambient temperatures
The speed of product, increases economic efficiency.
Currently, for the study on the synthesis of Early-strength polycarboxylate superplasticizer, there are mainly two types of approach: (1) compounding: in plain edition
Being added in polycarboxylate water-reducer has early powerful inorganic or organic ingredient, and the approach morning powerful ingredient volume is not easily-controllable
System, it is unfavorable to develop to concrete strength, and compound system is easily layered, and storage stability is deteriorated.(2) it synthesizes: with synthesis
Method, synthesize Early-strength polycarboxylate superplasticizer using the modifiable property of its molecule, and with Raolical polymerizable.
For example, patent CN201510736253.X discloses a kind of Early-strength polycarboxylate superplasticizer of carbon containing oxa- ring
Preparation method and products thereof, the patent are reacted with maleic anhydride under cryogenic by amido tetrahydrofuran, pass through acid anhydrides
Ring-opening reaction and amido tetrahydrofuran-compound form amide key connection, and then by it under the conditions of room temperature or low-temp reaction and not
Saturated carboxylic acid, unsaturated polyether carry out free radicals copolymerization reaction, so that preparation has the polycarboxylate water-reducer of carbon oxa- ring structure.
Though the Early-strength polycarboxylate superplasticizer of patent synthesis improves early strength of concrete, unsaturated tetrahydro to a certain extent
The requirement of furan compound preparation process is harsh, is not suitable for industrial production.
Patent 201410187323.6 discloses a kind of preparation of Early-strength polycarboxylate superplasticizer that triisopropanolamine is modified
Method, this method are modified water-reducing agent using maleic acid triisopropanolamine ester, obtain Early-strength polycarboxylate superplasticizer, this subtracts
Aqua to the effect of haveing a certain upgrade of concrete component early strength, but promoted it is limited, and the polycarboxylate water-reducer volume compared with
Greatly, at high cost, it is unfavorable for large-scale promotion application.
From the foregoing, the preparation of Early-strength polycarboxylate superplasticizer has certain problems at present, so search out one kind
Addition content is few, is remarkably improved early strength, the Early-strength polycarboxylate superplasticizer tool that preparation process is more easy compared with the prior art
There is important meaning.
Summary of the invention
A series of problems, such as insufficient for early strength of concrete caused by existing polycarboxylate water-reducer, the present invention provides
A kind of Early-strength polycarboxylate superplasticizer, the water-reducing agent is with the change of the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group
Closing object is unsaturated early strong monomer, and the modification by unsaturated early strong monomer to water-reducing agent can effectively facilitate cement minerals water
Solution effectively improves the early strength of cement, concrete structure, shortens setting time, improves production efficiency.
The present invention also provides the preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, this method safe operation is simple, nothing
It needs to heat, energy consumption is lower, environmentally protective.
It is unsaturated early that the present invention, which selects the beta-unsaturated esters of alcohol-containing amine groups and the compound of unsaturated phosphinylidyne-containing amine group,
Strong monomer is modified water-reducing agent, and being added into diminishing agent molecule has early powerful alcohol amine groups and amide group,
Both groups can promote C3A aquation forms entringite, effectively mineral aquation initial stage is inhibited to form loose structure, promotes water
The hydrolysis of mud mineral is accelerated to enter hydrated cementitious accelerated period, shortens setting time, improves early strength, efficiently solve in engineering
Stubborn problem.
Early-strength type polycarboxylate water-reducer be made from the following raw materials in parts by weight: unsaturated polyether 120 ~
160 parts, 8 ~ 20 parts of unsaturated carboxylic acid, 1 ~ 6 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group compound 0.5 ~
4 parts, 2 ~ 4 parts of oxidant, 0.3 ~ 0.8 part of reducing agent, 0.6 ~ 1.5 part of chain-transferring agent.
Preferably, Early-strength polycarboxylate superplasticizer is to be made of raw material from the following weight: 120 parts of unsaturated polyether, no
10-11 parts of saturated carboxylic acid, 1 ~ 2 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group 0.5 ~ 1 part of compound, oxygen
2-3 parts of agent, 0.3-0.5 parts of reducing agent, 0.7-0.75 parts of chain-transferring agent.
Further, the unsaturated polyether be relative molecular mass 3000 ~ 5000 isobutene alcohol polyoxyethylene ether or
Person's isoamyl alcohol polyoxyethylene ether.
Further, the unsaturated carboxylic acid is one of acrylic acid, maleic acid, methacrylic acid and itaconic acid or more
Kind.
Further, the compound of the unsaturated phosphinylidyne-containing amine group is acrylamide, 2- acrylamide -2- methyl-prop sulphur
Acid or N hydroxymethyl acrylamide.
Further, the oxidant is one of ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide or a variety of.
Further, the reducing agent is one of bisulfites, sulphite, ascorbic acid and thiosulfate
Or it is several.
Further, the chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid or methacrylic sulfonic acid
Sodium.
Further, the beta-unsaturated esters of alcohol-containing amine groups of the present invention are that inventor obtains by itself research,
With preferable early strong effect, the beta-unsaturated esters of the alcohol-containing amine groups are by alcamine compound and unsaturated acid anhydride through esterification
And it obtains.
Further, the alcamine compound be diethanol monoisopropanolamine or monoethanol diisopropanolamine (DIPA), it is described not
Being saturated acid anhydrides is maleic anhydride or itaconic anhydride.Preferably, the molar ratio of alcamine compound and unsaturated acid anhydride be 0.8 ~
1.2:1.
Further, specific reaction step is as follows: alcamine compound being mixed with propionic acid, unsaturated acids is then added
Acid anhydride, catalyst and polymerization inhibitor carry out esterification, obtain the beta-unsaturated esters of alcohol-containing amine groups.
Further, the effect of propionic acid: 1, as solvent；2, inhibit the amidation process of alcamine compound and acid anhydrides；
3, be conducive to improve esterification yield.Preferably, the molar ratio of alcamine compound and propionic acid is 0.8 ~ 1.2:1.
Further, the catalyst is p-methyl benzenesulfonic acid or phosphorus pentoxide, and the polymerization inhibitor is hydroquinone or right
Hydroxyanisol.The dosage of catalyst is 2.5 ~ 3.5wt% of alcamine compound, and the dosage of polymerization inhibitor is alcamine compound
0.04 ~ 0.07wt%.
Further, alcamine compound is reacted at 50 ~ 60 DEG C with propionic acid.
Further, alcamine compound is reacted at 100 ~ 110 DEG C with unsaturated acid anhydride.After reaction, subtract
Propionic acid is distilled off in pressure, obtains the beta-unsaturated esters of alcohol-containing amine groups.
The present invention also provides the preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, the water-reducing agent be unsaturated polyether,
The compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group oxidant, reducing agent and
Chain-transferring agent effect is lower to carry out what Raolical polymerizable was prepared.
Further, Early-strength polycarboxylate superplasticizer of the present invention prepare when the following steps are included:
(1) compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group is soluble in water, it obtains
A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) unsaturated polyether is soluble in water, it stirs evenly, oxidant is then added, stir 5-15 minutes, then start simultaneously
A material and B material is added dropwise, after wherein A drop adds 1.5 ~ 3h, B drop that 2 ~ 4h, A material and B is added to expect equal completion of dropwise addition, curing 1 that the reaction was continued
~ 3h, then adjusting solid content is 35 ~ 45wt%, obtains Early-strength polycarboxylate superplasticizer.
Further, in step (1) and (2), each raw material is completely dissolved by the dosage satisfaction of water.
Further, the beta-unsaturated esters of the alcohol-containing amine groups are prepared using method disclosed above.
Further, water-reducing agent is prepared at normal temperature, and without heating, low energy consumption, environmentally protective.
Further, solid content is preferably 39 ~ 41wt% in gained Early-strength polycarboxylate superplasticizer.
Early-strength water-reducing agent of the present invention can be used in cement and concrete component, and addition content is few, addition content 1% with
Under good diminishing and early function can be realized (in terms of cement), have to the early strength of cement and concrete component very aobvious
The castering action of work.
The invention has the benefit that
1, water-reducing agent of the present invention takes the unsaturated polyether with long side chain, has one to the early strength of cement and concrete component
Fixed humidification；The compound of the beta-unsaturated esters and unsaturated phosphinylidyne-containing amine group that select alcohol-containing amine groups is unsaturated early strong single
Body, alcohol amine groups therein and amide group can promote C3A aquation generates entringite, accelerates to enter hydrated cementitious accelerated period, contracting
Short cement setting time improves the production efficiency of cement and concrete component to improve early strength.Meanwhile water-reducing agent point
Carboxylic acid group and ester group in son can make it have good dispersibility and dispersion retentivity, also have to the raising of early strength
Positive effect.
2, Early-strength polycarboxylate superplasticizer of the present invention by unsaturated polyether, unsaturated carboxylic acid, alcohol-containing amine groups unsaturation
The compound of ester and unsaturated phosphinylidyne-containing amine group passes through free radical polymerization in redox system and under chain-transferring agent effect
Reaction is prepared.The water-reducing agent preparation method is simple, and preparation process is easy to control, and yield is high, is not necessarily to heat source, at low cost, green
Colour circle is protected, and early strength of concrete can be improved compared with low-dosage, with good application prospect and large-scale promotion
Application value.
Specific embodiment
In the following, the present invention is further expalined and is illustrated by specific embodiment, following embodiments, which only play, to be shown
Example effect, is not defined protection scope.
The preparation of the beta-unsaturated esters of alcohol-containing amine groups
Embodiment 1
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the DEIPA(diethanol monoisopropanolamine of 16.3g)
Be placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, control temperature less than 55 DEG C, then be added 9.8g maleic anhydride,
0.47g catalyst p-methyl benzenesulfonic acid and 0.0094g hydroquinone of polymerization retarder, control reaction temperature is at 105 DEG C or so, the reaction time
It is no longer reduced to acid value, terminates reaction, vacuum distillation removes propionic acid to get the beta-unsaturated esters A of alcohol-containing amine groups, structural formula is arrived
It is as follows:
Embodiment 2
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the EDIPA(monoethanol diisopropanolamine (DIPA) of 17.7g)
It is placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, and controls temperature less than 58 DEG C, the maleic acid of 9.8g is then added
Acid anhydride, 0.50g catalyst p-methyl benzenesulfonic acid and 0.01g hydroquinone of polymerization retarder control reaction temperature at 110 DEG C or so, reaction
Between no longer reduced to acid value, terminate reaction, vacuum distillation remove propionic acid to get arrive alcohol-containing amine groups beta-unsaturated esters B, structure
Formula is as follows:
Embodiment 3
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the DEIPA(diethanol monoisopropanolamine of 16.3g)
Be placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, control temperature at 60 DEG C, then be added 13.1g itaconic anhydride,
0.52g catalyst phosphorus pentoxide and 0.01g polymerization inhibitor p-hydroxyanisole control reaction temperature at 105 DEG C or so, reaction
Between do not reduced to acid value, terminate reaction, vacuum distillation remove propionic acid to get arrive alcohol-containing amine groups beta-unsaturated esters C, structure
Formula is as follows:
The preparation of Early-strength polycarboxylate superplasticizer
Embodiment 4
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters A 1.57g of the alcohol-containing amine groups of embodiment 1, acrylamide 0.71g, hydrogen peroxide 2.4g, Vitamin C
Sour 0.4g, thioacetic acid 0.72g.
120g isoamyl alcohol polyoxyethylene ether is added into the four-hole boiling flask for the 500mL being fixed on electric mixing device
(relative molecular mass 3000), deionized water 80g stirs to being completely dissolved, 2.4g hydrogen peroxide and 5.0g deionization is then added
The initiation liquid that water mixes, stir 10min after begin to use peristaltic pump be added dropwise A material and B material, A material by 10.4g acrylic acid,
Beta-unsaturated esters A, 0.71g acrylamide of alcohol-containing amine groups prepared by 1.57g embodiment 1 and the mixed solution of 40g deionized water
Composition, the at the uniform velocity completion of dropwise addition in 2 hours, B expect by 0.4g ascorbic acid, the mixing of 0.72g thioacetic acid and 50g deionized water
Solution composition, the at the uniform velocity completion of dropwise addition in 2.5 hours.After A material and B drop add, continue stirring curing 1.5 hours, then
Moisturizing to water-reducing agent solid content is 40%, i.e. synthesis Early-strength polycarboxylate superplasticizer.
Embodiment 5
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters B 1.57g of the alcohol-containing amine groups of embodiment 2,2- acrylamide-2-methyl propane sulfonic 2.1g, dioxygen
Water 2.4g, ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 6
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters C 1.57g of the alcohol-containing amine groups of embodiment 3, N hydroxymethyl acrylamide 1.1g, hydrogen peroxide 2.4g,
Ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 7
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 9.2g, beta-unsaturated esters B 1.8g of the alcohol-containing amine groups of embodiment 2,2- acrylamide-2-methyl propane sulfonic 2.1g, hydrogen peroxide
3.0g, ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 8
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters C 1.6g of the alcohol-containing amine groups of embodiment 3, N hydroxymethyl acrylamide 1.1g, hydrogen peroxide 2.4g,
Ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 9
The formula of Early-strength polycarboxylate superplasticizer are as follows: the isobutene alcohol polyoxyethylene ether 140g of relative molecular mass 3000, Malaysia
Sour 20g, beta-unsaturated esters A 3g of the alcohol-containing amine groups of embodiment 1, acrylamide 4g, ammonium persulfate 2g, sulphite 0.8g, first
Base sodium allylsulfonate 1g.
Preparation method is referring to embodiment 4.
Embodiment 10
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 160g, the methyl of relative molecular mass 5000
Acrylic acid 8g, beta-unsaturated esters A 6g of the alcohol-containing amine groups of embodiment 1, acrylamide 0.5g, sodium peroxydisulfate 4g, thiosulfate
0.3g, 3- mercaptopropionic acid 1.5g.
Preparation method is referring to embodiment 4.
Comparative example 1
Early-strength polycarboxylate superplasticizer is prepared according to the method for embodiment 4, unlike: it is added without the unsaturation of alcohol-containing amine groups
Ester A.
Comparative example 2
In equipped with stirring, temperature control and condensation reflux unit consersion unit, the triethanolamine of 14.9g is placed in four-hole bottle, is added
The propionic acid for entering 7.4g is neutralized, and controls temperature at 60 DEG C, then the maleic anhydride of addition 9.8g, 0.45g catalyst are to first
Benzene sulfonic acid and 0.0085g hydroquinone of polymerization retarder control reaction temperature at 105 DEG C or so, and the reaction time to acid value is not reducing,
Reaction is terminated, vacuum distillation removes propionic acid to get the beta-unsaturated esters D of alcohol-containing amine groups is arrived.
Early-strength polycarboxylate superplasticizer is prepared according to the method for embodiment 4, unlike: by the unsaturation of alcohol-containing amine groups
Ester A replaces with the beta-unsaturated esters D of alcohol-containing amine groups, and acrylamide is replaced with n-isopropyl acrylamide.
For the performance for verifying Early-strength polycarboxylate superplasticizer of the present invention, following experiments are carried out:
Example and the water-reducing agent 2.25g of comparative example, experimental water 157g, 42.5 ordinary silicon of scenery with hills and waters Eastern Mountain board PO respectively
Acid salt cement 450g is operated referring to GB.T17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " standard, measurement
Mortar specimen intensity.Test result is as shown in table 1.
By above-mentioned experimental result it can be found that adding the pressure resistance of mortar 1d, 3d, 28d of water-reducing agent of the embodiment of the present invention
Degree is significantly greater than the mortar compression strength for adding comparative example water-reducing agent, it can be seen that, early-strength polycarboxylic acids incorporated in the present invention subtracts
Aqua can be obviously promoted the early strength of cement-based material at low dosage.
The foregoing is only a preferred embodiment of the present invention, it will be appreciated by those of skill in the art that
In the case where not departing from present inventive concept and range defined by claims, various modifications can be made to the present invention, are added
Adduction replacement.
Claims (10)
1. a kind of Early-strength polycarboxylate superplasticizer, it is characterized in that being made of raw material from the following weight: unsaturated polyether 120 ~ 160
Part, 1 ~ 6 part of the beta-unsaturated esters of 8 ~ 20 parts of unsaturated carboxylic acid, alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group compound 0.5 ~ 4
Part, 2 ~ 4 parts of oxidant, 0.3 ~ 0.8 part of reducing agent, 0.6 ~ 1.5 part of chain-transferring agent；The beta-unsaturated esters of the alcohol-containing amine groups are by alcohol
Aminated compounds and unsaturated acid anhydride are obtained through esterification.
2. Early-strength polycarboxylate superplasticizer according to claim 1, it is characterized in that being made of raw material from the following weight: no
It is saturated 120 parts of polyethers, 10-11 part of unsaturated carboxylic acid, 1 ~ 2 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturation phosphinylidyne-containing amine group
0.5 ~ 1 part of compound, 2-3 parts of oxidant, 0.3-0.5 parts of reducing agent, 0.7-0.75 parts of chain-transferring agent.
3. Early-strength polycarboxylate superplasticizer according to claim 1 or 2, it is characterized in that: the alcamine compound is two
Ethyl alcohol monoisopropanolamine or monoethanol diisopropanolamine (DIPA), the unsaturated acid anhydride are maleic anhydride or itaconic anhydride；Preferably, alcohol
The molar ratio of aminated compounds and unsaturated acid anhydride is 0.8 ~ 1.2:1.
4. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturation amide-containing
The compound of group is acrylamide, 2- acrylamide-2-methyl propane sulfonic or N hydroxymethyl acrylamide.
5. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturated polyether is phase
To the isobutene alcohol polyoxyethylene ether or isoamyl alcohol polyoxyethylene ether of molecular mass 3000 ~ 5000；The unsaturated carboxylic acid
For one of acrylic acid, maleic acid, methacrylic acid and itaconic acid or a variety of；The oxidant is ammonium persulfate, persulfuric acid
One of sodium and hydrogen peroxide are a variety of；The reducing agent is bisulfites, sulphite, ascorbic acid and thiosulfuric acid
One or more of salt；The chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid or methacrylic sulfonic acid
Sodium.
6. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturation of alcohol-containing amine groups
The preparation method of ester includes: to mix alcamine compound with propionic acid, be then added unsaturated acid anhydride, catalyst and polymerization inhibitor into
Row esterification obtains the beta-unsaturated esters of alcohol-containing amine groups.
7. Early-strength polycarboxylate superplasticizer according to claim 6, it is characterized in that: the catalyst be p-methyl benzenesulfonic acid or
Phosphorus pentoxide, the polymerization inhibitor are hydroquinone or p-hydroxyanisole；Preferably, mole of alcamine compound and propionic acid
Than being the 2.5 ~ 3.5% of alcamine compound for the dosage of 0.8 ~ 1.2:1, catalyst, the dosage of polymerization inhibitor is alcamine compound
0.04 ~ 0.07%.
8. Early-strength polycarboxylate superplasticizer according to claim 6, it is characterized in that: alcamine compound and propionic acid 50 ~
It is reacted at 60 DEG C；Then it is reacted at 100 ~ 110 DEG C with unsaturated acid anhydride again.
9. a kind of preparation method of Early-strength polycarboxylate superplasticizer described in claim 1, it is characterized in that: the poly- carboxylic of the early-strength
Sour water-reducing agent by unsaturated polyether, unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group chemical combination
Object carries out Raolical polymerizable under the effect of oxidant, reducing agent and chain-transferring agent and is prepared.
10. preparation method according to claim 9, it is characterized in that the following steps are included:
(1) compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group is soluble in water, it obtains
A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) unsaturated polyether is soluble in water, it stirs evenly, oxidant is then added, stir 5-15 minutes, then start simultaneously
A material and B material is added dropwise, after wherein A drop adds 1.5 ~ 3h, B drop that 2 ~ 4h, A material and B is added to expect equal completion of dropwise addition, curing 1 that the reaction was continued
~ 3h, then adjusting solid content is 35 ~ 45wt%, obtains Early-strength polycarboxylate superplasticizer.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109867757A (en) * | 2019-02-21 | 2019-06-11 | 天水师范学院 | A kind of preparation method and system of stalk-starch conversion synthesis early strong concrete water-reducing agent |
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| CN112625232A (en) * | 2020-11-26 | 2021-04-09 | 山西佳维新材料股份有限公司 | Unsaturated amino polyoxyethylene ether and polycarboxylate superplasticizer as well as synthesis method and application thereof |
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| CN112708041A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN112708042A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112708046A (en) * | 2019-12-23 | 2021-04-27 | 科之杰新材料集团有限公司 | Ether super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113248663A (en) * | 2021-07-05 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
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| CN115745470A (en) * | 2022-11-11 | 2023-03-07 | 河海大学 | Cement-based material interface reinforcing agent and preparation method and application thereof |
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| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109867757B (en) * | 2019-02-21 | 2021-09-28 | 天水师范学院 | Preparation method and system for synthesizing early-strength concrete water reducer by modifying straw and starch |
| CN109867757A (en) * | 2019-02-21 | 2019-06-11 | 天水师范学院 | A kind of preparation method and system of stalk-starch conversion synthesis early strong concrete water-reducing agent |
| CN110451839A (en) * | 2019-08-20 | 2019-11-15 | 重庆腾治科技有限公司 | A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN110451839B (en) * | 2019-08-20 | 2021-11-02 | 重庆腾治科技有限公司 | Early-strength polycarboxylate superplasticizer and preparation method and application thereof |
| CN112708042B (en) * | 2019-11-25 | 2021-11-19 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112708041A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN112708042A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112608421B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| WO2021103473A1 (en) * | 2019-11-25 | 2021-06-03 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof |
| CN112608420B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN112708041B (en) * | 2019-11-25 | 2021-12-24 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN112708046A (en) * | 2019-12-23 | 2021-04-27 | 科之杰新材料集团有限公司 | Ether super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN112708046B (en) * | 2019-12-23 | 2022-10-28 | 科之杰新材料集团有限公司 | Ether super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN112708043A (en) * | 2019-12-23 | 2021-04-27 | 科之杰新材料集团有限公司 | Amine ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN112708043B (en) * | 2019-12-23 | 2022-05-10 | 科之杰新材料集团有限公司 | Amine ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN112625232A (en) * | 2020-11-26 | 2021-04-09 | 山西佳维新材料股份有限公司 | Unsaturated amino polyoxyethylene ether and polycarboxylate superplasticizer as well as synthesis method and application thereof |
| CN113248663A (en) * | 2021-07-05 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113248663B (en) * | 2021-07-05 | 2022-03-18 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113980196A (en) * | 2021-10-18 | 2022-01-28 | 佳化化学科技发展（上海）有限公司 | Polycarboxylic acid polymer and preparation method and application thereof |
| CN113980196B (en) * | 2021-10-18 | 2023-09-15 | 佳化化学科技发展（上海）有限公司 | Polycarboxylic acid polymer and preparation method and application thereof |
| CN115286749A (en) * | 2022-08-22 | 2022-11-04 | 上海抚佳精细化工有限公司 | Polycarboxylic acid polymer and preparation method and application thereof |
| CN115745470A (en) * | 2022-11-11 | 2023-03-07 | 河海大学 | Cement-based material interface reinforcing agent and preparation method and application thereof |
| CN115745470B (en) * | 2022-11-11 | 2023-07-21 | 河海大学 | Cement-based material interface reinforcing agent and preparation method and application thereof |
| CN116003018A (en) * | 2022-12-27 | 2023-04-25 | 麻城湖北大学产业技术研究院 | Additive for shortening setting time of cement concrete |
| CN116003018B (en) * | 2022-12-27 | 2024-02-02 | 麻城湖北大学产业技术研究院 | Additive for shortening setting time of cement concrete |
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