CN106565122A - Polymeric grinding aid, and preparation method and application thereof - Google Patents
Polymeric grinding aid, and preparation method and application thereof Download PDFInfo
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- CN106565122A CN106565122A CN201610911194.XA CN201610911194A CN106565122A CN 106565122 A CN106565122 A CN 106565122A CN 201610911194 A CN201610911194 A CN 201610911194A CN 106565122 A CN106565122 A CN 106565122A
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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
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a polymeric grinding aid, and a preparation method and an application thereof. The polymeric grinding aid comprises a polyether monomer, a sulfonic acid monomer, a carboxylic acid monomer and a modified triethanolamine monomer. The polymeric grinding aid prepared in the invention can be applied to cement. The prepared polymeric grinding aid has the advantages of good grinding aiding performance, high compressive strength, stable physicochemical performances, low effective proportion in cement, stable performances, reduction of unfavorable influences on the cement use process, and guaranteeing of safe proceeding of production.
Description
Technical field
The invention belongs to technical field of cement production, and in particular to a kind of Mcromolecular grinding aid and preparation method thereof and should
With.
Background technology
Existing grinding aid mostly is Compositional type grinding aid, is mainly obtained by triethanolamine compounding, and its volume is high, and cost is also occupied
It is high not under；Meanwhile, it is poor, quick to the addition change of volume in actual use to there is grinding aid stability in Compositional type grinding aid
The problems such as sense, the selectivity to cement additive are projected with additive poor compatibility, and these problems give actual production band
Many troubles are carried out.
The content of the invention
The present invention is directed to the deficiencies in the prior art, and primary and foremost purpose is to provide a kind of Mcromolecular grinding aid.
Second object of the present invention is to provide a kind of preparation method and application of Mcromolecular grinding aid.
To reach above-mentioned purpose, the solution of the present invention is：
A kind of Mcromolecular grinding aid, its structural formula are as follows：
Wherein, R is the one kind in R1, R2 and R3, and R1 is triethanolamine acrylate, and R2 is triethanolamine methacrylic acid
Ester, R3 are triethanolamine maleate, and B is H or CH3, a, b are the integer more than 0, n values between 20-80.
A kind of preparation method of Mcromolecular grinding aid, which comprises the steps：
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, intensification obtains mixed solution；
(2), in mixed solution Deca by modified triethanolamine class monomer, carboxylic acid type monomer and remainder polyethers list
Solution and initiator solution that body is configured to, after completion of dropping, react 1-3 hours, afterwards at 50-80 DEG C at 80 DEG C -120 DEG C
Lower insulation, obtains copolymer；
(3), treat that copolymer is lowered the temperature, add alkali liquor to adjust pH value, obtain macromolecule polymer solution；
(4), alcaminess material is added into macromolecule polymer solution, obtain Mcromolecular grinding aid.
Preferably, polyethers monomer is selected from allyl amine polyethers, and molecular weight is 400～2000.
Preferably, polyethers monomer is one or more of allyl polyglycol or methyl enol polyoxyethylene ether.
Preferably, carboxylic acid type monomer is the one kind in acrylic acid, methacrylic acid and maleic anhydride.
Preferably, initiator is redox initiator.
Preferably, alkali liquor is content 40 ± 10wt% sodium hydroxide solutions.
Preferably, alcaminess material is one or more of triethanolamine or triisopropanolamine.
Preferably, modified triethanolamine is triethanolamine acrylate, triethanolamine methacrylate and triethanolamine
One kind in maleate.
Preferably, sulfonic acid monomers are methylpropene sodium sulfonate.
Preferably, the mol ratio of methacrylic acid, acrylic acid, maleic anhydride and triethanolamine is 0-1:0‐1:0‐1:1.
Preferably, methylpropene sodium sulfonate, modified triethanolamine, allyl polyglycol and methyl enol polyoxyethylene ether
Mol ratio be 0.5-3:0.5‐2:0.25‐0.5:0‐0.5.
Preferably, the mol ratio of a part of polyethers monomer and remainder polyethers monomer is 1:1.
Preferably, in step (1), the temperature of intensification is 70～90 DEG C.
Preferably, in step (2), the time of Deca is 2～6h.
Preferably, in step (3), plus the pH value after people's alkali liquor is 7.0 ± 0.5.
Preferably, the preparation method of triethanolamine acrylate is comprised the following steps：
(1), triethanolamine and toluene equimolar are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of backflow, obtains
To the first mixed solution；
(2), when the temperature of the first mixed solution is down to 60 ± 20 DEG C, add 1 ± 0.6mol acrylic acid and 1-2wt% dense
Temperature is increased to 120 ± 10 DEG C by sulphuric acid, is maintained 2 ± 1h of thermotonuses, is obtained the first synthetic；
(3), after the cooling of the first synthetic, the pH of the first synthetic is adjusted to into 7.0 with 0.5 ± 0.2mol/LNaOH solution
± 0.5, obtain triethanolamine acrylate.
Preferably, the preparation method of triethanolamine methacrylate is comprised the following steps：
(1), triethanolamine and toluene equimolar are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of backflow, obtains
To the second mixed solution；
(2), when the temperature of the second mixed solution is down to 60 ± 20 DEG C, 1 ± 0.5mol methacrylic acids and 1- are added
Temperature is increased to 105 ± 15 DEG C by 2wt% concentrated sulphuric acids, is maintained 2 ± 1h of thermotonuses, is obtained the second synthetic；
(3), after the cooling of the second synthetic, the pH of the second synthetic is adjusted to 0.5 ± 0.2mol/L NaOH solutions
7.0 ± 0.5, obtain triethanolamine methacrylate.
Preferably, the preparation method of triethanolamine maleate is comprised the following steps：
(1), acetic acid and triethanolamine equimolar are mixed, reaction temperature is 60 ± 10 DEG C, obtains the 3rd mixed solution；
(2) 1 ± 0.5mol maleic anhydrides and 2 ± 1mol p-methyl benzenesulfonic acid are added in the 3rd mixed solution, temperature is maintained
4 ± 2h is reacted in 115 ± 15 DEG C, obtain the 3rd synthetic；
(3), after the cooling of the 3rd synthetic, the pH of the 3rd synthetic is adjusted to into 7.0 ± 0.5 with triethanolamine, three are obtained
Ethanolamine maleate.
A kind of above-mentioned Mcromolecular grinding aid is applied in cement.
Preferably, addition content of the Mcromolecular grinding aid in cement is：Mcromolecular grinding aid account for cement quality 0.02～
0.08%.
Due to adopting such scheme, the invention has the beneficial effects as follows：
First, by the flexible design to molecular structure in Mcromolecular grinding aid, the product of preparation can meet the present invention
Requirement of the different enterprises to cement, thus, the volume that occurs during which obviating cement use is high, grinding aid stability difference and into
The problems such as this is high.
Secondly, the Mcromolecular grinding aid that prepared by the present invention, its addition content in cement are 0.03wt%, relative to blank
For cement, its effective volume is low, grinding aid is functional, comprcssive strength is high, therefore, properties of product prepared by the present invention are stable,
Which is reduced to the adverse effect during cement use, it is ensured that the safety of production is carried out.
Finally, simple production process of the present invention, easy control of reaction conditions and to produce equipment requirements it is low, therefore, which has
Beneficial to industrialized popularization and application.
Specific embodiment
The invention provides a kind of Mcromolecular grinding aid and its preparation method and application.
<Mcromolecular grinding aid>
A kind of Mcromolecular grinding aid, its structural formula are as follows：
Wherein, R is the one kind in R1, R2 and R3, and R1 is triethanolamine acrylate, and R2 is triethanolamine methacrylic acid
Ester, R3 are triethanolamine maleate, and B is H or CH3, a, b are the integer more than 0, n values between 20-80.
<The preparation method of Mcromolecular grinding aid>
A kind of preparation method of Mcromolecular grinding aid, which comprises the steps：
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, intensification obtains mixed solution；
(2), in mixed solution Deca by modified triethanolamine class monomer, carboxylic acid type monomer and remainder polyethers list
Solution and initiator solution that body is configured to, after completion of dropping, react 1-3 hours, afterwards at 50-80 DEG C at 80 DEG C -120 DEG C
Lower insulation, obtains copolymer；
(3), treat that copolymer is lowered the temperature, add alkali liquor to adjust pH value, obtain macromolecule polymer solution；
(4), alcaminess material is added into macromolecule polymer solution, obtain Mcromolecular grinding aid.
Wherein, polyethers monomer can be allyl amine polyethers, and molecular weight is 400～2000；The preferably poly- second of pi-allyl
One or more of glycol (APEG) or methyl enol polyoxyethylene ether (TPEG).
Carboxylic acid type monomer can be preferably the one kind in acrylic acid (AA), methacrylic acid (MAA) or maleic anhydride (MA).
Initiator can be redox initiator, the preferably one kind in Ammonium persulfate. (APS) and potassium peroxydisulfate.
Initiator amount can be polyethers monomer, sulfonic acid monomers, modified triethanolamine class monomer and carboxylic acid type monomer
Gross mass 1～8%.
Alkali liquor can be preferably content 40 ± 10wt% sodium hydroxide solutions.
Alcaminess material can be preferably one or more of triethanolamine (TEA) or triisopropanolamine.
Modified triethanolamine can be preferably triethanolamine acrylate (TEA-AA), triethanolamine methacrylate
(TEA-MAA) one kind and in triethanolamine maleate (TEA-MA).
Sulfonic acid monomers can be preferably methylpropene sodium sulfonate (SMAS).
The mol ratio of methacrylic acid, acrylic acid, maleic anhydride and triethanolamine can be preferably 0-1:0‐1:0‐1:1.
Methylpropene sodium sulfonate, modified triethanolamine, allyl polyglycol and methyl enol polyoxyethylene ether mole
Than 0.5-3 can be preferably:0.5‐2:0.25‐0.5:0‐0.5.
The mol ratio of a part of polyethers monomer and remainder polyethers monomer can be 1:1.
In step (1), the temperature of intensification can be 70～90 DEG C, preferably 80 DEG C.
In step (2), the time of Deca can be 2～6h, preferably 3h.
In step (3), add the pH value after alkali liquor be 7.0 ± 0.5, preferably 7.0.
<The preparation method of triethanolamine acrylate>
The preparation method of triethanolamine acrylate is comprised the following steps：
(1), 1 ± 0.5mol triethanolamine and 1 ± 0.5mol toluene are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C times
1 ± 0.5h of stream, obtains the first mixed solution；
(2), when the temperature of the first mixed solution is down to 60 ± 20 DEG C, add 1 ± 0.6mol acrylic acid and 1-2wt% dense
Temperature is increased to 120 ± 10 DEG C by sulphuric acid (as catalyst), is maintained 2 ± 1h of thermotonuses, is obtained the first synthetic；
(3), after the cooling of the first synthetic, the pH of the first synthetic is adjusted to into 7.0 with 0.5 ± 0.2mol/LNaOH solution
± 0.5, obtain triethanolamine acrylate.
Wherein, in step (1), triethanolamine and toluene can be preferably 1mol.
In step (1), heated and stirred simultaneously rises warming middle-JIAO " intensification " and can be preferably 90 DEG C, and the time of backflow can be preferably
1h。
In step (2), the temperature that the first mixed solution declines can be preferably 60 DEG C, and acrylic acid can be preferably
1mol, elevated temperature can be preferably 120 DEG C, maintain the time of thermotonuses be preferably 1h.
In step (3), NaOH solution can be preferably 0.5mol/L, and the pH of the first synthetic can be preferably 7.0.
<The preparation method of triethanolamine methacrylate>
The preparation method of triethanolamine methacrylate is comprised the following steps：
(1), 1 ± 0.5mol triethanolamine and 1 ± 0.5mol toluene are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C times
1 ± 0.5h of stream, obtains the second mixed solution；
(2), when the temperature of the second mixed solution is down to 60 ± 20 DEG C, 1 ± 0.5mol methacrylic acids and 1- are added
Temperature is increased to 105 ± 15 DEG C by 2wt% concentrated sulphuric acids (as catalyst), is maintained 2 ± 1h of thermotonuses, is obtained the second synthesis
Thing；
(3), after the cooling of the second synthetic, the pH of the second synthetic is adjusted to 0.5 ± 0.2mol/L NaOH solutions
7.0 ± 0.5, obtain triethanolamine methacrylate.
Wherein, in step (1), triethanolamine and toluene can be preferably 1mol.
In step (1), heated and stirred simultaneously rises warming middle-JIAO " intensification " and can be preferably 90 DEG C, and the time of backflow can be preferably
1h。
In step (2), the temperature that the second mixed solution declines can be preferably 60 DEG C, and methacrylic acid can be preferably
1mol, elevated temperature can be preferably 105 DEG C, maintain the time of thermotonuses be preferably 1h.
In step (3), NaOH solution can be preferably 0.5mol/L, and the pH of the second synthetic can be preferably 7.0.
<The preparation method of triethanolamine maleate>
The preparation method of triethanolamine maleate is comprised the following steps：
(1), 1 ± 0.5mol acetic acid and 1 ± 0.5mol triethanolamine are mixed, reaction temperature is 60 ± 10 DEG C, obtains the
Three mixed solutions；
(2) 1 ± 0.5mol maleic anhydrides and 2 ± 1mol p-methyl benzenesulfonic acid are added (as catalysis in the 3rd mixed solution,
Agent), maintain temperature 4 ± 2h to be reacted in 115 ± 15 DEG C, obtain the 3rd synthetic；
(3), after the cooling of the 3rd synthetic, the pH of the 3rd synthetic is adjusted to into 7.0 ± 0.5 with triethanolamine, three are obtained
Ethanolamine maleate.
Wherein, in step (1), acetic acid and triethanolamine can be preferably 1mol.
In step (1), the temperature of reaction can be preferably 60 DEG C.
In step (2), maleic anhydride and p-methyl benzenesulfonic acid can be preferably 1mol, and the temperature of maintenance can be preferably
115 DEG C, the time of reaction can be preferably 4h.
In step (3), the pH of the 3rd synthetic can be preferably 7.0.
<The application of Mcromolecular grinding aid>
Can be applied in cement by Mcromolecular grinding aid prepared by above-mentioned preparation method.
Wherein, addition content of the Mcromolecular grinding aid in cement can for Mcromolecular grinding aid account for cement quality 0.02～
0.08%.
Below in conjunction with illustrated embodiment, the present invention is further illustrated.
Embodiment 1：
The preparation method of the Mcromolecular grinding aid of the present embodiment, which comprises the following steps：
(1), by 20g allyl polyglycols (APEG), 3.95g methylpropene sodium sulfonates (SMAS) and 33g deionized waters
Mixing, is warming up to 80 DEG C and obtains mixed solution；
(2), to Deca A liquid in above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine methacrylates
(TEA-MAA), the solution that 10g allyl polyglycols (APEG) and 15g deionized waters are configured to, B liquid are by the 3% of 5.5g
The solution that Ammonium persulfate. (APS) (as initiator) and 15g deionized waters are configured to, A liquid and the continuous Deca of B liquid stir 3h,
1h is reacted at 90 DEG C, is incubated at 70 DEG C afterwards, is obtained copolymer；
(3), treat that copolymer is cooled to room temperature, add the neutralization of 40wt% sodium hydroxide solutions, pH is adjusted to 7.0, obtain height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtain Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG) and triethanolamine methacrylate
(TEA-MAA) mol ratio is 1:0.5:1.
In step (1), methylpropene sodium sulfonate (SMAS), modified triethanolamine, allyl polyglycol (APEG)
Mol ratio is in 0.5-3:0.5‐2:It is possible within 0.25-0.5.
In step (1), the temperature of intensification is possible within 70～90 DEG C.
In step (2), the time of Deca within 2～6h, the temperature of reaction within 80 DEG C～120 DEG C, reaction
Time can be with 1～3h.
In step (2), the temperature of insulation is possible within 50～80 DEG C.
In step (3), the content of sodium hydroxide is possible within 40 ± 10wt%.
In step (4), plus the pH value in alkali liquor with after is also possible within 7.0 ± 0.5.
Embodiment 2：
The preparation method of the Mcromolecular grinding aid of the present embodiment, which comprises the following steps：
(1), by 20g allyl polyglycols (APEG), 3.95g methylpropene sodium sulfonates (SMAS) and 33g deionized waters
Mixing, is warming up to 80 DEG C and obtains mixed solution；
(2), to Deca A liquid in above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine methacrylates
(TEA-MAA), the solution that 10g allyl polyglycols (APEG) and 15g deionized waters are configured to, B liquid are by the 4% of 5.5g
The solution that Ammonium persulfate. (APS) (as initiator) and 15g deionized waters are configured to, A liquid and the continuous Deca of B liquid stir 3h,
1h is reacted at 90 DEG C, is incubated at 70 DEG C afterwards, is obtained copolymer；
(3), treat that copolymer is cooled to room temperature, add the neutralization of 40wt% sodium hydroxide solutions, pH is adjusted to 7.0, obtain height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtain Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG) and triethanolamine methacrylate
(TEA-MAA) mol ratio is 1:0.5:1.
Embodiment 3：
The preparation method of the Mcromolecular grinding aid of the present embodiment, which comprises the following steps：
(1), 10g allyl polyglycols (APEG), 3.95g methylpropene sodium sulfonates (SMAS), 10g methyl enol are gathered
Oxygen vinyl Ether (TPEG) and the mixing of 33g deionized waters, are warming up to 80 DEG C and obtain mixed solution；
(2), to Deca A liquid in above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine maleate (TEA-
What MA), 5g allyl polyglycols (APEG), 5g methyl enol polyoxyethylene ether (TPEG) and 15g deionized waters were configured to is molten
Liquid, B liquid are the solution being configured to by 5% Ammonium persulfate. (APS) (as initiator) and 15g deionized waters of 5.5g, A liquid and B
The continuous Deca of liquid stirs 3h, and 1h is reacted at 90 DEG C, is incubated afterwards, obtains copolymer at 70 DEG C；
(3), treat that copolymer is cooled to room temperature, add the neutralization of 40wt% sodium hydroxide solutions, pH is adjusted to 7.0, obtain height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtain Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG), methyl enol polyoxyethylene ether
(TPEG) and triethanolamine maleate (TEA-MA) mol ratio be 1:0.25:0.25:1.
<Experiment>
Carried out as material respectively with the cement for adding the product of above-described embodiment with blank cement (not mixing any auxiliary agent)
It is following to test.
The purpose of this experiment is the grinding aid performance and physics for adding the cement of Mcromolecular grinding aid under the suitable volume of research
The situation of change of performance.
The cement of addition 0.03wt% Mcromolecular grinding aids and blank cement (not mixing any auxiliary agent) are tested respectively,
The grinding aid performance and physical property situation of change of the Mcromolecular grinding aid cement and blank cement under 0.03wt% volumes are determined, such as
Shown in table 1.
Table 1：The grinding aid performance and physical property change of the cement of addition 0.03wt% Mcromolecular grinding aids and blank cement
Value
Wherein：A0 is blank cement, and A1, A2 and A3 respectively add the water of the Mcromolecular grinding aid of embodiment 1,2 and 3
Mud.
Above-mentioned experiment in strict accordance with《Common portland cement》(National Standard of the People's Republic of China GB175-2007) and
《Cement grinding aid industry standard》(building material industry standard JC/T667-2004) and carry out.
As can be seen from the above table, under suitable volume, add the cement of Mcromolecular grinding aid relative to blank cement
Speech, as the prolongation of grinding time, the cement grinding for adding Mcromolecular grinding aid obtain more and more thinner, its specific surface area has larger
Improve；And the fineness of cement grinding and the inversely proportional relation of value is tailed over, and in the case of above-mentioned identical grinding, addition macromolecule grinding aid
45 μm of the cement of agent tail over value and have declined, therefore, Mcromolecular grinding aid prepared by the present invention shows good grinding aid
Energy；Additionally, during 3d and 28d, the compression strength value for adding the cement of Mcromolecular grinding aid has by a relatively large margin than blank cement
Raising, the comprcssive strength for further relating to the Mcromolecular grinding aid of present invention preparation is high；Addition 0.03wt% Mcromolecular grinding aids
Cement and blank cement the thick water consumption of standard and change setting time it is little, the physical and chemical performance for both illustrate is held at surely
In fixed acceptability limit, i.e., physical and chemical performance is stable.
The above-mentioned description to embodiment is to be understood that for the ease of those skilled in the art and use this
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiment, without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment.
Those skilled in the art's principle of the invention, the improvement made without departing from scope of the invention and modification all should be at these
Within the protection domain of invention.
Claims (9)
1. a kind of Mcromolecular grinding aid, it is characterised in that：Structural formula is as follows：
Wherein, R is the one kind in R1, R2 and R3, and R1 is triethanolamine acrylate, and R2 is triethanolamine methacrylate,
R3 is triethanolamine maleate, and B is H or CH3, and a, b are the integer more than 0, n values between 20-80.
2. a kind of preparation method of Mcromolecular grinding aid as claimed in claim 1, it is characterised in that：Comprise the steps：
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, intensification obtains mixed solution；
(2), in the mixed solution Deca by modified triethanolamine class monomer, carboxylic acid type monomer and remainder polyethers list
Solution and initiator solution that body is configured to, after completion of dropping, react 1-3 hours, afterwards at 50-80 DEG C at 80 DEG C -120 DEG C
Lower insulation, obtains copolymer；
(3) the copolymer cooling, is treated, is added alkali liquor to adjust pH value, is obtained macromolecule polymer solution；
(4), alcaminess material is added into the macromolecule polymer solution, obtain the Mcromolecular grinding aid.
3. preparation method according to claim 2, it is characterised in that：The polyethers monomer is selected from allyl amine polyethers,
Molecular weight is 400～2000；
Preferably, the polyethers monomer is one or more of allyl polyglycol or methyl enol polyoxyethylene ether；With/
Or,
The carboxylic acid type monomer is the one kind in acrylic acid, methacrylic acid and maleic anhydride；And/or,
The initiator is redox initiator；And/or,
The alkali liquor is content 40 ± 10wt% sodium hydroxide solutions；And/or,
The alcaminess material is one or more of triethanolamine or triisopropanolamine；And/or,
The modified triethanolamine is triethanolamine acrylate, triethanolamine methacrylate and triethanolamine maleate
In one kind；And/or,
The sulfonic acid monomers are methylpropene sodium sulfonate；And/or,
The mol ratio of the methacrylic acid, the acrylic acid, the maleic anhydride and the triethanolamine is 0-1:0‐1:0‐
1:1；And/or,
The methylpropene sodium sulfonate, the modified triethanolamine, the allyl polyglycol and the methyl enol polyoxy
The mol ratio of vinyl Ether is 0.5-3:0.5‐2:0.25‐0.5:0‐0.5.
4. preparation method according to claim 2, it is characterised in that：A part of polyethers monomer and the remainder
The mol ratio of segregation ether type monomer is 1:1；And/or,
In the step (1), the temperature of intensification is 70～90 DEG C；And/or,
In the step (2), the time of Deca is 2～6h；And/or,
In the step (3), the pH value after alkali liquor is added to be 7.0 ± 0.5.
5. Mcromolecular grinding aid according to claim 3, it is characterised in that：The preparation side of the triethanolamine acrylate
Method is comprised the following steps：
(1), triethanolamine and toluene equimolar are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of backflow, obtains the
One mixed solution；
(2), when the temperature of first mixed solution is down to 60 ± 20 DEG C, add 1 ± 0.6mol acrylic acid and 1-2wt% dense
Temperature is increased to 120 ± 10 DEG C by sulphuric acid, is maintained 2 ± 1h of thermotonuses, is obtained the first synthetic；
(3), after first synthetic cooling, the pH of first synthetic is adjusted with 0.5 ± 0.2mol/LNaOH solution
To 7.0 ± 0.5, the triethanolamine acrylate is obtained.
6. Mcromolecular grinding aid according to claim 3, it is characterised in that：The system of the triethanolamine methacrylate
Preparation Method is comprised the following steps：
(1), triethanolamine and toluene equimolar are mixed, heated and stirred is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of backflow, obtains the
Two mixed solutions；
(2), when the temperature of second mixed solution is down to 60 ± 20 DEG C, 1 ± 0.5mol methacrylic acids and 1- are added
Temperature is increased to 105 ± 15 DEG C by 2wt% concentrated sulphuric acids, is maintained 2 ± 1h of thermotonuses, is obtained the second synthetic；
(3), after second synthetic cooling, the pH of second synthetic is adjusted with 0.5 ± 0.2mol/L NaOH solutions
To 7.0 ± 0.5, the triethanolamine methacrylate is obtained.
7. Mcromolecular grinding aid according to claim 3, it is characterised in that：The preparation side of the triethanolamine maleate
Method is comprised the following steps：
(1), acetic acid and triethanolamine equimolar are mixed, reaction temperature is 60 ± 10 DEG C, obtains the 3rd mixed solution；
(2) 1 ± 0.5mol maleic anhydrides and 2 ± 1mol p-methyl benzenesulfonic acid are added in the 3rd mixed solution, temperature is maintained
4 ± 2h is reacted in 115 ± 15 DEG C, obtain the 3rd synthetic；
(3), after the 3rd synthetic cooling, the pH of the 3rd synthetic is adjusted to into 7.0 ± 0.5 with triethanolamine, is obtained
To the triethanolamine maleate.
8. a kind of Mcromolecular grinding aid as claimed in claim 1 is applied in cement.
9. application according to claim 8, it is characterised in that：Addition content of the Mcromolecular grinding aid in cement be：
The Mcromolecular grinding aid accounts for the 0.02～0.08% of the cement quality.
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| CN109593206A (en) * | 2018-11-07 | 2019-04-09 | 上海东升新材料有限公司 | A kind of hyperbranched coarse whiting ground dispersant and preparation method thereof |
| CN109748535A (en) * | 2019-03-29 | 2019-05-14 | 日照弗尔曼新材料科技有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN116143439A (en) * | 2023-02-20 | 2023-05-23 | 宜春红狮水泥有限公司 | Preparation method of novel cement grinding aid |
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| CN102249586A (en) * | 2011-05-13 | 2011-11-23 | 洛阳万顺建材有限公司 | Grinding-assistant reinforcing agent for mineral powder |
| CN102603226A (en) * | 2012-03-20 | 2012-07-25 | 柳州宝能建材科技有限公司 | Liquid cement grinding aid |
| CN102745917A (en) * | 2012-06-29 | 2012-10-24 | 酒钢(集团)宏达建材有限责任公司 | Slag vertical mill grinding assisting activating agent and its compounding method |
| CN102942324A (en) * | 2012-12-04 | 2013-02-27 | 山东宏艺科技股份有限公司 | Grinding aid for slag cement |
| CN105731855A (en) * | 2016-01-11 | 2016-07-06 | 东源县弘朝科技有限公司 | Vertical mill slag grinding aid and preparation method thereof |
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| CN102249586A (en) * | 2011-05-13 | 2011-11-23 | 洛阳万顺建材有限公司 | Grinding-assistant reinforcing agent for mineral powder |
| CN102603226A (en) * | 2012-03-20 | 2012-07-25 | 柳州宝能建材科技有限公司 | Liquid cement grinding aid |
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| CN102942324A (en) * | 2012-12-04 | 2013-02-27 | 山东宏艺科技股份有限公司 | Grinding aid for slag cement |
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| CN109593206A (en) * | 2018-11-07 | 2019-04-09 | 上海东升新材料有限公司 | A kind of hyperbranched coarse whiting ground dispersant and preparation method thereof |
| CN109748535A (en) * | 2019-03-29 | 2019-05-14 | 日照弗尔曼新材料科技有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN109748535B (en) * | 2019-03-29 | 2021-05-28 | 日照弗尔曼新材料科技有限公司 | Cement grinding aid and preparation method thereof |
| CN116143439A (en) * | 2023-02-20 | 2023-05-23 | 宜春红狮水泥有限公司 | Preparation method of novel cement grinding aid |
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