CN106565122B - Mcromolecular grinding aid and its preparation method and application - Google Patents
Mcromolecular grinding aid and its preparation method and application Download PDFInfo
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- CN106565122B CN106565122B CN201610911194.XA CN201610911194A CN106565122B CN 106565122 B CN106565122 B CN 106565122B CN 201610911194 A CN201610911194 A CN 201610911194A CN 106565122 B CN106565122 B CN 106565122B
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- triethanolamine
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
Abstract
The present invention provides a kind of Mcromolecular grinding aid and its preparation method and application, raw materials for production include: polyethers monomer, sulfonic acid monomers, carboxylic acid type monomer and modified triethanolamine class monomer etc..Mcromolecular grinding aid prepared by the present invention is applied in cement.Mcromolecular grinding aid prepared by the present invention has good grinding aid performance and higher compression strength, physical and chemical performance also stable；In addition, its effective volume in cement is lower, performance is stablized, and reduces it to the adverse effect in cement use process, ensure that the safety of production carries out.
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 answer
With.
Background technique
Existing grinding aid is mostly Compositional type grinding aid, mainly compounds to obtain by triethanolamine, and volume is high, and cost also occupies
It is high not under；Meanwhile to there is grinding aid stability in actual use poor, quick to the addition of volume variation for Compositional type grinding aid
The problems such as sense, and additive poor compatibility prominent to the selectivity of cement additive, and these problems give actual production band
Many troubles are carried out.
Summary of the invention
In view of the deficiencies of the prior art, primary and foremost purpose is to provide a kind of Mcromolecular grinding aid to the present invention.
Second object of the present invention is to provide a kind of preparation method and application of Mcromolecular grinding aid.
In order to achieve the above objectives, solution of the invention is:
A kind of Mcromolecular grinding aid, structural formula are as follows:
Wherein, one of R R1, R2 and R3, R1 are triethanolamine acrylate, and R2 is triethanolamine methacrylic acid
Ester, R3 are triethanolamine maleate, and B is H or CH3, a, b are the integer greater than 0, n value between 20-80.
A kind of preparation method of Mcromolecular grinding aid comprising following steps:
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, heating obtains mixed solution；
(2), it is added dropwise in mixed solution by modified triethanolamine class monomer, carboxylic acid type monomer and remainder polyethers list
The solution and initiator solution that body is configured to after being added dropwise, react 1-3 hours, later at 50-80 DEG C at 80 DEG C -120 DEG C
Lower heat preservation, obtains copolymer；
(3), cool down to copolymer, lye is added and adjusts pH value, obtains macromolecule polymer solution；
(4), hydramine substance is added into macromolecule polymer solution, obtains 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 one of acrylic acid, methacrylic acid and maleic anhydride.
Preferably, initiator is redox initiator.
Preferably, lye is 40 ± 10wt% of content sodium hydroxide solution.
Preferably, hydramine substance is one or more of triethanolamine or triisopropanolamine.
Preferably, modified triethanolamine is triethanolamine acrylate, triethanolamine methacrylate and triethanolamine
One of maleate.
Preferably, sulfonic acid monomers are methylpropene sodium sulfonate.
Preferably, the molar 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
Molar ratio be 0.5-3:0.5-2:0.25-0.5:0-0.5.
Preferably, the molar ratio of a part of polyethers monomer and remainder polyethers monomer is 1:1.
Preferably, in step (1), the temperature of heating is 70~90 DEG C.
Preferably, in step (2), the time of dropwise addition is 2~6h.
Preferably, in step (3), the pH value after adding people's lye is 7.0 ± 0.5.
Preferably, triethanolamine acrylate preparation method the following steps are included:
(1), triethanolamine and toluene equimolar are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of reflux, obtains
To the first mixed solution；
(2), when the temperature of the first mixed solution is down to 60 ± 20 DEG C, 1 ± 0.6mol acrylic acid is added and 1-2wt% is dense
Sulfuric acid raises the temperature to 120 ± 10 DEG C, maintains 2 ± 1h of thermotonus, obtains the first synthetic；
(3), after the first synthetic is cooling, the pH of the first synthetic is adjusted to 7.0 with 0.5 ± 0.2mol/LNaOH solution
± 0.5, obtain triethanolamine acrylate.
Preferably, triethanolamine methacrylate preparation method the following steps are included:
(1), triethanolamine and toluene equimolar are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of reflux, 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 acid and 1- is added
The 2wt% concentrated sulfuric acid raises the temperature to 105 ± 15 DEG C, maintains 2 ± 1h of thermotonus, obtains the second synthetic；
(3), after the second synthetic is cooling, the pH of the second synthetic is adjusted to 0.5 ± 0.2mol/L NaOH solution
7.0 ± 0.5, obtain triethanolamine methacrylate.
Preferably, triethanolamine maleate preparation method the following steps are included:
(1), acetic acid and triethanolamine equimolar are mixed, reaction temperature is 60 ± 10 DEG C, obtains third mixed solution；
(2), to addition 1 ± 0.5mol maleic anhydride and 2 ± 1mol p-methyl benzenesulfonic acid in third mixed solution, temperature is maintained
In 115 ± 15 DEG C of 4 ± 2h of reaction, third synthetic is obtained；
(3), after third synthetic is cooling, the pH of third synthetic is adjusted to 7.0 ± 0.5 with triethanolamine, obtains three
Ethanol amine maleate.
A kind of above-mentioned Mcromolecular grinding aid is applied in cement.
Preferably, addition content of the Mcromolecular grinding aid in cement are as follows: Mcromolecular grinding aid account for cement quality 0.02~
0.08%.
By adopting the above scheme, the beneficial effects of the present invention are:
Firstly, the present invention, by the flexible design to molecular structure in Mcromolecular grinding aid, the product of preparation can satisfy
Requirement of the different enterprises to cement, thus, high, grinding aid stability difference which obviate the volumes occurred in cement use process and at
The problems such as this is high.
Secondly, Mcromolecular grinding aid prepared by the present invention, the addition content in cement is 0.03wt%, relative to blank
For cement, effective volume is low, grinding aid is functional, compression strength is high, and therefore, products of the present invention performance is stablized,
Reduce it to the adverse effect in cement use process, ensure that the safety of production carries out.
Finally, simple production process of the present invention, easy control of reaction conditions and to production equipment require it is low, therefore, have
Conducive to industrialized popularization and application.
Specific embodiment
The present invention provides a kind of Mcromolecular grinding aids and its preparation method and application.
<Mcromolecular grinding aid>
A kind of Mcromolecular grinding aid, structural formula are as follows:
Wherein, one of R R1, R2 and R3, R1 are triethanolamine acrylate, and R2 is triethanolamine methacrylic acid
Ester, R3 are triethanolamine maleate, and B is H or CH3, a, b are the integer greater than 0, n value between 20-80.
<preparation method of Mcromolecular grinding aid>
A kind of preparation method of Mcromolecular grinding aid comprising following steps:
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, heating obtains mixed solution；
(2), it is added dropwise in mixed solution by modified triethanolamine class monomer, carboxylic acid type monomer and remainder polyethers list
The solution and initiator solution that body is configured to after being added dropwise, react 1-3 hours, later at 50-80 DEG C at 80 DEG C -120 DEG C
Lower heat preservation, obtains copolymer；
(3), cool down to copolymer, lye is added and adjusts pH value, obtains macromolecule polymer solution；
(4), hydramine substance is added into macromolecule polymer solution, obtains Mcromolecular grinding aid.
Wherein, polyethers monomer can be allyl amine polyethers, and molecular weight is 400~2000；The preferably poly- second of allyl
One or more of glycol (APEG) or methyl enol polyoxyethylene ether (TPEG).
Carboxylic acid type monomer can be preferably one of acrylic acid (AA), methacrylic acid (MAA) or maleic anhydride (MA).
Initiator can be redox initiator, preferably one of 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%.
Lye can be preferably content 40 ± 10wt% sodium hydroxide solution.
Hydramine substance can be preferably one or more of triethanolamine (TEA) or triisopropanolamine.
Modified triethanolamine can be preferably triethanolamine acrylate (TEA-AA), triethanolamine methacrylate
(TEA-MAA) and one of triethanolamine maleate (TEA-MA).
Sulfonic acid monomers can be preferably methylpropene sodium sulfonate (SMAS).
Methacrylic acid, acrylic acid, maleic anhydride and triethanolamine molar ratio can be preferably 0-1:0-1:0-1:1.
Methylpropene sodium sulfonate, modified triethanolamine, allyl polyglycol and methyl enol polyoxyethylene ether mole
Than that can be preferably 0.5-3:0.5-2:0.25-0.5:0-0.5.
The molar ratio of a part of polyethers monomer and remainder polyethers monomer can be 1:1.
In step (1), the temperature of heating can be 70~90 DEG C, preferably 80 DEG C.
In step (2), the time of dropwise addition can be 2~6h, preferably 3h.
In step (3), the pH value after lye is added can be 7.0 ± 0.5, preferably 7.0.
<preparation method of triethanolamine acrylate>
The preparation method of triethanolamine acrylate the following steps are included:
(1), 1 ± 0.5mol triethanolamine and 1 ± 0.5mol toluene are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C times
1 ± 0.5h is flowed, the first mixed solution is obtained；
(2), when the temperature of the first mixed solution is down to 60 ± 20 DEG C, 1 ± 0.6mol acrylic acid is added and 1-2wt% is dense
Sulfuric acid (as catalyst) raises the temperature to 120 ± 10 DEG C, maintains 2 ± 1h of thermotonus, obtains the first synthetic；
(3), after the first synthetic is cooling, the pH of the first synthetic is adjusted to 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), heating stirring and in heating up " heating " can be preferably 90 DEG C, the time of reflux can be preferably
1h。
In step (2), the temperature of the first mixed solution decline can be preferably 60 DEG C, and acrylic acid can be preferably
1mol, raised temperature can be preferably 120 DEG C, and maintaining the time of thermotonus can 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.
<preparation method of triethanolamine methacrylate>
The preparation method of triethanolamine methacrylate the following steps are included:
(1), 1 ± 0.5mol triethanolamine and 1 ± 0.5mol toluene are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C times
1 ± 0.5h is flowed, the second mixed solution is obtained；
(2), when the temperature of the second mixed solution is down to 60 ± 20 DEG C, 1 ± 0.5mol methacrylic acid and 1- is added
The 2wt% concentrated sulfuric acid (as catalyst) raises the temperature to 105 ± 15 DEG C, maintains 2 ± 1h of thermotonus, obtains the second synthesis
Object；
(3), after the second synthetic is cooling, the pH of the second synthetic is adjusted to 0.5 ± 0.2mol/L NaOH solution
7.0 ± 0.5, obtain triethanolamine methacrylate.
Wherein, in step (1), triethanolamine and toluene can be preferably 1mol.
In step (1), heating stirring and in heating up " heating " can be preferably 90 DEG C, the time of reflux can be preferably
1h。
In step (2), the temperature of the second mixed solution decline can be preferably 60 DEG C, and methacrylic acid can be preferably
1mol, raised temperature can be preferably 105 DEG C, and maintaining the time of thermotonus can 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.
<preparation method of triethanolamine maleate>
The preparation method of triethanolamine maleate the following steps are included:
(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), to addition 1 ± 0.5mol maleic anhydride in third mixed solution and 2 ± 1mol p-methyl benzenesulfonic acid (as catalysis
Agent), it maintains temperature in 115 ± 15 DEG C of 4 ± 2h of reaction, obtains third synthetic；
(3), after third synthetic is cooling, the pH of third synthetic is adjusted to 7.0 ± 0.5 with triethanolamine, obtains three
Ethanol amine 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 third synthetic can be preferably 7.0.
<application of Mcromolecular grinding aid>
The Mcromolecular grinding aid prepared by above-mentioned preparation method can be applied in cement.
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 comprising following steps:
(1), by 20g allyl polyglycol (APEG), 3.95g methylpropene sodium sulfonate (SMAS) and 33g deionized water
Mixing, is warming up to 80 DEG C and obtains mixed solution；
(2), A liquid is added dropwise into above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine methacrylate
(TEA-MAA), the solution that 10g allyl polyglycol (APEG) and 15g deionized water are configured to, B liquid are by the 3% of 5.5g
Stirring 3h is continuously added dropwise in the solution that ammonium persulfate (APS) (as initiator) and 15g deionized water are configured to, A liquid and B liquid,
1h is reacted at 90 DEG C, is kept the temperature at 70 DEG C later, is obtained copolymer；
(3), it is cooled to room temperature to copolymer, 40wt% sodium hydroxide solution is added and neutralizes, adjusts pH to 7.0, obtains height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtains Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG) and triethanolamine methacrylate
(TEA-MAA) molar ratio is 1:0.5:1.
In step (1), methylpropene sodium sulfonate (SMAS), modified triethanolamine, allyl polyglycol (APEG)
Molar ratio is possible within 0.5-3:0.5-2:0.25-0.5.
In step (1), the temperature of heating is possible within 70~90 DEG C.
In step (2), the time of dropwise addition within 2~6h, the temperature of reaction within 80 DEG C~120 DEG C, reaction
Time can be within 1~3h.
In step (2), the temperature of heat preservation is possible within 50~80 DEG C.
In step (3), the content of sodium hydroxide is possible within 40 ± 10wt%.
In step (4), the pH value after adding lye to neutralize is also possible within 7.0 ± 0.5.
Embodiment 2:
The preparation method of the Mcromolecular grinding aid of the present embodiment comprising following steps:
(1), by 20g allyl polyglycol (APEG), 3.95g methylpropene sodium sulfonate (SMAS) and 33g deionized water
Mixing, is warming up to 80 DEG C and obtains mixed solution；
(2), A liquid is added dropwise into above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine methacrylate
(TEA-MAA), the solution that 10g allyl polyglycol (APEG) and 15g deionized water are configured to, B liquid are by the 4% of 5.5g
Stirring 3h is continuously added dropwise in the solution that ammonium persulfate (APS) (as initiator) and 15g deionized water are configured to, A liquid and B liquid,
1h is reacted at 90 DEG C, is kept the temperature at 70 DEG C later, is obtained copolymer；
(3), it is cooled to room temperature to copolymer, 40wt% sodium hydroxide solution is added and neutralizes, adjusts pH to 7.0, obtains height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtains Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG) and triethanolamine methacrylate
(TEA-MAA) molar ratio is 1:0.5:1.
Embodiment 3:
The preparation method of the Mcromolecular grinding aid of the present embodiment comprising following steps:
(1), 10g allyl polyglycol (APEG), 3.95g methylpropene sodium sulfonate (SMAS), 10g methyl enol is poly-
Ethylene oxide ether (TPEG) and the mixing of 33g deionized water, are warming up to 80 DEG C and obtain mixed solution；
(2), A liquid is added dropwise into above-mentioned mixed solution and B liquid, A liquid is by 2.15g triethanolamine maleate (TEA-
MA), 5g allyl polyglycol (APEG), 5g methyl enol polyoxyethylene ether (TPEG) and 15g deionized water are configured to molten
Liquid, B liquid are the solution being configured to by 5% ammonium persulfate (APS) (as initiator) and 15g deionized water of 5.5g, A liquid and B
Stirring 3h is continuously added dropwise in liquid, and 1h is reacted at 90 DEG C, keeps the temperature at 70 DEG C later, obtains copolymer；
(3), it is cooled to room temperature to copolymer, 40wt% sodium hydroxide solution is added and neutralizes, adjusts pH to 7.0, obtains height
Molecularly Imprinted Polymer solution；
(4), 5g triethanolamine (TEA) is added into macromolecule polymer solution, obtains Mcromolecular grinding aid.
Wherein, methylpropene sodium sulfonate (SMAS), allyl polyglycol (APEG), methyl enol polyoxyethylene ether
(TPEG) and the molar ratio of triethanolamine maleate (TEA-MA) is 1:0.25:0.25:1.
<experiment>
It is that material carries out respectively to add cement and the blank cement (not mixing any auxiliary agent) of the product of above-described embodiment
Following experiment.
The purpose of this experiment is to study under suitable volume, adds the grinding aid performance and physics of the cement of Mcromolecular grinding aid
The situation of change of performance.
The cement and blank cement (not mixing any auxiliary agent) for adding 0.03wt% Mcromolecular grinding aid 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% volume are measured, such as
Shown in table 1.
Table 1: grinding aid performance and the physical property variation of the cement and blank cement of addition 0.03wt% Mcromolecular grinding aid
Value
Wherein: A0 is blank cement, and A1, A2 and A3 are respectively the water for adding 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 professional 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 and
Speech, with the extension of grinding time, the cement grinding for adding Mcromolecular grinding aid obtains more and more thinner, and specific surface area has larger
It improves；And the fineness of cement grinding and the inversely proportional relationship of value is tailed over, and in above-mentioned identical grinding, addition macromolecule grinding aid
45 μm of the cement of agent tail over value and are declined, and therefore, Mcromolecular grinding aid prepared by the present invention shows good grinding aid
Energy；In addition, there is by a relatively large margin the compression strength value for adding the cement of Mcromolecular grinding aid than blank cement when 3d and 28d
Raising, the compression strength for further relating to Mcromolecular grinding aid prepared by the present invention is high；Add 0.03wt% Mcromolecular grinding aid
Cement and blank cement the thick water consumption of standard and setting time variation less, the physical and chemical performance both illustrated is held at surely
In fixed acceptability limit, i.e., physical and chemical performance is stablized.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
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 embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (15)
1. a kind of Mcromolecular grinding aid, it is characterised in that: structural formula is as follows:
Wherein, one of R R1, R2 and R3, R1 are triethanolamine acrylate, and R2 is triethanolamine methacrylate,
R3 is triethanolamine maleate, and B is H or CH3One or more of, a, b are the integer greater than 0, and n takes between 20-80
Value；
The preparation method of the Mcromolecular grinding aid includes the following steps:
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, heating obtains mixed solution；
(2), it is added dropwise in the mixed solution and is configured to by modified triethanolamine class monomer and remainder polyethers monomer
Solution and initiator solution after being added dropwise, react 1-3 hours at 80-120 DEG C, keep the temperature, obtain at 50-80 DEG C later
Copolymer；
(3), cool down to the copolymer, lye is added and adjusts pH value, obtains macromolecule polymer solution；
(4), hydramine substance is added into the macromolecule polymer solution, obtains the Mcromolecular grinding aid；
The polyethers monomer is selected from one or more of allyl polyglycol or methyl enol polyoxyethylene ether；
The modified triethanolamine class monomer is selected from triethanolamine acrylate, triethanolamine methacrylate and triethanolamine
One of maleate.
2. a kind of preparation method of Mcromolecular grinding aid as described in claim 1, characterized by the following steps:
(1), a part of polyethers monomer, sulfonic acid monomers and deionized water are mixed, heating obtains mixed solution；
(2), it is added dropwise in the mixed solution and is configured to by modified triethanolamine class monomer and remainder polyethers monomer
Solution and initiator solution after being added dropwise, react 1-3 hours at 80 DEG C -120 DEG C, keep the temperature, obtain at 50-80 DEG C later
To copolymer；
(3), cool down to the copolymer, lye is added and adjusts pH value, obtains macromolecule polymer solution；
(4), hydramine substance is added into the macromolecule polymer solution, obtains the Mcromolecular grinding aid；
The modified triethanolamine class monomer is selected from triethanolamine acrylate, triethanolamine methacrylate and triethanolamine
One of maleate.
3. preparation method according to claim 2, it is characterised in that: the initiator is redox initiator.
4. preparation method according to claim 2, it is characterised in that: the lye is 40 ± 10wt% of content sodium hydroxide
Solution.
5. preparation method according to claim 2, it is characterised in that: the hydramine substance is different selected from triethanolamine or three
One or more of Propanolamine.
6. preparation method according to claim 2, it is characterised in that: the sulfonic acid monomers, the modified triethanolamine
The molar ratio of class monomer, the allyl polyglycol and the methyl enol polyoxyethylene ether is 0.5-3:0.5-2:0.25-
0.5:0‐0.5。
7. preparation method according to claim 2, it is characterised in that: a part of polyethers monomer and the remainder
The molar ratio for dividing polyethers monomer is 1:1.
8. preparation method according to claim 2, it is characterised in that: in the step (1), the temperature of heating is 70~90
℃。
9. preparation method according to claim 2, it is characterised in that: in the step (2), the time of dropwise addition is 2~6h.
10. preparation method according to claim 2, it is characterised in that: the pH value in the step (3), after lye is added
It is 7.0 ± 0.5.
11. preparation method according to claim 2, it is characterised in that: the preparation method of the triethanolamine acrylate
The following steps are included:
(1), triethanolamine and toluene equimolar are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of reflux, obtains the
One mixed solution；
(2), when the temperature of first mixed solution is down to 60 ± 20 DEG C, 1 ± 0.6mol acrylic acid is added and 1-2wt% is dense
Sulfuric acid raises the temperature to 120 ± 10 DEG C, maintains 2 ± 1h of thermotonus, obtains the first synthetic；
(3), after first synthetic is cooling, with 0.5 ± 0.2mol/L NaOH solution by the pH tune of first synthetic
To 7.0 ± 0.5, the triethanolamine acrylate is obtained.
12. preparation method according to claim 2, it is characterised in that: the preparation of the triethanolamine methacrylate
Method the following steps are included:
(1), triethanolamine and toluene equimolar are mixed, heating stirring is simultaneously warming up to 90 ± 10 DEG C of 1 ± 0.5h of reflux, obtains the
Two mixed solutions；
(2), when the temperature of second mixed solution is down to 60 ± 20 DEG C, 1 ± 0.5mol methacrylic acid and 1- is added
The 2wt% concentrated sulfuric acid raises the temperature to 105 ± 15 DEG C, maintains 2 ± 1h of thermotonus, obtains the second synthetic；
(3), after second synthetic is cooling, with 0.5 ± 0.2mol/L NaOH solution by the pH tune of second synthetic
To 7.0 ± 0.5, the triethanolamine methacrylate is obtained.
13. preparation method according to claim 2, it is characterised in that: the preparation method of the triethanolamine maleate
The following steps are included:
(1), acetic acid and triethanolamine equimolar are mixed, reaction temperature is 60 ± 10 DEG C, obtains third mixed solution；
(2), to addition 1 ± 0.5mol maleic anhydride and 2 ± 1mol p-methyl benzenesulfonic acid in the third mixed solution, temperature is maintained
In 115 ± 15 DEG C of 4 ± 2h of reaction, third synthetic is obtained；
(3), after the third synthetic is cooling, the pH of the third synthetic is adjusted to 7.0 ± 0.5 with triethanolamine, is obtained
To the triethanolamine maleate.
14. a kind of application of Mcromolecular grinding aid as described in claim 1 in cement.
15. application according to claim 14, it is characterised in that: addition content of the Mcromolecular grinding aid in cement
Are as follows: 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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