CN103641367B - A kind of composite cement grinding aid and preparation method thereof - Google Patents
A kind of composite cement grinding aid and preparation method thereof Download PDFInfo
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- CN103641367B CN103641367B CN201310717096.9A CN201310717096A CN103641367B CN 103641367 B CN103641367 B CN 103641367B CN 201310717096 A CN201310717096 A CN 201310717096A CN 103641367 B CN103641367 B CN 103641367B
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Abstract
The present invention relates to cement additive technical field, particularly a kind of composite cement grinding aid, containing super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol.Volume in cement is the 0.04%-0.05% of cement weight.Be that the composite cement grinding aid of main component significantly improves fine particle content in cement with super-branched polyesteramide, improve grinding aid efficiency, reduce production cost, affect the performance of cement hardly, be a kind of cement grinding aid of excellent effect easy to use, there is good market development prospect.
Description
Technical field
The present invention relates to cement additive technical field, particularly a kind of composite cement grinding aid, also relate to the preparation method of described composite cement grinding aid.
Background technology
Current China manufacture of cement is generally divided into three steps, prepares raw material, calcination of chamotte, pulverizing cement.Wherein in pulverizing cement process, electric energy more than 95% is all wasted because changing into heat energy; When cement grinding attenuates, easy adhesive aggregation is agglomerating simultaneously reduces mill efficiency.In order to improve cement grinding efficiency, reducing power consumption in cement pulverizing course, increasing the addition content of blended material, thus reduce cement cost, generally will add cement grinding aid.
Cement grinding aid can form coated film at cement particle surface, stops the reunion of cement, improves powder fluidity, improves the fineness of cement, increases the specific surface area of cement, improves cement granules composition, significantly improves fine particle content.Thus reduction energy consumption.
Although the cement grinding aid on market can increase the addition content of blended material, reduce costs, cement later strength can be affected; And the cement grinding aid cost of excellent property is higher, wherein majority is again that small organic molecule is mixed, the less stable of this kind of grinding aid, and result of use fluctuation is comparatively large, and applicable surface is narrower.Usually needing to increase the consumption of grinding aid for improving output, improve manufacture of cement cost.
Summary of the invention
In order to solve, above existing cement grinding aid affects cement later strength, cost is high, the fluctuation of less stable, result of use is larger, the problem that applicable surface is narrower, the invention provides that a kind of volume is little, the basis that do not affect strength of cement improved the output of cement, reduce energy consumption, realize the composite cement grinding aid of pulverizing cement green, energy-saving and environmental protection.
Present invention also offers the preparation method of described composite cement grinding aid.
The present invention is achieved by the following measures:
A kind of composite cement grinding aid, the raw material containing following weight proportion:
Super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol weight ratio are 35-50:1:10-12:20:20-30:15-25:15-25.
A kind of composite cement grinding aid, the raw material containing following weight proportion:
Super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol, water weight ratio are 35-50:1:10-12:20:20-30:15-25:15-25:5-10.
Described composite cement grinding aid, the raw material containing following weight proportion:
Super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol weight ratio are 50:1:12:20:20:15:15.
Described composite cement grinding aid, super-branched polyesteramide is obtained by following steps: Succinic anhydried and diethanolamine reaction with same mole in solvent DMAc generates AB
2type monomer, AB
2type monomer and core molecule trolamine esterification under Catalyzed by p-Toluenesulfonic Acid condition.
Described composite cement grinding aid, core molecule trolamine and AB
2the mol ratio of type monomer is 1:3-21.
Described composite cement grinding aid, core molecule trolamine and AB
2the mol ratio of type monomer is 1:3,1:9 or 1:21.
Described composite cement grinding aid, the volume of described composite cement grinding aid in cement is the 0.04%-0.05% of cement weight.
First the present invention has synthesized a kind of modification hydramine, it is a kind of super-branched polyesteramide, we can carry out the number of this polymer ends alcohol amine groups of manual control by the algebraically controlling hyperbranched polymer, inquire into the mechanism of action of alcohol amine groups in cement grinding aid field whereby.The core molecule of this hyperbranched polymer is trolamine, and end contains the structure of similar trolamine.Its end structure number is controlled, then itself and the mixing of other small molecules auxiliary agents are made into novel concrete grinding aid.
In the present invention, main component super-branched polyesteramide compares some had special propertys with traditional linear macromolecule, and the molecular structure of the 3 D stereo shape of its uniqueness makes molecular chain without prehensile and nodeless mesh.Its solubility property is good, and viscosity is low, when molecular weight increases or concentration improves, still can keep lower viscosity, thus can reach good dispersion effect in cement.And its building-up process is relatively simple, does not need the separating-purifying of multistep, preparation is simple, and production cost is lower, is applicable to large-scale industrial production.
AB is made in this super-branched polyesteramide Succinic anhydried that the present invention introduces and diethanolamine 1:1 reaction
2type monomer, this monomer again with core molecule trolamine generation esterification.First-generation super-branched polyesteramide is obtained respectively, s-generation super-branched polyesteramide, third generation super-branched polyesteramide when both mol ratios are 1:3,1:9,1:21.Wherein in the first-generation, the s-generation, third generation super-branched polyesteramide, the ratio of terminal alcohol amine groups is 1:2:4.
Beneficial effect of the present invention:
Of the present invention is that the composite cement grinding aid of main component significantly improves fine particle content in cement with super-branched polyesteramide, improve grinding aid efficiency, reduce production cost, affect the performance of cement hardly, be a kind of cement grinding aid of excellent effect easy to use, there is good market development prospect.
Embodiment
Below the preparation method of hyperbranched type cement grinding aid of the present invention is described in more detail, its object is to design of the present invention and feature are described, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
example 1
(1) take 30.021g Succinic anhydried, 31.543 g diethanolamine, first diethanolamine is dissolved in appropriate DMAc, pours into after dissolving in the there-necked flask with magnetic stirring apparatus, the more appropriate DMAc of Succinic anhydried is dissolved; Then it being slowly added drop-wise to is equipped with in the there-necked flask of diethanolamine, and dropping limit, limit is stirred, and 1h-1.5h drips; Normal-temperature reaction 3 h-5h, the product of reaction is AB
2type monomer.In above-mentioned system, first add 60 mL toluene (toluene is water entrainer), then add 14.920g trolamine as core molecule, add 0.4 g tosic acid and make catalyzer; Then start heating, until boiling, in spherical condensation tube, have backflow to produce.Solvent after insulation reaction 7 h-8h in underpressure distillation removing system, obtains end and contains alcohol amine groups super-branched polyesteramide.
(2) by 8ml, 30 DEG C of water join in the large beaker of water-bath (30 DEG C), add 10g calcium lignin sulphonate and 1g cetyl alcohol, stir 20-30min and make it to mix; Add 20g urea and 30g sodium-acetate again, stir 15-20min to adding 24g ethylene glycol and 24g glycerol after mixing and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add the super-branched polyesteramide 36g that (1) is obtained, increase the temperature to 40 DEG C and stir the uniform mixture that 0.5h obtains and be cement grinding aid.
(3) composite cement grinding aid of the present invention of admixture 0.04%-0.05% in standard cement grog, according to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.
example 2
(1) take 30.021g Succinic anhydried, 31.543 g diethanolamine, first diethanolamine is dissolved in appropriate DMAc, pours into after dissolving in the there-necked flask with magnetic stirring apparatus, the more appropriate DMAc of Succinic anhydried is dissolved; Then it being slowly added drop-wise to is equipped with in the there-necked flask of diethanolamine, and dropping limit, limit is stirred, and 1h-1.5h drips; Normal-temperature reaction 3 h-5h, the product of reaction is AB
2type monomer.In above-mentioned system, first add 60 mL toluene (toluene is water entrainer), then add 4.973g trolamine as core molecule, add 0.4 g tosic acid and make catalyzer; Then start heating, until boiling, in spherical condensation tube, have backflow to produce.Solvent after insulation reaction 7 h-8h in underpressure distillation removing system, obtains end and contains alcohol amine groups super-branched polyesteramide.
(2) by 8ml, 30 DEG C of water join in the large beaker of water-bath (30 DEG C), add 10g calcium lignin sulphonate and 1g cetyl alcohol, stir 20-30min and make it to mix; Add 20g urea and 30g sodium-acetate again, stir 15-20min to adding 24g ethylene glycol and 24g glycerol after mixing and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add the super-branched polyesteramide 36g that (1) is obtained, increase the temperature to 40 DEG C and stir the uniform mixture that 0.5h obtains and be cement grinding aid.
(3) composite cement grinding aid of the present invention of admixture 0.04%-0.05% in standard cement grog, according to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.
example 3
(1) take 30.021g Succinic anhydried, 31.543 g diethanolamine, first diethanolamine is dissolved in appropriate DMAc, pours into after dissolving in the there-necked flask with magnetic stirring apparatus, the more appropriate DMAc of Succinic anhydried is dissolved; Then it being slowly added drop-wise to is equipped with in the there-necked flask of diethanolamine, and dropping limit, limit is stirred, and 1h-1.5h drips; Normal-temperature reaction 3 h-5h, the product of reaction is AB
2type monomer.In above-mentioned system, first add 60 mL toluene (toluene is water entrainer), then add 2.131g trolamine as core molecule, add 0.4 g tosic acid and make catalyzer; Then start heating, until boiling, in spherical condensation tube, have backflow to produce.Solvent after insulation reaction 7 h-8h in underpressure distillation removing system, obtains end and contains alcohol amine groups super-branched polyesteramide.
(2) by 8ml, 30 DEG C of water join in the large beaker of water-bath (30 DEG C), add 10g calcium lignin sulphonate and 1g cetyl alcohol, stir 20-30min and make it to mix; Add 20g urea and 30g sodium-acetate again, stir 15-20min to adding 24g ethylene glycol and 24g glycerol after mixing and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add the super-branched polyesteramide 36g that (1) is obtained, increase the temperature to 40 DEG C and stir the uniform mixture that 0.5h obtains and be cement grinding aid.
(3) composite cement grinding aid of the present invention of admixture 0.04%-0.05% in standard cement grog, according to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.
example 4
(1) super-branched polyesteramide is prepared according in above-described embodiment 1.
(2) by 10ml, 30 DEG C of water join in the large beaker of water-bath (30 DEG C), add 12g calcium lignin sulphonate and 1g cetyl alcohol, stir 20-30min and make it to mix; Add 20g urea and 20g sodium-acetate again, stir 15-20min to adding 15g ethylene glycol and 15g glycerol after mixing and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add the super-branched polyesteramide 50g that (1) is obtained, increase the temperature to 40 DEG C and stir the uniform mixture that 0.5h obtains and be cement grinding aid.
(3) composite cement grinding aid of the present invention of admixture 0.04%-0.05% in standard cement grog, according to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.
example 5
(1) super-branched polyesteramide is prepared according in above-described embodiment 1.
(2) by 10ml, 30 DEG C of water join in the large beaker of water-bath (30 DEG C), add 12g calcium lignin sulphonate and 1g cetyl alcohol, stir 20-30min and make it to mix; Add 20g urea and 30g sodium-acetate again, stir 15-20min to adding 25g ethylene glycol and 25g glycerol after mixing and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add the super-branched polyesteramide 35g that (1) is obtained, increase the temperature to 40 DEG C and stir the uniform mixture that 0.5h obtains and be cement grinding aid.
(3) composite cement grinding aid of the present invention of admixture 0.04%-0.05% in standard cement grog, according to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.
performance test
Admixture composite cement grinding aid of the present invention in standard cement grog.According to the composite cement grinding aid of GB GB/T26748-2011 test synthesis.With the grinding aid grinding aid in contrast that trolamine replaces super-branched polyesteramide to obtain.
Carried out performance test to the cement grinding aid that above-mentioned example obtains, data are as follows:
Claims (6)
1. a composite cement grinding aid, is characterized in that the raw material containing following weight proportion:
Super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol, water weight ratio are 35-50:1:10-12:20:20-30:15-25:15-25:5-10;
Super-branched polyesteramide is obtained by following steps: Succinic anhydried and diethanolamine reaction with same mole in solvent DMAc generates AB
2type monomer, AB
2type monomer and core molecule trolamine esterification under Catalyzed by p-Toluenesulfonic Acid condition.
2. composite cement grinding aid according to claim 1, is characterized in that the raw material containing following weight proportion:
Super-branched polyesteramide, cetyl alcohol, calcium lignin sulphonate, urea, sodium-acetate, ethylene glycol, glycerol weight ratio are 50:1:12:20:20:15:15.
3. composite cement grinding aid according to claim 1, is characterized in that core molecule trolamine and AB
2the mol ratio of type monomer is 1:3-21.
4. composite cement grinding aid according to claim 1, is characterized in that core molecule trolamine and AB
2the mol ratio of type monomer is 1:3,1:9 or 1:21.
5. composite cement grinding aid according to claim 1, is characterized in that the volume of described composite cement grinding aid in cement is the 0.04%-0.05% of cement weight.
6. a preparation method for the composite cement grinding aid according to any one of claim 1-5, is characterized in that the water of 30 DEG C, calcium lignin sulphonate and cetyl alcohol to mix, stirs 20-30min and make it to mix; Add urea and sodium-acetate again, stirring 15-20min to mixing, adding ethylene glycol and glycerol and being warmed up to 35 DEG C, stir 0.5h and make it to mix; Add super-branched polyesteramide, increase the temperature to 40 DEG C and stir 0.5h and obtain uniform mixture, be composite cement grinding aid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103864319B (en) * | 2014-03-31 | 2015-09-23 | 江苏融达新材料股份有限公司 | A kind of steel slag grinding aid and preparation method thereof |
| CN105271881A (en) * | 2015-11-04 | 2016-01-27 | 江苏名和集团有限公司 | Cement grinding aid and preparation method and use method thereof |
| CN106746840A (en) * | 2015-11-20 | 2017-05-31 | 甘肃曼特睿尔公路材料研发有限责任公司 | A kind of cement grinding aid |
| CN106082761A (en) * | 2016-06-24 | 2016-11-09 | 桂林华越环保科技有限公司 | A kind of retardation setting type cement grinding aid |
| CN108516842A (en) * | 2018-04-19 | 2018-09-11 | 田秋珍 | A kind of ceramic grind additives |
| CN111072308B (en) * | 2020-01-03 | 2021-07-23 | 桂林理工大学 | Concrete anticorrosive agent and preparation method thereof |
| CN111943537B (en) * | 2020-08-07 | 2022-03-15 | 绍兴柯桥第三水泥有限公司 | Masonry cement and preparation method thereof |
| CN115745460B (en) * | 2022-12-21 | 2023-07-28 | 洛阳奥百思特水泥技术有限公司 | Cement raw material energy-saving auxiliary agent and preparation method and application thereof |
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| KR100686790B1 (en) * | 2004-05-13 | 2007-02-23 | 경남유화 주식회사 | Cement grinding aid composition |
| CN101065338A (en) * | 2004-06-21 | 2007-10-31 | Sika技术股份公司 | Cement grinding aid |
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| CN1858014A (en) * | 2006-01-04 | 2006-11-08 | 胡佩龙 | Cement grinding aids |
| CN101182149A (en) * | 2007-11-19 | 2008-05-21 | 李军 | Composite activated cement reinforced grinding aids containing polycarboxylic acid series and method for preparing the same |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
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