CN103113510A - Synthetic method of polyethylene glycol amine ester-carboxylic acid macromolecule grinding aid - Google Patents
Synthetic method of polyethylene glycol amine ester-carboxylic acid macromolecule grinding aid Download PDFInfo
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- CN103113510A CN103113510A CN2013100487022A CN201310048702A CN103113510A CN 103113510 A CN103113510 A CN 103113510A CN 2013100487022 A CN2013100487022 A CN 2013100487022A CN 201310048702 A CN201310048702 A CN 201310048702A CN 103113510 A CN103113510 A CN 103113510A
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- maleic anhydride
- vinylformic acid
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Abstract
The invention relates to a synthetic method of a polyethylene glycol amine ester-carboxylic acid macromolecule grinding aid. The synthetic method comprises the following steps of: weighing crylic acid, triisopropanolamine and maleic anhydride according to molar ratio of raw materials, firstly adding the maleic anhydride and the triisopropanolamine, and heating for reaction to obtain solution 1; then neutralizing the crylic acid by NaOH solution to obtain solution 2; dropwise adding an initiator peroxosulfuric acid after the two solutions are mixed, and stirring for reaction to obtain the polyethylene glycol amine ester-carboxylic acid macromolecule grinding aid. By utilizing the synthetic method, the effective mixing amount of the grinding aid can be greatly reduced to reduce the production cost.
Description
Technical field
The invention belongs to grinding aid and synthesize the field, relate to a kind of synthetic method and technique for preparing toxilic acid tri-isopropanolamine ester-sodium acrylate Mcromolecular grinding aid.
Background technology
In cement pulverizing course, mix a certain amount of grinding aid, utilize grinding aid to have the characteristics of surfactivity and electric charge dissemination, to the material surface carrying out physical and chemical modified, thereby improve the grindability of material, alleviate the adhesive aggregation effect between particle, improve the mobility of ball mill materials inside, realize the purpose of ball grinder saving energy high yield.Can also optimize the cement granules grating under the prerequisite that does not increase grinding time simultaneously, improve the specific surface area of cement, and then improve the early strength of cement.Cement grinding aid divides liquid and the large class of powder two, and liquid grinding aid is little because of addition content, the convenient main product that becomes existing market of metering.Again take composite grinding aid product as main, composite grinding aid is by amine in liquid grinding aid, and the single small molecules such as alcamines is mixed and joined inorganic salt, molasses or sulfonated lignin etc. and be composited.This series products generally can improve grinding-aid effect 10% left and right, and the short-term mechanical strength improves 5 ~ 10%, but its effective volume is high, has not only improved the cost of cement, also makes the cement performance stability decreases.Due to the complicated component of composite grinding aid product, grinding-aid effect is unstable, and in most of product, saltiness is large, and cement performance is had certain negative impact.Therefore the Polymer Synthesizing grinding aid will become the developing direction of following grinding aid.
Summary of the invention
The object of the invention is to by optimization grinding aid production technique and formula, and then significantly reduce effective volume and the production cost of grinding aid, a kind of alkanolamine ester-polymers of carboxylic acid Mcromolecular grinding aid and preparation method thereof is provided.
Technical scheme of the present invention is: take vinylformic acid, tri-isopropanolamine, maleic anhydride, sodium hydroxide as raw material, and synthetic alkanolamine ester-polymers of carboxylic acid Mcromolecular grinding aid, its macromolecular compound is to use following general formula:
The molecular formula of described vinylformic acid, tri-isopropanolamine, maleic anhydride and structural formula are as follows respectively:
Vinylformic acid
Molecular formula is: C
3H
4O
2
Structural formula is as follows:
Tri-isopropanolamine
Molecular formula is: C
9H
21O
3N
Structural formula is as follows:
Maleic anhydride
Molecular formula is: C
4H
2O
3
Structural formula is as follows:
The reaction equation of above-mentioned steps is as follows:
Processing step of the present invention is as follows:
1, take vinylformic acid, tri-isopropanolamine, maleic anhydride by the feed molar proportioning, vinylformic acid: maleic anhydride: tri-isopropanolamine=1.6 ~ 2.4: 0.8 ~ 1.2: 1;
2, be equipped with during magnetic stirring apparatus, prolong, temperature take into account the container of heating in water bath, add maleic anhydride and tri-isopropanolamine by above mole of proportioning, after heated and stirred 2h, cooling, with deionized water, esterification products being diluted to mass concentration is 40% ~ 60%, obtains solution 1;
3, with NaOH solution, vinylformic acid is neutralized to pH=8, and adding distil water is 30% ~ 40% with this solution dilution to containing the vinylformic acid mass concentration, obtains solution 2;
4, press maleic anhydride and acrylic acid mol ratio 1:1, take solution 2 and join in solution 1, be heated to 80 ~ 90 ℃ of constant temperature;
5, drip initiator ammonium persulfate in step 4 solution, continue simultaneously to replenish and drip solution 2 until till dripping, the amount of substance of initiator is 1 ~ 4% of vinylformic acid and maleic anhydride amount of substance sum, and time for adding is controlled in 2 ~ 3 hours and dropwises, and continues stirring reaction 1 ~ 2 hour;
6, with products therefrom neutralization, then to be diluted with water to solid content be 20% ~ 40%, and the gained weak yellow liquid is the Mcromolecular grinding aid of poly-alkanolamine ester-carboxylic acid of the present invention.
The invention has the advantages that:
1. the Mcromolecular grinding aid of the poly-alkanolamine ester-carboxylic acid of products obtained therefrom of the present invention is due to the effect of functional group on molecular chain, grinding-aid effect and cement is early stage and in good effect is arranged aspect the lifting of intensity for a long time.On grinding-aid effect, can improve 10% than the cement specific surface area that does not use grinding aid; Three days strength ratios of cement do not use grinding aid to improve raising 5% when strength ratio was used grinding aid in 15%, 28 day.
2. the effective volume of products obtained therefrom of the present invention is low, recommends consumption to be controlled in 0.03%, and its physicochemical property are stable, are long placed in and never degenerate, and do not contain the objectionable impuritiess such as Cl ion.Cement performance is had no adverse effects, can use safely.
3. production technique of the present invention is simple, and raw material is cheap, and is easy to operate.Do not produce in actual production human body, environmentally hazardous substance, no waste discharge meets the cleaner production requirement.
Embodiment
In the following stated example, all proportioning raw materials are all according to the mol ratio metering, take tri-isopropanolamine as object of reference.
Embodiment 1
By mole proportioning: vinylformic acid: maleic anhydride: tri-isopropanolamine=1.6: 0.8: 1.0 is got raw material ready.
Being equipped with during magnetic stirring apparatus, prolong, temperature take into account the container of heating in water bath, add maleic anhydride and tri-isopropanolamine by above mole of proportioning, cooling after heated and stirred 2h, with deionized water, esterification products being diluted to mass concentration is 50%, obtains solution 1.
With NaOH solution, vinylformic acid is neutralized to pH=8, and adding distil water is 30% with this solution dilution to containing the vinylformic acid mass concentration, obtains solution 2.
By maleic anhydride: the vinylformic acid mol ratio is 1:1, and the solution 2 that takes is joined in solution 1, is heated to 90 ℃ of constant temperature; When dripping initiator ammonium persulfate, continue to replenish dropping solution 2, until add; The amount of substance of initiator is 2% of vinylformic acid and maleic anhydride amount of substance sum, and time for adding is controlled in 2 hours and dropwises, and continues stirring reaction 1 hour.At last with products therefrom neutralization, then to be diluted with water to solid content be 30%, and the gained weak yellow liquid is the Mcromolecular grinding aid of poly-alkanolamine ester-carboxylic acid of the present invention.
Embodiment 2
By mole proportioning: vinylformic acid: maleic anhydride: tri-isopropanolamine=2.0: 1.0: 1.0 is got raw material ready.
Technological process and embodiment 1 are same.
Embodiment 3
By mole proportioning: vinylformic acid: maleic anhydride: tri-isopropanolamine=3.6: 1.2: 1.0 is got raw material ready.
The little mill verification experimental verification of product of the present invention:
The grinding aid product of the present invention that embodiment 1,2,3 is obtained under equal conditions carries out respectively little mill test with the cement clinker of not mixing grinding aid, obtains that the grinding aid of Mcromolecular grinding aid and reinforced effects see Table 1, table 2.
The grinding-aid effect of table 1 Mcromolecular grinding aid
Remarks: the blank sample of specimen coding: A0 in upper table; A1, A2, A3 are respectively embodiment 1,2,3 Mcromolecular grinding aids that obtain.
The reinforced effects of table 2 Mcromolecular grinding aid
Remarks: the blank sample of specimen coding: A0 in upper table; A1, A2, A3 are respectively embodiment 1,2,3 Mcromolecular grinding aids that obtain.
Claims (1)
1. the synthetic method of the Mcromolecular grinding aid of a poly-alkanolamine ester-carboxylic acid is characterized in that:
(1) take vinylformic acid, tri-isopropanolamine, maleic anhydride by the feed molar proportioning, vinylformic acid: maleic anhydride: tri-isopropanolamine=1.6-2.4: 0.8-1.2: 1;
(2) be equipped with during magnetic stirring apparatus, prolong, temperature take into account the container of heating in water bath, add maleic anhydride and tri-isopropanolamine by above mole of proportioning, after heated and stirred 2h, cooling, with deionized water, esterification products being diluted to mass concentration is 40%-60%, obtains solution 1;
(3) with NaOH solution, vinylformic acid is neutralized to pH=8, and adding distil water is 30%-40% with this solution dilution to containing the vinylformic acid mass concentration, obtains solution 2;
(4) press maleic anhydride and acrylic acid mol ratio 1:1, take solution 2 and join in solution 1, be heated to constant temperature 80-90 ℃;
(5) drip initiator ammonium persulfate in step (4) solution, continue simultaneously to replenish and drip solution 2 until till dripping, the amount of substance of initiator is the 1-4% of vinylformic acid and maleic anhydride amount of substance sum, time for adding is controlled in 2-3 hour and dropwises, and continues stirring reaction 1-2 hour;
(6) with products therefrom neutralization, then to be diluted with water to solid content be 20%-40%, and the gained weak yellow liquid is the Mcromolecular grinding aid of poly-alkanolamine ester-carboxylic acid of the present invention.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274625A (en) * | 2013-05-28 | 2013-09-04 | 杭州斯曼特建材科技有限公司 | Modified poly(hydramine) macromolecular compound cement grinding aid and preparation method thereof |
| CN103936934A (en) * | 2014-05-06 | 2014-07-23 | 武汉理工大学 | Preparation method of triisopropanolamine modified early strength polycarboxylate superplasticizer |
| CN104478285A (en) * | 2014-12-23 | 2015-04-01 | 湖州绿色建材开发有限公司 | Activation enhancer applied to cement concrete as well as application and preparation method of activation enhancer |
| CN106977159A (en) * | 2017-05-08 | 2017-07-25 | 天津市滨涛混凝土有限公司 | Ultra-retardation concrete and preparation method thereof |
| CN109053957A (en) * | 2018-08-25 | 2018-12-21 | 广州吉前化工有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN109320124A (en) * | 2018-08-25 | 2019-02-12 | 广州吉前化工有限公司 | A kind of modified polycarboxylic acid alkanolamine ester high-molecular cement grinding aid 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 |
| CN110078407A (en) * | 2019-05-21 | 2019-08-02 | 扬州大学 | A kind of morning strong hyperbranched poly carboxylic acid water reducer and preparation method thereof |
| CN111689715A (en) * | 2020-05-26 | 2020-09-22 | 贵州石博士科技有限公司 | Yield-increasing reinforced cement grinding aid and preparation method thereof |
| CN114907031A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive, application thereof and cement production process |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274625B (en) * | 2013-05-28 | 2015-02-25 | 杭州斯曼特建材科技有限公司 | Modified poly(hydramine) macromolecular compound cement grinding aid and preparation method thereof |
| CN103274625A (en) * | 2013-05-28 | 2013-09-04 | 杭州斯曼特建材科技有限公司 | Modified poly(hydramine) macromolecular compound cement grinding aid and preparation method thereof |
| CN103936934A (en) * | 2014-05-06 | 2014-07-23 | 武汉理工大学 | Preparation method of triisopropanolamine modified early strength polycarboxylate superplasticizer |
| CN104478285A (en) * | 2014-12-23 | 2015-04-01 | 湖州绿色建材开发有限公司 | Activation enhancer applied to cement concrete as well as application and preparation method of activation enhancer |
| CN104478285B (en) * | 2014-12-23 | 2016-06-15 | 湖州绿色建材开发有限公司 | A kind of it is applied to the activation reinforcing agent of cement concrete, purposes and preparation method thereof |
| CN106977159B (en) * | 2017-05-08 | 2019-03-01 | 天津市滨涛混凝土有限公司 | Ultra-retardation concrete and preparation method thereof |
| CN106977159A (en) * | 2017-05-08 | 2017-07-25 | 天津市滨涛混凝土有限公司 | Ultra-retardation concrete and preparation method thereof |
| CN109053957A (en) * | 2018-08-25 | 2018-12-21 | 广州吉前化工有限公司 | A kind of cement grinding aid and preparation method thereof |
| CN109320124A (en) * | 2018-08-25 | 2019-02-12 | 广州吉前化工有限公司 | A kind of modified polycarboxylic acid alkanolamine ester high-molecular cement grinding aid 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 |
| CN110078407A (en) * | 2019-05-21 | 2019-08-02 | 扬州大学 | A kind of morning strong hyperbranched poly carboxylic acid water reducer and preparation method thereof |
| CN110078407B (en) * | 2019-05-21 | 2021-06-25 | 扬州大学 | Early-strength hyperbranched polycarboxylate superplasticizer and preparation method thereof |
| CN111689715A (en) * | 2020-05-26 | 2020-09-22 | 贵州石博士科技有限公司 | Yield-increasing reinforced cement grinding aid and preparation method thereof |
| CN114907031A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive, application thereof and cement production process |
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Application publication date: 20130522 |