CN104788038A - Modified melamine water reducer and preparation method thereof - Google Patents
Modified melamine water reducer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of concrete admixture and discloses a modified melamine water reducer and a preparation method thereof. An organic long chain is introduced to a molecular terminal position of the modified melamine water reducer, the mole ratio of a long-chain raw material to formaldehyde is 1:1 during synthesis of the organic long chain, and the mole ratio of melamine to formaldehyde to sodium hydrogen sulfite to a terminal-group long chain is 1: (3.5-3.8): (1.5-2.0): (0.03-0.05). The invention further discloses the preparation method of the modified melamine water reducer. The preparation method comprises steps as follows: synthesizing the terminal-group long chain; adding formaldehyde and sodium hydrogen sulfite for hydroxymethylation and sulfonation reactions of melamine; performing a condensation polymerization reaction under the acidic condition; adding alkali for reforming and weak bond fission of polymer molecules, and removing formaldehyde residues. A water reducer molecule main chain is introduced to a terminal position of the long chain through a condensation reaction of hydroxyl groups in a solution, space steric hindrance is added to a dispersion system, the repulsive interaction among cement particles is further improved, and the water reducing effect is further improved.
Description
Technical field
The present invention relates to concrete admixture field, particularly relate to a kind of modified melamine water reducer and preparation method thereof.
Background technology
Water reducer is a kind of maintaining under the constant condition of concrete slump, can reduce the concrete admixture of mixing water amount.Mostly belong to anion surfactant, have sulfonated lignin, naphthalene sulphonate formaldehyde polymkeric substance etc.There is dissemination to cement granules after adding concrete mix, its workability can be improved, reduce unit consumption of water, concrete strength is increased and improves weather resistance; Or minimizing unit cement consumption, save cement.
According to chemical composition form, water reducer has following classification usually: lignin sulfonate water reducer class, naphthalene series high-efficiency water-reducing agent class, melamine superplasticizer class, Amino-sulfonic Acid-based Water-reducer class, fatty acid series height water reducer class and polycarboxylate series high-performance dehydragent class.
Melamine superplasticizer is high with water-reducing rate, cement good dispersity, cement adaptability are good, low air-entraining performance, to have fine aluminium acid salt cement good adaptability and and other additives the advantage such as compositely can to use and be widely used.Melamine water reducing agent is by trimeric cyanamide by carrying out hydroxymethylation again by sodium bisulfite sulfonation with formaldehyde, then carries out monomer condenses when sulfuric acid exists, and thus chemical name is generally sulfonated melamine compound resin, belongs to anion surfactant.Such water reducer outward appearance is white powder, soluble in water, and to powder body material good dispersity, water-reducing rate is high, its mobility and self-healing good.
Traditional melamine class water reducer preparation is divided into four steps: methylolation, sulfonation, polycondensation and alkalescence are reformed.But traditional water reducer and preparation technology thereof possess certain limitation or defect, in as large in slump-loss and preparation process, the formaldehyde environmental pollution that volatilizees is serious.Therefore in the recent period there is a lot of technique to production process modification for these defects, modification, mostly to have concentrated on and reduce production cost, improve water-reducing rate, improve the aspects such as shelf stability.
Such as described in CN101845132 B, for the high production cost caused of trimeric cyanamide cost of material this problem high, use appropriate cheap urea to replace part trimeric cyanamide, also can synthesize corresponding melamine-urea water reducer.The advantage of this invention is significantly to reduce production cost while not reducing water-reducing effect.But also there is corresponding shortcoming: in production process and follow-up use, urea can decompose and discharges ammonia, and this also can bring problem of environmental pollution.
What patent 102304211B proposed for another example a kind ofly improves the method for water-reducing rate by improving sulphonation rate.The method is divided into three steps: sulfonation reaction, condensation reaction, secondary sulfonation reaction.Total feed ratio meets trimeric cyanamide: formaldehyde: sulphite sulphonating agent=1:(4.0-6.0): (1.2-2.0).Be exactly after traditional method sintetics, again carry out methylolation and sulfonation, thus at the remaining activity position of trimeric cyanamide grafting SO again
3 2-, reach the problem improving sulphonation rate.The method is only by increasing the mode of sulfonation group quantity to improve diminishing efficiency, there is certain limitation, in addition in methylolation sulfonation process, PH when dripping formaldehyde is 11.0-12.0, under this PH environment, very easily there is Cannizzaro reaction in formaldehyde, thus causes methylol rate wayward, the stability that impact is produced.
Summary of the invention
Technical problem to be solved by this invention is, large for the slump-loss of melamine class water reducer in prior art, the formaldehyde volatilization defects such as environmental pollution is serious in preparation process, the invention provides a kind of modified melamine water reducer and preparation method thereof, by a kind of mode at end-group polymer long-chain comparatively easily realized in solution building-up process, by the condensation reaction between hydroxyl, organic long-chain is introduced melamine water reducing agent molecular backbone chain in end position, increase sterically hindered in dispersion system to realization, repulsive interaction between further raising cement granules, so that significantly improve water-reducing effect.
In order to solve the problems of the technologies described above, the invention provides a kind of modified melamine water reducer and preparation method thereof, the concrete technical scheme adopted is: introduce organic long-chain in melamine water reducing agent molecular end position, and during synthesis organic long-chain, raw material molar ratio is: long-chain raw material: formaldehyde=1:1; Raw material molar ratio of the present invention is: trimeric cyanamide: formaldehyde: sodium bisulfite: end group long-chain=1:3.5 ~ 3.8:1.5 ~ 2.0:0.03 ~ 0.05.
Described long-chain raw material is the long-chain organism containing secondary amine or the long-chain organism containing primary amine.
Described long-chain raw material can be octacosyl primary amine, ceryl primary amine or 4-octadecyl aniline.
Described formaldehyde is the one in paraformaldehyde or 20 ~ 37% formalins.
Described sulfuric acid is the sulphuric acid soln of 10%.
The invention also discloses a kind of preparation method of modified melamine water reducer, comprise the following steps:
S1, add formaldehyde solution and long-chain raw material successively, regulator solution pH value is 8.0 ~ 9.5, keeps 80 ~ 90 DEG C of temperature to continue reactions 0.5 ~ 2 hour, carries out the hydroxymethylation of long-chain raw material;
S2, in another reaction vessel, add trimeric cyanamide and formaldehyde solution successively, be heated to 50 ~ 70 DEG C, stirring reaction 40 ~ 60 minutes, carries out the hydroxymethylation of trimeric cyanamide;
S3, in the product of S2, add sodium bisulfite, heat to 80 ~ 90 DEG C of reactions 0.5 ~ 2 hour, regulator solution pH value is 10.0 ~ 12.0, carries out sulfonation reaction to completing methylolated trimeric cyanamide;
S4, in the product of S3, add the product of S1, be 4.5 ~ 6.5 with sulfuric acid regulation solution pH value, continue reaction 1 ~ 2 hour, carry out polycondensation; The mode that product in S3 adds the product of S1 is specially dropping;
S5, to add alkali regulator solution pH value be 11.0 ~ 12.0,80 ~ 100 DEG C of reactions 0.5 ~ 2 hour, carries out polymer molecule reformation, weak bond fracture and remove residues of formaldehyde in the basic conditions; By dripping alkali lye in reaction soln in S5, regulator solution pH value is 11.0 ~ 12.0.
The invention has the beneficial effects as follows:
1) the present invention introduces long-chain end group on traditional melamine water reducing agent, utilizes the space steric effect of organic chain compound, the distance between cement granules is further increased, improves diminishing efficiency;
2) the present invention adopts the mode at end-group polymer long-chain comparatively easily realized in solution building-up process, abandoned employing High Temperature High Pressure grafting alcohols to melamine monomer, increase sterically hindered process limitation;
3) the present invention is by the condensation reaction between hydroxyl, the raw material long-chain after methylolation is introduced water reducer molecular backbone chain in end position, increases sterically hindered in dispersion system, improves the repulsive interaction between cement granules further, significantly improves water-reducing effect.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below the present invention is described in further detail.
Embodiment 1
A kind of modified melamine water reducer, introduces organic long-chain in melamine water reducing agent molecular end position, and during synthesis organic long-chain, raw material molar ratio is: long-chain raw material: formaldehyde=1:1; Raw material molar ratio of the present invention is: trimeric cyanamide: formaldehyde: sodium bisulfite: end group long-chain=1:3.5:1.5:0.03.
Described long-chain raw material is octacosyl primary amine.
Described formaldehyde is 37% formalin.
Described sulfuric acid is the sulphuric acid soln of 10%.
The preparation method of above-mentioned modified melamine water reducer, comprises the following steps:
S1, add formaldehyde solution and long-chain raw material successively, regulator solution pH value is 8.0, keeps 80 ~ 90 DEG C of temperature to continue reactions 0.5 ~ 2 hour, carries out the hydroxymethylation of long-chain raw material;
S2, in another reaction vessel, add trimeric cyanamide and formaldehyde solution successively, be heated to 50 DEG C, stirring reaction 60 minutes, carries out the hydroxymethylation of trimeric cyanamide;
S3, in the product of S2, add sodium bisulfite, heat to 80 DEG C of reactions 2 hours, regulator solution pH value is 11.0, carries out sulfonation reaction to completing methylolated trimeric cyanamide;
S4, be 4.5 with sulfuric acid regulation solution pH value, in the product of S3, add the product of S1, continue reaction 1 hour, carry out polycondensation; By the concrete mode that sulfuric acid regulation solution pH value is 4.5 be: drip the sulphuric acid soln of 10% in reaction soln; The mode adding the product of S1 in the product of S3 is specially dropping;
S5, to add alkali regulator solution pH value be 12.0,100 DEG C of reactions 0.5 hour, carries out polymer molecule reformation, weak bond fracture and remove residues of formaldehyde in the basic conditions; The alkali added is sodium hydroxide, and by dripping alkali lye in reaction soln in the S5 of described preparation method, regulator solution pH value is 12.0.
In the present embodiment, the paste flowing degree of described modified melamine water reducer can rise to 275mm, has had and has significantly improved, significantly improve water-reducing effect relative to the average paste flowing degree 240mm of commercially available prod.
Embodiment 2:
A kind of modified melamine water reducer, introduces organic long-chain in melamine water reducing agent molecular end position, and during synthesis organic long-chain, raw material molar ratio is: long-chain raw material: formaldehyde=1:1; Raw material molar ratio of the present invention is: trimeric cyanamide: formaldehyde: sodium bisulfite: end group long-chain=1:3.8:2.0:0.05.
Described long-chain raw material is 4-octadecyl aniline.
Described formaldehyde is 37% formalin.
Described sulfuric acid is the sulphuric acid soln of 10%.
The preparation method of above-mentioned modified melamine water reducer, comprises the following steps:
S1, add formaldehyde solution and long-chain raw material successively, regulator solution pH value is 9.5, keeps 90 DEG C of temperature to continue reactions 0.5 hour, carries out the hydroxymethylation of long-chain raw material;
S2, in another reaction vessel, add trimeric cyanamide and formaldehyde solution successively, be heated to 70 DEG C, stirring reaction 40 minutes, carries out the hydroxymethylation of trimeric cyanamide;
S3, in the product of S2, add sodium bisulfite, heat to 90 DEG C of reactions 0.5 hour, regulator solution pH value is 11.0, carries out sulfonation reaction to completing methylolated trimeric cyanamide;
S4, use sulfuric acid regulation solution pH value to 6.5, add the product of S1, continue reaction 2 hours, carry out polycondensation in the product of S3; By the concrete mode of sulfuric acid regulation solution pH value to 6.5 be: drip the sulphuric acid soln of 10% in reaction soln; The mode adding the product of S1 in the product of S3 is specially dropping;
S5, to add alkali regulator solution pH value be 12.0,100 DEG C of reactions 0.5 hour, carries out polymer molecule reformation, weak bond fracture and remove residues of formaldehyde in the basic conditions; The alkali added is sodium hydroxide, and by dripping alkali lye in reaction soln in the S5 of described preparation method, regulator solution pH value is 12.0.
In the present embodiment, the paste flowing degree of described modified melamine water reducer can rise to 270mm, has had and has significantly improved, significantly improve water-reducing effect relative to the average paste flowing degree 240mm of commercially available prod.
The correlation parameter of embodiment is as shown in the table:
The experimental data of the paste flowing degree of embodiment 3-7 is as shown in the table:
The invention has the beneficial effects as follows:
1) the present invention introduces end group long-chain on traditional melamine water reducing agent, utilizes the space steric effect of organic chain compound, the distance between cement granules is further increased, improves diminishing efficiency;
2) the present invention adopts the mode comparatively easily realized in solution building-up process at end-group polymer long-chain, abandoned employing High Temperature High Pressure grafting alcohols to melamine monomer, increase sterically hindered process limitation;
3) the present invention is by the condensation reaction between hydroxyl, the raw material long-chain after methylolation is introduced water reducer molecular backbone chain in end position, increases sterically hindered in dispersion system, improves the repulsive interaction between cement granules further, significantly improves water-reducing effect.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a modified melamine water reducer, is characterized in that, introduces organic long-chain in melamine water reducing agent molecular end position, and during synthesis organic long-chain, raw material molar ratio is: long-chain raw material: formaldehyde=1:1; Raw material molar ratio of the present invention is: trimeric cyanamide: formaldehyde: sodium bisulfite: end group long-chain=1:3.5 ~ 3.8:1.5 ~ 2.0:0.03 ~ 0.05.
2. a kind of modified melamine water reducer according to claim 1, is characterized in that, described long-chain raw material is the long-chain organism containing secondary amine or the long-chain organism containing primary amine.
3. a kind of modified melamine water reducer according to claim 2, is characterized in that, described long-chain raw material is octacosyl primary amine, ceryl primary amine or 4-octadecyl aniline.
4. a kind of modified melamine water reducer according to claim 1 and 2, is characterized in that, described formaldehyde uses paraformaldehyde or 20 ~ 37% formalins.
5. a kind of modified melamine water reducer according to claim 4, is characterized in that, described sulfuric acid is the sulphuric acid soln of 10%.
6. a preparation method for modified melamine water reducer, is characterized in that, comprises the following steps:
S1, add formaldehyde solution and long-chain raw material successively, regulator solution pH value is 8.0 ~ 9.5, keeps 80 ~ 90 DEG C of temperature to continue reactions 0.5 ~ 2 hour, carries out the hydroxymethylation of long-chain raw material;
S2, in another reaction vessel, add trimeric cyanamide and formaldehyde solution successively, be heated to 50 ~ 70 DEG C, stirring reaction 40 ~ 60 minutes, carries out the hydroxymethylation of trimeric cyanamide;
S3, in the product of S2, add sodium bisulfite, heat to 80 ~ 90 DEG C of reactions 0.5 ~ 2 hour, regulator solution pH value is 10.0 ~ 12.0, carries out sulfonation reaction to completing methylolated trimeric cyanamide;
S4, be 4.5 ~ 6.5 with sulfuric acid regulation solution pH value, in the product of S3, add the product of S1, continue reaction 1 ~ 2 hour, carry out polycondensation;
S5, to add alkali regulator solution pH value be 11.0 ~ 12.0, at 80-100 DEG C of reaction 0.5-2 hour, carries out polymer molecule reformation, weak bond fracture and remove residues of formaldehyde in the basic conditions.
7. the preparation method of a kind of modified melamine water reducer according to claim 6, is characterized in that, the mode adding the product of S1 in the step S4 of described preparation method in the product of S3 is specially dropping.
8. the preparation method of a kind of modified melamine water reducer according to claim 7, is characterized in that, the alkali added in the S5 of described preparation method is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide.
9. the preparation method of a kind of modified melamine water reducer according to claim 7 or 8, is characterized in that, pass through the sulphuric acid soln of dropping 10% in the S4 of described preparation method in reaction soln, regulator solution pH value is 4.5 ~ 6.5.
10. the preparation method of a kind of modified melamine water reducer according to claim 9, is characterized in that, by dripping alkali lye in reaction soln in the S5 of described preparation method, regulator solution pH value is 11.0 ~ 12.0.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820300A (en) * | 2016-03-15 | 2016-08-03 | 苏州市兴邦化学建材有限公司 | Synthesis method of melamine water reducer for desulfurized gypsum |
| CN111197299A (en) * | 2020-01-14 | 2020-05-26 | 南昌航空大学 | Preparation and construction method of geotechnical impermeable material |
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| JP2000302510A (en) * | 1999-04-20 | 2000-10-31 | Mitsui Chemicals Inc | Cement admixture |
| CN101723615A (en) * | 2009-12-18 | 2010-06-09 | 江苏特密斯混凝土外加剂有限公司 | Method for preparing novel sulfamic acid high-efficiency concrete water reducing agent |
| CN102321229A (en) * | 2011-05-27 | 2012-01-18 | 江苏博特新材料有限公司 | Modified sulfonated melamine-formaldehyde condensation polymer water reducing agent and preparation method thereof |
| CN102452806A (en) * | 2010-10-18 | 2012-05-16 | 江苏汇迪建材有限公司 | Novel melamine water reducer and preparation method |
| CN102898058A (en) * | 2012-11-01 | 2013-01-30 | 徐友娟 | Low-cost melamine water reducing agent and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302510A (en) * | 1999-04-20 | 2000-10-31 | Mitsui Chemicals Inc | Cement admixture |
| CN101723615A (en) * | 2009-12-18 | 2010-06-09 | 江苏特密斯混凝土外加剂有限公司 | Method for preparing novel sulfamic acid high-efficiency concrete water reducing agent |
| CN102452806A (en) * | 2010-10-18 | 2012-05-16 | 江苏汇迪建材有限公司 | Novel melamine water reducer and preparation method |
| CN102321229A (en) * | 2011-05-27 | 2012-01-18 | 江苏博特新材料有限公司 | Modified sulfonated melamine-formaldehyde condensation polymer water reducing agent and preparation method thereof |
| CN102898058A (en) * | 2012-11-01 | 2013-01-30 | 徐友娟 | Low-cost melamine water reducing agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820300A (en) * | 2016-03-15 | 2016-08-03 | 苏州市兴邦化学建材有限公司 | Synthesis method of melamine water reducer for desulfurized gypsum |
| CN111197299A (en) * | 2020-01-14 | 2020-05-26 | 南昌航空大学 | Preparation and construction method of geotechnical impermeable material |
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