CN102992683B - Melamine high-efficiency water reducing agent and preparation method thereof - Google Patents
Melamine high-efficiency water reducing agent and preparation method thereof Download PDFInfo
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- CN102992683B CN102992683B CN201210376760.3A CN201210376760A CN102992683B CN 102992683 B CN102992683 B CN 102992683B CN 201210376760 A CN201210376760 A CN 201210376760A CN 102992683 B CN102992683 B CN 102992683B
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Abstract
The invention discloses a melamine high-efficiency water reducing agent and a preparation method thereof. The melamine high-efficiency water reducing agent is prepared from melamine, aldehyde acid and/or ester thereof, water, a sulfonating agent, an organic acid catalyst, and an alkaline neutralizer by reaction. Furthermore, the preparation method of the melamine high-efficiency water reducing agent is also disclosed by the invention. The water reducing agent disclosed by the invention is high in water-reducing rate, small in slump loss, good in cement adaptability, free of formaldehyde pollution in a production process, and especially suitable for dry-mixed mortar and a prefabricated part.
Description
Technical field
The invention belongs to technical field of concrete additives, be specifically related to a kind of novel melamine high efficiency water reducing agent and preparation method thereof.
Background technology
Melamine class water reducer is a kind of Soluble Anions resin, has significant diminishing, early potent fruit, and the time of coagulation substantially do not affected on coagulation and air content, on steam-cured coagulation and the first-class adaptability of clear water coagulation good.Therefore, on colored coagulation, in plastering, prefabricated components, good application is obtained.
Traditional Product Process is because the water-reducing rate of melamine high-efficiency water-reducing agent is not high, slump-loss is very fast, production process is complicated and be difficult to control, and be attended by the pollution of formaldehyde in process of production, and also poor to the adaptability of cement, the application of melamine high-efficiency water-reducing agent is restricted.
For solving the aforesaid drawbacks, the research of a large amount of modification is carried out to it both at home and abroad.Carry out the optimization of technique on the one hand, comprise the optimization to reactions steps, secondary adds formaldehyde method and the screening of sulphonating agent, and water-reducing rate is improved to some extent, but fundamentally do not improve the performance of water reducer.Studied by properties-correcting agent on the other hand, comprise properties-correcting agent such as adopting aromatic carboxylic acid, be greatly improved owing to introducing organic hydroxy-acid group to water-reducing rate, but slump-loss is still serious.
Summary of the invention
For the defect of prior art, the invention discloses the structure that a kind of melamine high-efficiency water-reducing agent fundamentally improves trimeric cyanamide, disclosed water reducer water-reducing rate is high, little loss of slump, and cement adaptability is good, formaldehydeless pollution in production process.Further the invention also discloses the preparation method of described water reducer.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of melamine high-efficiency water-reducing agent, is reacted made by trimeric cyanamide, aldehydic acid and/or its ester, water, sulphonating agent, Organic Acid and Base neutralizing agent.
The concrete structure of the water reducer using different aldehydic acid, sulphonating agent, Organic Acid and Base neutralizing agent etc. to obtain can be different, and such as, following structural formula illustrates a kind of node configuration of water reducer
In the present invention, according to the needs of preparation technology, the consumption of each composition used can be adjusted accordingly, in large industrial production, the carrying out of chemical reaction not carries out according to the ratio of simple chemical equation as is known to the person skilled in the art, and should be taken into account that various situation is that various composition retains necessary amount of redundancy thus makes reaction more complete.In the preferred case, in the present invention, the usage ratio of each composition is (with molar ratio computing): trimeric cyanamide: aldehydic acid and/or its ester: water: sulphonating agent: organic acid: alkaline neutraliser=1: (1.5 ~ 2.5): 16: (1.0 ~ 1.5): (0.5 ~ 1.0): (0.4 ~ 0.8).
Accordingly, the invention discloses the preparation method of above-mentioned water reducer, comprise with trimeric cyanamide, aldehydic acid and/or its ester for monomer, and be aided with Organic Acid and Base neutralizing agent, sulphonating agent in proportion under the temperature condition of 60 ~ 90 degrees Celsius, make the step of melamine high-efficiency water-reducing agent through methylolation, sulfonation, condensation and rearrangement reaction, concrete step is as follows:
(1) hydroxymethylation: trimeric cyanamide and aldehydic acid and/or its ester are heated to 60 ~ 75 degrees Celsius and carry out hydroxymethylation, be incubated 1 hour, wherein the molar ratio of trimeric cyanamide and aldehydic acid and/or its ester is 1: (1.5 ~ 2.5);
(2) sulfonation reaction, adjust ph 10 ~ 11, adds sulphonating agent, is warming up to 80 ~ 90 degrees Celsius, is incubated 1 ~ 2 hour, and the mol ratio of sulphonating agent and trimeric cyanamide is 1: (1.0 ~ 1.5);
(3) condensation reaction and rearrangement reaction: adopt organic acid acid for adjusting pH value to be 5 ~ 6, carry out condensation reaction, react 1 ~ 2 hour, add alkaline neutraliser adjust ph 8 ~ 9, continue stirring 0.5 ~ 1 hour, obtain described melamine high-efficiency water-reducing agent thus.
By above-mentioned preparation method, water reducer of the present invention introduces aldehydic acid (ester) molecule and participates in reaction, molecular chain adds a large amount of hydroxy-acid groups or ester group, melamine high-efficiency water-reducing agent is made to have very high water-reducing rate compared with traditional product, and due to the slow release effect of ester group, make trimeric cyanamide have good slump retention performance simultaneously, lose relatively little, and it is better to cement adaptability, condensation reaction is carried out using organic acid as catalyzer in formula, because hydrogen ion dissociation is slower, gelation in production process is made to be able to fine control.
Of the present invention be described in further detail and specifically implement in; the invention discloses the preferred type of various compositions used; so that better, clearer description the present invention; but this detailed description does not form special restriction of the present invention; do not rely on these detailed information and adopt other general chemical materials of the technology of the present invention field; as long as it meets the above-mentioned restriction done each moiety title of the present invention, still belong to protection scope of the present invention.
In the present invention, described aldehydic acid and/or its ester comprise oxoethanoic acid, malonaldehydic acid, glyoxalic acid methylester, glyoxylic acid ethyl ester, a kind of in malonaldehydic acid methyl esters, malonaldehydic acid ethyl ester and/or more than one mixture.
In the present invention, described organic acid comprises a kind of in acetic acid, propionic acid, oxyacetic acid, Sulphanilic Acid, citric acid and/or more than one mixture.
In the present invention, described alkaline neutraliser comprises sodium hydroxide, potassium hydroxide, a kind of in trolamine, diethanolamine and/or more than one mixture.
In above-mentioned raw materials, usually used is one or both mixture, is convenient to control consumption.
Compared with prior art, water reducer of the present invention has following technical superiority:
1. water-reducing rate is higher, and different volume water-reducing rates can reach 25% ~ 35%, under lower volume, have good dispersiveness to cement.
2. concrete slump loss is little, and workability is better, is conducive to concrete construction and builds.
3. the adaptability of cement is better, all has good dispersive ability to conventional cement.
4. formaldehydeless pollution in production process, belongs to environmentfriendly products.
Embodiment
In conjunction with the invention spirit that embodiment can better understand the present invention; but the present invention is not restricted to only adopt following method to realize; those skilled in the art carry out according to existing general knowledge on this basis change, replacement etc. still belong to protection scope of the present invention, and protection scope of the present invention is covered by its claim and equivalents thereof.
Embodiment 1
By trimeric cyanamide: oxoethanoic acid: water: sulphonating agent: catalyzer: alkali neutralizing agent=1: 1.5: 16: 1.2: 0.6: 0.55 (each component all in molar ratio) feeds intake, heat up from 65 to 80 DEG C, through hydroxymethylation, sulfonation reaction, condensation reaction and rearrangement reaction step, obtain the transparent liquid of thick pale yellow after reaction in 4 hours, obtain the melamine high-efficiency water-reducing agent of solid content 40%.
Embodiment 2
By trimeric cyanamide: oxoethanoic acid: glyoxalic acid methylester: water: sulphonating agent: catalyzer: alkali neutralizing agent=1: 0.5: 1.5: 16: 1.0: 0.6: 0.55 (each component all in molar ratio) feeds intake, heat up from 60 to 85 DEG C, through hydroxymethylation, sulfonation reaction, condensation reaction and rearrangement reaction step, obtain the transparent liquid of light yellow look thickness after reaction in 4 hours, obtain the melamine high-efficiency water-reducing agent of solid content 40%.
Embodiment 3
By trimeric cyanamide: glyoxylic acid ethyl ester: water: sulphonating agent: catalyzer: alkali neutralizing agent=1: 2.2: 16: 1.2: 0.6: 0.55 (each component all in molar ratio) feeds intake, heat up from 65 to 85 DEG C, through hydroxymethylation, sulfonation reaction, condensation reaction and rearrangement reaction step, obtain the transparent liquid of colorless viscous after reaction in 6 hours, obtain the melamine high-efficiency water-reducing agent of solid content 40%.
Application Example 1
In order to evaluate the dispersing property to cement of melamine high-efficiency water-reducing agent of the present invention, according to the method measuring flowing degree of net paste of cement in GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", reference cement 300g, amount of water is 87g, the solid volume of folding of water reducer is 0.4% of cement quality, adopt clean slurry stirrer to carry out testing initial paste flowing degree and 1 paste flowing degree as a child, experimental result is in table 1 (note: commercially available SM represents the trimeric cyanamide SM high efficiency water reducing agent of current main flow).
The flowing degree of net paste of cement experiment of table 1 melamine high-efficiency water-reducing agent
| Sample number into spectrum | Volume | Initial paste flowing degree/mm | 1 hour paste flowing degree/mm |
| Embodiment 1 | 0.4％ | 250 | 225 |
| Embodiment 2 | 0.4％ | 215 | 210 |
| Embodiment 3 | 0.4％ | 185 | 205 |
| Commercially available SM | 0.6％ | 215 | 130 |
Application Example 2
In order to evaluate the adaptability to cement of novel melamine high efficiency water reducing agent of the present invention, according to the method measuring flowing degree of net paste of cement in GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", cement 300g, amount of water is 87g, comparative sample selects the SM product test on market, adopt clean slurry stirrer to carry out testing initial paste flowing degree, experimental result is in table 2.
Table 2 melamine high-efficiency water-reducing agent is to the experiment of different flowing degree of net paste of cement
Can be found out by above-mentioned experimental result, aldehydic acid (ester) is incorporated in molecular structure by the preparation method of melamine high-efficiency water-reducing agent of the present invention, improves the water-reducing rate of water reducer, produces formaldehydeless pollution and belongs to environmentfriendly products.The melamine high-efficiency water-reducing agent prepared by present method has excellent dispersing property and adaptability to cement, and better than commercially available melamine water reducing agent performance.
Claims (2)
1. a melamine high-efficiency water-reducing agent, is characterized in that, described melamine high-efficiency water-reducing agent is reacted made by the mixture of trimeric cyanamide, aldehydic acid ester or aldehydic acid ester and aldehydic acid, water, sulphonating agent, Organic Acid and Base neutralizing agent; Wherein, the usage ratio of each composition is, with molar ratio computing: trimeric cyanamide: the mixture of aldehydic acid ester or aldehydic acid ester and aldehydic acid: water: sulphonating agent: organic acid: alkaline neutraliser=1:(1.5 ~ 2.5): 16:(1.0 ~ 1.5): (0.5 ~ 1.0): (0.4 ~ 0.8);
Wherein, described aldehydic acid is oxoethanoic acid and/or malonaldehydic acid, and described aldehydic acid ester is glyoxalic acid methylester, glyoxylic acid ethyl ester, a kind of in malonaldehydic acid methyl esters, malonaldehydic acid ethyl ester and/or more than one mixture; Described organic acid comprises a kind of in acetic acid, propionic acid, oxyacetic acid, Sulphanilic Acid, citric acid and/or more than one mixture; Described alkaline neutraliser comprises sodium hydroxide, potassium hydroxide, a kind of in trolamine, diethanolamine and/or more than one mixture.
2. the preparation method of the melamine high-efficiency water-reducing agent of claim 1, it is characterized in that, concrete comprises the steps: (1) hydroxymethylation: the mixture of trimeric cyanamide and aldehydic acid ester or aldehydic acid ester and aldehydic acid is heated to 60 ~ 75 degrees Celsius and carries out hydroxymethylation, be incubated 1 hour; (2) sulfonation reaction: adjust ph, to 10 ~ 11, adds sulphonating agent, is warming up to 80 ~ 90 degrees Celsius, is incubated 1 ~ 2 hour; (3) condensation reaction and rearrangement reaction: with organic acid adjust ph for 5 ~ 6, carries out condensation reaction, reacts 1 ~ 2 hour, adds alkaline neutraliser adjust ph 8 ~ 9, continues stirring 0.5 ~ 1 hour, to obtain final product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020173723A1 (en) * | 2019-02-27 | 2020-09-03 | Basf Se | Mixture comprising glyoxylic acid or condensation or addition products thereof |
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| CN111247113B (en) * | 2017-10-20 | 2022-06-10 | 建筑研究和技术有限公司 | Setting control composition for bonding systems |
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| CN1095385A (en) * | 1994-01-26 | 1994-11-23 | 华南理工大学 | The preparation method of high-sulfonated melamine compound resin |
| US5891983A (en) * | 1996-07-09 | 1999-04-06 | Skw Trostberg Aktiengesellschaft | Water-soluble formaldehyde-free polycondensation products based on amino-s-triazines |
| 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 |
| CN101845132A (en) * | 2010-05-06 | 2010-09-29 | 山东宏艺科技股份有限公司 | Modified melamine high-efficiency water reducing agent with low cost |
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Patent Citations (4)
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| CN1095385A (en) * | 1994-01-26 | 1994-11-23 | 华南理工大学 | The preparation method of high-sulfonated melamine compound resin |
| US5891983A (en) * | 1996-07-09 | 1999-04-06 | Skw Trostberg Aktiengesellschaft | Water-soluble formaldehyde-free polycondensation products based on amino-s-triazines |
| 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 |
| CN101845132A (en) * | 2010-05-06 | 2010-09-29 | 山东宏艺科技股份有限公司 | Modified melamine high-efficiency water reducing agent with low cost |
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| effect of some water-soluble melamine formaldehyde-free polycondensates on the rheological properties of cement pastes;Ismail Aiad;《Journal of applied polymer science》;20051231;第98卷;第2212-2218页 * |
| 吴兆强 等.磺化三聚氰胺甲醛树脂合成的磺化工艺及磺化结构分析.《华南师范大学学报(自然科学版)》.2005,(第1期),第71-76页. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020173723A1 (en) * | 2019-02-27 | 2020-09-03 | Basf Se | Mixture comprising glyoxylic acid or condensation or addition products thereof |
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Effective date of registration: 20161109 Address after: 414009 Industrial Park, Yunxi District, Hunan, Yueyang Patentee after: Yueyang Oriental Yuhong Waterproof Technology Co., Ltd. Patentee after: Beijing Oriental Yuhong Waterproof Technology Co., Ltd. Address before: 100123 Beijing, Gaobeidian, Kang Kang home district, building 4, building No. Patentee before: Beijing Oriental Yuhong Waterproof Technology Co., Ltd. |