CN1634794A - High efficiency aliphatic sulfonate water reducing agent and method for preparing same - Google Patents
High efficiency aliphatic sulfonate water reducing agent and method for preparing same Download PDFInfo
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Abstract
The present invention relates to a high efficiency water reducing agent for manufacturing high performance cement based material such as high-strength concrete, fluid state and/or pumping concrete, etc. and method for preparing same. The invention takes ketones compound and aldehydes as condensation monomer, and sulphite as sulphonating agent, and take condensation reaction in alkaline aqueous solution. Then a water-soluble high-polymer condensate containing hydrophilic group such as sulfonic group, carboxy, hydroxyl, etc. in molecule with molecular weight ranging from 3000 to 10000 is obtained. By changing the matching, charging sequence of raw material, the technological process is simplified, the reaction time is shortened, and burst boiling and geling phenomena are also avoided at the same time. By controlling charging rate and condensation temperature, the condensation product is made with required molecular weight and can meet application performance. The fatty group sulphonate condensation compound made by the invention can be served as high efficiency water reducing agent of cement concrete, the water reducing, dispersion and reinforcing effects are better than the traditional albocarbon group high efficiency water reducing agent. The water reducing agent provided by the invention has the advantages of wide raw material source, simple synthesizing process, clean and suitable for industrial production.
Description
Technical Field
The invention relates to an aliphatic sulfonate high-efficiency water reducing agent and a preparation method thereof. The composition and molecular structure of the high-efficiency water reducing agent are different from the naphthalene high-efficiency water reducing agent and the melamine high-efficiency water reducing agent which are used in the past, and the high-efficiency water reducing agent can be used as a cement concrete high-efficiency water reducing agent, a refractory casting material dispersing agent, a water-coal-slurry dispersing agent, an oil well water agent drag reducer and the like in the building industry.
Background
The research on the synthesis, manufacture and application performance of the naphthalene-based superplasticizer begins in the early 70 s in China, UNF-5 and FDN series superplasticizer products (CN1030574 and CN1107447) are successively developed, and the naphthalene-based superplasticizer is widely applied to the industries of buildings, hydropower, traffic, coal mines and the like. On the basis, in consideration of the limitation of industrial naphthalene and refined naphthalene raw materials, the high-efficiency water reducing agent product (CN1083030A) which takes coking byproducts (oil naphthalene, anthracene oil and indene) except the industrial naphthalene and the refined naphthalene as main raw materials is successfully researched and developed, and industrial production and application are realized, wherein the varieties comprise the Jian-1 high-efficiency water reducing agent (oil naphthalene as the main raw material) and the AF high-efficiency water reducing agent (anthracene oil as the main raw material) which are used up to now. In the later 70 s, the melamine formaldehyde resin high-efficiency water reducing agent is successfully researched and developed in China, and cannot be popularized and applied in a large scale due to high price.
In the beginning of the 90 s in the 20 th century, on one hand, due to the reasons of short supply of industrial naphthalene, large fluctuation of the price of the industrial naphthalene and the like in China, and on the other hand, naphthalene series and melamine series have the defects of performance, such as low water reducing rate, poor adaptability to cement varieties and the like, and various countries pay attention to the development of non-naphthalene high-efficiency water reducing agents. The aliphatic sulfonate high-efficiency water reducing agent is a novel high-efficiency water reducing agent different from naphthalene and melamine. From the data at home and abroad, the research on the ketone-aldehyde condensation compound as the drag reducer of oil well cement has been carried out in the petroleum drilling industry in China. In our national patents CN 1050211a and CN 1066448A, methods for producing cement drag reducing agents for oil wells using acetone and formaldehyde are described, wherein the polymer condensates are developed for mud drag reducing agents for oil industry well drilling, and the main problem to be solved is to maintain good dispersibility of the slurry at high temperature or in high salt concentration solution. The problem of application as a concrete high-efficiency water reducing agent in the construction industry is not involved. Further, Japanese patent No. Sho 59-206427 and U.S. Pat. No. 6,264,539 also relate to a method for producing a slurry dispersant, a water-retaining agent and the like for well drilling in the petroleum industry by using a ketone-aldehyde condensate. The main problem solved is mainly the stability of the slurry under high temperature condition, and the technology for the cement concrete industry is not involved. In short, it is clear from the literature that there is no technical product of aliphatic sulfonates as various high-efficiency water reducing agents for producing various cement concretes. The related patents mainly relate to mud drag reducers in the oil well drilling industry, which are greatly different from the use conditions and technical requirements of high-efficiency water reducers in the construction industry, and the manufacturing process of the mud drag reducers is complex and has long reaction time. The invention aims to solve the problems that the process is simplified, the reaction time is shortened, the phenomena of bumping and gelling in the reaction are avoided, and the aliphatic sulfonate high-efficiency water reducing agent which is suitable for the building industry and has proper molecular weight and functional groups is synthesized by changing the proportion of raw materials and the feeding sequence.
Disclosure of Invention
The invention relates to an aliphatic sulfonate high-efficiency water reducing agent, which is prepared by using ketone and aldehyde compounds as condensation monomers and sulfite as a sulfonating agent through chemical synthesis in an aqueous solution, contains hydrophilic groups such as hydroxyl, carboxyl, sulfonic group and carbonyl, and has the number average molecular weight of 3000-10000.
The invention also relates to a preparation method of the aliphatic sulfonate high-efficiency water reducing agent, which comprises the following steps: firstly, water is put into a reaction vessel, and a sulfonating agent is put into the reaction vessel to carry out hydrolysis reaction of the sulfonating agent; then, putting the ketone compound into the solution to carry out sulfonation reflux reaction of the ketone compound; then, dripping formaldehyde into the solution at the temperature of 40-60 ℃ to carry out carbonylation exothermic reaction, and heating the solution to 85-96 ℃ after finishing adding the formaldehyde; then, carrying out high-temperature condensation reaction at the temperature of 95-110 ℃; and finally, cooling the mixed solution to obtain the liquid water reducing agent.
Furthermore, the raw materials of the high efficiency water reducing agent comprise a ketone compound, an aldehyde compound, a sulfite and water in a molar ratio of 1: 1.5-3.0: 0.33-0.8: 8-15.
Furthermore, in the raw materials of the high-efficiency water reducing agent, the ketone compound refers to one or more of acetone, butanone, cyclohexanone, methyl ethyl ketone, acetophenone and the like; the aldehyde compounds are formaldehyde, paraformaldehyde, acetaldehyde, furfural, crotonaldehyde and the like; the sulfonating agent comprises one or more of sodium sulfite, sodium bisulfite and sodium pyrosulfite. The end point of the reaction of the product is determined by sampling and analyzing the dispersibility of the product.
When the synthesis reaction is carried out according to different raw material ratios, the system sometimes has a gelation phenomenon. The gel formed produces an crosslinked network structure with reduced or no water solubility, and thus does not disperse cement particles. The occurrence of gelation is greatly related to the amount of the sulfonating agent and the reaction temperature during the reaction. Both aldehydes and ketones can be considered as difunctional compounds in the reaction system. The condensation reaction between them, even if carried out to the full extent, gives only a linear polycondensate without the appearance of crosslinked gels, whereas in the presence of sodium sulfite:
the product obtained after addition of sodium bisulfite to acetone had virtually 4 functional groups. If the ratio of the molecules in the reaction system is as usual: HCHO: CH3COCH3When 2: 1, the average functionality of the system is:
according to the theoretical formula of functionality:
p-degree of polymerization, Xf-average degree of condensation.
When gelation occurs, X → ℃ ≧ and P ═ 2/(8/3) ═ 75% are considered. I.e. the gel point is approached by the time the reaction degree reaches 75%. In fact, the actual degree of reaction to the gel point tends to be higher, since the acetone of the reaction system is generally not able to be added completely. In order to avoid the cross-linking reaction, the dosage of the sulfonating agent and the proportion of the sulfonating agent to the ketone compound, the reaction time and the temperature are strictly controlled.
The key point of the preparation method is that the molecular weight of the obtained aliphatic high-molecular condensation compound is controlled within 3000-10000 by controlling the proportion, the feeding sequence, the reaction steps and parameters of raw materials, and hydrophilic functional groups such as sulfonic group, hydroxyl group, carboxyl group, carbonyl group and the like are contained in molecules of the condensation compound.
Furthermore, in the method for preparing the high-efficiency water reducing agent, the processes of sulfite hydrolysis and sulfonation reflux reaction of ketone compounds are carried out at the temperature of 30-65 ℃ for 30-60 minutes.
Furthermore, in the method for preparing the high-efficiency water reducing agent, the adding speed is slow and gradually accelerated when formaldehyde is dropwise added in the carbonylation exothermic reaction process.
Furthermore, in the method for preparing the high-efficiency water reducing agent, the high-temperature condensation reaction lasts for 2-6 hours.
Still further, the liquid product is neutralized with formic acid or acetic acid.
Compared with the prior art, the method provided by the invention has the following advantages: (1) by adjusting the raw material ratio and the feeding sequence, the reaction at each stage is stable and easy to control; the phenomena of bumping and gelling in the condensation reaction are avoided; (2) the condensation product prepared by the method has stable performance, can be stored for at least two years, has no crystallization within minus 8 ℃, and is suitable for construction in winter; (3) compared with the production process of the high-efficiency water reducing agent in the prior art, the method provided by the invention has the advantages of short production period, low energy consumption (only about 1/2 of naphthalene), and simple equipment; (4) the preparation process of the method has no discharge of three wastes (waste water, waste gas and waste residue), no pollution to the environment, no odor of the product and good use environment; (5) the aliphatic sulfonate high-efficiency water reducing agent prepared by the method has better performance than a naphthalene high-efficiency water reducing agent, high water reducing rate (up to 30 percent), quick strength increase and good adaptability to cement varieties; (6) the aliphatic sulfonate high-efficiency water reducing agent prepared by the method has the advantages of wide raw materials and low cost, is suitable for building engineering in the industries of construction, hydropower, traffic and the like, and has good application prospect.
Drawings
FIG. 1 is an infrared spectrum of the aliphatic sulfonate superplasticizer of the invention.
Detailed Description
Example 1
The synthesis reactions described in this example and each of the following examples were carried out in a reaction vessel equipped with an electric stirrer, a thermometer, a dropping funnel and a reflux condenser.
Firstly, 12.5 mol of water is put into a reaction vessel, preheated to 30 ℃, and then 0.52 mol of anhydrous sodium sulfite is added for hydrolysis reaction of a sulfonating agent; then, adding 0.96 mol of acetone, and carrying out reflux reaction for 30-60 minutes; then dropwise adding 2.2 mol of formaldehyde with the concentration of 37% into the solution from a dropping funnel to perform carbonylation reaction, wherein the temperature for adding the formaldehyde is 40-60 ℃, the formaldehyde is slowly dropwise added, and then the adding speed of the formaldehyde is gradually increased; after the formaldehyde is added, the temperature of the reaction system is automatically increased to 85-96 ℃; and heating to 90-110 ℃, reacting for 2-6 hours at the temperature, and performing high-temperature condensation reaction to obtain liquid with the concentration of 30-40%, namely the aliphatic sulfonate high-efficiency water reducing agent.
Example 2
Firstly, 8.3 mol of water is put into a reaction vessel, preheated to 30 ℃, and then 0.62 mol of anhydrous sodium sulfite is added for hydrolysis reaction of a sulfonating agent; then, adding 0.51 mol of cyclohexanone, and carrying out reflux reaction for 30-60 minutes; then 0.87 mol of formaldehyde with the concentration of 37% is dripped into the solution from a dropping funnel for carbonylation, the temperature for adding the formaldehyde is 40-60 ℃, the formaldehyde is slowly dripped when the formaldehyde is started, and then the adding speed of the formaldehyde is graduallyincreased; after the formaldehyde is added, the temperature of the reaction system is automatically increased to 85-96 ℃; and heating to 90-110 ℃, reacting for 2-6 hours at the temperature, and performing high-temperature condensation reaction to obtain amber transparent liquid with the concentration of about 40%, namely the aliphatic sulfonate high-efficiency water reducer.
Example 3
Firstly, 11 mol of water is put into a reaction vessel, preheated to 30 ℃, and then 0.67 mol of anhydrous sodium sulfite is added for hydrolysis reaction of a sulfonating agent; then, adding 0.96 mol of acetone, and carrying out reflux reaction for 30-60 minutes; then dropwise adding 2.23 mol of formaldehyde with the concentration of 37% into the solution from a dropping funnel to perform carbonylation reaction, wherein the temperature for adding the formaldehyde is 40-60 ℃, the formaldehyde is slowly dropwise added, and then the adding speed of the formaldehyde is gradually increased; after the formaldehyde is added, the temperature of the reaction system is automatically increased to 85-96 ℃; and heating to 90-110 ℃, reacting for 2-6 hours at the temperature, and performing high-temperature condensation reaction to obtain liquid with the concentration of 30-40%, namely the aliphatic sulfonate high-efficiency water reducing agent.
Example 4
Firstly, 12 mol of water is put into a reaction vessel, preheated to 30 ℃, and then 0.5 mol of anhydrous sodium sulfite and 0.2 mol of sodium pyrosulfite are added for hydrolysis reaction of a sulfonating agent; then, adding 0.95 mol of acetone, and carrying out reflux reaction for 30-60 minutes; then dropwise adding 2.45 mol% of formaldehyde with the concentration of 37% into the solution from a dropping funnel to perform carbonylation reaction, wherein the temperature for adding the formaldehyde is 40-60 ℃, theformaldehyde is slowly dropwise added, and then the adding speed of the formaldehyde is gradually increased; after the formaldehyde is added, the temperature of the reaction system is automatically increased to 85-96 ℃; and heating to 90-110 ℃, reacting for 2-6 hours at the temperature, and performing high-temperature condensation reaction to obtain liquid with the concentration of 30-40%, namely the aliphatic sulfonate high-efficiency water reducing agent.
Example 5
Firstly, 12 mol of water is put into a reaction vessel, preheated to 30 ℃, and then 0.52 mol of anhydrous sodium sulfite and a catalyst (such as 0.5g of caustic soda) are added for hydrolysis reaction of a sulfonating agent; then, adding 0.95 mol of acetone, and carrying out reflux reaction for 30-60 minutes; then dropwise adding 2.45 mol% of formaldehyde with the concentration of 37% into the solution from a dropping funnel to perform carbonylation reaction, wherein the temperature for adding the formaldehyde is 40-60 ℃, the formaldehyde is slowly dropwise added, and then the adding speed of the formaldehyde is gradually increased; after the formaldehyde is added, the temperature of the reaction system is automatically increased to 85-96 ℃; and heating to 90-110 ℃, reacting for 2-6 hours at the temperature, and performing high-temperature condensation reaction to obtain liquid with the concentration of 30-40%, namely the aliphatic sulfonate high-efficiency water reducing agent.
The above examples only illustrate the production of the aliphatic sulfonate superplasticizer of the present invention using different raw materials, but in order not to repeat the description, a large number of experiments have been conducted for each example, and specific values are given in each example, such as the temperature at which formaldehyde is initially added is 40 to 60 ℃ (40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ in the actual experiment), and after the addition of formaldehyde, the solution is heated to 85 to 96 ℃ (85 ℃, 88 ℃, 90 ℃, 93 ℃, 95.5 ℃, 96 ℃ in the actual experiment), and the high-temperature condensation reaction is conducted under the conditions of 90 to 110 ℃ (90 ℃, 96 ℃, 100 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 108 ℃, 110 ℃ in the actual experiment).
The synthesized polymer sample was dried, ground, tableted with KBr, and measured for its infrared spectrum curve with SDXC infrared spectrometer, as shown in fig. 1. Wherein: 3428cm-1Is a hydroxyl stretching vibration peak; 2924-2700 cm-1Is a C-H bond stretching vibration peak on an aliphatic molecular chain; 1702cm-1Is a carbonyl absorption peak; 1603cm-1Is the carboxyl salt absorption peak; 1183cm-1Is a sulfonic acid group absorption peak; 1044 is the vibration of the sulfonic acid structure. Therefore, the high efficiency water reducing agent contains functional groups such as hydroxyl, carbonyl, sulfonic acid group and the like in molecules, wherein the hydroxyl and the sulfonic acid group are strong hydrophilic groups, when the admixture is added into cement slurry, an electric double layer is formed, so that electrostatic repulsion is generated to disperse cement particles, and stirring water is released to achieve the water reducing plasticizing effect.
The thermal stability of the synthesized product was examined by using DSC-2C differential scanning calorimeter of TGS-2 type manufactured by QERRIN-ELMER. The weight loss of 7.73% is caused by water volatilization in the range of 50-100 ℃. In the range of 100.2-199.5 deg.c, there is peak around 100 deg.c, and Differential Scanning Calorimetry (DSC) curve is made to show that there is one melting peak at 372.06 deg.c caused by the melting of low molecular matter. The chemical analysis result shows that the content of sodium sulfate in the condensation compound is less than 0.5 percent, the phenomenon of sodium sulfate crystallization can not occur at low temperature in winter, and the problem caused by sodium sulfate crystallization of a common naphthalene-based high-efficiency water reducing agent liquid product in concrete construction in winter is solved.
The samples synthesized in the above-mentioned experimental examples were subjected to fluidity tests in accordance with the cement paste fluidity test method described in GB 8077-87 "concrete admixture homogeneity test method". As comparison, the results of the tests using the currently commonly used naphthalene superplasticizer FDN and UNF products are also shown in Table 1. The fluidity of the cement paste doped with the high efficiency water reducing agent of the invention is measured by using a coaxial rotary viscosity agent, and the result is shown in Table 2. The water reducing rate and the reinforcing effect on concrete of the superplasticizer sample 3 of the present invention are shown in table 3.
TABLE 1 Cement paste fluidity (mm)
TABLE 2 rheological parameters of cement slurries with admixtures
| W/C | Kind of additive | Mixing amount% | Rheological parameters | |
| ηpl，Pa·S | τo，Pa | |||
| 0.4 | Is free of | --- | 0.5650 | 16.8980 |
| 0.4 | Example 3 | 0.3 | 0.1145 | 3.1487 |
| 0.4 | Example 3 | 0.5 | 0.1075 | 2.3460 |
| 0.4 | FDN | 0.3 | 0.2300 | 4.7680 |
| 0.4 | FDN | 0.5 | 0.1815 | 4.3355 |
| 0.4 | UNF-5 | 0.3 | 0.2450 | 5.1230 |
| 0.4 | UNF-5 | 0.5 | 0.1924 | 4.6236 |
TABLE 3 Water-reducing ratio of Admixture and compressive Strength of concrete
| Concrete mixing ratio, kg/m3 | Example 3 ％ | Water reduction rate ％ | Slump cm | Strength, MPa | |||||
| 3d | 7d | 28d | |||||||
| C | S | G | W | ||||||
| 310 | 740 | 1110 | 190 | 0.0 | 0.0 | 8.0 | 16.2/100 | 23.6/100 | 36.4/100 |
| 310 | 740 | 1110 | 171 | 0.2 | 9.8 | 7.0 | 23.1/142 | 29.5/125 | 40.4/111 |
| 310 | 740 | 1110 | 165 | 0.4 | 13.1 | 9.0 | 26.1/161 | 34.1/144 | 43.4/119 |
| 310 | 740 | 1110 | 156 | 0.6 | 18.0 | 7.0 | 32.8/202 | 39.3/166 | 48.1/132 |
| 310 | 740 | 1110 | 146 | 0.8 | 23.0 | 8.0 | 35.5/219 | 40.9/173 | 51.5/141 |
| 310 | 740 | 1110 | 142 | 1.0 | 25.2 | 8.5 | 39.0/241 | 45.4/192 | 55.6/153 |
| 310 | 740 | 1110 | 132 | 1.2 | 30.5 | 7.8 | 41.2/254 | 47.0/199 | 58.7/161 |
| 310 | 740 | 1110 | 129 | 1.5 | 32.0 | 8.5 | 42.1/260 | 50.7/215 | 61.4/168 |
The test results show that the high-efficiency water reducing agent prepared by the method has better dispersion effect than naphthalene high-efficiency water reducing agents, and the cement paste fluidity of the high-efficiency water reducing agent is higher than that of FDN and UNF naphthalene high-efficiency water reducing agents under the same mixing amount. The test result of the rheological parameters also shows that the high-efficiency water reducing agent prepared by the method can better reduce the yield value and the plastic viscosity of the cement paste under the same mixing amount. Water reducing rate and concrete strength test show that the water reducing rate of the high efficiency water reducing agent prepared by the method can reach 30 percent, and the strength value of concrete in each order period is obviously increased. By combining the test results, the high-efficiency water reducing agent prepared by the method has excellent water reducing dispersion effect and reinforcing performance, is a novel concrete high-efficiency water reducing agent with excellent performance, and has good application prospect.
Claims (10)
1. A method for preparing aliphatic sulfonate high-efficiency water reducing agent, using ketone and aldehyde compounds as condensation monomers, using sulfite and/or pyrosulfite as sulfonating agent, chemically synthesizing aliphatic sulfonate water reducing agent in aqueous solution, comprising the following steps:
firstly, water is put into a reaction vessel, and a sulfonating agent is put into the reaction vessel to carry out hydrolysis reaction of the sulfonating agent;
then, putting the ketone compound into the solution to carry out sulfonation reflux reaction of the ketone compound;
then, dripping an aldehyde compound into the solution at the temperature of 40-60 ℃ to carry out carbonylation exothermic reaction, and heating the solution to 85-96 ℃ after finishing adding formaldehyde;
then, carrying out high-temperature condensation reaction at the temperature of 90-110 ℃;
and finally, cooling the mixed solution to obtain the liquid water reducing agent.
2. The process for preparing aliphatic sulfonate superplasticizer according to claim 1, wherein the molar ratio of the ketone compound, the aldehyde compound, the sulfite and the water is 1: 1.5-3.0: 0.33-0.8: 8-15.
3. The process for producing an aliphatic sulfonate superplasticizer according to claim 1 or 2, wherein the ketone compound is acetone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone or the like; the aldehyde compounds are formaldehyde, paraformaldehyde, acetaldehyde, furfural, crotonaldehyde and the like; the sulfonating agent comprises one or more of sodium sulfite, sodium bisulfite and sodium pyrosulfite.
4. The method of claim 1, wherein the hydrolysis of sulfite and the sulfonation reflux reaction of the ketone compound are carried out at 30-65 ℃ for 30-60 minutes.
5. The process for producing an aliphatic sulfonate superplasticizer according to claim 1, wherein the addition rate is initially slow and gradually increased when the aldehyde compound is added dropwise during the exothermic carbonylation reaction.
6. The method according to claim 1, wherein the high-temperature condensation reaction is continued for 2 to 6 hours.
7. The process for producing an aliphatic sulfonate superplasticizer according to claim 1, wherein acetone and formaldehyde are used as condensation monomers, and anhydrous sodium sulfite is used as a sulfonating agent.
8. The process for producing an aliphatic sulfonate superplasticizer according to claim 1, wherein cyclohexanone and formaldehyde are used as condensation monomers, and anhydrous sodium sulfite is used as a sulfonating agent.
9. The process for producing an aliphatic sulfonate superplasticizer according to claim 1, wherein cyclohexanone and formaldehyde are used as condensation monomers, and anhydrous sodium sulfite and sodium metabisulfite are used as sulfonating agents.
10. An aliphatic sulfonate high-efficiency water reducing agent for construction industry is characterized in that: ketone and aldehyde compounds are used as condensation monomers, sulfite and/or pyrosulfite are used as sulfonating agents, the condensation products are chemically synthesized in aqueous solution, the molecules of the condensation products contain hydrophilic groups such as hydroxyl, carboxyl, sulfonic acid group and carbonyl, and the number average molecular weight ranges from 3000 to 10000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1066448A (en) * | 1991-05-08 | 1992-11-25 | 中原石油勘探局钻井工程服务公司 | The manufacture method of sulphonated acetone formaldehyde polycondensates |
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