CN100415675C - 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 producing high-strength cement based material, such as high-strength concrete, fluidized and/or pumping concrete, etc. and a producing method thereof. The present invention adopts a carbonyl containing ketone compound and aldehydes as condensation monomers, and sulphite as a sulfonating agent, and carries out condensation reaction in an alkaline aqueous solution; then a water-soluble high-polymer condensation compound containing hydrophilic groups such as a sulfonic group, carboxyl, hydroxyl, etc. in molecules with the molecular weight of 3000 to 10000 is produced. By changing the proportion and charging sequence of raw material, the technological processes are simplified, the reaction time is shortened, and the phenomena of burst boiling and gelling in the reaction are avoided; by controlling the feeding speed and condensation temperature, the condensation product with the required molecular weight is produced to meet the application performance. The produced fatty group sulphonate condensation compound can be used as a high-efficiency water-reducing agent for cement concrete, and the water-reducing, dispersion and reinforcing effects are better than a traditional albocarbon group high-efficiency water-reducing agent. The water-reducing agent produced with the present invention has the advantages of wide source of raw material, simple synthesizing technology and cleanness, and thus, the water-reducing agent is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Aliphatic sulfonate superplasticizer and its preparation method.The composition of this high efficiency water reducing agent and molecular structure are different from previously used naphthalene series high-efficiency water-reducing agent and melamine series high-efficiency water-reducing agent, the cement concrete highly-efficient water reducer that can be used as building industry, fire-resistant pouring material dispersion agent, coal water slurry dispersing agent and oil well aqua flow improver etc.
Background technology
China begins the research of synthetic manufacturing of naphthalene series high-efficiency water-reducing agent and application performance from the initial stage seventies, successively succeed in developing UNF-5, (CN1030574 CN1107447), and obtains widespread use in industries such as building, water power, traffic, collieries to the high efficiency water reducing agent product of FDN series.On this basis, consider the limitation of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and refined naphthalene raw material, successfully researched and developed with the coke by-products outside NAPTHALENE FLAKES. (INDUSTRIAL GRADE and the refined naphthalene (oily naphthalene, carbolineum, benzofuran) is the high efficiency water reducing agent product (CN 1083030A) of main raw material(s), and suitability for industrialized production and application have been realized, these kinds comprise so far still what use builds-1 high efficiency water reducing agent (oily naphthalene is main raw material), AF high efficiency water reducing agent (carbolineum is main raw material).In the later stage seventies, China researchs and develops successful terpolycyantoamino-formaldehyde resin high efficiency water reducing agent, because price is higher, fails large-scale popularization to use.
Begin the nineties in 20th century, on the one hand because China's NAPTHALENE FLAKES. (INDUSTRIAL GRADE is in short supply, reasons such as the NAPTHALENE FLAKES. (INDUSTRIAL GRADE price volalility is big, naphthalene system and trimeric cyanamide are the performance defect of existence own on the other hand, not high enough as water-reducing rate, with cement type adaptive faculty difference etc., un-naphthalene water reducing agent is noted developing by various countries.The aliphatic sulfonate high efficiency water reducing agent is the new and effective water reducer that is different from naphthalene system and trimeric cyanamide system.From data at home and abroad, China's oil drilling well industry was once carried out the research of keto-aldehyde condenses as well cement tolerance blocking.In China patent CN 1050211A and CN 1066448A, described and used acetone and formaldehyde manufacturing to be used for the method for well cement tolerance blocking, the wherein said polymer condenses mud flow improver that all drilling well is used at the petroleum industry well is developed, and the subject matter of solution is at high temperature or keeps slurries to have the problem of good dispersion in the high salt concentration solution.Do not relate in building trade as the concrete high efficiency water reducing agent application problem.In addition, in clear 59-206427 of Japanese Patent and U.S. Pat 615394, also relate to methods such as the mud dispersion agent that utilizes ketone-aldehyde condensate to prepare the drilling well of petroleum industry well to use, water-holding agent.The subject matter that is solved mainly is the stability of slurries under hot conditions, does not relate to being used for the cement concrete industry technology.In a word, from the existing literature data as can be seen, also there is not the technical products of aliphatic sulfonic salt as the various high efficiency water reducing agents of making various cement concretes.Some patents that are associated are mainly concerned with the mud flow improver of oilwell drilling industry, and the working conditions and the technical requirements of the high efficiency water reducing agent of using with building trade have bigger difference, and the process for making complexity of these mud flow improvers, long reaction time.The problem to be solved in the present invention is by changing raw-material proportioning, order of addition(of ingredients), simplified technological process, shortened the reaction times, the generation of bumping and gel phenomenon in having avoided simultaneously reacting synthesizes and adapts to building trade aliphatic sulfonate high efficiency water reducing agent that use, that have suitable molecular weight and functional group.
Summary of the invention
The present invention relates to a kind of aliphatic sulfonate high efficiency water reducing agent, this water reducer uses ketone, aldehyde compound as the condensation monomer, with sulphite as sulphonating agent, chemosynthesis in the aqueous solution, contain hydrophilic radicals such as hydroxyl, carboxyl, sulfonic group, carbonyl, its number-average molecular weight scope is 3000～10000.
The invention still further relates to the manufacture method of this aliphatic sulfonate high efficiency water reducing agent, may further comprise the steps: at first, put into water in the reaction vessel, and sulphonating agent is put in the reaction vessel, carry out the sulphonating agent hydrolysis reaction; After this, ketone compounds is put into above-mentioned solution, carry out the sulfonation reflux reaction of ketone compounds; Then, under 40 ℃～60 ℃ conditions, in solution, drip formaldehyde, carry out the carbonylation thermopositive reaction, make solution be warming up to 85 ℃～96 ℃ after adding formaldehyde; Then, under 90 ℃～110 ℃ condition, carry out the pyrocondensation reaction; At last, above-mentioned mixed solution cooling is obtained the liquid water reducer.Wherein, in the raw material of this high efficiency water reducing agent, the mol ratio of ketone compounds, aldehyde compound, sulphite and water is 1: 1.5～3.0: 0.33～0.8: 8～15.
Further again, in the raw material of this high efficiency water reducing agent, ketone compounds comprises one or more of acetone, butanone, pimelinketone, methylethylketone, methyl phenyl ketone etc.; Aldehyde compound comprises a kind of of formaldehyde, Paraformaldehyde 96, acetaldehyde, furfural, crotonaldehyde etc.; Sulphonating agent comprises one or more of S-WAT, sodium bisulfite, Sodium Pyrosulfite.Judge the reaction end of product by the dispersiveness of sampling analysis product.
When carrying out building-up reactions by different proportioning raw materials, gel phenomenon can appear in system sometimes.Generate the gel after product and form cross-linked structure, water-soluble reduction or lose water-solublely fully thereby is not having dissemination to cement granules yet.The generation of gel phenomenon and the amount of the sulphonating agent in the reaction process and temperature of reaction control relation are very big.In reaction system, aldehyde and ketone can be regarded bifunctional compound as.Even the condensation reaction between them proceeds to completeness, also only can generate linear polycondensate and cross linked gel can not occur, and S-WAT is when existing:
Na
2SO
3+H
2O＝NaOH+NaHSO
3
Sodium bisulfite to the acetone addition after products therefrom had 4 functional groups in fact.If in molecule ratio common in the reaction system: HCHO: CH
3COCH
3=2: 1 o'clock, then the system average functionality was:
According to the functionality theoretical formula:
P---polyreaction degree, Xf---average condensation degree.
When gelation produces, can think X → ∝, then P=2/ (8/3)=75%.Promptly at level of response reach at 75% o'clock near gelation point.In fact, because the acetone of reaction system generally can not be fully by addition, so it is often higher to reach the real reaction degree of gelation point.For fear of crosslinking reaction, the consumption of sulphonating agent reaches with ratio, reaction times and the temperature of ketone compounds and all answers strict control.
The key of this preparation method invention is by controlling raw-material proportioning, order of addition(of ingredients), reactions steps and parameter, the molecular weight ranges of aliphatics polymer condenses that makes acquisition should comprise functional groups such as hydrophilic sulfonic group, hydroxyl, carboxyl, carbonyl in the condenses molecule in 3000～10000 scopes.
Further again, in the manufacture method of this high efficiency water reducing agent, the sulfonation reflux reaction process of sulphite hydrolysis and ketone compounds is carried out 30 ℃～65 ℃ condition, continues 30～60 minutes.
Further again, in the manufacture method of this high efficiency water reducing agent, in carrying out the carbonylation exothermal reaction process, when dripping formaldehyde, adding speed begins slowly, and accelerates gradually.
Further again, in the manufacture method of this high efficiency water reducing agent, the pyrocondensation reaction continues 2～6 hours.
Further again, with formic acid or acetic acid neutralising fluid product.
Method provided by the present invention is compared with technology in the past has following advantage: (1) by adjusting raw material ratio and order of addition(of ingredients), each elementary reaction is steady, is easy to control; Avoid the bumping in the condensation reaction and the generation of gel phenomenon; (2) by the condensation product stable performance of the inventive method preparation, can deposit at least 2 years, and occur with interior no crystallization, be suitable for winter construction at subzero 8 ℃; (3) compare with the production technique of high efficiency water reducing agent of the prior art, method provided by the invention is with short production cycle, energy consumption is low (have only naphthalene system about 1/2), equipment is simple; (4) there is not the three wastes (waste water,waste gas and industrial residue) discharging in the inventive method preparation process, environmentally safe, product itself is tasteless, and environment for use is good; (5) the aliphatic sulfonate high efficiency water reducing agent performance of the inventive method preparation is better than naphthalene series high-efficiency water-reducing agent, water-reducing rate height (can reach 30%), and gain in strength is fast, and cement type is adapted to the lover; (6) the aliphatic sulfonate high efficiency water reducing agent raw material of the inventive method preparation is extensive, and cost is low, is adapted to build, the construction work of industries such as water power, traffic, has a good application prospect.
Description of drawings
Fig. 1 is the infrared spectrogram of aliphatic sulfonate high efficiency water reducing agent of the present invention.
Embodiment
Embodiment 1
Present embodiment and the described respectively building-up reactions of following each embodiment are to carry out in the reaction vessel that is equipped with electric mixer, thermometer, dropping funnel and reflux exchanger.
At first, put into 12.5 moles water in the reaction vessel, be preheating to 30 ℃, add 0.52 mole sodium sulphite anhydrous 99.3 again, carry out the hydrolysis reaction of sulphonating agent; Subsequently, add 0.96 mole of acetone, back flow reaction 30～60 minutes; Dripping 2.2 moles, concentration from dropping funnel to above-mentioned solution then is 37% formaldehyde, carries out carbonylation reaction, and the temperature that begins to add formaldehyde is 40～60 ℃, and beginning formaldehyde will slowly drip, and accelerates formaldehyde then gradually and adds speed; After adding formaldehyde, the temperature of reaction system is elevated in 85～96 ℃ the scope automatically; Reheat is warming up to 90～110 ℃, reacts under this temperature 2～6 hours, carries out pyrocondensation reaction, obtains concentration and is 30～40% liquid and be the aliphatic sulfonate high efficiency water reducing agent.
Embodiment 2
At first, put into 8.3 moles water in the reaction vessel, be preheating to 30 ℃, add 0.62 mole sodium sulphite anhydrous 99.3 again, carry out the hydrolysis reaction of sulphonating agent; Subsequently, add 0.51 mole of pimelinketone, back flow reaction 30～60 minutes; Dripping 0.87 mole, concentration from dropping funnel to above-mentioned solution then is 37% formaldehyde, carries out carbonylation reaction, and the temperature that begins to add formaldehyde is 40～60 ℃, and beginning formaldehyde will slowly drip, and accelerates formaldehyde then gradually and adds speed; After adding formaldehyde, the temperature of reaction system is elevated in 85～96 ℃ the scope automatically; Reheat is warming up to 90～110 ℃, reacts under this temperature 2～6 hours, carries out pyrocondensation reaction, obtains concentration and is about 40% amber transparent liquid and be the aliphatic sulfonate high efficiency water reducing agent.
Embodiment 3
At first, put into 11 moles water in the reaction vessel, be preheating to 30 ℃, add 0.67 mole sodium sulphite anhydrous 99.3 again, carry out the hydrolysis reaction of sulphonating agent; Subsequently, add 0.96 mole of acetone, back flow reaction 30～60 minutes; Dripping 2.23 moles, concentration from dropping funnel to above-mentioned solution then is 37% formaldehyde, carries out carbonylation reaction, and the temperature that begins to add formaldehyde is 40～60 ℃, and beginning formaldehyde will slowly drip, and accelerates formaldehyde then gradually and adds speed; After adding formaldehyde, the temperature of reaction system is elevated in 85～96 ℃ the scope automatically; Reheat is warming up to 90～110 ℃, reacts under this temperature 2～6 hours, carries out pyrocondensation reaction, obtains concentration and is 30～40% liquid and be the aliphatic sulfonate high efficiency water reducing agent.
Embodiment 4
At first, put into 12 moles water in the reaction vessel, be preheating to 30 ℃, add 0.5 mole sodium sulphite anhydrous 99.3 and 0.2 mole Sodium Pyrosulfite again, carry out the hydrolysis reaction of sulphonating agent; Subsequently, add 0.95 mole of acetone, back flow reaction 30～60 minutes; Dripping 2.45 volumetric molar concentrations from dropping funnel to above-mentioned solution then is 37% formaldehyde, carries out carbonylation reaction, and the temperature that begins to add formaldehyde is 40～60 ℃, and beginning formaldehyde will slowly drip, and accelerates formaldehyde then gradually and adds speed; After adding formaldehyde, the temperature of reaction system is elevated in 85～96 ℃ the scope automatically; Reheat is warming up to 90～110 ℃, reacts under this temperature 2～6 hours, carries out pyrocondensation reaction, obtains concentration and is 30～40% liquid and be the aliphatic sulfonate high efficiency water reducing agent.
Embodiment 5
At first, put into 12 moles water in the reaction vessel, be preheating to 30 ℃, add 0.52 mole sodium sulphite anhydrous 99.3 and catalyzer (as caustic soda 0.5g) again, carry out the hydrolysis reaction of sulphonating agent; Subsequently, add 0.95 mole of acetone, back flow reaction 30～60 minutes; Dripping 2.45 volumetric molar concentrations from dropping funnel to above-mentioned solution then is 37% formaldehyde, carries out carbonylation reaction, and the temperature that begins to add formaldehyde is 40～60 ℃, and beginning formaldehyde will slowly drip, and accelerates formaldehyde then gradually and adds speed; After adding formaldehyde, the temperature of reaction system is elevated in 85～96 ℃ the scope automatically; Reheat is warming up to 90～110 ℃, reacts under this temperature 2～6 hours, carries out pyrocondensation reaction, obtains concentration and is 30～40% liquid and be the aliphatic sulfonate high efficiency water reducing agent.
More than each embodiment only illustrated and adopt different starting material to make aliphatic sulfonate high efficiency water reducing agent of the present invention, and for each embodiment, all done a large amount of experiments again, in order not to be repeated in this description, so in each embodiment, provided scope for concrete numerical value, for example, 40～60 ℃ (value is 40 ℃ in the actual experiment to begin to add the temperature of formaldehyde, 45 ℃, 50 ℃, 55 ℃, 60 ℃), add make solution be warming up to 85 ℃～96 ℃ behind the formaldehyde (value is 85 ℃ in the actual experiment, 88 ℃, 90 ℃, 93 ℃, 95.5 ℃, 96 ℃), (value is 90 ℃ in the actual experiment at 90～110 ℃, 96 ℃, 100 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 108 ℃, 110 ℃) condition under carry out pyrocondensation reaction.
Behind the dry grinding of institute's synthetic polymer samples, and with behind the KBr compressing tablet, with its infrared spectra curve of SDXC determination of infrared spectroscopy, as shown in Figure 1.Wherein: 3428cm
-1Be the hydroxyl stretching vibration peak; 2924---2700cm
-1Be the c h bond stretching vibration peak on the aliphatic molecules chain; 1702cm
-1Be carbonyl absorption peak; 1603cm
-1Be the carboxyl salt absorption peak; 1183cm
-1Be the sulfonic group absorption peak; 1044 is the sulfonic acid structural vibrations.This shows, contain functional groups such as hydroxyl, carbonyl, sulfonic group in the molecule of this high efficiency water reducing agent, wherein hydroxyl and sulfonic group are the strong hydrophilicity bases, when this class admixture joins in the cement slurry, form electrostatic double layer, produce electrostatic repulsion thus cement granules is disperseed, discharge mixing water and it is to the diminishing plasticizing effect.
Use QERRIN-ELMER company to produce the thermostability of TGS-2 type DSC-2C differential scanning calorimeter check synthetic product.In 50-100 ℃ of scope, weightless 7.73% is by due to the moisture evaporation.In 100.2---199.5 ℃ of scope, there is near 100 ℃ the peak to occur, for this reason, done differential scanning calorimetric curve (DSC), the result shows at 372.06 ℃ a melting peak is arranged, due to the lower-molecular substance fusion.Chemical analysis results shows, sodium sulphate content in the condenses of the present invention＜0.5% the sulfate crystal phenomenon can not occur under the winter low temperature, has solved the problem that common naphthalene series high-efficiency water-reducing agent liquid product sulfate crystal brings in the concreting in cold-weather.
With synthetic sample in the above-mentioned fact Example according to carrying out slump test about the flowing degree of net paste of cement test method among the GB 8077-87 " Methods for testing uniformity of concrete admixture ".As a comparison, adopt naphthalene series high-efficiency water-reducing agent FDN and UNF product commonly used at present also to test simultaneously, the results are shown in Table 1.Adopt the coaxial rotating viscosity agent to measure the cement paste flowability of mixing high efficiency water reducing agent of the present invention, result such as table 2.The water-reducing rate of high efficiency water reducing agent sample 3 of the present invention and concrete reinforced effects subtracted table 3.
Table 1 flowing degree of net paste of cement (mm)
Table 2 is mixed the rheological parameter of the cement slurry of admixture
The water-reducing rate of table 3 admixture and concrete ultimate compression strength
As can be seen from the test results, the high efficiency water reducing agent dispersion effect of the inventive method preparation is better than naphthalene series high-efficiency water-reducing agent, and its grout degree of mobilization is greater than FDN and UNF naphthalene series high-efficiency water-reducing agent under identical volume.The test result of rheological parameter shows that also the high efficiency water reducing agent of mixing the inventive method preparation under the identical volume can reduce the yield value and the plastic viscosity of grout better.Water-reducing rate and concrete strength test explanation, the high efficiency water reducing agent water-reducing rate of the inventive method preparation can reach 30%, and each makes the intensity level of phase significantly to increase concrete.Comprehensive above-mentioned test-results, the high efficiency water reducing agent of the inventive method manufacturing have excellent diminishing dispersion effect and strengthen the property, and are a kind of new concrete high efficiency water reducing agents of excellent performance, have good application prospects.
Claims (7)
1. the manufacture method of an aliphatic sulfonate high efficiency water reducing agent uses ketone, aldehyde compound as the condensation monomer, and as sulphonating agent, chemosynthesis aliphatic sulfonate water reducer in the aqueous solution may further comprise the steps with sulphite:
At first, put into water in the reaction vessel, and sulphonating agent is put in the reaction vessel, carry out the sulphonating agent hydrolysis reaction;
After this, ketone compounds is put into above-mentioned solution, carry out the sulfonation reflux reaction of ketone compounds;
Then, under 40 ℃～60 ℃ conditions, in solution, drip aldehyde compound, carry out the carbonylation thermopositive reaction, make solution be warming up to 85 ℃～96 ℃ automatically;
Then, under 90～110 ℃ condition, carry out the pyrocondensation reaction;
At last, above-mentioned mixed solution cooling is obtained the liquid water reducer,
Wherein ketone compounds comprises one or more in acetone, butanone, pimelinketone, methylethylketone, the methyl phenyl ketone; Aldehyde compound comprises a kind of in formaldehyde, Paraformaldehyde 96, acetaldehyde, furfural, the crotonaldehyde; Sulphonating agent comprises one or more of S-WAT, sodium bisulfite, Sodium Pyrosulfite, and the mol ratio of ketone compounds, aldehyde compound, sulphite and water is 1: 1.5～3.0: 0.33～0.8: 8～15.
2. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1, wherein the sulfonation reflux reaction process of sulphite hydrolysis and ketone compounds is carried out 30 ℃～65 ℃ condition, continues 30～60 minutes.
3. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1, wherein in carrying out the carbonylation exothermal reaction process, when dripping aldehyde compound, adding speed begins slowly, and accelerates gradually.
4. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1, pyrocondensation reaction wherein continues 2～6 hours.
5. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1 wherein uses acetone, formaldehyde to be the condensation monomer, uses sodium sulphite anhydrous 99.3 as sulphonating agent.
6. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1 wherein uses pimelinketone, formaldehyde to be the condensation monomer, uses sodium sulphite anhydrous 99.3 as sulphonating agent.
7. the manufacture method of aliphatic sulfonate high efficiency water reducing agent as claimed in claim 1 wherein uses pimelinketone, formaldehyde to be the condensation monomer, uses sodium sulphite anhydrous 99.3 and Sodium Pyrosulfite as sulphonating agent.
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