CN107352835B - High-performance antifreezing agent and preparation method thereof - Google Patents
High-performance antifreezing agent and preparation method thereof Download PDFInfo
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- CN107352835B CN107352835B CN201710579802.6A CN201710579802A CN107352835B CN 107352835 B CN107352835 B CN 107352835B CN 201710579802 A CN201710579802 A CN 201710579802A CN 107352835 B CN107352835 B CN 107352835B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention relates to a high-performance antifreezing agent which comprises, by weight, 20-30 parts of polyethylene glycol, 15-19 parts of 3,4,9, 10-perylene tetracarboxylic anhydride, 2.5-5 parts of an initiator A, 1-5 parts of concentrated sulfuric acid, 15-21 parts of D-allyl glycine, 0.9-3 parts of a molecular weight regulator, 5-9 parts of an initiator B, 60-80 parts of deionized water and 1-3 parts of NaOH solid particles. The high-performance antifreezing agent has good antifreezing performance.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a high-performance antifreezing agent and a preparation method thereof.
Background
The construction of concrete at low temperature is very disadvantageous, and the guarantee of the progress and quality of the concrete in the low-temperature construction process is a concern. At present, the concrete is generally doped with the antifreezing agent, and the method has simple construction and better antifreezing effect, so the method is widely applied.
At present, the synthesis process of the antifreeze is mainly that a macromonomer with polymerization activity is prepared through esterification reaction, then monomers with a certain proportion are mixed together, and solution polymerization is directly adopted to obtain a finished product. However, in the process of preparing the macromonomer, due to the reasons of difficult control of process conditions and the like, the esterification rate is difficult to control, so that the molecular weight of the antifreezing agent is difficult to control, the relative molecular mass of the antifreezing agent is too large or too small, the antifreezing effect on concrete is poor, and the requirement of low-temperature use cannot be met.
Disclosure of Invention
The invention aims to provide a high-performance antifreezing agent, wherein an esterified active macromonomer keeps a relatively stable esterification rate, and the high-performance antifreezing agent has good antifreezing performance on concrete.
The above object of the present invention is achieved by the following technical solutions: the high-performance antifreezing agent comprises, by weight, 20-30 parts of polyethylene glycol, 15-19 parts of 3,4,9, 10-perylene tetracarboxylic anhydride, 2.5-5 parts of an initiator A, 1-5 parts of concentrated sulfuric acid, 15-21 parts of D-allyl glycine, 0.9-3 parts of a molecular weight regulator, 5-9 parts of an initiator B, 60-80 parts of deionized water, 1-3 parts of NaOH solid particles, 1-3 parts of alkylphenol-ethylene oxide condensation compounds, 6-9 parts of polydimethylsiloxane and 3-6 parts of an antifreezing material.
By adopting the technical scheme, the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride are subjected to esterification reaction to generate an active macromonomer; then the generated active macromonomer and D-allyl glycine are subjected to polymerization reaction to obtain a high polymer; the generated high polymer is compounded with an antifreezing material, an alkylphenol-ethylene oxide condensate and polydimethylsiloxane to generate the high-performance antifreezing agent.
Preferably, the molecular weight of the polyethylene glycol is 8000-10000.
By adopting the technical scheme, the molecular weight of the prepared high-performance antifreezing agent is adjusted by controlling the molecular weight of the polyethylene glycol.
Preferably, the initiator A is a mixture of 4, 4' -dihydroxybiphenyl and 4-hexyl-1, 3-benzenediol.
Preferably, the mass ratio of the 4, 4' -dihydroxybiphenyl to the 4-hexyl-1, 3-benzenediol is 2: 3.
By adopting the technical scheme, the 4, 4' -dihydroxybiphenyl and the 4-hexyl-1, 3-benzenediol are compounded for use, so that the esterification rate of the prepared macromonomer is improved.
Preferably, the initiator is a mixture of B potassium persulfate, ammonium persulfate and sodium persulfate.
Preferably, the mass ratio of the potassium persulfate to the ammonium persulfate to the sodium persulfate is 1: 1.
By adopting the technical scheme, the polymerization degree of the high-performance antifreezing agent is improved by the compound use of potassium sulfate, ammonium persulfate and sodium persulfate.
Preferably, the molecular weight regulator in the polymerization step is one or more of dodecyl mercaptan, 3-mercaptoacetic acid and 3-mercaptopropionic acid.
By adopting the technical scheme, the molecular weight of the high-performance antifreezing agent is improved by using dodecyl mercaptan, 3-mercaptoacetic acid and 3-mercaptopropionic acid.
Preferably, the antifreezing material is a mixture of sodium nitrite, calcium nitrate and ethylene glycol.
By adopting the technical scheme, the high-performance antifreezing agent is prepared by compounding the sodium nitrite, the calcium nitrate and the glycol with the prepared high polymer.
The invention also aims to provide a preparation method of the high-performance antifreeze.
The invention is realized by the following technical scheme, and the preparation method of the high-performance antifreezing agent comprises the following steps:
esterification: taking polyethylene glycol and 3,4,9, 10-perylene tetracarboxylic anhydride, melting the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride, adding into a reaction kettle at the same time, uniformly stirring, filling nitrogen, adding an initiator A, raising the temperature of the reaction kettle to 250-300 ℃, uniformly stirring for 2-3 h, adding concentrated sulfuric acid, continuously raising the temperature of the reaction kettle to 300-330 ℃, uniformly stirring for 3-4 h, and obtaining an esterified macromonomer after the reaction is finished;
polymerization: uniformly mixing the prepared macromonomer, D-allyl glycine and a molecular weight regulator to obtain a mixture C; and (3) uniformly mixing the initiator B and deionized water to obtain a mixture D. Heating the reaction kettle to 100-120 ℃, simultaneously dropwise adding the mixture C and the mixture D, keeping the temperature for 2-2.5 hours after the mixture C and the mixture D are dropwise added for 4-5 hours;
neutralizing: cooling the polymerized product to 55-60 ℃, adding NaOH solid particles while stirring, and adjusting the pH value to 6-7; compounding: and adding the alkylphenol ethylene oxide condensate, polydimethylsiloxane and an antifreezing material into the neutralized product, and fully stirring to prepare the high-performance antifreezing agent.
By adopting the technical scheme, firstly, the proper esterification rate of macromolecular active monomers generated by the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride is ensured in the esterification reaction process by adjusting the reaction parameters in the esterification step; then the synthesized macromolecular active monomer and D-allyl glycine are subjected to polymerization reaction, and the high-performance antifreezing agent is prepared by controlling the reaction parameters of the polymerization reaction.
Preferably, the flow of nitrogen introduced into the reaction kettle in the esterification process is 15-29 m2/h。
By adopting the technical scheme, in the esterification reaction process of the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride, the pressure inside the reaction kettle is ensured to be constant by controlling the flow of nitrogen introduced into the reaction kettle, so that the prepared high-performance antifreezing agent has good antifreezing performance.
In conclusion, the invention has the following beneficial effects:
1. the high-performance antifreezing agent generated in the polymerization process of the macromonomer has good antifreezing performance by adjusting the esterification rate of the macromonomer generated by the esterification reaction.
2. The concrete mixed with the high-performance antifreezing agent has good durability and strength.
3. The prepared high-performance antifreezing agent can be used at the temperature of minus 20 ℃.
Detailed Description
All materials referred to in the examples of the present invention are commercially available.
The specifications of the samples used in the examples are shown in table 1.
TABLE 1 specification of samples used in the following examples
Deionized water is self-made by a deionized water device.
The raw material ratios used in the examples are shown in Table 2.
TABLE 2 component contents in the examples
Wherein, in examples 1 to 4, the molecular weight of the polyethylene glycol is 9000; in examples 5 to 6, the molecular weight of polyethylene glycol was 8000; in examples 7 to 8, the molecular weight of polyethylene glycol was 10000.
The preparation method of the high-performance antifreeze in the above embodiments is as follows:
esterification: taking polyethylene glycol and 3,4,9, 10-perylene tetracarboxylic anhydride, melting the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride, and then mixing the molten polyethylene glycol and the molten 3,4,9, 10-perylene tetracarboxylic anhydrideAdding the mixture into a reaction kettle, uniformly stirring, introducing nitrogen with the nitrogen flow being S, simultaneously adding an initiator A, and raising the temperature T of the reaction kettle1Stirring is carried out uniformly t1Adding concentrated sulfuric acid, and continuously raising the temperature T of the reaction kettle2Stirring is carried out uniformly t2After the reaction is finished, obtaining the esterified macromonomer;
polymerization: uniformly mixing the prepared macromonomer, D-allyl glycine and a molecular weight regulator to obtain a mixture C; uniformly mixing the initiator B and deionized water to obtain a mixture D; heating the reaction kettle to T3Simultaneously dropwise adding the mixture C and the mixture D, wherein the mixture C and the mixture D are at t3After the dripping is finished, keeping the temperature t4；
Neutralizing: cooling the polymerized product to T4Adding NaOH solid particles while stirring, and adjusting the pH value to be neutral;
compounding: and adding the alkylphenol ethylene oxide condensate, polydimethylsiloxane and an antifreezing material into the neutralized product, and fully stirring to prepare the high-performance antifreezing agent.
The process parameters used in the examples are shown in table 3.
TABLE 3 Process parameters in the examples
The evaluation indexes and the detection methods adopted by the high-performance antifreezing agent prepared in the above embodiments are as follows:
cement paste fluidity: the cement paste fluidity of the high-performance antifreezing agent is measured according to GB/T8077 'test method for homogeneity of concrete admixture'.
Compressive strength: the cement and the high-performance antifreezing agent are prepared into a standard test block, and the compression strength with 95% guarantee rate is measured on 7 days and 28 days according to GB/T50010 concrete structure design Specification.
Slump and slump loss over time: the slump of the high-performance antifreezing agent prepared in each example when the agent is taken out of the machine and after the agent is placed for 1h is measured according to the specification in GB/T50080 Standard test method for Performance of ordinary concrete mixtures.
The esterification rate: accurately weighing m mass of reactant0From which w is taken out accurately1About 0.5g of the pre-reaction mixture is placed in a 250mL conical flask, 40mL of deionized water and 2-3 drops of phenolphthalein are added, the solution is measured by 0.1mol/L of NaOH standard solution, the solution is measured in parallel for three times, and the volume of the consumed standard NaOH solution is V1mL; accurately weighing the mass of the reacted reaction product, and taking out w1About 0.5g of reaction product, titrated in parallel three times, consumed a standard NaOH solution volume V2mL, calculating the esterification rate, [ V ]1×CNaoH(m0-3w1)×10-3]/w1。
The performance indexes of the above examples are shown in table 4.
TABLE 4 Performance test results for the high performance antifreeze prepared in each of the examples
As can be seen from the table, the high-performance antifreezing agent prepared by the method has good antifreezing performance and meets the construction specification requirement of the high-performance antifreezing agent.
Comparative examples 1 to 7
Among them, comparative example 1 is different from example 1 in that the molecular weight of polyethylene glycol is 1000.
Comparative example 2 differs from example 1 in that the molecular weight of the polyethylene glycol is 100000.
Comparative example 3 differs from example 1 in that no initiator a was added in the esterification step.
Comparative example 4 differs from example 1 in that no molecular weight regulator was added in the polymerization step.
Comparative example 5 differs from example 1 in that no nitrogen was fed in the esterification step.
Comparative example 6 differs from example 1 by T1The temperature was 200 ℃.
Comparative example 7 differs from example 1 by T2The temperature was 250 ℃.
The performance indexes of the above respective proportions are shown in Table 5.
TABLE 5 Performance test results for antifreeze prepared in each comparative example
As can be seen from the above table, the molecular weights of the polyethylene glycols in comparative example 1 and comparative example 2 were 1000 and 10000, respectively. When the molecular weight of the polyethylene glycol is 1000, the relative molecular weight of the synthesized antifreezing agent is too small, the slump maintaining capability of the antifreezing agent is not high, and the slump loss value is large; when the molecular weight of the polyethylene glycol is 10000, the dispersion performance of the synthesized antifreezing agent is poor, and the antifreezing performance is poor.
Comparative example 3 no initiator a was added, the esterification reaction of polyethylene glycol with 3,4,9, 10-perylene tetracarboxylic anhydride was slow, resulting in low esterification rate of the prepared macromonomer. In comparative example 4, no molecular weight regulator was added, and during the polymerization of the esterified macromonomer and D-allylglycine, the polymerization process was slow and the molecular weight of the antifreeze could not be effectively increased, resulting in poor antifreeze performance of the prepared antifreeze.
In the comparative example 5, nitrogen is not introduced, the internal pressure of the reaction kettle is low, the esterification reaction of the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride is slow, the esterification rate of the prepared active macromonomer is low, and the antifreezing performance of the generated antifreezing agent is poor.
Reaction kettle temperature T in comparative example 6 and comparative example 71And T2The esterification reaction process of the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride is slow, and more byproducts are generated in the esterification process, so that the esterification rate of the prepared active macromonomer is low, and the antifreezing performance of the generated antifreezing agent is poor.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (6)
1. A high-performance antifreezing agent is characterized by comprising the following raw materials in parts by weight: 20-30 parts of polyethylene glycol, 15-19 parts of 3,4,9, 10-perylene tetracarboxylic anhydride, 2.5-5 parts of an initiator A, 1-5 parts of concentrated sulfuric acid, 15-21 parts of D-allyl glycine, 0.9-3 parts of a molecular weight regulator, 5-9 parts of an initiator B, 60-80 parts of deionized water, 1-3 parts of NaOH solid particles, 1-3 parts of an alkylphenol ethylene oxide condensate, 6-9 parts of polydimethylsiloxane and 3-6 parts of an antifreezing material;
wherein the initiator A is 4, 4' -dihydroxybiphenyl and 4-hexyl-1, 3-benzenediol with the mass ratio of 2: 3, and the initiator B is potassium persulfate, ammonium persulfate and sodium persulfate with the mass ratio of 1: 1;
the high-performance antifreezing agent is prepared by the following method, and comprises the following steps:
esterification: taking polyethylene glycol and 3,4,9, 10-perylene tetracarboxylic anhydride, melting the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride, adding into a reaction kettle at the same time, uniformly stirring, filling nitrogen, adding an initiator A, raising the temperature of the reaction kettle to 250-300 ℃, uniformly stirring for 2-3 h, adding concentrated sulfuric acid, continuously raising the temperature of the reaction kettle to 300-330 ℃, uniformly stirring for 3-4 h, and obtaining an esterified macromonomer after the reaction is finished;
polymerization: uniformly mixing the prepared macromonomer, D-allyl glycine and a molecular weight regulator to obtain a mixture C; uniformly mixing the initiator B and deionized water to obtain a mixture D; heating the reaction kettle to 100-120 ℃, simultaneously dropwise adding the mixture C and the mixture D, keeping the temperature for 2-2.5 hours after the mixture C and the mixture D are dropwise added for 4-5 hours;
neutralizing: cooling the polymerized product to 55-60 ℃, adding NaOH solid particles while stirring, and adjusting the pH value to 6-7; compounding: and adding the alkylphenol ethylene oxide condensate, polydimethylsiloxane and an antifreezing material into the neutralized product, and fully stirring to prepare the high-performance antifreezing agent.
2. The high performance antifreeze according to claim 1, wherein said polyethylene glycol has a molecular weight of 8000 to 10000.
3. The high performance antifreeze according to claim 1, wherein said molecular weight modifier in said polymerization step is one or more selected from the group consisting of dodecanethiol, 3-mercaptoacetic acid, and 3-mercaptopropionic acid.
4. The high performance antifreeze of claim 1, wherein said antifreeze material is a mixture of sodium nitrite, calcium nitrate, and ethylene glycol.
5. A method for preparing the high performance antifreeze of claim 1, comprising the steps of:
esterification: taking polyethylene glycol and 3,4,9, 10-perylene tetracarboxylic anhydride, melting the polyethylene glycol and the 3,4,9, 10-perylene tetracarboxylic anhydride, adding into a reaction kettle at the same time, uniformly stirring, filling nitrogen, adding an initiator A, raising the temperature of the reaction kettle to 250-300 ℃, uniformly stirring for 2-3 h, adding concentrated sulfuric acid, continuously raising the temperature of the reaction kettle to 300-330 ℃, uniformly stirring for 3-4 h, and obtaining an esterified macromonomer after the reaction is finished;
polymerization: uniformly mixing the prepared macromonomer, D-allyl glycine and a molecular weight regulator to obtain a mixture C; uniformly mixing the initiator B and deionized water to obtain a mixture D; heating the reaction kettle to 100-120 ℃, simultaneously dropwise adding the mixture C and the mixture D, keeping the temperature for 2-2.5 hours after the mixture C and the mixture D are dropwise added for 4-5 hours;
neutralizing: cooling the polymerized product to 55-60 ℃, adding NaOH solid particles while stirring, and adjusting the pH value to 6-7; compounding: and adding the alkylphenol ethylene oxide condensate, polydimethylsiloxane and an antifreezing material into the neutralized product, and fully stirring to prepare the high-performance antifreezing agent.
6. The preparation method of the high-performance antifreeze according to claim 5, wherein the flow of nitrogen introduced into the reaction kettle in the esterification process is 15-29 m2/h。
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| JP2002038152A (en) * | 2000-07-24 | 2002-02-06 | Nippon Shokubai Co Ltd | Water-reducing agent for soil |
| US7271214B2 (en) * | 2003-06-23 | 2007-09-18 | Geo Specialty Chemicals, Inc. | Cement dispersant and methods of making and using the same |
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| CN100491282C (en) * | 2007-04-27 | 2009-05-27 | 北京工业大学 | Preparation method of high-performance dehydragent for graft copolymerization for carboxylate |
| CN102161572B (en) * | 2010-12-22 | 2013-01-30 | 马清浩 | Polyester type carboxylic acid series water reducing agent and preparation method thereof |
| CN102557515B (en) * | 2012-03-09 | 2013-11-20 | 天津诺德建筑材料有限公司 | Anti-freezing agent for concretes |
| CN104556800A (en) * | 2015-02-04 | 2015-04-29 | 刘国政 | Concrete antifreezing agent and concrete |
| CN106810100B (en) * | 2016-12-23 | 2019-11-08 | 河南奥思达新材料有限公司 | A kind of anti-freeze type water-reducing agent and its preparation process |
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| JP2002038152A (en) * | 2000-07-24 | 2002-02-06 | Nippon Shokubai Co Ltd | Water-reducing agent for soil |
| US7271214B2 (en) * | 2003-06-23 | 2007-09-18 | Geo Specialty Chemicals, Inc. | Cement dispersant and methods of making and using the same |
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