CN114369371A - Biological antifreeze protein-based ice-suppressing foamed asphalt and preparation method thereof - Google Patents
Biological antifreeze protein-based ice-suppressing foamed asphalt and preparation method thereof Download PDFInfo
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- CN114369371A CN114369371A CN202111558161.9A CN202111558161A CN114369371A CN 114369371 A CN114369371 A CN 114369371A CN 202111558161 A CN202111558161 A CN 202111558161A CN 114369371 A CN114369371 A CN 114369371A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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Abstract
An ice-inhibiting foamed asphalt based on biological antifreeze protein and a preparation method thereof, the preparation steps are as follows: respectively placing the weighed methoxy polyethylene glycol and the tenebrio molitor antifreeze protein into containers, and then respectively dissolving the containers in a phosphate buffer solution; mixing the two solutions, centrifuging, and reacting at 4-6 deg.C for 24 hr under stirring; heating matrix asphalt into a fluid state, placing the fluid state in foaming equipment, and adding a foaming agent and water under stirring; and mixing the products, adding the polysorbate at a constant speed under stirring, and continuously stirring to obtain the ice inhibiting foamed asphalt. The biological antifreeze protein-based ice-suppressing foamed asphalt disclosed by the invention is wide in raw material source, environment-friendly, easy to realize in production process, free from ice coagulation at-4-0 ℃, remarkable in ice-suppressing effect and suitable for the surface course of various grades of asphalt roads. Has great significance for the application and the popularization of the foam asphalt warm mixing technology and the promotion of the highway construction in China.
Description
Technical Field
The invention belongs to the technical field of asphalt pavement materials, and particularly relates to ice-inhibiting foamed asphalt based on biological antifreeze protein and a preparation method thereof.
Background
In most areas of China, the temperature is low in winter, snow accumulated on roads is frozen in rainy and snowy weather, the friction coefficient of the road surface is greatly reduced, traffic accidents are caused frequently, and the traveling safety of people is seriously threatened. Therefore, it is necessary to effectively remove the accumulated ice and snow on the road surface in time, thereby improving the safety guarantee of people going out and reducing the economic and property loss.
At present, the common ice and snow removing modes at home and abroad are mainly divided into active ice and snow inhibition and passive ice and snow inhibition. The passive snow and ice removing measures mainly comprise manual or mechanical clearing and spreading of a snow melting agent. Common snow melting agents are chloride and acetate salts. The snow-melting agent is spread to remove snow with good effect and quick effect, but the spreading of a large amount of chloride causes serious pollution to the environment, and the snow-melting agent is not suitable for long-term and large-scale use; acetate, although having the advantage of being eco-friendly, cannot be used in a wide range due to its expensive price. Manpower and material resources are consumed for manual and mechanical clearing, normal traffic is obstructed, and safety risks exist to a certain degree. The active ice-suppressing snow-removing method is characterized in that in the pavement paving process, the asphalt is modified and modified by a material with ice-suppressing effect and is used for building ice-suppressing snow-melting asphalt concrete pavements. The active ice suppression and snow removal method can effectively suppress the ice and snow accumulated on the road surface in time, save manpower and material resources and ensure normal traffic.
At present, the active ice suppression and snow removal method for roads mainly comprises two types of paving ice suppression emulsion coatings and ice suppression substance modified emulsified asphalt, but the method has obvious limitations in the actual use process. When the ice-suppressing emulsion coating for paving the road reduces the anti-skid effect of the road surface, the road surface is easy to peel off and has poor durability; the emulsified asphalt modified by the ice-inhibiting substances is greatly influenced by temperature and water, and is not suitable for heavy-load traffic conditions.
The problems restrict the wide application and development of the active ice-suppressing snow-removing method. The foam warm mix asphalt has stable performance and is suitable for various grades of highway asphalt pavements. In addition, the foam asphalt warm mixing technology reduces the emission of carbon dioxide in production and use, and has obvious benefit in the aspect of environmental protection. The antifreeze protein in the organism can effectively reduce the freezing point, inhibit the formation of ice nucleus, play the roles of inhibiting ice and resisting freeze, and has wide source and environmental protection. At present, the research on the products for using the biological antifreeze protein modified foamed asphalt for road ice inhibition is not mature in China, and further development and improvement are needed.
Disclosure of Invention
The technical problem to be solved is as follows: in view of the above, the invention provides an ice-suppressing foamed asphalt based on biological antifreeze protein and a preparation method thereof, and solves the problems of untimely deicing and snow removal, traffic obstruction, manpower and material resource consumption, environmental pollution, insufficient durability and the like in the prior art. The asphalt pavement is suitable for the surface course of asphalt roads of various grades.
The technical scheme is as follows: a preparation method of ice-inhibiting foamed asphalt based on biological antifreeze protein comprises the following steps of (1) step one: 90-100 parts of matrix asphalt, 5-10 parts of water, 1-3 parts of foaming agent, 5-10 parts of tenebrio molitor antifreeze protein, 3-6 parts of methoxy polyethylene glycol, 0.5-1.5 parts of polysorbate and 1-2 parts of phosphate buffer solution; (2) step two: respectively placing the weighed methoxy polyethylene glycol and the tenebrio molitor antifreeze protein into containers, and then respectively dissolving the containers in a phosphate buffer solution; mixing the two solutions, centrifuging, and reacting at 4-6 deg.C and 3000r/min for 24 hr; (3) step three: heating matrix asphalt to 150-155 ℃, placing the matrix asphalt in a foaming device in a fluid state, adding a foaming agent and water at 70-80 ℃ at a stirring speed of 300-400r/min, and stirring for 35-40 min; (4) step four: and (3) mixing the products prepared in the second step and the third step, adding the polysorbate at a constant speed at a stirring speed of 400r/min at 300-.
Preferably, the base asphalt in the first step is any one of No. 70 or No. 90 road petroleum asphalt.
Preferably, in the first step, the foaming agent is at least one of cetyl trimethyl ammonium bromide and diamine type middle-split cation asphalt emulsifier.
Preferably, in the step one, the methoxypolyethylene glycol is any one of methoxypolyethylene glycol succinimidyl ester aminocarboxymethyl methyl ester (mPEG-NHS), methoxypolyethylene glycol-succinimidyl glutarate (mPEG-SG) or methoxypolyethylene glycol-succinic acid monoester-hydroxysuccinimide ester (mPEG-SS).
Preferably, the polysorbate in step one is any one of polysorbate-40, polysorbate-60 or polysorbate-80.
Preferably, in the first step, the phosphate buffer is at least one of sodium phosphate buffer and potassium phosphate buffer, the pH value of the phosphate buffer is 6-7, and the concentration of the phosphate buffer is 0.8-1.2 mol/L.
Preferably, the purity of the yellow mealworm antifreeze protein is not less than 98 percent
Preferably, 95 parts of No. 90 matrix asphalt, 15 parts of water, 2 parts of diamine type middle-split cationic asphalt emulsifier, 10 parts of tenebrio molitor antifreeze protein, 6 parts of mPEG-NHS, 601.5 parts of polysorbate and 2 parts of sodium phosphate buffer solution are adopted, wherein the pH value of the sodium phosphate buffer solution is 7, and the concentration is 0.8 mol/L.
The preparation method comprises the following specific steps: (1) modifying yellow mealworm antifreeze protein: respectively placing the weighed mPEG-NHS and the tenebrio molitor antifreeze protein into test tubes, respectively pouring the same amount of sodium phosphate buffer solution into two centrifuge tubes, and uniformly mixing by shaking; pouring the two solutions into the same centrifugal tube, placing the centrifugal tube in a centrifugal machine, and reacting at 4 ℃ at the rotating speed of 2800r/min for 24 hours; (2) preparing foamed asphalt: heating No. 90 matrix asphalt to 155 ℃, placing in foaming equipment, keeping at 155 ℃, sequentially adding a diamine type medium-cracked cationic asphalt emulsifier and water at 80 ℃ at a stirring speed of 350r/min, and stirring for 40 min; (3) the ice-inhibiting foamed asphalt based on the biological antifreeze protein comprises the following components: and (2) maintaining the rotation speed of foaming equipment at 350r/min and the temperature at 130 ℃, sequentially adding the solution prepared in the step (1) and polysorbate-60 at a constant speed, and continuously stirring for 30min to obtain the biological antifreeze protein-based foamed asphalt with the ice inhibition effect.
The biological antifreeze protein-based ice-suppressing foamed asphalt prepared by the preparation method.
Has the advantages that: the biological antifreeze protein ice-suppressing foamed asphalt has wide material sources, is environment-friendly, has an obvious ice-suppressing effect and is free from ice coagulation at-4-0 ℃ and suitable for the surface course of asphalt roads of various grades, and the production process is easy to realize. Has great significance for the application and the popularization of the foam asphalt warm mixing technology and the promotion of the highway construction in China.
Detailed Description
The following are examples describing the present invention in detail. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
Example 1
Weighing the following raw materials in parts by weight:
90 parts of No. 70 matrix asphalt, 10 parts of water, 1 part of hexadecyl trimethyl ammonium bromide, 5 parts of tenebrio molitor antifreeze protein, 3 parts of mPEG-SG, 401 parts of polysorbate, and 1 part of sodium phosphate buffer (pH is 6, and the concentration is 0.9 mol/L).
The preparation steps are as follows:
(1) modified flour weevil antifreeze protein. And respectively placing the weighed mPEG-SG and the flour weevil antifreeze protein into test tubes, then respectively pouring the same amount of sodium phosphate buffer solution into two centrifuge tubes, and uniformly mixing by shaking. Then pouring the two solutions into the same centrifuge tube, placing the centrifuge tube in a centrifuge, and reacting the two solutions at 5 ℃ for 24 hours at the rotating speed of 3000 r/min.
(2) And (4) preparing foamed asphalt. Heating No. 70 matrix asphalt to 150 deg.C, placing in foaming equipment, maintaining at 150 deg.C, sequentially adding cetyl trimethyl ammonium bromide and 70 deg.C water at stirring speed of 400r/min, and stirring for 35 min.
(3) And (3) preparing the ice-inhibiting foamed asphalt based on the biological antifreeze protein. And (2) adjusting the rotation speed of foaming equipment to 300r/min and the temperature to 135 ℃, sequentially adding the solution prepared in the step (1) and the polysorbate-40 at a constant speed, and continuing stirring for 30 min. The foamed asphalt with the ice inhibition effect based on the biological antifreeze protein is prepared.
Example 2
Weighing the following raw materials in parts by weight:
95 parts of No. 90 matrix asphalt, 15 parts of water, 2 parts of diamine type middle-split cationic asphalt emulsifier, 10 parts of tenebrio molitor antifreeze protein, 6 parts of mPEG-NHS, 601.5 parts of polysorbate, and 2 parts of sodium phosphate buffer (with the pH value of 7 and the concentration of 0.8 mol/L).
The preparation steps are as follows:
(1) modified flour weevil antifreeze protein. And respectively placing the weighed mPEG-NHS and the tenebrio molitor antifreeze protein into test tubes, respectively pouring the same amount of sodium phosphate buffer solution into two centrifuge tubes, and uniformly mixing by shaking. The two solutions were poured into the same centrifuge tube and placed in a centrifuge for reaction at 2800r/min at 4 ℃ for 24 hours.
(2) And (4) preparing foamed asphalt. Heating No. 90 matrix asphalt to 155 deg.C, placing in foaming equipment, maintaining at 155 deg.C, sequentially adding diamine type middle-split cation asphalt emulsifier and 80 deg.C water at stirring speed of 350r/min, and stirring for 40 min.
(3) An ice-suppressing foamed asphalt based on biological antifreeze proteins. And (3) maintaining the rotation speed of foaming equipment at 350r/min and the temperature at 130 ℃, sequentially adding the solution prepared in the step (1) and polysorbate-60 at a constant speed, and continuing stirring for 30 min. The foamed asphalt with the ice inhibition effect based on the biological antifreeze protein is prepared.
Example 3
Weighing the following raw materials in parts by weight:
90 parts of No. 90 matrix asphalt, 10 parts of water, 1.5 parts of hexadecyl trimethyl ammonium bromide, 8 parts of tenebrio molitor antifreeze protein, 4 parts of mPEG-SS, 601 parts of polysorbate-601 and 1.5 parts of potassium phosphate buffer (pH is 6, and the concentration is 1.2 mol/L).
The preparation steps are as follows:
(1) modified flour weevil antifreeze protein. And respectively placing the weighed mPEG-SS and the flour weevil antifreeze protein into test tubes, respectively pouring the same amount of potassium phosphate buffer solution into two centrifuge tubes, and uniformly mixing by shaking. The two solutions were poured into the same centrifuge tube and placed in a centrifuge for reaction at a rotational speed of 2900r/min at 6 ℃ for 23 hours.
(2) And (4) preparing foamed asphalt. Heating No. 90 matrix asphalt to 150 deg.C, placing in foaming equipment, maintaining at 150 deg.C, sequentially adding cetyl trimethyl ammonium bromide and 75 deg.C water at stirring speed of 400r/min, and stirring for 40 min.
(3) An ice-suppressing foamed asphalt based on biological antifreeze proteins. And (2) adjusting the rotation speed of foaming equipment to 370r/min and the temperature to 135 ℃, sequentially adding the solution prepared in the step (1) and polysorbate-60 at a constant speed, and continuing stirring for 25 min. The foamed asphalt with the ice inhibition effect based on the biological antifreeze protein is prepared.
Comparative example 1
Weighing the following raw materials in parts by weight:
100 parts of No. 90 matrix asphalt, 5 parts of water and 2 parts of hexadecyl trimethyl ammonium bromide.
The preparation steps are as follows:
heating No. 90 matrix asphalt to 155 deg.C to flow state, placing in foaming equipment and maintaining at 155 deg.C, sequentially adding cetyl trimethyl ammonium bromide and 75 deg.C water under stirring speed of 400r/min, and stirring for 40 min.
Comparative example 2
Weighing the following raw materials in parts by weight:
100 parts of No. 70 matrix asphalt, 8 parts of water, hexadecyl trimethyl ammonium bromide and 2 parts of diamine type medium-cracked cationic asphalt emulsifier.
The preparation steps are as follows:
heating No. 70 matrix asphalt to 150 deg.C to flow state, placing in foaming equipment, maintaining at 150 deg.C, and sequentially adding hexadecyl trimethyl at uniform speed under stirring speed of 380 r/min. Stirring ammonium bromide, diamine type middle-split cation asphalt emulsifier and water at 80 deg.C for 35 min.
Evaluation of Effect
The effect evaluation was performed on the bio-antifreeze protein-based ice-suppressing foamed asphalt of examples 1 to 3 and the conventional water-blown foamed asphalt of comparative examples 1 to 2, and the main detection indexes included expansion rate, half-life, ductility, softening point, penetration and freezing rate. The results are shown in the following table:
performance test results of foamed asphalt prepared in examples and comparative examples
The expansion rate and half-life index of the examples 1-3 significantly exceed the requirements of the road asphalt pavement regeneration technical specification (JTG/T5521-2019) of the department of transportation, that the expansion rate is more than 10 and the half-life is more than 8 s. From the above, the biological antifreeze protein-based ice-suppressing foamed asphalt has a larger expansion rate and a longer half-life than the conventional water-blown foamed asphalt. This indicates that the ice-suppressing foamed asphalt based on the biological antifreeze protein is more fully foamed and the water is more uniformly and stably distributed in the asphalt.
The experimental results comparing examples 1-3 with comparative examples 1-2 show that all the examples have better ductility (5 ℃), softening point and penetration (25 ℃) indexes than all the comparative examples, and show that the viscosity, plasticity and temperature sensing performance of the biological antifreeze protein-based ice suppressing foamed asphalt is better than that of the conventional water-blown foamed asphalt. Compared with comparative examples 1 and 2, the ice-freezing rate of examples 1 and 3 is greatly reduced at-4 to 0 ℃. Example 2 the ice coagulation rate at-4-0 ℃ is 0, and no ice coagulation phenomenon is generated, which shows that the biological antifreeze protein-based ice inhibition foamed asphalt prepared by the invention has a remarkable ice inhibition effect.
Claims (10)
1. The preparation method of the ice-inhibiting foamed asphalt based on the biological antifreeze protein is characterized by comprising the following steps of (1): 90-100 parts of matrix asphalt, 5-10 parts of water, 1-3 parts of foaming agent, 5-10 parts of tenebrio molitor antifreeze protein, 3-6 parts of methoxy polyethylene glycol, 0.5-1.5 parts of polysorbate and 1-2 parts of phosphate buffer solution; (2) step two: respectively placing the weighed methoxy polyethylene glycol and the tenebrio molitor antifreeze protein into containers, and then respectively dissolving the containers in a phosphate buffer solution; mixing the two solutions, centrifuging, and reacting at 4-6 deg.C and 3000r/min for 24 hr; (3) step three: heating matrix asphalt to 150-155 ℃, placing the matrix asphalt in a foaming device in a fluid state, adding a foaming agent and water at 70-80 ℃ at a stirring speed of 300-400r/min, and stirring for 35-40 min; (4) step four: and (3) mixing the products prepared in the second step and the third step, adding the polysorbate at a constant speed at a stirring speed of 400r/min at 300-.
2. The method for preparing the biological antifreeze protein-based ice-suppressing foamed asphalt according to claim 1, wherein the base asphalt in the first step is any one of No. 70 or No. 90 road petroleum asphalt.
3. The method for preparing the anti-icing foamed asphalt based on the biological antifreeze protein as claimed in claim 1, wherein the foaming agent in the first step is at least one of cetyl trimethyl ammonium bromide and diamine type middle-split cation asphalt emulsifier.
4. The method for preparing ice-suppressing foamed asphalt based on biological antifreeze protein according to claim 1, wherein the methoxypolyethylene glycol is any one of methoxypolyethylene glycol succinimidyl ester aminocarboxymethyl methyl ester (mPEG-NHS), methoxypolyethylene glycol-succinimidyl glutarate (mPEG-SG) or methoxypolyethylene glycol-succinic acid monoester-hydroxysuccinimide ester (mPEG-SS) in the step one.
5. The method for preparing the anti-icing foamed asphalt based on the biological antifreeze protein as claimed in claim 1, wherein the polysorbate is any one of polysorbate-40, polysorbate-60 or polysorbate-80 in the step one.
6. The method for preparing the anti-icing foamed asphalt based on the biological antifreeze protein as claimed in claim 1, wherein the phosphate buffer in the first step is at least one of sodium phosphate buffer and potassium phosphate buffer, and the phosphate buffer has a pH value of 6-7 and a concentration of 0.8-1.2 mol/L.
7. The method for preparing the anti-icing foamed asphalt based on the biological antifreeze protein as claimed in claim 1, wherein the purity of the yellow mealworm antifreeze protein is not less than 98%.
8. The preparation method of the biological antifreeze protein-based ice-suppressing foamed asphalt is characterized by comprising the following steps of 95 parts of No. 90 matrix asphalt, 15 parts of water, 2 parts of diamine type middle-split cation asphalt emulsifier, 10 parts of tenebrio molitor antifreeze protein, 6 parts of mPEG-NHS, 601.5 parts of polysorbate-601.5 and 2 parts of sodium phosphate buffer, wherein the pH value of the sodium phosphate buffer is 7, and the concentration of the sodium phosphate buffer is 0.8 mol/L.
9. The preparation method of the biological antifreeze protein-based ice-suppressing foamed asphalt according to claim 8, which is characterized by comprising the following steps: (1) modifying yellow mealworm antifreeze protein: respectively placing the weighed mPEG-NHS and the tenebrio molitor antifreeze protein into test tubes, respectively pouring the same amount of sodium phosphate buffer solution into two centrifuge tubes, and uniformly mixing by shaking; pouring the two solutions into the same centrifugal tube, placing the centrifugal tube in a centrifugal machine, and reacting at 4 ℃ at the rotating speed of 2800r/min for 24 hours; (2) preparing foamed asphalt: heating No. 90 matrix asphalt to 155 ℃, placing in foaming equipment, keeping at 155 ℃, sequentially adding a diamine type medium-cracked cationic asphalt emulsifier and water at 80 ℃ at a stirring speed of 350r/min, and stirring for 40 min; (3) the ice-inhibiting foamed asphalt based on the biological antifreeze protein comprises the following components: and (2) maintaining the rotation speed of foaming equipment at 350r/min and the temperature at 130 ℃, sequentially adding the solution prepared in the step (1) and polysorbate-60 at a constant speed, and continuously stirring for 30min to obtain the biological antifreeze protein-based foamed asphalt with the ice inhibition effect.
10. An ice-suppressing foamed asphalt based on biological antifreeze protein prepared by the preparation method of any one of claims 1 to 9.
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