Organic zirconium phosphate modifier based on waste plastic derivative, anti-aging asphalt-based material and preparation method thereof

Abstract

The invention discloses an organized zirconium phosphate modifier based on waste plastic derivatives, an anti-aging asphalt-based material and a preparation method of the organized zirconium phosphate modifier and the anti-aging asphalt-based material, and belongs to the field of preparation of building materials.The organized zirconium phosphate modifier based on the waste plastic derivatives is added into asphalt, and the organized zirconium phosphate modifier has a layered structure, so that the anti-aging asphalt-based material is prepared; ultraviolet rays can be effectively absorbed, and the ultraviolet aging resistance of the asphalt is greatly improved. In addition, a large number of active sites also exist on the surface of zirconium phosphate, the effect of capturing free radicals can be achieved, the free radicals are prevented from participating in the oxidation reaction, and therefore a certain anti-oxidation function is achieved.

Description

Technical Field

[0001] The invention belongs to the field of building material preparation, and in particular relates to an organic zirconium phosphate modifier based on waste plastic derivatives, an aging-resistant asphalt-based material and a preparation method thereof. Background Art

[0002] Asphalt pavement has become the preferred pavement type for high-grade highways due to its excellent road performance. However, asphalt, as an organic material, is easily affected by high temperature and ultraviolet radiation, causing thermal and photo-oxidative aging, which makes the asphalt hard and brittle, leading to cracks, rutting, potholes and spalling on the asphalt pavement, which greatly damages the performance of the asphalt pavement and shortens its service life.

[0003] At present, the technical measures for improving the anti-aging of asphalt at home and abroad are mainly focused on: adding layered inorganic substances such as nano-TiO2, CeO2, carbon black, montmorillonite, and layered double hydroxide to asphalt can improve its anti-ultraviolet aging performance to a certain extent. Patent CN108410191A uses strong acid to etch magnesium-aluminum-based layered double hydroxide, and improves the problem of easy agglomeration of magnesium-aluminum-based layered double hydroxide and poor compatibility with asphalt through surface etching, while improving the anti-ultraviolet aging performance of asphalt.

[0004] With the rapid development of the global economy and the accelerated advancement of urbanization, the amount of waste plastics generated has increased dramatically, posing a huge challenge to environmental protection and resource recycling. The application of waste plastics in asphalt modification provides some help for the recycling of waste plastics. Chinese patent CN106751957A proposes a method for preparing waste plastic modified asphalt, which improves the strength, stability and viscosity of asphalt at high temperatures.

[0005] Zirconium phosphate is an inorganic material that can be mixed with asphalt to improve the performance of asphalt through its physical and chemical properties. For example, zirconium phosphate can improve the high temperature performance and anti-aging performance of asphalt, thereby extending the service life of asphalt. There are few reports on the technology of combining waste plastics and zirconium phosphate to improve the anti-aging performance of asphalt. Summary of the invention

[0006] The purpose of the present invention is to provide an organic zirconium phosphate modifier based on waste plastic derivatives, an aging-resistant asphalt-based material and a preparation method thereof, so as to solve the problems existing in the above-mentioned prior art. The present invention uses waste plastics to perform intercalation treatment on zirconium phosphate, and introduces waste plastic derivatives into zirconium phosphate through intercalation treatment to obtain an organic zirconium phosphate modifier based on waste plastic derivatives, thereby achieving the organicization of zirconium phosphate and greatly improving the compatibility of zirconium phosphate with asphalt. By using waste plastic derivatives to perform intercalation modification on zirconium phosphate, agglomeration between zirconium phosphate particles can be effectively avoided, its compatibility with asphalt can be improved, and its ultraviolet absorption performance can be greatly improved. It is applied to asphalt anti-aging modification, which can further effectively improve the anti-ultraviolet aging performance of the obtained modified asphalt.

[0007] One of the technical solutions provided by the present invention:

[0008] The organic zirconium phosphate modifier based on waste plastic derivatives is obtained by intercalating zirconium phosphate with waste plastic derivatives.

[0009] The second technical solution provided by the present invention is:

[0010] The invention discloses a method for preparing an organic zirconium phosphate modifier based on waste plastic derivatives. The method comprises the following steps: adding zirconium phosphate and waste plastic derivatives into distilled water, controlling the liquid-solid ratio, ultrasonically treating the waste plastic derivatives for 40 to 80 minutes, centrifuging, washing, filtering and vacuum drying the resulting waste plastic derivatives to obtain the organic zirconium phosphate modifier based on waste plastic derivatives.

[0011] Preferably, the mass ratio of the zirconium phosphate to the waste plastic derivative is 1:(0.5-2).

[0012] Preferably, the liquid-to-solid ratio is 100 mL / g.

[0013] Zirconium phosphate, as a material with a layered structure, can effectively absorb ultraviolet radiation. Through the intercalation process, foreign substances can be embedded between the layers without destroying the original layered structure. Waste plastic derivatives can be used as intercalation materials to achieve the organicization of zirconium phosphate, thereby increasing the compatibility of zirconium phosphate particles with asphalt. The introduction of this organic zirconium phosphate can greatly improve the chemical resistance of asphalt, and the modified asphalt has good storage stability.

[0014] The organic zirconium phosphate modifier is prepared by intercalating zirconium phosphate with a derivative of waste plastics. The waste plastics can be waste polyethylene terephthalate (PET) plastics, aging-resistant asphalt-based waste polyurethane (PU) plastics. PET is a common plastic waste with a wide source, easy to obtain and process, and a relatively stable and controllable modification effect. Preferably, waste PET plastics.

[0015] Preferably, the preparation method of the waste plastic derivative is: mixing waste plastic flakes, an amine-dissolving agent and a catalyst under a nitrogen atmosphere, heating and stirring the mixture for reaction, condensing and refluxing, collecting the reaction product by vacuum filtration, then filtering with deionized water at least three times, collecting the residual material on the filter paper, and finally vacuum drying to constant weight to obtain the waste plastic derivative.

[0016] More preferably, the mass ratio of the waste plastic flakes, the aminolysis agent and the catalyst is 1:(1-3):0.01.

[0017] More preferably, the aminolysis agent includes one or more of monoamine, diamine, polyamine and polyamide, preferably triethylenetetramine.

[0018] Adding a catalyst during the aminolysis of waste plastics can greatly increase the reaction rate. The catalyst includes one or more of glacial acetic acid, sodium acetate, potassium sulfate, zinc acetate and dibutyltin oxide.

[0019] More preferably, the heating and stirring reaction is: stirring at 140°C to 180°C and a rotation speed of 300 to 800 rpm.

[0020] More preferably, the condensation reflux time is 1 to 3 hours.

[0021] Waste plastics are decomposed by aminolysis, and the decomposition products contain amino groups, which is conducive to the subsequent realization of zirconium phosphate intercalation. Waste plastics are usually realized under the action of aminolysis bases and catalysts. Various monoamines, diamines, polyamines, and polyamides can play the role of aminolysis agents. Triethylenetetramine is preferred. Triethylenetetramine molecules contain multiple amino groups, have strong dispersibility and solubility, are highly reactive with the ester group of PET, and have good aminolysis effects. In addition, triethylenetetramine has a high boiling point, and the reaction temperature is relatively easy to control.

[0022] The third technical solution provided by the present invention is:

[0023] An aging-resistant asphalt comprises the following raw materials, measured by weight: 100 parts of base asphalt and 5 to 15 parts of the above-mentioned organic zirconium phosphate modifier based on waste plastic derivatives.

[0024] The base asphalt is a road petroleum asphalt-based material, and 70# asphalt is preferred. 70# asphalt has relatively stable chemical properties, moderate viscosity and large market supply.

[0025] The fourth technical solution provided by the present invention is:

[0026] A method for preparing the above-mentioned aging-resistant asphalt-based material comprises weighing a base asphalt and an organic zirconium phosphate modifier based on waste plastic derivatives; heating the base asphalt to 140-160°C, adding the organic zirconium phosphate modifier based on waste plastic derivatives, and performing high-speed shear stirring to prepare the aging-resistant asphalt-based material.

[0027] Preferably, the specific operation of high-speed shear stirring is: stirring at a speed of 4000 to 5000 rpm for 0.5 to 1 hour using a high-speed shearing machine.

[0028] Compared with the prior art, the present invention has the following advantages and technical effects:

[0029] During the zirconium phosphate intercalation process, it is difficult for the molecular structure to enter the interlayer when it is large, resulting in intercalation difficulties. The present invention uses waste plastic derivatives for intercalation. The waste plastic derivatives have different molecular sizes. The smaller molecules first enter the interlayer, further expanding the interlayer spacing, gradually increasing the success rate of macromolecular intercalation, successfully introducing long-chain structures into zirconium phosphate particles, increasing the affinity between zirconium phosphate and asphalt molecules, improving the compatibility between zirconium phosphate and asphalt, and greatly improving the storage stability of modified asphalt.

[0030] The present invention adds an organic zirconium phosphate modifier based on waste plastic derivatives to asphalt. Based on the layered structure of the modifier, it can effectively absorb ultraviolet rays and greatly improve the anti-ultraviolet aging ability of asphalt. In addition, there are also a large number of active sites on the surface of zirconium phosphate, which can play a role in free radical capture and inhibit the oxidation reaction involving free radicals, thereby playing a certain antioxidant function.

[0031] The present invention uses waste plastics in the asphalt modification process, makes a certain contribution to the recycling of waste plastics, and is in line with the concept of sustainable development. DETAILED DESCRIPTION

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0034] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0035] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0036] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0037] In the embodiments of the present invention, “parts” refer to “parts by mass” unless otherwise specified.

[0038] Example 1: A method for preparing an aging-resistant asphalt-based material

[0039] 1) Add waste plastic flakes (PET), aminolysis agent (triethylenetetramine), and catalyst (zinc acetate) in a mass ratio of 1:2:0.01 to a round-bottom flask under a nitrogen atmosphere, stir the mixture at 180°C, at a speed of 600 rpm, and reflux for 2 hours. After the reaction is completed, collect the reaction product by vacuum filtration, and then filter it three times with deionized water, collect the residual material on the filter paper, and vacuum dry it to constant weight to obtain a waste plastic derivative;

[0040] 2) taking zirconium phosphate and the waste plastic derivative prepared in step 1) in a mass ratio of 1:1, adding them into distilled water, controlling the liquid-to-solid ratio to be 100 mL / g, and ultrasonically treating for 60 min; centrifuging the obtained product, washing it with ethanol for 3 times, filtering it, and vacuum drying it to constant weight to obtain an organic zirconium phosphate modifier based on the waste plastic derivative;

[0041] 3) Weigh 100 parts of 70# asphalt and heat it to 160°C, add 10 parts of the organic zirconium phosphate modifier based on waste plastic derivatives prepared in step 2), stir at 4500 rpm for 45 minutes using a high-speed shearing machine to prepare an aging-resistant asphalt-based material.

[0042] Example 2

[0043] 1) Add waste plastic flakes (PET), an amine hydrolyzing agent (triethylenetetramine), and a catalyst (zinc acetate) in a mass ratio of 1:1:0.01 to a round-bottom flask under a nitrogen atmosphere; stir the mixture at 140°C, at a speed of 400 rpm, and reflux under condensation for 2 hours. After the reaction is completed, collect the reaction product by vacuum filtration, and then filter it three times with deionized water, collect the residual material on the filter paper, and vacuum dry it to constant weight to obtain a waste plastic derivative;

[0044] 2) taking zirconium phosphate and the waste plastic derivative prepared in step 1) in a mass ratio of 1:0.5, adding them into distilled water, controlling the liquid-to-solid ratio to be 100 mL / g, and ultrasonically treating for 40 min; centrifuging, washing, filtering, and vacuum drying the obtained product to constant weight to obtain an organic zirconium phosphate modifier based on the waste plastic derivative;

[0045] 3) Weigh 100 parts of 70# asphalt and heat it to 160°C; add 5 parts of the organic zirconium phosphate modifier based on waste plastic derivatives prepared in step 2), stir at 4000 rpm for 30 minutes using a high-speed shearing machine to prepare an aging-resistant asphalt-based material.

[0046] Example 3

[0047] 1) Add waste plastic flakes, an amine hydrolyzing agent (triethylenetetramine), and a catalyst (zinc acetate) in a mass ratio of 1:3:0.01 to a round-bottom flask under a nitrogen atmosphere; stir the mixture at 180°C, at a speed of 800 rpm, and reflux for 2 hours. After the reaction is completed, collect the reaction product by vacuum filtration, and then filter it three times with deionized water, collect the residual material on the filter paper, and vacuum dry it to constant weight to obtain a waste plastic derivative;

[0048] 2) taking zirconium phosphate and the waste plastic derivative prepared in step 1) in a mass ratio of 1:2, adding them into distilled water, controlling the liquid-to-solid ratio to be 100 mL / g, and ultrasonically treating for 80 min; centrifuging, washing, filtering, and vacuum drying the obtained product to constant weight to obtain an organic zirconium phosphate modifier based on the waste plastic derivative;

[0049] 3) Weigh 100 parts of 70# asphalt and heat it to 160°C; add 15 parts of the organic zirconium phosphate modifier based on waste plastic derivatives prepared in step 2), stir at 5000 rpm for 60 minutes using a high-speed shearing machine to prepare an aging-resistant asphalt-based material.

[0050] Comparative Example 1

[0051] The same as Example 1, except that in step 3), 3 parts of the organic zirconium phosphate modifier based on waste plastic derivatives prepared in step 2) are added.

[0052] Comparative Example 2

[0053] The same as Example 1, except that 20 parts of the organic zirconium phosphate modifier based on waste plastic derivatives prepared in step 2) are added.

[0054] Comparative Example 3

[0055] 100 parts of 70# asphalt were weighed and heated to 160°C; 10 parts of zirconium phosphate were added, and the mixture was stirred at 4500 rpm for 60 minutes using a high-speed shearing machine to prepare a zirconium phosphate-modified asphalt-based material.

[0056] Comparative Example 4

[0057] The same as Example 1, except that in step 2), zirconium phosphate and waste plastic derivative are taken in a mass ratio of 1:0.3.

[0058] Comparative Example 5

[0059] The same as Example 1, except that in step 2), zirconium phosphate and waste plastic derivative are taken in a mass ratio of 1:3.

[0060] Comparative Example 6

[0061] Same as Comparative Example 4, except that the ultrasonic treatment was performed for 30 min in step 2).

[0062] Comparative Example 7

[0063] Same as Comparative Example 4, except that the ultrasonic treatment was performed for 90 min in step 2).

[0064] In order to verify the relevant performance of the aging-resistant asphalt-based material prepared by the present invention, the base asphalt, the modified asphalt of Examples 1 to 3, and Comparative Examples 1 to 7 were subjected to separation experiments according to the current industry standard "Technical Specifications for Highway Asphalt Pavement Construction" (JTG F40-2004) to analyze the storage stability of asphalt. In addition, the asphalt samples were subjected to UV aging experiments (UV intensity 800w / m 2 , temperature is 60℃, aging time is 3 days), and a dynamic shear rheometer is used to carry out temperature scanning experiments on the samples before and after aging, and the complex modulus aging index (CAI) and phase aging index (PAI) are calculated to evaluate the anti-aging ability of asphalt. The smaller the value of the complex modulus aging index and the larger the value of the phase aging index, the stronger the anti-aging ability of asphalt. The aging index calculation formula is as follows, and the measurement results are shown in Table 1.

[0065]

[0066] Where: aging represents the index after aging, and origin represents the index before aging.

[0067] The experimental data are shown in the following table:

[0068] Table 1

[0069]

[0070]

[0071] Note: The softening point difference value is the difference between the softening points of the upper and lower layers after the asphalt separation test. The larger the softening point difference value, the worse the asphalt storage stability, and the smaller the softening point difference value, the better the asphalt storage stability.

[0072] By comparing 70# base asphalt, Example 1, Comparative Example 1 and Comparative Example 2, it is shown that the dosage of the organic zirconium phosphate modifier based on waste plastic derivatives in the asphalt preparation process is too low, and the improvement of the asphalt's anti-ultraviolet aging performance is not obvious; if the modifier dosage is too high, the storage stability of the asphalt will be greatly reduced.

[0073] By comparing Example 1 and Comparative Example 3, it is found that the asphalt stability and anti-aging performance of Example 1 are better than those of Comparative Example 3. The possible reason is that inserting waste plastic derivatives into zirconium phosphate can significantly improve the compatibility of zirconium phosphate and asphalt, thereby improving the stability and anti-aging performance of asphalt.

[0074] By comparing Example 1 and Comparative Examples 4 to 7, it can be concluded that during the intercalation process of waste plastic derivatives, too little derivative or too short ultrasonic time will lead to insufficient intercalation of the plastic derivatives, seriously affecting the storage stability of the modified asphalt; during the intercalation process of waste plastic derivatives, too much derivative or too long ultrasonic time will hardly improve the modification effect compared with the asphalt prepared in Example 1.

[0075] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. An organic zirconium phosphate modifier based on waste plastic derivatives, characterized in that: It is obtained by intercalating zirconium phosphate with waste plastic derivatives.

2. The method for preparing an organic zirconium phosphate modifier based on waste plastic derivatives according to claim 1, characterized in that: Zirconium phosphate and waste plastic derivatives are added into distilled water, the liquid-solid ratio is controlled, ultrasonic treatment is performed for 40 to 80 minutes, and then centrifugation, washing, suction filtration, and vacuum drying are performed to constant weight to prepare the organic zirconium phosphate modifier based on waste plastic derivatives.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the zirconium phosphate to the waste plastic derivative is 1:(0.5-2).

4. The preparation method according to claim 2, characterized in that: The liquid-to-solid ratio is 100 mL / g.

5. The preparation method according to claim 3, characterized in that: The preparation method of the waste plastic derivative is as follows: waste plastic flakes, an amine-dissolving agent and a catalyst are mixed under a nitrogen atmosphere, the mixture is heated and stirred for reaction, condensed and refluxed, a reaction product is collected by vacuum filtration, and then filtered at least three times with deionized water to collect the residual material on the filter paper, and finally vacuum dried to constant weight to obtain the waste plastic derivative.

6. The preparation method according to claim 5, characterized in that: The mass ratio of the waste plastic flakes, the amine decomposition agent and the catalyst is 1:(1-3):0.

01.

7. The preparation method according to claim 5, characterized in that: The aminolysis agent includes one or more of monoamine, diamine, polyamine and polyamide, and the catalyst includes one or more of glacial acetic acid, sodium acetate, potassium sulfate, zinc acetate and dibutyltin oxide.

8. The preparation method according to claim 5, characterized in that: The heating and stirring reaction is: stirring at 140° C. to 180° C. and a rotation speed of 300 to 800 rpm.

9. An aging-resistant asphalt-based material, characterized in that: The raw materials are as follows, calculated by weight: 100 parts of base asphalt and 5 to 15 parts of the organic zirconium phosphate modifier based on waste plastic derivatives as described in claim 1.

10. A method for preparing the aging-resistant asphalt-based material according to claim 9, characterized in that: Weigh base asphalt and an organic zirconium phosphate modifier based on waste plastic derivatives; heat the base asphalt to 140-160° C., add the organic zirconium phosphate modifier based on waste plastic derivatives, and perform high-speed shear stirring to prepare the aging-resistant asphalt-based material.

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