CN111849180A - Compound rock modified asphalt mixture additive - Google Patents

Compound rock modified asphalt mixture additive Download PDF

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Publication number
CN111849180A
CN111849180A CN202010663033.XA CN202010663033A CN111849180A CN 111849180 A CN111849180 A CN 111849180A CN 202010663033 A CN202010663033 A CN 202010663033A CN 111849180 A CN111849180 A CN 111849180A
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molecular polymer
high molecular
organic high
asphalt
asphalt mixture
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盘力宁
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Guangxi Luguan Technology Investment Development Co Ltd
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Guangxi Luguan Technology Investment Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02Macromolecular compounds
    • C04B26/26Bituminous materials, e.g. tar, pitch
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/329Phosphorus containing acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention provides a compound rock modified asphalt mixture additive, which takes natural rock asphalt as a main raw material, is assisted by organic high molecular polymer, water-soluble chitosan, polyphosphoric acid and other raw materials, and achieves the purposes of improving the high-temperature deformation resistance, the water damage resistance and the low-temperature crack resistance of a road modified asphalt composite material through the molecular crosslinking, condensation, association and complexing coordination of the organic high molecular polymer, the rock asphalt, the chitosan and the polyphosphoric acid.

Description

Compound rock modified asphalt mixture additive
Technical Field
The invention relates to the technical field of engineering materials, in particular to a compound rock modified asphalt mixture additive.
Background
The composition and structure of the common petroleum asphalt determine that the common petroleum asphalt has poor high-low temperature stability, high temperature flowing tendency, low temperature brittle fracture tendency and insufficient elasticity and aging resistance, and the common petroleum asphalt is difficult to meet the use requirement of high-grade highways. The modification of common petroleum asphalt is the practical requirement of the road petroleum asphalt pavement material. The popularization and application of the modified asphalt composite material for the green and environment-friendly road become necessary roads for building resource-saving and environment-friendly road materials.
The rock asphalt is an asphalt substance generated by petroleum depositing and changing in rock crack for hundreds of millions of years under the comprehensive action of heat, pressure, oxidation, catalyst and microbes, and is a natural solid asphalt with a relatively large molecular weight. The notification about the main technical policy of water route transportation of the printing and issuing highway (the file No. 2014 165) issued by the department of transportation in China 2014 in 8 months encourages the popularization and application of modified asphalt mixtures such as natural rock asphalt. The rock asphalt is used as an asphalt solid substance, has stable property, strong oxidation resistance and strong binding capacity with aggregate, is a natural excellent petroleum-based asphalt modifier, and is already applied to the modification of road petroleum asphalt and the engineering practice application.
However, due to the influence of factors such as production area and source, the natural rock asphalt as a modifier in practice has the disadvantages of insufficient high-temperature deformation resistance and water damage resistance, insufficient low-temperature crack resistance and the like, and too much rock asphalt causes problems of reduced asphalt ductility and the like, so that a novel compound rock modified asphalt mixture additive needs to be developed deeply.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a compound rock modified asphalt mixture additive which can improve the high-temperature deformation resistance, the water damage resistance and the low-temperature crack resistance of a road modified asphalt composite material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a compound rock modified asphalt mixture additive is prepared from the following raw materials in parts by weight: 60-90 parts of rock asphalt, 15-25 parts of organic high molecular polymer, 3-8 parts of polyphosphoric acid, 1-3 parts of water-soluble chitosan and 2-7 parts of color masterbatch, wherein the organic high molecular polymer is polyethylene or polypropylene.
Preferably, the organic high molecular polymer is modified polyethylene or polypropylene, and is specifically prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1-3: 2-6;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking polyethylene/polypropylene powder with small molecular weight in 2-5 wt% strong acid water solution in 10-15 times of the weight of the powder, adding the solution into a reaction kettle, adding 2-3 times of potassium permanganate in weight parts, 0.01-0.02 weight part of nitro compound and 0.005-0.009 weight part of metallocene catalyst, stirring uniformly, closing the reaction kettle to react, controlling the reaction temperature to be 95-100 ℃ and the pressure to be 2 x 105~3×105Pa, the reaction time is 20-30h, the reaction is finished, then the filtration is carried out, and a pneumatic drier is used for drying, thus obtaining a first organic high molecular polymer;
The preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 10-15 times of 1-3 wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.001-0.005 part by weight of nickel catalyst and 0.001-0.005 part by weight of triethylamine, uniformly stirring, closing the reaction kettle, introducing 2-5 Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 80-90 ℃, completing the reaction until no hydrogen is absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
More preferably, the organic high molecular polymer is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer in a weight ratio of 1: 2.
Preferably, the rock asphalt has a natural asphalt content of more than 30%, a softening point of more than 80 ℃, calcium carbonate of more than 30wt%, a flash point temperature of more than 250 ℃, a heating loss of less than 2.0%, a water content of less than 2%, and a maximum particle size of less than 1.5 mm.
Preferably, the chitosan is water-soluble chitosan, the deacetylation degree is more than 80%, and the molecular weight is more than or equal to 100 ten thousand.
Preferably, the polymerization degree of the polyphosphoric acid is 50-100, and the maximum particle size of the particles is less than 1000 nm.
The invention further provides a preparation method of the compound rock modified asphalt mixture additive, which comprises the following steps:
S1, weighing rock asphalt, an organic high-molecular polymer, polyphosphoric acid, chitosan and a color master batch in parts by weight, crushing the rock asphalt, heating to 30-35 ℃, drying, and sieving to control the maximum particle size of rock asphalt particles to be less than 1.0 mm;
s2, uniformly mixing chitosan and an organic high molecular polymer, standing for more than 2min, and then mixing with polyphosphoric acid and a color master batch to obtain a modified auxiliary material;
and S3, stirring and uniformly mixing the rock asphalt treated in the step S1 and the modified auxiliary material obtained in the step S2 to obtain the compound rock modified asphalt mixture additive.
The invention further provides application of the compound rock modified asphalt mixture additive in preparing asphalt mixtures.
The above-mentioned application, preferably, comprises the steps of:
(1) heating the aggregate to 180-190 ℃;
(2) heating the matrix asphalt to 145-155 ℃;
(3) heating an asphalt mixture mixing container to 150-170 ℃;
(4) adding the aggregate heated to 180 ℃ and 190 ℃ into an asphalt mixture mixing container for dry mixing for 30-120 s;
(5) adding the compound rock modified asphalt mixture additive with the dosage of 1-2% of the mass of the asphalt mixture into an asphalt mixture mixing container, and dry-mixing for 60-240 s;
(6) Quantitatively adding the matrix asphalt heated to 145-155 ℃ into an asphalt mixture mixing container to be stirred for 80-300s, and controlling the oil-stone ratio to be 3.5-5%;
(7) adding the mineral powder into an asphalt mixture mixing container, mixing for 80-240s, and keeping the temperature at 150 ℃ and 170 ℃ in the mixing process to obtain the asphalt mixture.
The composite rock modified asphalt mixture additive is added with an organic high molecular polymer, polyphosphoric acid, water-soluble chitosan and rock asphalt for compounding, wherein the organic high molecular polymer is one of polyethylene and polypropylene. Wherein:
organic high molecular polymer: the organic high molecular polymer can generate molecular crosslinking condensation association and complexing coordination with rock asphalt, chitosan and polyphosphoric acid, accelerates the copolymerization crosslinking grafting of micromolecule free components in the asphalt and the high molecular polymer to form an interlocking interpenetrating grid continuous phase, and is blended, melted and polymerized to form an organic-inorganic hybrid high polymer elastomer, so that the aim of double modification of aggregate and matrix asphalt is fulfilled, the comprehensive aims of strengthening, toughening and ageing resistance of the asphalt mixture are fulfilled, the organic high molecular polymer can fill gaps among aggregates to form a more compact framework structure, and the elasticity, the adhesion and the rigidity of the asphalt mixture are effectively improved, so that the high-temperature deformation resistance, the low-temperature crack resistance and the water loss resistance of the compound rock modified asphalt mixture are remarkably improved.
Water-soluble chitosan: the water-soluble chitosan can be blended with rock asphalt and matrix asphalt to be melted and polymerized to obtain a high-molecular graft copolymer, the crosslinking condensation polymerization effect is enhanced, the oxidation resistance and stability of the asphalt mixture can be further improved, and the amino in the chitosan interacts with metal elements in the asphalt mixture and polyphosphoric acid, so that the comprehensive performances of the asphalt mixture such as high-temperature deformation resistance, water damage resistance, ageing resistance, ductility and the like can be better improved.
Polyphosphoric acid: because the polyphosphoric acid has the level of the nano particles, the polyphosphoric acid composition is easy to permeate into rock asphalt, the permanent deformation resistance of the asphalt mixture is improved comprehensively, and the storage stability of the compound rock modified asphalt mixture additive can be greatly improved; the polyphosphoric acid can exert the ultrahigh permeability, and can interact with organic high-molecular polymer, color master batch, rock asphalt and matrix asphalt, so that the comprehensive performances of the asphalt mixture such as high-temperature deformation resistance, water damage resistance, ageing resistance, ductility and the like are improved.
Although polyethylene or polypropylene can be copolymerized, crosslinked and grafted with rock asphalt, polyphosphoric acid and asphalt, the surface polarity of the polyethylene or polypropylene is lower, the high-temperature solubility is slightly poor, the self dispersibility and the copolymerization, crosslinked and grafted stability with the asphalt and the rock asphalt need to be further enhanced, the polyethylene or the polypropylene is preferably subjected to surface modification, molecular chains of the polyethylene or the polypropylene are provided with hydroxyl and carboxyl through the oxidation action of potassium permanganate and sulfuric acid, and also are provided with a certain amount of aldehyde groups to form a first organic high molecular polymer, the aldehyde groups in the first organic high molecular polymer are further reduced, the polarity of the modified polyethylene or the polypropylene is increased, hydrogen is added, the aldehyde groups are subjected to catalytic reduction under the action of a catalyst to form a second organic high molecular polymer, and the second organic high molecular polymer has more hydroxyl groups, the molecular chain of the mixed first organic high molecular polymer and the second organic high molecular polymer has rich hydroxyl and carboxyl, so that the polarity and the hydrophilicity of the polyethylene or polypropylene molecular chain can be better enhanced, the dissolving temperature of the polyethylene or polypropylene molecular chain is reduced, the dispersity of the polyethylene or polypropylene molecular chain can be better improved, the molecular crosslinking condensation effect and the complexing coordination effect of the hydroxyl and the carboxyl are exerted, and the stability of the copolymerization crosslinking grafting of the polyethylene or polypropylene molecular chain and asphalt and rock asphalt is improved.
The invention takes natural rock asphalt as a main raw material, is assisted by organic high molecular polymer, water-soluble chitosan, polyphosphoric acid and other raw materials, adopts an externally-doped direct-throwing construction, and in the process of heating and blending, the organic high molecular polymer, the rock asphalt, the chitosan and the polyphosphoric acid generate molecular crosslinking condensation association and complexing coordination, so that the copolymerization crosslinking grafting of small molecular free components in the asphalt and the high molecular polymer is accelerated to form an interlocked interpenetrating grid continuous phase, and the organic-inorganic hybrid high polymer elastomer is formed by blending, melting and polymerization, thereby achieving the purpose of double modification of aggregate and matrix asphalt and achieving the comprehensive purposes of strengthening, toughening and anti-aging of the asphalt mixture. The additive also increases the adhesiveness of the aggregate surface, fills gaps among the aggregates, forms a more compact framework structure, and effectively improves the elasticity, the adhesiveness and the rigidity of the asphalt mixture, thereby obviously improving the high-temperature deformation resistance, the low-temperature crack resistance and the water damage resistance of the compound rock modified asphalt mixture.
The additive of the compound rock modified asphalt mixture is applied to asphalt modification, remarkable effect is achieved in the paving of solid asphalt roads in China, all indexes are superior to the standard of the department of transportation, wherein the high-temperature anti-rutting performance of the compound rock modified asphalt mixture is improved by 3 times compared with the standard of the department of transportation (JT/T860.5-2014), the dynamic stability can reach 10000 times/mm on average, the soaking Marshall residual stability and the freeze-thaw splitting strength of the compound rock modified asphalt mixture are improved by more than 20% compared with the standard of the department of transportation (JT/T860.5-2014), and the additive is more excellent and more remarkable than the performance of the same product. The additive of the compound rock modified asphalt mixture adopts the most advanced 'external-doping direct-casting' construction, is beneficial to reducing electricity and oil consumption, and reduces the aging phenomenon of repeated heating of asphalt.
Because the additive product of the compound rock modified asphalt mixture contains a certain amount of natural asphalt, when the additive product is used for modifying asphalt, the dosage of the asphalt is reduced by 10 to 15 percent compared with the conventional dosage. The asphalt road paved by the modified asphalt of the compound rock modified asphalt mixture can be completely made of domestic asphalt without adding anti-rutting agent products, and the situation that China depends on expensive imported asphalt and anti-rutting agent products for a long time to build roads is ended.
Detailed Description
The present invention is further described with reference to the following examples, but the present invention is not limited to the scope of the examples, and any modifications or changes that can be easily made by those skilled in the art without departing from the technical solution of the present invention will fall within the scope of the claims of the present invention.
Table 1 raw material ratio of composite rock modified asphalt mixture additive
Figure 451382DEST_PATH_IMAGE002
Figure 964927DEST_PATH_IMAGE004
Figure 462774DEST_PATH_IMAGE006
The methods for producing the modified polyethylene I, modified polyethylene II, modified polyethylene III, modified polypropylene I, modified polypropylene II and modified polyethylene III are shown in examples 9 to 10, examples 17 to 18 and examples 21 to 22.
Example 9
The preparation method of the modified polyethylene I comprises the following steps:
the modified polyethylene I is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1: 2;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking polyethylene powder with small molecular weight in 13 times of 3wt% strong acid aqueous solution, adding into a reaction kettle, adding 3 times of potassium permanganate, 0.01 part of nitro compound and 0.008 part of metallocene catalyst, stirring uniformly, closing the reaction kettle to react, controlling the reaction temperature to be 95-100 ℃, and the pressure to be 2.5 multiplied by 105Pa, the reaction time is 28h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 13 times of 2wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.002 weight part of nickel catalyst and 0.002 weight part of triethylamine, uniformly stirring, closing the reaction kettle, introducing 4Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction until no hydrogen is absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
Example 10
The preparation method of the modified polyethylene II comprises the following steps:
the modified polyethylene II is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 2: 5;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking small molecular weight polyethylene powder in 15 times of 2wt% strong acid water solution, adding into a reaction kettle, adding 2.5 times of potassium permanganate, 0.015 part of nitro compound and 0.005 part of metallocene catalyst, stirring, closing the reaction kettle to react, controlling the reaction temperature to be 95-100 ℃, and the pressure to be 3 multiplied by 105Pa, the reaction time is 26h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 15 times of 1wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.001 part by weight of nickel catalyst and 0.001 part by weight of triethylamine, uniformly stirring, closing the reaction kettle, introducing 3Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction until no hydrogen is absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
Example 17
The preparation method of the modified polyethylene III comprises the following steps:
the modified polyethylene III is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1: 3;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking small molecular weight polyethylene powder in 11 times of 5wt% strong acid water solution, adding into a reaction kettle, adding 2 times of potassium permanganate, 0.02 part of nitro compound and 0.009 part of metallocene catalyst, stirring, closing the reaction kettle to react, controlling the reaction temperature at 95-100 deg.C and the pressure at 3 × 105Pa, the reaction time is 30h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 10 times of 3wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.005 part by weight of nickel catalyst and 0.005 part by weight of triethylamine, uniformly stirring, closing the reaction kettle, introducing 2Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction when hydrogen is not absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
Example 18
The preparation method of the modified polypropylene I comprises the following steps:
the modified polypropylene I is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1: 2;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking the polypropylene powder with small molecular weight in a 3wt% strong acid aqueous solution 13 times the weight of the polypropylene powder, adding the solution into a reaction kettle, adding 3 times the weight of potassium permanganate, 0.01 part of nitro compound and 0.007 part of metallocene catalyst, uniformly stirring, closing the reaction kettle to perform reaction, controlling the reaction temperature to be 95-100 ℃ and the pressure to be 2.6 multiplied by 105Pa, the reaction time is 28h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 13 times of 2wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.002 weight part of nickel catalyst and 0.002 weight part of triethylamine, uniformly stirring, closing the reaction kettle, introducing 4Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction until no hydrogen is absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
Example 21
The preparation method of the modified polypropylene II comprises the following steps:
the modified polypropylene II is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 2: 5;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking the polypropylene powder with small molecular weight in 15 times of 2wt% strong acidAdding the aqueous solution into a reaction kettle, adding 2.6 times of potassium permanganate, 0.015 part of nitro compound and 0.005 part of metallocene catalyst by weight, uniformly stirring, closing the reaction kettle to react, controlling the reaction temperature to be 95-100 ℃ and the pressure to be 3 multiplied by 105Pa, the reaction time is 27h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 15 times of 1.5wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.001 weight part of nickel catalyst and 0.0015 weight part of triethylamine, uniformly stirring, closing the reaction kettle, introducing 4Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction when the reaction does not absorb hydrogen, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
Example 22
The preparation method of the modified polypropylene III comprises the following steps:
the modified polypropylene III is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1: 3;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking small molecular weight polypropylene powder in 11 times weight of 5wt% strong acid water solution, adding into a reaction kettle, adding 2 times weight of potassium permanganate, 0.02 weight of nitro compound and 0.009 weight of metallocene catalyst, stirring well, closing the reaction kettle to react, controlling the reaction temperature at 95-100 deg.C and the pressure at 3 × 105Pa, the reaction time is 30h, filtering is carried out after the reaction is finished, and drying is carried out by an airflow dryer to obtain a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 13 times of 2wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.004 weight part of nickel catalyst and 0.003 weight part of triethylamine, uniformly stirring, closing the reaction kettle, introducing 5Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 85-90 ℃, completing the reaction until hydrogen is not absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
The preparation method of the compound rock modified asphalt mixture additive comprises the following steps: s1, weighing rock asphalt, an organic high-molecular polymer, polyphosphoric acid, chitosan and a color master batch in parts by weight, crushing the rock asphalt, heating to 30-35 ℃, drying, and sieving to control the maximum particle size of rock asphalt particles to be less than 1.0 mm; s2, uniformly mixing chitosan and an organic high molecular polymer, standing for 3min, and then mixing with polyphosphoric acid and a color master batch to obtain a modified auxiliary material; and S3, stirring and uniformly mixing the rock asphalt treated in the step S1 and the modified auxiliary material obtained in the step S2 to obtain the compound rock modified asphalt mixture additive.
The raw material components require that:
rock asphalt: black brown powder, natural asphalt content is more than 30%, softening point is more than 80 ℃, calcium carbonate is more than 30wt%, flash point temperature is more than 250 ℃, heating loss is less than 2.0%, water content is less than 2%, and maximum particle size of particles is less than 1.5 mm. This example uses rock bitumen purchased from Qingdao American Union energy Co.
Water-soluble chitosan: the deacetylation degree is more than 80 percent, and the molecular weight is more than or equal to 100 ten thousand. This example uses chitosan purchased from Shanghai Luo's biosciences, Inc.
Polyphosphoric acid: the polymerization degree is 50-100, and the maximum particle size of the particles is less than 1000 nm. This example uses polyphosphoric acid purchased from chemical company, Inc. in Shanghai.
Color masterbatch: the maximum particle size of the particles is less than 1.0 mm. This example uses a color masterbatch purchased from Shenzhen Weichang pigment Limited.
Polyethylene: the polymerization degree is less than 3000. This example uses polyethylene purchased from Shanghai Bighanda chemical Co., Ltd.
Polypropylene: the degree of polymerization is less than 4500. This example uses polypropylene purchased from Shanghai Bighanda chemical Co., Ltd.
The method for using the compound rock modified asphalt mixture additive of the embodiments 1-8 and 25-31 in modified asphalt comprises the following steps: (1) heating the aggregate to 190 ℃; (2) heating the base asphalt to 150 ℃; (3) heating an asphalt mixture mixing container to 170 ℃; (4) adding the aggregate heated to 180 ℃ and 190 ℃ into an asphalt mixture mixing container for dry mixing for 30 s; (5) adding the compound rock modified asphalt mixture additive with the dosage of 1 percent of the mass of the asphalt mixture into an asphalt mixture mixing container, and dry-mixing for 90 s; (6) quantitatively adding the matrix asphalt heated to 150 ℃ into an asphalt mixture mixing container, and stirring for 90s, wherein the oil-stone ratio is controlled to be 4.2-4.5%; (7) adding the mineral powder into an asphalt mixture mixing container, mixing for 90s, and keeping the temperature at 165-170 ℃ in the mixing process to obtain the asphalt mixture.
The method for using the compound rock modified asphalt mixture additive of the embodiments 9 to 24 in modified asphalt comprises the following steps: (1) heating the aggregate to 180 ℃; (2) heating the base asphalt to 145 ℃; (3) heating an asphalt mixture mixing container to 155 ℃; (4) adding the aggregate heated to 180 ℃ into an asphalt mixture mixing container and dry-mixing for 30 s; (5) adding the compound rock modified asphalt mixture additive with the dosage of 1 percent of the mass of the asphalt mixture into an asphalt mixture mixing container, and dry-mixing for 90 s; (6) quantitatively adding the matrix asphalt heated to 145 ℃ into an asphalt mixture mixing container, and stirring for 80s, wherein the oil-stone ratio is controlled to be 3.9-4.3%; (7) adding the mineral powder into an asphalt mixture mixing container, mixing for 90s, and keeping the temperature at 150 ℃ and 155 ℃ in the mixing process to obtain the asphalt mixture.
In the asphalt mixture, the weight ratio of the aggregate, the matrix asphalt and the mineral powder is as follows: 85-90 parts of aggregate, 4-6 parts of matrix asphalt and 3-5 parts of mineral powder; wherein the aggregate is natural aggregate, including broken stone and river sand; the mineral powder is limestone mineral powder; the matrix asphalt is petroleum asphalt.
And (3) carrying out test piece molding on the mixed asphalt mixture according to the compaction temperature. According to a test method of T0702-2011 and T0709-2011 in road engineering asphalt and asphalt mixture test specification JTGE20-2011, a Marshall test piece is formed by adopting an optimal oilstone ratio, and a water-soaking Marshall test is carried out. According to a test method of T0702-2011 in road engineering asphalt and asphalt mixture test regulation JTGE20-2011, a Marshall test piece is molded by compacting 50 times on two sides of the optimal oilstone ratio respectively, and a freeze-thaw splitting test is carried out according to a method of T0729-2000. According to a test method of T0719-2011 in road engineering asphalt and asphalt mixture test specification JTGE20-2011, a rutting test is carried out under the conditions that the test temperature is 60 +/-1 ℃ and the load wheel pressure is 0.7 +/-0.05 MPa, and the high-temperature stability performance of the mixture is tested. The results are shown in Table 2.
Table 2 test results of test pieces made of modified asphalt mixtures according to examples
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Figure 185879DEST_PATH_IMAGE008
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Claims (9)

1. A compound rock modified asphalt mixture additive is characterized in that,
the composition is prepared from the following raw materials in parts by weight: 60-90 parts of rock asphalt, 15-25 parts of organic high molecular polymer, 3-8 parts of polyphosphoric acid, 1-3 parts of water-soluble chitosan and 2-7 parts of color masterbatch, wherein the organic high molecular polymer is polyethylene or polypropylene.
2. The compound rock modified asphalt mixture additive as claimed in claim 1, wherein,
the organic high molecular polymer is modified polyethylene or polypropylene, and is specifically prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1-3: 2-6;
the preparation method of the first organic high molecular polymer comprises the following steps: soaking polyethylene/polypropylene powder with small molecular weight in 2-5 wt% strong acid water solution in 10-15 times of the weight of the powder, adding the solution into a reaction kettle, adding 2-3 times of potassium permanganate in weight parts, 0.01-0.02 of nitro compound in weight parts and 0.005-0.009 of metallocene catalyst in weight parts,stirring uniformly, closing the reaction kettle to carry out reaction, controlling the reaction temperature to be 95-100 ℃ and the pressure to be 2 multiplied by 10 5~3×105Pa, the reaction time is 20-30h, the reaction is finished, then the filtration is carried out, and a pneumatic drier is used for drying, thus obtaining a first organic high molecular polymer;
the preparation method of the second organic high molecular polymer comprises the following steps: soaking the first organic high molecular polymer in 10-15 times of 1-3 wt% strong alkali aqueous solution, adding the first organic high molecular polymer into a reaction kettle, adding 0.001-0.005 part by weight of nickel catalyst and 0.001-0.005 part by weight of triethylamine, uniformly stirring, closing the reaction kettle, introducing 2-5 Mpa hydrogen into the reaction kettle, controlling the reaction temperature to be 80-90 ℃, completing the reaction until no hydrogen is absorbed, filtering, and drying by an airflow dryer to obtain the second organic high molecular polymer.
3. The compound rock modified asphalt mixture additive as claimed in claim 2, wherein,
the organic high molecular polymer is prepared by mixing a first organic high molecular polymer and a second organic high molecular polymer according to the weight ratio of 1: 2.
4. The compound rock modified asphalt mixture additive as claimed in claim 1, wherein,
the rock asphalt has natural asphalt content higher than 30%, softening point higher than 80 deg.c, calcium carbonate higher than 30wt%, flash point temperature higher than 250 deg.c, heating loss lower than 2.0%, water content lower than 2% and maximum grain size lower than 1.5 mm.
5. The compound rock modified asphalt mixture additive as claimed in claim 1, wherein,
the water-soluble chitosan has a deacetylation degree of more than 80 percent and a molecular weight of more than or equal to 100 ten thousand.
6. The compound rock modified asphalt mixture additive as claimed in claim 1, wherein,
the polymerization degree of the polyphosphoric acid is 50-100, and the maximum particle size of the particles is less than 1000 nm.
7. The preparation method of the compound rock modified asphalt mixture additive as defined in any one of claims 1 to 6, which is characterized by comprising the following steps:
s1, weighing rock asphalt, an organic high-molecular polymer, polyphosphoric acid, chitosan and a color master batch in parts by weight, crushing the rock asphalt, heating to 30-35 ℃, drying, and sieving to control the maximum particle size of rock asphalt particles to be less than 1.0 mm;
s2, uniformly mixing chitosan and an organic high molecular polymer, standing for more than 2min, and then mixing with polyphosphoric acid and a color master batch to obtain a modified auxiliary material;
and S3, stirring and uniformly mixing the rock asphalt treated in the step S1 and the modified auxiliary material obtained in the step S2 to obtain the compound rock modified asphalt mixture additive.
8. The use of the compound rock modified asphalt mixture additive of any one of claims 1 to 6 in the preparation of asphalt mixtures.
9. Use according to claim 8, characterized in that it comprises the following steps:
(1) heating the aggregate to 180-190 ℃;
(2) heating the matrix asphalt to 145-155 ℃;
(3) heating an asphalt mixture mixing container to 150-170 ℃;
(4) adding the aggregate heated to 180 ℃ and 190 ℃ into an asphalt mixture mixing container for dry mixing for 30-120 s;
(5) adding the compound rock modified asphalt mixture additive with the dosage of 1-2% of the mass of the asphalt mixture into an asphalt mixture mixing container, and dry-mixing for 60-240 s;
(6) quantitatively adding the matrix asphalt heated to 145-155 ℃ into an asphalt mixture mixing container to be stirred for 80-300s, and controlling the oil-stone ratio to be 3.5-5%;
(7) adding the mineral powder into an asphalt mixture mixing container, mixing for 80-240s, and keeping the temperature at 150 ℃ and 170 ℃ in the mixing process to obtain the asphalt mixture.
CN202010663033.XA 2020-07-10 2020-07-10 Compound rock modified asphalt mixture additive Pending CN111849180A (en)

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