CN113277777B - Thermosetting natural rubber asphalt mixture and preparation method thereof - Google Patents

Thermosetting natural rubber asphalt mixture and preparation method thereof Download PDF

Info

Publication number
CN113277777B
CN113277777B CN202110633142.1A CN202110633142A CN113277777B CN 113277777 B CN113277777 B CN 113277777B CN 202110633142 A CN202110633142 A CN 202110633142A CN 113277777 B CN113277777 B CN 113277777B
Authority
CN
China
Prior art keywords
asphalt
natural rubber
aggregate
mixture
vulcanizing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110633142.1A
Other languages
Chinese (zh)
Other versions
CN113277777A (en
Inventor
郭荣鑫
晏永
夏海廷
杨洋
颜峰
林志伟
马倩敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN202110633142.1A priority Critical patent/CN113277777B/en
Publication of CN113277777A publication Critical patent/CN113277777A/en
Application granted granted Critical
Publication of CN113277777B publication Critical patent/CN113277777B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/26—Bituminous materials, e.g. tar, pitch
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a thermosetting natural rubber asphalt mixture and a preparation method thereof, wherein the mixture comprises aggregate, a rubber asphalt precursor, a vulcanizing agent and a reaction accelerator, and the mass ratio of the rubber asphalt precursor to the vulcanizing agent to the reaction accelerator is 500:8-51:0-6; the mass of the rubber asphalt precursor is 3.5% -7% of the mass of the aggregate; the rubber asphalt precursor comprises the following components in percentage by mass: the mass ratio of the matrix asphalt to the natural rubber emulsion to the oil-based compatibilizer is 100 to 8 to 20 and 4 to 10. The mixture is thermosetting, has excellent high-temperature stability and low-temperature performance, obviously improves the tensile property, has high modulus, good elasticity and reduced temperature sensitivity, has Marshall stability of 20 KN-40 KN, can effectively overstress road surfaces, and is an asphalt road surface road construction material with excellent performance.

Description

Thermosetting natural rubber asphalt mixture and preparation method thereof
Technical field:
the invention belongs to the technical field of road engineering asphalt mixtures, and particularly relates to a thermosetting natural rubber asphalt mixture and a preparation method thereof.
The background technology is as follows:
in recent years, with the high-speed development of economy in China, the freight vehicles in China have structural changes of reduced vehicle number, increased total tonnage and greatly increased bicycle load. The expressway and the national province trunk face more serious heavy load and overload challenges, and higher requirements on the rut resistance and fatigue resistance of the pavement are provided. In order to prolong the service life of asphalt pavement, asphalt cement with more excellent service performance is needed. At present, the main stream is to add a modifier into asphalt for physical modification, and the common asphalt modifier at present mainly comprises SBS, SBR, waste rubber powder and the like.
The natural rubber is a green renewable biomass asphalt modifier, and has wide application prospect. However, the natural rubber is simply added into the asphalt, and uniformly dispersed by stirring, high-speed shearing and other modes, so that the high-low temperature performance and durability of the asphalt are improved, but the performance improvement range is limited. The natural rubber has good compatibility with asphalt, has good viscoelasticity, belongs to a renewable resource, and is an environment-friendly asphalt modifier. Natural rubber production countries such as malaysia and thailand have a strong desire to use natural rubber for asphalt modification, and it is desired to expand the consumer market of natural rubber. Malaysia has achieved some results in the modification of asphalt with natural rubber, which has been studied freshly in China. The company of Hainan natural rubber industry group Co., ltd and Malaysia rubber agency in Jilong slope of Malaysia conducted negotiations and signed a cooperation memo on the natural rubber modified asphalt road on 12 months and 20 days 2019.
The natural rubber is used as a renewable resource and as a modifier of asphalt, and has wide application prospect. However, at present, natural rubber is simply added into asphalt, and uniformly dispersed by stirring, high-speed shearing and other modes, so that the high-low temperature performance and durability of the asphalt can be improved, but the performance improvement range is limited. The natural rubber modified asphalt has the problems of cost, technology and the like, is popularized and used in China, and needs further intensive research.
The background technology is as follows:
the inventors of the present application found in a large number of experiments and microscopic experiments that when the amount of the natural rubber emulsion added is small, the rubber is linearly dispersed and separated from each other in the asphalt (e.g., when the amount of the 3% natural rubber emulsion is added in fig. 1, the rubber is distributed in a dot form), and the natural rubber asphalt still mainly exhibits the asphalt property at this time, and cannot achieve the desired material property. The further increase of the amount of the natural rubber emulsion is found by a fluorescence microscope: when the addition amount of the natural rubber emulsion reaches 8% of the mass of asphalt, the natural rubber forms a net structure (shown in figure 2) in the asphalt, and the net structure is more obvious and stable along with the continuous increase of the addition amount of the natural rubber emulsion; the viscosity of the natural rubber asphalt is increased, the natural rubber asphalt is not suitable to be mixed with aggregate to form asphalt mixture, and the viscosity of the natural rubber asphalt can be reduced after the low-viscosity and stable oil-based compatibilizer is increased through the adjustment of the ratio of the natural rubber emulsion to the oil-based compatibilizer. The inventors have observed that the oil-based compatibilizer chosen does not disrupt the formed rubber network. The natural rubber in the asphalt is vulcanized, so that the strength and network density of the natural rubber are further enhanced, the natural rubber in the natural rubber asphalt and the asphalt form an IPN network inter-string structure, the vulcanized natural rubber is not soft at high temperature and not brittle at low temperature, the thermosetting property of the vulcanized natural rubber is endowed, the high-temperature stability and the low-temperature crack resistance of the material are greatly improved, and the material is a high-quality road pavement material. Whereas asphalt is mainly applied in the form of asphalt mixture in pavement engineering, the inventors have made use of the above findings to prepare thermosetting natural rubber asphalt mixture.
Based on the research results, the invention claims the following technical scheme:
a thermosetting natural rubber asphalt mixture comprises aggregate, rubber asphalt precursor, vulcanizing agent and reaction promoter,
the mass ratio of the rubber asphalt precursor to the vulcanizing agent to the reaction accelerator is 500:8-51:0-6;
the mass of the rubber asphalt precursor is 3.5% -7% of the mass of the aggregate;
the rubber asphalt precursor comprises the following components in percentage by mass: the mass ratio of the matrix asphalt to the natural rubber emulsion to the oil-based compatibilizer is 100 to 8 to 20 and 4 to 10.
The aggregate is natural aggregate or regenerated aggregate,
preferably, the natural aggregate is limestone aggregate or basalt aggregate;
the mass ratio of the rubber asphalt precursor to the vulcanizing agent to the reaction accelerator is 500:8.5-51:0-5.08 or 500:8.93-50.85:0.89-5.08;
the mass ratio of the matrix asphalt to the natural rubber emulsion to the oil-based compatibilizer is 100:12-20:4-10, or 100:12-16:4-10.
The matrix asphalt is grade A petroleum asphalt for 50# road, 70# road or 90# road;
the solid content of the natural rubber emulsion is not less than 50%.
The vulcanizing agent is vulcanizing agent A or vulcanizing agent B;
the vulcanizing agent A comprises sulfur, zinc oxide and stearic acid in a mass ratio of 5-7:8-12:3-5;
the vulcanizing agent B comprises phenolic resin and an active agent, wherein the active agent is metal chloride containing crystal water, and the active agent is FeCl 3 ﹒6H 2 O or SnCl 2 ﹒2H 2 O or ZnCl 2 ﹒1.5H 2 O。
The reaction promoter is one or a mixture of a plurality of thiazole or sulfenamide or thiuram promoters;
the oil-based compatibilizer is one or a mixture of more than one of naphthenic hydrocarbon or aromatic hydrocarbon, preferably naphthenic oil.
The thiazole reaction promoter is promoter M2-mercaptobenzothiazole, the sulfenamide reaction promoter is promoter CZ N-cyclohexyl-2-benzothiazole sulfenamide, and the thiuram reaction promoter is promoter TMDM tetramethylthiuram monosulfide.
Preferably, the vulcanizing agent consists of sulfur, zinc oxide and stearic acid, the reaction accelerator is accelerator M2-mercaptobenzothiazole, and the oil-based compatibilizer is naphthenic oil; the natural rubber emulsion is low-ammonia natural rubber emulsion preserved by ammonia water.
The invention also provides a preparation method of any thermosetting natural rubber asphalt mixture, which comprises the following steps:
(1) Preparing a rubber asphalt precursor: heating matrix asphalt until the matrix asphalt is melted, adding an oil-based compatibilizer, stirring uniformly under the heat preservation condition, adding natural rubber emulsion under the heat preservation and stirring condition, and putting the mixture into a baking oven at 100-140 ℃ to develop until no obvious bubbles exist, thus obtaining a rubber asphalt precursor;
(2) Preparing a vulcanizing agent: weighing and uniformly mixing the components of the vulcanizing agent according to a proportion to obtain the vulcanizing agent;
(3) Preparing an asphalt mixture: heating aggregate, mixing the aggregate with the rubber asphalt precursor prepared in the step (1), adding the vulcanizing agent and the reaction promoter prepared in the step (2) after mixing, molding, vulcanizing, and obtaining the thermosetting natural rubber asphalt mixture after the crosslinking reaction is completed.
The step (1) specifically comprises the following steps: heating and melting matrix asphalt in a baking oven at 120-160 ℃, adding an oil-based compatibilizer, stirring for 4-7 min under the conditions of heat preservation and stirring speed of 500-1500 rpm, adding all natural rubber emulsion at the speed of adding natural rubber emulsion with the mass of 0.1-0.4% of the matrix asphalt per minute under the conditions of heat preservation and stirring speed, and placing the mixture in the baking oven at 100-140 ℃ for development for 1-2 h until no foam is generated after the addition is completed, thus obtaining the rubber asphalt precursor.
The step (3) is specifically as follows: heating aggregate to 140-200 ℃, placing the rubber asphalt precursor obtained in the step (1) and the heated aggregate at 120-180 ℃ for mixing for at least 60s, adding the vulcanizing agent and the reaction promoter obtained in the step (2), and continuing mixing for at least 60s; compacting and molding at 120-180 ℃, then preserving heat for 4-8 hours at 120-160 ℃, and completing the crosslinking reaction of rubber in asphalt to obtain a thermosetting natural rubber asphalt mixture;
the preferable mixing time is 60s to 180s.
The beneficial effects of the invention are as follows:
1. according to the invention, the natural rubber asphalt is vulcanized, and the biomass material is used as a modifier to replace the existing general petroleum-based modifier, so that the carbon emission can be reduced, and the carbon neutralization can be realized. The method of the invention finally produces a thermosetting material which is solid at high temperature (120-160 ℃) and is a unique new material (the existing natural rubber modified asphalt is thermoplastic, but the invention is thermosetting), and the thermosetting material has not yet appeared in the market and research fields.
2. The oil-based compatibilizer is used for initiatively enabling high-doping amount natural rubber to be uniformly distributed in asphalt, and the high-doping amount vulcanizing agent is used for enabling the natural rubber in the asphalt to undergo a crosslinking reaction, so that an IPN interpenetrating network structure is formed between the vulcanized rubber and the asphalt, the natural rubber asphalt is converted into a thermosetting material from thermoplastic, and the performance of asphalt cement is greatly improved; compared with matrix asphalt and SBS modified asphalt, the cured rubber asphalt has the advantages that the rubber in the asphalt forms a cross-linked thermosetting network after cross-linking reaction, and is essentially transformed from the material, so that the low-temperature cracking resistance and high-temperature stability of the rubber asphalt material are improved, the tensile property is obviously improved, the modulus is high, the elasticity is good, and the temperature sensitivity is reduced.
3. The preparation method is simple and has few steps, the preparation difficulty of the thermosetting rubber asphalt mixture is reduced, the stability of the performance of the thermosetting rubber asphalt mixture is ensured, the quality control process difficulty of the material in actual application is reduced, and the quality defect caused by raw material variation or insufficient control of the preparation process is avoided.
4. The preparation requirement and the cost of the thermosetting rubber asphalt mixture are reduced, so that the high-performance paving material of the natural rubber asphalt can be applied to more projects, and is hopeful to be used for improving the highway quality in China, and has a large market prospect.
Drawings
FIG. 1 is a graph of the punctiform distribution of rubber in asphalt at 3% natural rubber emulsion loading.
FIG. 2 is a graph of the network distribution of rubber in asphalt at 8% natural rubber emulsion loading.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Main materials, reagent sources:
the matrix asphalt, sulfur, zinc oxide, stearic acid, tetramethyl dithiothiuram TMTD and 2-mercapto benzothiazole used in the invention: are all conventional in the art and are commercially available.
Naphthenic oil: n24 naphthenic oils were purchased from Shandong Tai petrochemical technology Co.
Natural rubber emulsion: the emulsion is a low-ammonia concentrated natural rubber emulsion, and the solid content of the emulsion is about 55 percent.
The mineral aggregate is limestone aggregate, and is obtained from the mountain stope of Huaning county, yunnan province.
The aggregate synthesis grading is shown in Table 1. Through experiments, the on-site mix proportion of the grading is designed to be 5% of the optimal oil-stone proportion.
TABLE 1 aggregate synthesis target gradation pass rate
Mesh size/mm 16 13.2 9.5 4.75 2.36 1.18 0.6 0.3 0.15 0.075
Pass rate/% 100 97.3 74.4 42.6 36.2 28.4 16.7 11.2 8.2 5.5
Example 1
1. Blank examples and comparative examples were prepared
(1) Blank examples
The preparation method comprises the following steps: 1000g of 70# matrix asphalt is taken, placed in a 140 ℃ oven for heating and melting, 40g of naphthenic oil is added, after stirring for 5min at the speed of 140 ℃ and 500rpm, 80g of natural rubber emulsion is added at the speed of adding natural rubber emulsion with the mass of 0.1% of the asphalt per minute, stirring is continuously carried out in the adding process, stirring is stopped for 5min after the adding is finished, and the stirring is continuously carried out in the 110 ℃ oven until no foam is generated, thus obtaining the natural rubber asphalt.
And weighing 10kg of limestone aggregate with each particle size according to a target grade, heating to 160 ℃, adding 500g of prepared natural rubber asphalt according to the optimal oil-stone ratio of 5% of the grading shown in table 1, and mixing for 120s to obtain the natural rubber asphalt mixture.
(2) Comparative example 1
The preparation method comprises the following steps:
1000g of 70# matrix asphalt is taken, heated and melted at 145 ℃, 80g of natural rubber emulsion is added, and after being stirred uniformly, the mixture is put into a 145 ℃ oven for swelling and development for 1 hour; and then taking out the mixture, and shearing the mixture at a high speed at a temperature of 160 ℃ and a rotating speed of 4000rpm for 1h to obtain the natural rubber asphalt with rubber uniformly dispersed in the asphalt.
And (3) weighing 10kg of aggregate with each particle size of limestone aggregate according to a target grade, heating to 160 ℃, adding 500g of natural rubber asphalt prepared in the previous step, mixing for 120s, adding 0.6g of sulfur, 1g of zinc oxide, 0.4g of stearic acid and 0.4g of TMTD into the mixture according to a vulcanization formula, continuously stirring for 120s, and discharging. Compacting and molding at 150 ℃, and then placing the mixture in an environment of 160 ℃ for continuous heat preservation for 4 hours to obtain the thermoplastic natural rubber asphalt mixture.
(3) Comparative example 2
The preparation method comprises the following steps:
1000g of 70# matrix asphalt is taken, after heating and melting at 145 ℃, 40g of natural rubber emulsion is added, and after being stirred uniformly, the mixture is put into a 145 ℃ oven for swelling and development for 1 hour; and then taking out the mixture, and shearing the mixture at a high speed at a temperature of 160 ℃ and a rotating speed of 4000rpm for 1h to obtain the natural rubber asphalt with rubber uniformly dispersed in the asphalt.
And (3) weighing 10kg of aggregate with each particle size of limestone aggregate according to a target grade, heating to 160 ℃, adding 500g of natural rubber asphalt prepared in the previous step, stirring for 120s, adding 1.5g of sulfur, 2.5g of zinc oxide, 1g of stearic acid and 1g of TMTD into the mixture according to a vulcanization formula, continuously stirring for 120s, and discharging. Compacting and molding at 150 ℃, and then placing the mixture in an environment of 160 ℃ for continuous heat preservation for 4 hours to obtain the thermoplastic natural rubber asphalt mixture.
2. Preparation of inventive samples
The thermosetting natural rubber asphalt mixtures of experimental groups 1 to 8 of the present invention were prepared as follows:
(1) 1000g of matrix asphalt is taken, placed in an oven with 120-160 ℃ (corresponding to the asphalt heating temperature in table 2) for heating and melting, naphthenic oil is added, after stirring for 4-7 min under the conditions of heat preservation and stirring speed of 500-1500 rpm, a total of 80-200 g of natural rubber emulsion is added at the speed of adding the natural rubber emulsion with the mass of 0.1-0.4% of the matrix asphalt per minute under the conditions of heat preservation and stirring speed, and placed in the oven with 100-140 ℃ (corresponding to the development temperature in table 2) for development for 1-2 h until no foam is generated after the addition, and then the rubber asphalt precursor is obtained.
(2) And weighing sulfur, zinc oxide and stearic acid, mixing uniformly to obtain the vulcanizing agent.
(3) Weighing 10kg of limestone aggregate with each particle size according to a target grade, heating to 140-200 ℃ (corresponding to the aggregate heating temperature in table 4), taking 500g of the hot rubber asphalt precursor with the temperature of 100-140 ℃ obtained in the step (1), placing 10kg of heated aggregate into a stirring pot with the temperature of 120-180 ℃ (corresponding to the stirring temperature in table 4), stirring for 120s, adding the vulcanizing agent obtained in the step (2) and the reaction promoter M (2-mercaptobenzothiazole) into the stirring pot, and continuing stirring for 120s; and (3) compacting and molding in a molding instrument with the temperature of 120-180 ℃ (corresponding to the molding temperature in table 4), and then placing in an oven with the temperature of 120-160 ℃ (corresponding to the vulcanization temperature in table 4) to keep the temperature for 4-8 hours (corresponding to the vulcanization time in table 4), wherein the rubber completes the crosslinking reaction in the asphalt, thus obtaining the thermosetting natural rubber asphalt mixture.
The experimental groups 1, 3 and 4 adopt 70# matrix asphalt, the experimental groups 2, 5 and 8 adopt 90# matrix asphalt, and the experimental groups 6 and 7 adopt 50# matrix asphalt.
The specific raw material ratios and process parameters of experimental groups 1 to 8 are shown in tables 2 to 4:
TABLE 2 raw material ratios and Process parameters of the rubber asphalt precursor in step (1) of each experimental group
Figure GDA0004108506410000091
TABLE 3 amount of vulcanizing agent raw materials in step (2) in each experimental group
Figure GDA0004108506410000092
TABLE 4 Material usage and process parameters in step (3) for each experimental group
Figure GDA0004108506410000101
Experimental results: blank examples are 8% rubber emulsion blending amount, vulcanization is not carried out, and the obtained asphalt mixture presents thermoplasticity; in comparative example 1, 8% of the rubber emulsion is vulcanized, but the vulcanizing agent is smaller in blending amount, and the obtained asphalt mixture still presents thermoplasticity; in comparative example 2, the vulcanizing agent was vulcanized in a relatively high amount, but a 4% rubber emulsion was used in an amount sufficient to give an asphalt mixture which still exhibited thermoplasticity. In the experimental groups 1-8, the thermosetting rubber asphalt material is finally obtained by adding the vulcanizing agent with high rubber mixing amount and high mixing amount.
Example 2 product Performance test
According to JTG E20-2011, highway engineering asphalt and asphalt mixture test procedure, marshall stability, current value 15 ℃ splitting strength, 60 ℃ dynamic stability and-10 ℃ flexural tensile strain are selected as representative indexes, and performance tests are carried out on the samples of the experimental groups 1-8, the blank examples and the comparative examples prepared in example 1, and the test results are shown in Table 5.
The thermosetting natural rubber asphalt mixture provided by the invention has thermosetting characteristics (the mixture is not collapsed and loosened at 140 ℃), the characteristics endow the mixture with excellent high-temperature stability, and the dynamic stability is 4 times that of a blank example and 3 times that of a comparative example; and the tensile property of the rubber network still has better performance in low-temperature performance, and the bending tensile strain of the rubber network at-10 ℃ is equivalent to that of blank examples and comparative examples. In the scheme of the invention, the rubber network plays a role of network reinforcement on asphalt, the strength of the asphalt at normal temperature is enhanced, and the stability is 4 times that of a blank example and 3 times that of a comparative example. The thermosetting natural rubber asphalt mixture prepared by the invention is an asphalt pavement road building material with excellent performance.
The Marshall stability of the thermoplastic matrix asphalt/polymer asphalt mixture commonly used at present is generally lower than 20KN, the Marshall stability of the thermosetting epoxy asphalt mixture is generally higher than 40KN, and the Marshall stability of the thermosetting natural rubber asphalt mixture is between 20KN and 40KN, so that the pavement modulus can be effectively transited.
TABLE 5 Performance index of asphalt mixtures of different formulations
Figure GDA0004108506410000111
Figure GDA0004108506410000121
Remarks: by the table "experiment group 18% natural rubber emulsion+5 times vulcanizing agent) By way of example, 8% means that the mass percent of natural rubber emulsion to the base asphalt, and the 5-fold vulcanizing agent is 100% relative to the mass ratio of natural rubber to sulfur to zinc oxide to stearic acid in comparative example 1: 3:5:2, each hundred parts of natural rubber emulsion in the experimental group 1, the dosage of the vulcanizing agent is 5 times that of the comparative example; which is a kind ofThe natural rubber emulsion ratio calculation and vulcanizing agent multiple calculation of the rest experiment groups are analogized.

Claims (10)

1. A thermosetting natural rubber asphalt mixture is characterized in that: comprises aggregate, rubber asphalt precursor, vulcanizing agent and reaction promoter,
the mass ratio of the rubber asphalt precursor, the vulcanizing agent and the reaction accelerator is 500:8.93-50.85:0-5.08; the vulcanizing agent is vulcanizing agent A, and the vulcanizing agent A consists of sulfur, zinc oxide and stearic acid in a mass ratio of 5-7:8-12:3-5; the reaction promoter is one or a mixture of a plurality of thiazole or sulfenamide or thiuram promoters;
the mass of the rubber asphalt precursor is 3.5% -7% of the mass of the aggregate;
the rubber asphalt precursor comprises the following components in percentage by mass: the mass ratio of the matrix asphalt to the natural rubber emulsion to the oil-based compatibilizer is 100:8-20:4-10; the oil-based compatibilizer is naphthenic oil; the solid content of the natural rubber emulsion is not less than 50%;
the preparation method of the thermosetting natural rubber asphalt mixture comprises the following steps:
(1) Preparing a rubber asphalt precursor: heating matrix asphalt until the matrix asphalt is melted, adding an oil-based compatibilizer, stirring uniformly under the heat preservation condition, adding natural rubber emulsion under the heat preservation and stirring condition, and putting the mixture into a baking oven at 100-140 ℃ to develop until no obvious bubbles exist, thus obtaining a rubber asphalt precursor;
(2) Preparing a vulcanizing agent: weighing and uniformly mixing the components of the vulcanizing agent according to a proportion to obtain the vulcanizing agent;
(3) Preparing an asphalt mixture: heating aggregate, mixing the aggregate with the rubber asphalt precursor prepared in the step (1), adding the vulcanizing agent and the reaction promoter prepared in the step (2) after mixing, molding, vulcanizing, and obtaining the thermosetting natural rubber asphalt mixture after the crosslinking reaction is completed.
2. The thermoset natural rubber asphalt mixture of claim 1, wherein: the aggregate is natural aggregate or regenerated aggregate,
the mass ratio of the matrix asphalt to the natural rubber emulsion to the oil-based compatibilizer is 100:12-20:4-10, or 100:12-16:4-10.
3. The thermoset natural rubber asphalt mixture of claim 2, wherein: the natural aggregate is limestone aggregate or basalt aggregate.
4. The thermoset natural rubber asphalt mixture of claim 1, wherein:
the matrix asphalt is grade A petroleum asphalt for 50# road, 70# road or 90# road.
5. The thermoset natural rubber asphalt mixture of claim 1, wherein: the thiazole reaction promoter is promoter M2-mercaptobenzothiazole, the sulfenamide reaction promoter is promoter CZ N-cyclohexyl-2-benzothiazole sulfenamide, and the thiuram reaction promoter is promoter TMDM tetramethylthiuram monosulfide.
6. The thermoset natural rubber asphalt mixture of claim 1, wherein: the reaction promoter is promoter M2-mercaptobenzothiazole; the natural rubber emulsion is low-ammonia natural rubber emulsion preserved by ammonia water.
7. A method for preparing a thermosetting natural rubber asphalt mixture according to any one of claims 1 to 6, comprising the steps of:
(1) Preparing a rubber asphalt precursor: heating matrix asphalt until the matrix asphalt is melted, adding an oil-based compatibilizer, stirring uniformly under the heat preservation condition, adding natural rubber emulsion under the heat preservation and stirring condition, and putting the mixture into a baking oven at 100-140 ℃ to develop until no obvious bubbles exist, thus obtaining a rubber asphalt precursor;
(2) Preparing a vulcanizing agent: weighing and uniformly mixing the components of the vulcanizing agent according to a proportion to obtain the vulcanizing agent;
(3) Preparing an asphalt mixture: heating aggregate, mixing the aggregate with the rubber asphalt precursor prepared in the step (1), adding the vulcanizing agent and the reaction promoter prepared in the step (2) after mixing, molding, vulcanizing, and obtaining the thermosetting natural rubber asphalt mixture after the crosslinking reaction is completed.
8. The method of claim 7, wherein: the step (1) specifically comprises the following steps: heating and melting matrix asphalt in a baking oven at 120-160 ℃, adding an oil-based compatibilizer, stirring for 4-7 min under the conditions of heat preservation and stirring speed of 500-1500 rpm, adding all natural rubber emulsion at the speed of adding natural rubber emulsion with the mass of 0.1-0.4% of the matrix asphalt per minute under the conditions of heat preservation and stirring speed, and placing the mixture in the baking oven at 100-140 ℃ for development for 1-2 h until no foam is generated after the addition is completed, thus obtaining the rubber asphalt precursor.
9. The method of claim 7, wherein: the step (3) is specifically as follows: heating aggregate to 140-200 ℃, placing the rubber asphalt precursor obtained in the step (1) and the heated aggregate at 120-180 ℃ for mixing for at least 60s, adding the vulcanizing agent and the reaction promoter obtained in the step (2), and continuing mixing for at least 60s; compacting and molding at 120-180 ℃, then preserving heat for 4-8 hours at 120-160 ℃, and completing the crosslinking reaction of the rubber in the asphalt to obtain the thermosetting natural rubber asphalt mixture.
10. The method of claim 9, wherein:
the mixing time is 60-180 s.
CN202110633142.1A 2021-06-07 2021-06-07 Thermosetting natural rubber asphalt mixture and preparation method thereof Active CN113277777B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110633142.1A CN113277777B (en) 2021-06-07 2021-06-07 Thermosetting natural rubber asphalt mixture and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110633142.1A CN113277777B (en) 2021-06-07 2021-06-07 Thermosetting natural rubber asphalt mixture and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113277777A CN113277777A (en) 2021-08-20
CN113277777B true CN113277777B (en) 2023-04-21

Family

ID=77283608

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110633142.1A Active CN113277777B (en) 2021-06-07 2021-06-07 Thermosetting natural rubber asphalt mixture and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113277777B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956897B (en) * 2021-11-26 2023-09-01 昆明理工大学 Automatic production line for natural rubber emulsion modified asphalt and asphalt production method

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101967286B (en) * 2010-10-18 2012-07-25 武汉工程大学 Modified thermosetting epoxy bitumen material and preparation method thereof
CN104725883B (en) * 2015-04-20 2017-10-24 武汉理工大学 A kind of high-viscosity high-elasticity asphalt being modified based on rubber particle surface, SMA asphalts and preparation method thereof
CN109306095A (en) * 2018-09-26 2019-02-05 上海仁聚新材料科技有限公司 Toughening asphalt modifier, toughening composite modified asphalt, asphalt and preparation method thereof
CN110591397A (en) * 2019-09-17 2019-12-20 云南畅坦科技有限公司 High-strength toughened fast-curing chemically modified resin asphalt for permeable pavement and preparation method thereof
CN111073320B (en) * 2019-12-30 2022-06-07 海南天然橡胶产业集团股份有限公司 Natural rubber modified asphalt and preparation method thereof
CN111349345A (en) * 2020-04-03 2020-06-30 大连理工大学 Vulcanized natural rubber modified asphalt and preparation method thereof

Also Published As

Publication number Publication date
CN113277777A (en) 2021-08-20

Similar Documents

Publication Publication Date Title
WO2014129758A1 (en) Novel highly viscoelastic warm mix modifier composition and preparation method therefor, and new and regenerated warm mix modified asphalt concrete mixture composition and preparation method therefor
CN104725883A (en) High-viscosity high-elasticity asphalt based on surface modification of rubber particles, and high-viscosity high-elasticity SMA (stone mastic asphalt) mixture based on surface modification of rubber particles and preparing method thereof
CN105236831A (en) Aged-asphalt regeneration agent, regenerated asphalt mixture and preparation method of two
CN101003688A (en) High performance pavement material of epoxy asphalt, preparation method and application
WO2012103691A1 (en) Road asphalt modified by composite modifier and preparation method thereof
CN113277777B (en) Thermosetting natural rubber asphalt mixture and preparation method thereof
CN114380539B (en) Asphalt cold-patch material prepared from recycled glass fiber reinforced plastics
CN102504556A (en) High-grade road asphalt prepared from coal tar pitch
CN112280322A (en) MXene modified color asphalt binder and preparation method thereof
CN102329103A (en) Hot-mix cold-lay rubber asphalt mixture
CN101439946B (en) Preparation of modified rubber asphalt mixture
CN114716839B (en) Modified asphalt for heavy-duty pavement, modified asphalt mixture and preparation method thereof
CN101348350A (en) Waste rubber powder composite modified asphalt and preparation thereof
CN106700572A (en) Long-life POE-SBS composite modified asphalt and preparation method thereof
CN105130280A (en) Rubber asphalt mixture
CN114804722A (en) High-performance rubber asphalt mixture based on soft and hard asphalt compounding, and preparation method and application thereof
KR20100040588A (en) Modified asphalt composition used in treated fine waste epdm powder
CN113248934B (en) Thermosetting vulcanized natural rubber modified asphalt material and preparation method thereof
CN113527899A (en) Cast modified asphalt and cast modified asphalt concrete
CN108192156A (en) Triangle rubber sizing material and preparation method under a kind of all-steel giant-scale engineering radial
CN116477877A (en) Fiber-reinforced high-toughness asphalt mixture and preparation method thereof
CN113817333B (en) High-viscosity modified asphalt, preparation method thereof and OGFC (one glass batch fiber reinforced plastic) asphalt mixture
CN114350167B (en) PG82-22 modified asphalt and its preparing method
CN113277776B (en) Microwave vulcanized thermosetting natural rubber asphalt mixture and preparation method thereof
CN115651345B (en) Method for preparing modified asphalt from petroleum asphalt

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant