CN111606602B - Cold-patch rubber asphalt mixture and preparation method thereof - Google Patents

Cold-patch rubber asphalt mixture and preparation method thereof Download PDF

Info

Publication number
CN111606602B
CN111606602B CN201910142491.6A CN201910142491A CN111606602B CN 111606602 B CN111606602 B CN 111606602B CN 201910142491 A CN201910142491 A CN 201910142491A CN 111606602 B CN111606602 B CN 111606602B
Authority
CN
China
Prior art keywords
rubber
cold
asphalt
patch
linearized
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
CN201910142491.6A
Other languages
Chinese (zh)
Other versions
CN111606602A (en
Inventor
江宽
董进学
董大伟
刘双旺
李田田
武晋巍
王重阳
冯亚琴
刘晓楠
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.)
Beijng Environmental Protection Technology Co ltd Wing Tai Luther
Original Assignee
Beijng Environmental Protection Technology Co ltd Wing Tai Luther
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 Beijng Environmental Protection Technology Co ltd Wing Tai Luther filed Critical Beijng Environmental Protection Technology Co ltd Wing Tai Luther
Priority to CN201910142491.6A priority Critical patent/CN111606602B/en
Publication of CN111606602A publication Critical patent/CN111606602A/en
Application granted granted Critical
Publication of CN111606602B publication Critical patent/CN111606602B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

The invention provides a cold-patch rubber asphalt mixture and a preparation method thereof. The cold-patch rubber asphalt mixture comprises aggregate, filler and cold-patch rubber asphalt mixed liquor; the cold-patch rubber asphalt mixed solution comprises asphalt, linearized active rubber, olefin polymer and diluent, wherein the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%. The linearized active rubber has the performance similar to that of an elastomer polymer, can replace the elastomer polymer to be applied to cold patch asphalt, enhances the strength of the cold patch asphalt, and can greatly reduce the cost of the cold patch asphalt. Meanwhile, compared with the cross-linked waste rubber powder, the cross-linked structure of the linear active rubber is basically damaged, and the capability of absorbing light components and diluents of the asphalt is greatly weakened, so that the linear active rubber can be added in a large proportion, and the normal-temperature fluidity of the cold patch asphalt is not influenced while the performance of the cold patch asphalt is enhanced.

Description

Cold-patch rubber asphalt mixture and preparation method thereof
Technical Field
The invention relates to the field of pavement asphalt materials, in particular to a cold-patch rubber asphalt mixture and a preparation method thereof.
Background
With the development of the transportation industry, the traffic flow of the pavement is increased day by day, the frequency of pavement damage is increased gradually, and pavement pit slot repairing is an important link of pavement maintenance. The main mode of pavement repair is to adopt hot asphalt mixture to carry out on-site repair, but the mode is greatly influenced by seasons and can not repair the pits on the pavement on site at any time. The road surface cold patch asphalt material is produced, and has the advantages of simple operation, long storage period, good repair quality, environmental protection and the like, and has very wide application.
The cold construction asphalt mixture sold in the market at present is prepared by diluting viscous asphalt into liquid asphalt, namely adding part of a diluent into the viscous asphalt. Such as: the patent CN102702761A discloses a cold patch asphalt modified liquid and a preparation method thereof, wherein the modified liquid is prepared from 5-8% of SBR and/or SBS, 3-5% of naphthenic oil, 3-5% of glycerol, 3-5% of dibutyl ester, 0-3% of anti-stripping agent and the balance of heavy diesel oil. Patent CN105001656B discloses a normal temperature asphalt modifier, normal temperature modified asphalt and warm-mix cold-paving asphalt concrete, wherein the normal temperature asphalt modifier is a mixture comprising waste engine oil, rubber tires and plastic extracts; the modified asphalt is obtained by adding a normal-temperature asphalt modifier into matrix asphalt at 130-150 ℃ and stirring. The normal temperature asphalt modifier in the scheme is a high molecular alloy of a high molecular interpenetrating network formed by blending three or more than three high molecular polymers of waste engine oil, rubber tires, plastic extracts and the like. The patent CN106116270A discloses a cold patch asphalt mixture used in a freezing period and a preparation method thereof, wherein a cold patch liquid comprises 12-15% of a diluent, 2-4% of petroleum resin, 8-10% of rubber powder, 2-4% of aromatic oil, 1.5-2% of a dispersing agent and the balance of No. 90 grade A asphalt.
However, the current cold-patch rubber asphalt has the following defects:
defect one: the existing cold patch asphalt is basically composed of asphalt, an elastomer polymer, micromolecular solvent oil, a volatile diluent and petroleum resin. The addition of petroleum resin and elastomer polymer in a large proportion causes the cold patch asphalt to have higher cost, which is not beneficial to the market popularization and application of the technology;
and defect two: the addition of the small molecular solvent oil can increase the normal temperature fluidity of the asphalt, but can also cause the asphalt to be further softened, and seriously affect the strength of the cold-patch asphalt mixture;
and a third defect: if the waste rubber powder is added to replace part of the elastomer polymer in consideration of cost, the cold patch asphalt is thickened due to strong oil absorption swelling capacity of the waste rubber powder due to the crosslinking property of the waste rubber powder, so that the normal-temperature viscosity of the cold patch asphalt is increased, and the cold patch asphalt is not favorable for storage and mixing; meanwhile, the cross-linked state of the rubber powder limits the chain motion capability of the macromolecular rubber, and the contribution to the strength of the macromolecular rubber in the cold patch asphalt is insufficient.
For the above reasons, there is a need to provide a cold-patch rubber asphalt mixture with low cost and high strength.
Disclosure of Invention
The invention mainly aims to provide a cold-patch rubber asphalt mixture and a preparation method thereof, and aims to solve the problem that the cold-patch rubber asphalt mixture in the prior art cannot give consideration to low cost and high strength.
In order to achieve the above object, according to one aspect of the present invention, there is provided a cold-patch rubber asphalt mixture comprising an aggregate, a filler and a cold-patch rubber asphalt mixture; the cold-patch rubber asphalt mixed solution comprises asphalt, linearized active rubber, olefin polymer and diluent, wherein the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%.
Further, the linearized molecules in the linearized active rubber comprise gradient small molecules and macromolecular polymers, the molecular weight of the gradient small molecules is 500-10000, and the molecular weight of the macromolecular polymers is more than 10000; preferably, in the linearized molecules, the weight percentage of the gradient small molecules is 10-20%, and the weight percentage of the macromolecular polymer is 80-90%.
Further, the cold-patch rubber asphalt mixed solution comprises, by weight, 100 parts of asphalt, 15-30 parts of linearized active rubber, 0.5-2 parts of olefin polymer and 2-12 parts of diluent; preferably, the cold-patch rubber asphalt mixture comprises 100 parts by weight of asphalt, 20-30 parts by weight of linearized active rubber, 1-2 parts by weight of olefin polymer and 2-5 parts by weight of diluent.
Furthermore, the cold-patch rubber asphalt mixed solution also comprises 0.05 to 1.5 parts by weight of elastomer polymer, 0.05 to 2 parts by weight of petroleum resin and 0.1 to 3 parts by weight of anti-stripping agent.
Further, the elastomer polymer is selected from one or more of SBS, SEBS, SIS, SBR, EVA and POE; preferably, the petroleum resin is selected from one or more of C5 petroleum resin, C9 petroleum resin, phenolic resin and terpene resin; preferably, the anti-stripping agent is selected from one or more of p-amino benzamide, m-amino benzylamine, silane coupling agent and sodium lignosulfonate.
Further, the olefin polymer has a molecular weight of 3000 to 7000 and a melting point of 90 to 125 ℃; preferably, the olefin polymer is selected from one or more of polyethylene wax, oxidized polyethylene wax, sasobit wax and polyamide wax; preferably, the diluent is selected from diesel and/or kerosene.
Further, the cold-patch rubber asphalt mixture comprises 100 parts by weight of aggregate, 2-7 parts by weight of filler and 1-8 parts by weight of cold-patch rubber asphalt mixed solution; preferably, the aggregate is selected from basalt and/or limestone; preferably, the filler is selected from lime powder and/or slag powder.
According to another aspect of the invention, a preparation method of the cold-patch rubber asphalt mixture is also provided, which comprises the following steps: mixing and dispersing asphalt, linearized active rubber, olefin polymer and a diluent to obtain a cold-patch rubber asphalt mixed solution; wherein the linearized active rubber is obtained by waste rubber powder desulfurization treatment, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75 percent; and mixing the aggregate, the filler and the cold-patch rubber asphalt mixed solution to obtain the cold-patch rubber asphalt mixture.
Further, the process of mixing and dispersing to obtain the cold patch rubber asphalt mixed solution comprises the following steps: heating the asphalt to 150-185 ℃, adding an olefin polymer, and stirring for 30-60 min at a stirring speed of 1000-2000 rpm to form a first mixture; adding linear active rubber into the first mixture, and stirring for 60-120 min at the conditions that the temperature is 150-185 ℃ and the stirring speed is 1000-2000 rpm to form a second mixture; cooling the second mixture to 110-130 ℃, adding a diluent, and stirring for 30-60 min at a stirring speed of 1000-2000 rpm to obtain a cold-patch rubber asphalt mixture; preferably, during the addition of the olefin polymer, petroleum resin is added simultaneously; during the addition of the linearized active rubber, the elastomeric polymer and the antistripping agent are added simultaneously.
Further, the process of mixing the aggregate, the filler and the cold-patch rubber asphalt mixed solution comprises the following steps: heating the cold-patch rubber asphalt mixed solution to 40-80 ℃, and stirring for 30-60 min at a stirring speed of 500-1000 rpm in a heat preservation manner; putting the aggregate and the filler into a stirring cylinder, and stirring for 30-90 s under the condition that the stirring speed is 200-500 rpm; and (3) adding the cold-patch rubber asphalt mixed solution into the mixture of the aggregate and the filler, and stirring for 60-240 seconds at a stirring speed of 200-500 rpm to obtain the cold-patch rubber asphalt mixture.
Further, before the mixing and dispersing step, the preparation method also comprises a step of preparing the linearization active rubber, wherein the linearization active rubber is prepared by the following method: in supercritical carbon dioxide, placing a mixture of waste rubber powder and a photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain linear active rubber; preferably, the photocatalyst is a composite inorganic photocatalyst; more preferably, the photocatalyst is selected from Co-doped TiO2、ZrO2/ZnO composite and ZrO2/TiO2One or more of the complexes; further preferably, the amount of the photocatalyst is 0.5 to 3% by weight of the waste rubber powder.
Further, before the mixing and dispersing step, the preparation method further comprises the step of preparing a linearized active rubber prepared by the following method: pretreating the waste rubber powder and a regenerant at the temperature of 60-150 ℃ for 10-30 min, and standing at the temperature of 50-120 ℃ for 6-36 h to obtain a pretreated product; extruding the pretreated product in a screw extruder, wherein the extrusion temperature is 100-480 ℃, the extrusion pressure is 3-15 Mpa, and the reaction time is 1-15 min, so as to obtain the linearized active rubber; preferably, the regenerant comprises a softener selected from one or more of coal tar, pine tar, tall oil, naphthenic oil, dipentene, paraffin oil, oleic acid and rosin, and an activator selected from one or more of aromatic disulfide, polyalkylphenol sulfide, phenyl mercaptan and n-butylamine; preferably, the weight ratio of the waste rubber powder to the softener to the activator is 100: (5-30): (0.5-5).
Further, before the mixing and dispersing step, the preparation method further comprises the step of preparing a linearized active rubber prepared by the following method: placing waste rubber powder into a vertical depolymerizer, adding a solvent, a desulfurization catalyst and a cocatalyst, and then performing desulfurization reaction at the temperature of 160-180 ℃ and under the pressure of 0.5-0.7 MPa to obtain linear active rubber; wherein the solvent is paraffin oil and/or solid coumarone, the desulfurization catalyst is phthalic anhydride, and the cocatalyst is formalin and/or resorcinol.
The cold-patch rubber asphalt mixture provided by the invention comprises aggregate, filler and a cold-patch rubber asphalt mixed solution, wherein the cold-patch rubber asphalt mixed solution comprises asphalt, linear active rubber, olefin polymer and a diluent. The linear active rubber with the weight percentage content of linear molecules being more than or equal to 75 percent is added on the basis of the asphalt, most of rubber molecules in the linear active rubber are linear molecules, the flexible chain structure of the rubber molecules is reserved, the linear active rubber has the performance similar to that of an elastomer polymer, the linear active rubber can replace the elastomer polymer to be applied to cold patch asphalt, the strength of the cold patch asphalt is enhanced, and meanwhile, the cost of the cold patch asphalt can be greatly reduced. Meanwhile, compared with the cross-linked waste rubber powder, the cross-linked structure of the linear active rubber is basically damaged, and the capability of absorbing light components and diluents of the asphalt is greatly weakened, so that the linear active rubber can be added in a large proportion, and the normal-temperature fluidity of the cold patch asphalt is not influenced while the performance of the cold patch asphalt is enhanced. In addition, the addition of the olefin polymer can further enhance the strength of the cold patch asphalt.
In a word, the cold-patch rubber asphalt mixture provided by the invention has the advantages of low cost and high strength, and has a wide application prospect.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the present application as claimed.
As described in the background of the invention section, the cold patch asphalt in the prior art has the problems of high cost or poor normal temperature fluidity and low strength after application.
In order to solve the problems, the invention provides a cold-patch rubber asphalt mixture which comprises aggregate, a filler and a cold-patch rubber asphalt mixed solution; the cold-patch rubber asphalt mixture comprises asphalt, linearized active rubber, olefin polymer and diluent, wherein the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%.
The cold-patch rubber asphalt mixture provided by the invention comprises aggregate, filler and a cold-patch rubber asphalt mixed solution, wherein the cold-patch rubber asphalt mixed solution comprises asphalt, linear active rubber, olefin polymer and a diluent. The linear active rubber with the weight percentage content of linear molecules being more than or equal to 75 percent is added on the basis of the asphalt, most of rubber molecules in the linear active rubber are linear molecules, the flexible chain structure of the rubber molecules is reserved, the linear active rubber has the performance similar to that of an elastomer polymer, the linear active rubber can replace the elastomer polymer to be applied to cold patch asphalt, the strength of the cold patch asphalt is enhanced, and meanwhile, the cost of the cold patch asphalt can be greatly reduced. Meanwhile, compared with the cross-linked waste rubber powder, the cross-linked structure of the linear active rubber is basically damaged, and the capability of absorbing light components and diluents of the asphalt is greatly weakened, so that the linear active rubber can be added in a large proportion, and the normal-temperature fluidity of the cold patch asphalt is not influenced while the performance of the cold patch asphalt is enhanced.
In addition, the double bond content of the olefin polymer is low, the hard chain segment content is high, the strength of the olefin polymer is higher than that of the linearized active rubber, and the compounded olefin polymer can strengthen a molecular network in the molecular network of the linearized active rubber and further strengthen the strength of the cold patch asphalt.
In a word, the cold-patch rubber asphalt mixture provided by the invention has the advantages of low cost and high strength, and has a wide application prospect.
The linearized active rubber adopted in the cold patch rubber asphalt mixed solution is obtained by waste rubber powder desulfurization treatment, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%, so that the linearized active rubber can replace an elastomer polymer to be applied to cold patch asphalt, the strength of the cold patch asphalt is enhanced, and the cost of the cold patch asphalt can be greatly reduced. In a preferred embodiment, the linearized molecules in the linearized active rubber comprise a gradient of small molecules with a molecular weight of 500 to 10000 and a macromolecular polymer with a molecular weight > 10000. The macromolecular polymer with the molecular weight more than 10000 can more effectively exert the low-temperature flexibility and elasticity of the rubber, has a molecular chain structure more similar to that of an elastomer polymer and a molecular weight more close to that of the elastomer polymer, can more fully replace the application of the macromolecular polymer in cold patch asphalt, and enhances the strength of the cold patch asphalt. The molecular weight of the gradient micromolecules with the molecular weight of 500-10000 is larger than that of the traditional micromolecule solvent oil, and the softening degree of the asphalt can be reduced while plasticizing the asphalt, so that the micromolecule solvent oil can be replaced, the using amount of a diluent can be correspondingly reduced, and the cold patch asphalt can keep normal-temperature fluidity and further assist in increasing the strength of the cold patch asphalt.
More preferably, in the linearized molecules, the weight percentage of the gradient small molecules is 10-20%, and the weight percentage of the macromolecular polymer is 80-90%. Therefore, the comprehensive effect of the two components is more favorably exerted, the characteristics of the linear active rubber are fully exerted, the strength and the normal temperature fluidity of the cold patch asphalt are improved, and the excessively low softening point of the cold patch rubber asphalt is further avoided.
In order to further improve the comprehensive performance of the cold-patch rubber asphalt mixture, in a preferred embodiment, the cold-patch rubber asphalt mixture comprises 100 parts of asphalt, 15-30 parts of linearized active rubber, 0.5-2 parts of olefin polymer and 2-12 parts of diluent by weight; preferably, the cold-patch rubber asphalt mixed solution comprises 100 parts by weight of asphalt, 20-30 parts by weight of linearized active rubber, 1-2 parts by weight of olefin polymer and 2-5 parts by weight of diluent. As described above, the linear active rubber is adopted in the invention, so that the linear active rubber can maintain the properties such as strength, normal temperature fluidity and the like of the cold patch asphalt on the basis of large-proportion addition, and particularly can fully replace an elastomer polymer to reduce the cost of the cold patch asphalt.
In order to further improve various performances of the cold patch asphalt, in a preferred embodiment, the cold patch rubber asphalt mixed solution further comprises 0.05-1.5 parts of elastomer polymer, 0.05-2 parts of petroleum resin and 0.1-3 parts of anti-stripping agent by weight. The cold-patch asphalt has better comprehensive performance by adding the elastomer polymer and the petroleum resin in lower parts by weight. The addition of the anti-stripping agent is beneficial to improving the anti-stripping performance of the cold patch asphalt.
The elastomeric polymers, petroleum resins, anti-stripping agents, etc. described above may be of the type conventionally used in cold patch asphalt, and in a preferred embodiment, the elastomeric polymers include, but are not limited to, one or more of SBS, SEBS, SIS, SBR, EVA and POE; preferably, the petroleum resin includes, but is not limited to, one or more of C5 petroleum resin, C9 petroleum resin, phenolic resin, and terpene resin; preferably, the anti-stripping agent includes, but is not limited to, one or more of para-amino-benzamide, meta-amino benzylamine, silane coupling agent, and sodium lignosulfonate.
In a preferred embodiment, the olefin polymer has a molecular weight of 3000 to 7000 and a melting point of 90 to 125 ℃. The olefin polymer with small molecular weight has small influence on the normal-temperature fluidity of the asphalt, and is beneficial to enhancing the cold-patch asphalt and keeping the normal-temperature fluidity of the cold-patch asphalt. Preferably, the olefinic polymer includes, but is not limited to, one or more of polyethylene wax, oxidized polyethylene wax, sasobit wax, and polyamide wax.
Preferably, the diluent includes, but is not limited to, diesel and/or kerosene.
The amount and type of the aggregate and the filler adopted in the mixture can be the amount and type commonly used in the field, and in a preferred embodiment, the cold-patch rubber asphalt mixture comprises 100 parts by weight of aggregate, 2-7 parts by weight of filler and 1-8 parts by weight of cold-patch rubber asphalt mixed solution; preferably, the aggregate is selected from basalt and/or limestone; preferably, the filler is selected from lime powder and/or slag powder.
According to another aspect of the present invention, there is also provided a method for preparing a cold-patch rubber asphalt mixture, which comprises the following steps: mixing and dispersing asphalt, linearized active rubber, olefin polymer and a diluent to obtain a cold-patch rubber asphalt mixed solution; wherein the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75 percent; and mixing the aggregate, the filler and the cold-patch rubber asphalt mixed solution to obtain the cold-patch rubber asphalt mixture.
By adopting the preparation method, the asphalt, the linearized active rubber, the olefin polymer and the diluent are mixed and dispersed to obtain a cold-patch rubber asphalt mixed solution, and then the aggregate, the filler and the cold-patch rubber asphalt mixed solution are mixed to obtain a cold-patch rubber asphalt mixture. The linear active rubber with the weight percentage content of linear molecules being more than or equal to 75 percent is added on the basis of the asphalt, most of rubber molecules in the linear active rubber are linear molecules, the flexible chain structure of the rubber molecules is reserved, the linear active rubber has the performance similar to that of an elastomer polymer, the linear active rubber can replace the elastomer polymer to be applied to the cold patch asphalt, the strength of the cold patch asphalt is enhanced, and meanwhile, the cost of the cold patch asphalt can be greatly reduced. Meanwhile, compared with the cross-linked waste rubber powder, the cross-linked structure of the linear active rubber is basically damaged, and the capability of absorbing light components and diluents of the asphalt is greatly weakened, so that the linear active rubber can be added in a large proportion, and the normal temperature fluidity of the cold patch asphalt is not influenced while the performance of the cold patch asphalt is enhanced. In addition, the double bond content of the olefin polymer is low, the hard chain segment content is high, the strength of the olefin polymer is higher than that of the linearized active rubber, and the compounded olefin polymer can strengthen a molecular network in the molecular network of the linearized active rubber and further strengthen the strength of the cold patch asphalt.
The process conditions in the preparation process can be adjusted, and preferably, the mixing and dispersing process comprises the following steps: heating asphalt to 150-185 ℃, adding an olefin polymer, and stirring at a stirring speed of 1000-2000 rpm for 30-60 ℃ in a heat preservation manner to form a first mixture; adding linear active rubber into the first mixture, and stirring at the temperature of 150-185 ℃ and the stirring speed of 1000-2000 rpm for 60-120 ℃ in a heat preservation manner to form a second mixture; and cooling the second mixture to 110-130 ℃, adding a diluent, and stirring for 30-60 min at the stirring speed of 1000-2000 rpm to obtain the cold-patch rubber asphalt mixed solution.
Preferably, during the addition of the olefin polymer, petroleum resin is added simultaneously; during the addition of the linearized active rubber, the elastomeric polymer and the antistripping agent are added simultaneously.
In a preferred embodiment, the process of mixing the aggregate, the filler and the cold-patch rubber asphalt mixture comprises the following steps: heating the cold patch rubber asphalt mixed solution to 40-80 ℃, and stirring for 30-60 min at a stirring speed of 500-1000 rpm in a heat preservation manner; putting the aggregate and the filler into a stirring cylinder, and stirring for 30-90 s under the condition that the stirring speed is 200-500 rpm; and (3) adding the cold-patch rubber asphalt mixed solution into the mixture of the aggregate and the filler, and stirring for 60-240 s under the condition that the stirring speed is 200-500 rpm to obtain the cold-patch rubber asphalt mixture.
Before the mixing and dispersing step, the preparation method preferably further comprises a step of preparing a linearized active rubber which can be prepared by subjecting the waste rubber powder to physical shear desulfurization or high-temperature decoction degradation, and preferably comprises the following steps:
physical shearing desulfurization:
pretreating the waste rubber powder and a regenerant at the temperature of 60-150 ℃ for 10-30 min, and standing at the temperature of 50-120 ℃ for 6-36 h to obtain a pretreated product; and extruding the pretreated product in a screw extruder, wherein the extrusion temperature is 100-480 ℃, the extrusion pressure is 3-15 Mpa, and the reaction time is 1-15 min, so as to obtain the linearized active rubber. Preferably, the regenerant comprises a softener selected from one or more of coal tar, pine tar, tall oil, naphthenic oil, dipentene, paraffin oil, oleic acid, and rosin, and an activator selected from one or more of aromatic disulfide, polyalkylphenol sulfide, phenyl mercaptan, and n-butylamine. Preferably, the weight ratio of the waste rubber powder to the softening agent to the activating agent is 100: (5-30): (0.5-5).
Degradation by a high-temperature boiling method:
placing waste rubber powder into a vertical depolymerizer, adding a solvent, a desulfurization catalyst and a cocatalyst, and then performing desulfurization reaction at 160-180 ℃ under the pressure of 0.5-0.7 MPa to obtain linearized active rubber; wherein the solvent is paraffin oil and/or solid coumarone, the desulfurization catalyst is phthalic anhydride, and the cocatalyst is formalin and/or resorcinol. Preferably, the raw materials in the preparation method comprise the following components in parts by weight: 100 parts of 20-50-mesh waste rubber powder, 70-90 parts of paraffin oil, 10-30 parts of solid coumarone, 2-5 parts of phthalic anhydride, 4-6 parts of formaldehyde aqueous solution and 0.2-0.5 part of resorcinol.
Compared with the physical shearing desulfurization or high-temperature boiling degradation, the more preferable linear active rubber is prepared by adopting the following method:
in supercritical carbon dioxide, the mixture of waste rubber powder and photocatalyst is put under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber. The waste rubber powder can be swelled by using the supercritical carbon dioxide, so that the aperture of the three-dimensional cross-linked network in the waste rubber powder is increased, and the photocatalyst is permeated into the waste rubber powder from the surface by virtue of the diffusion effect of the supercritical carbon dioxide fluid. Secondly, the photocatalyst generates a large amount of active groups under the irradiation of ultraviolet light to catalyze the breakage of S-S bonds in the waste rubber powder, thereby realizing the desulfurization and crosslinking of the waste rubber powder. Particularly, since the supercritical carbon dioxide also has an excellent dissolving effect, the linear molecules formed by the desulfurization and de-crosslinking on the surface of the waste rubber powder can be rapidly peeled off from the surface of the waste rubber powder and dissolved in the supercritical carbon dioxide. Along with the continuous reaction, the waste rubber powder continuously carries out the circulation of 'catalyst surface permeation, photocatalytic desulfurization and desulfurization linear molecule stripping and dissolving' till the whole waste rubber powder is desulfurized and de-crosslinked to form the linear active rubber.
Different from the mechanical shearing desulfurization regeneration method, the photocatalytic desulfurization is carried out under the swelling action of supercritical carbon dioxide, so that the method has higher selectivity on the breaking point of a cross-linked network, and the breaking point is mostly at the S-S bond cross-linking part. While the breaking point of mechanical shear desulfurization is a diversified breaking point that is not selective for S-S bond crosslinks. Therefore, based on the preparation method, the linearization structure of the rubber can be more completely maintained, and the regenerated linearization active rubber has higher molecular weight and correspondingly maintains higher performance.
Compared with the mode of degradation by a high-temperature boiling method, the photocatalytic desulfurization is carried out under the swelling action of supercritical carbon dioxide without adding a chemical desulfurizer, so that the problems of delayed vulcanization, secondary degradation and the like caused by chemical desulfurization and residue are avoided. Meanwhile, a large amount of softening aids are not added to the high-temperature boiling method, so that the influence of the softening aids on the performance of the cold patch asphalt, such as the influence on the strength of the cold patch asphalt, can be avoided.
The above-mentioned photocatalyst may be of a type commonly used in the field of photocatalytic technology. In a preferred embodiment, the photocatalyst is a composite inorganic photocatalyst. The composite inorganic photocatalyst has higher catalytic activity and higher selective fracture performance on S-S crosslinking points in waste rubber powder. More preferably, the photocatalyst is selected from Co-doped TiO2、ZrO2/ZnO composite and ZrO2/TiO2One or more of the complexes. Several kinds of composite inorganic lightThe surface area of the catalyst is greatly increased, so that the probability of exciting the photohole electrons under ultraviolet irradiation is further increased, and the photohole electrons have higher catalytic activity. Meanwhile, the photocatalysts are remained in the linearized active rubber and are more suitable as fillers of the linearized active rubber, and the photocatalysts can play a certain auxiliary role in reinforcing cold patch asphalt.
In a preferred embodiment, the preparation method comprises the following steps: mixing waste rubber powder with a photocatalyst to obtain a mixture; under the condition of stirring, putting the mixture into supercritical carbon dioxide for swelling treatment to obtain a swelling mixture; and irradiating ultraviolet light to the swelling mixture in supercritical carbon dioxide to perform photocatalytic desulfurization reaction, thereby obtaining the linearized active rubber.
Thus, mixing the waste rubber powder with the photocatalyst in advance enables the photocatalyst to be dispersed in the waste rubber powder in advance. And secondly, the mixture is placed in supercritical carbon dioxide under the condition of stirring for swelling treatment, so that the diffusion effect of the supercritical carbon dioxide fluid can be fully exerted, the waste rubber powder is swelled as soon as possible, and the photocatalyst is permeated into the surface of the waste rubber powder more quickly. Finally, irradiating ultraviolet light in the system to carry out photocatalytic desulfurization reaction. In the actual operation process, the desulfurization efficiency of the waste rubber powder can be further improved according to the process.
In a preferred embodiment, the swelling treatment step comprises: injecting carbon dioxide gas into a system in which the mixture is located, and then adjusting the temperature of the system to 80-140 ℃ and the pressure to 10-35 MPa to convert the carbon dioxide gas into a supercritical state so as to form supercritical carbon dioxide; and swelling the mixture for 30-120 min under the stirring condition that the stirring speed is 200-700 rpm, so as to obtain a swelling mixture. The swelling treatment is carried out in the process, the aperture of the cross-linked network of the waste rubber powder is larger, and the photocatalyst can more fully permeate and more uniformly disperse in the rubber network, so that on one hand, the desulfurization efficiency of the waste rubber powder can be further improved, and meanwhile, the number of the broken S-S bonds can be further improved, thereby improving the desulfurization degree of the waste rubber powder and obtaining the desulfurized rubber with higher linearization degree.
More preferably, the swelling treatment step comprises: injecting carbon dioxide gas into a system where the mixture is located, and then adjusting the temperature of the system to 105-140 ℃ and the pressure to 28-35 MPa to convert the carbon dioxide gas into a supercritical state so as to form supercritical carbon dioxide; and swelling the mixture for 90-120 min under the condition that the stirring speed is 500-700 rpm, so as to obtain a swelling mixture. The desulfurization efficiency and desulfurization degree under the process condition are higher.
In a preferred embodiment, in the step of photocatalytic desulfurization, the reaction temperature is 80-140 ℃ and the reaction pressure is 10-35 MPa. Under the reaction conditions, the S-S bond desulfurization selectivity of the photocatalyst is higher, and the desulfurization degree and the desulfurization linearization degree of the waste rubber powder are higher. More preferably, the reaction temperature in the step of the photocatalytic desulfurization reaction is 105-140 ℃, and the reaction pressure is 28-35 MPa. In the actual production process, after the photocatalytic desulfurization reaction is finished, the method preferably further comprises the following steps: and (3) decompressing the reaction system, recovering carbon dioxide, stopping illumination and cooling to obtain the linearized active rubber.
In a preferred embodiment, in the step of photocatalytic desulfurization, the illumination time of the ultraviolet light is 5 to 30min, preferably 20 to 30min, and the wavelength of the ultraviolet light is 300 to 400nm, preferably 350 to 390 nm. Under the illumination condition, the photocatalyst has higher activity, and the desulfurization effect of the waste rubber powder is better.
In a preferred embodiment, the step of mixing the waste rubber powder with the photocatalyst comprises: and stirring and mixing the waste rubber powder and the photocatalyst for 5-30 min under the condition that the stirring speed is 700-1500 rpm to obtain a mixture. The waste rubber powder and the photocatalyst are mixed according to the process, and the waste rubber powder and the photocatalyst can be mutually dispersed more fully. Preferably, the waste rubber powder and the photocatalyst are stirred and mixed to the temperature of 60-85 ℃ to obtain a mixture. Shear heating can occur in the stirring process, the stirring and mixing temperature is controlled to be 60-85 ℃, and performance influence caused by overheating can be prevented on the basis of sufficient dispersion.
As described above, based on the diffusivity and good solubility of supercritical carbon dioxide, the cyclic process of "catalyst surface permeation-photocatalytic desulfurization-desulfurization linear molecular stripping dissolution" is continuously performed in the step of photocatalytic desulfurization reaction of waste rubber powder, which enables the preparation method to achieve a higher desulfurization degree by using the cyclic process with less photocatalyst. For the purpose of saving energy and improving the desulfurization efficiency and the desulfurization degree, in a preferred embodiment, the amount of the photocatalyst is 0.5 to 3% by weight, preferably 2 to 3% by weight, based on the waste rubber powder.
In a preferred embodiment, the particle size of the waste rubber powder is 80-120 meshes; preferably, the waste rubber powder is one or more of waste tire rubber powder, waste sole rubber powder and waste conveyor belt rubber powder.
In addition, the preparation method is suitable for waste rubber powder commonly used in the field, such as one or more of waste nitrile rubber powder, waste natural rubber powder, waste butyl rubber powder, waste ethylene propylene rubber powder and waste styrene butadiene rubber powder.
The beneficial effects of the present invention are further illustrated by the following examples:
preparation of linearized active rubber:
examples 1 to 17
In these examples, the following processes were used to conduct the devulcanization regeneration of the waste rubber:
step 1: putting 80-mesh waste tire rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 1000rpm for 20min to 70 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture;
and 2, step: putting the mixture into a supercritical carbon dioxide reaction kettle, injecting carbon dioxide gas into the reaction kettle by using a high-pressure pump to adjust the pressure in the reaction kettle, and simultaneously heating to convert the carbon dioxide gas into a supercritical state; starting stirring to swell the mixture in supercritical carbon dioxide to obtain a swollen mixture;
and step 3: maintaining the supercritical carbon dioxide environment, starting a built-in ultraviolet light source to perform ultraviolet irradiation on the swelling mixture, and irradiating for a certain time;
and 4, step 4: and (4) releasing pressure, recovering carbon dioxide gas, stopping illumination, cooling, taking out a target product and testing.
Examples 1 to 17 differ in the following parameters: the type and amount of the photocatalyst (weight percentage of the waste rubber powder), the temperature of the supercritical carbon dioxide system (same swelling temperature and desulfurization reaction temperature), the pressure (same swelling pressure and desulfurization reaction pressure), the swelling time, the ultraviolet light irradiation time and the ultraviolet light wavelength are shown in table 1:
TABLE 1
Figure BDA0001978975370000091
Figure BDA0001978975370000101
Example 18
The process flow in this example is the same as example 9, except that:
step 1: and (3) putting 120-mesh waste tire rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 700rpm for 30min to 60 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.
Example 19
The process flow in this example is the same as in example 10, except that:
step 1: and (3) putting 120-mesh waste sole rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 1500rpm for 30min to 85 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.
Example 20
The process flow in this example is the same as example 10, except that:
step 1: and (3) putting 80-mesh waste conveyor belt rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 600rpm for 10min to 40 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.
Example 21
100 parts of waste tire tread rubber powder with the particle size of 1mm are adopted, 6 parts of pine tar, 4 parts of naphthenic oil, 0.5 part of phenyl mercaptan and 0.5 part of n-butylamine are added as regenerants, and the mixture is mixed and stirred for 10min at the temperature of 100 ℃ in a stirrer and then is placed for 36h at the temperature of 50 ℃. It was then fed into a co-rotating twin-screw extruder (D30 mm, L/D52/1, six heating zones) via a feeding device: screw rotation speed 150rpm, 6 temperature zones: changing the internal thread composition of the screw at 120 ℃, 180 ℃, 230 ℃, 280 ℃, 150 ℃ and 100 ℃, and adding a right-handed thread element to ensure that the maximum pressure reaches 7.5 MPa. And reacting for 5min, and extruding by a screw extruder die to obtain the reclaimed rubber.
Example 22
100kg of 30-mesh vulcanized rubber powder was put into a vertical depolymerizer, and 70kg of paraffin oil, 22kg of solid coumarone resin, 3kg of phthalic anhydride, 4.5kg of formalin and 0.5kg of resorcinol were sequentially added. And sealing the material port, stirring, heating to 180 ℃, controlling the pressure to be 0.5MPa, reacting for 2.5 hours, cooling, discharging residual gas, discharging, and filtering by using a 100-mesh metal screen to obtain the reclaimed rubber.
Comparative example 1
100 parts of waste tire rubber powder and 10 parts of nano cadmium sulfide are stirred and mixed uniformly by a high-speed plasticizing reaction unit. The rotating speed of the reaction unit is firstly adjusted to 1200rpm, when the temperature reaches 90 ℃, stirring is stopped, the materials are put into a cooling unit, the rotating speed is 50rpm, and when the temperature is about 30 ℃, discharging is carried out. Placing the stirred material into a stirrer, and irradiating the material with ultraviolet lamp for 30 min. The UV lamp used was a 3kw high pressure mercury lamp with UV wavelength of 365 nm.
The main machine rotating speed of the double-screw extruder is adjusted to be 220rpm, the feeding rotating speed is adjusted to be 15rpm, and the temperatures of 7 temperature zones of the double screws are as follows: 54-67-77-76-79-73-42 ℃, the temperature of each area is not higher than 100 ℃, the production state at normal temperature and normal pressure is realized, and the discharge detection is carried out.
Comparative example 2
The process flow in this comparative example is the same as in example 10, except that the system temperature: 30 ℃, pressure 7MPa, critical parameters of CO 2: 31.26 deg.C and 7.29MPa, carbon dioxide is in non-supercritical state.
The devulcanization effect characterization was performed on the devulcanized reclaimed rubbers prepared in examples 1 to 22, comparative examples 1 and 2(D1 and D2), and the characterization results are shown in table 2, and the characterization methods are as follows:
the following treatments were carried out on each of the above products:
firstly, acetone is used as a solvent, and a Soxhlet extraction method is adopted to continuously extract for 48 hours until small molecules (acetone soluble substances) are completely extracted and separated by the acetone. Subsequently, the soluble fraction was dried in a vacuum drying oven until the mass was unchanged, the insoluble fraction was dried until the mass was unchanged, and secondary extraction was continued using toluene as a solvent to separate a macromolecular soluble substance (toluene soluble substance) and a crosslinked insoluble substance (gel).
The average molecular weights of the acetone soluble substance and the toluene soluble substance and the polymer polydispersity number PDI are respectively tested (GPC test can be simultaneously characterized, and the molecular weights and the polydispersity numbers PDI are respectively tested) by the following methods: acetone-soluble matter and toluene-soluble matter were sufficiently swollen with toluene, and the number average molecular weight (M) of the sample was measured by using a model 515-n) And calculating the polydispersity index (PDI) by taking tetrahydrofuran as a mobile phase and polystyrene as a standard sample, and measuring the temperature at 35 ℃.
The crosslink density of the gel was measured as follows: the crosslinking density test adopts an equilibrium swelling method. The weighed sample is put into a conical flask with a plug and a ground opening, which is filled with 150ml of good solvent (toluene is used as the good solvent in the experiment), and is immersed into a constant-temperature water bath, the solution is kept for 72 hours at 30 ℃, the sample is taken out after the balance is achieved, the mass of the sample is weighed by an analytical balance, and the sample is dried for 4 hours at 50 ℃ in a vacuum drier. When the sample swells in the appropriate solvent to equilibrium, the solvent molecules enter the crosslinked network at the same rate as they are expelled. And obtaining a crosslinking density formula, namely a Flory-Rehner formula, according to the basis of the rubber elasticity statistical theory.
TABLE 2
Figure BDA0001978975370000121
Figure BDA0001978975370000131
The gel content, the sol average molecular weight, the sol PDI and the gel crosslinking density are the most visual and accurate means for representing the degradation degree of the crosslinked rubber. The higher the sol content, the lower the gel content, and the lower the gel crosslink density, the higher the degree of degradation of the rubber. The higher the toluene solubles content and the higher the molecular weight at the same sol content, the higher the content of linearized macromolecules in the reclaimed rubber after decrosslinking. The weight percentage content of the linearized molecules is sol content/(sol content + gel content); the weight percentage of the gradient small molecules in the linearized molecule is acetone soluble content/(acetone soluble + toluene soluble content).
1. From the comparison of the data in the above examples and comparative example 2, it can be seen that: in the supercritical carbon dioxide fluid state, the same process means is adopted, and the desulfurization and degradation degree of the waste rubber is far higher than that in the non-supercritical state (the carbon dioxide critical point is 38 ℃ and 7.38 MPa). This is due to: in the supercritical state, the carbon dioxide fluid can fully exert the excellent dissolving and extracting performances of the rubber powder, and can fully dissolve linear macromolecules and micromolecules, the macromolecules firstly desulfurized and degraded on the surface of the waste rubber powder are disentangled through the swelling effect of the supercritical carbon dioxide fluid, and are peeled from the crosslinked rubber powder body and dissolved in the fluid. And then, under the action of illumination and a catalyst, the inner layer of the crosslinked rubber powder continues to be desulfurized and degraded and has the same action as the surface layer until the whole crosslinked waste rubber powder is desulfurized and degraded. The linearized active rubber is in a pasty and semi-fluid state at normal temperature. However, in a non-supercritical state, the surface of the waste rubber powder is subjected to desulfurization degradation under the action of illumination and a catalyst, and the surface layer subjected to desulfurization degradation still wraps the surface of the rubber powder due to the absence of the action of an external solvent, so that the rubber of the desulfurized surface layer blocks the penetration of ultraviolet light, namely, the illumination cannot reach the inside of the waste rubber powder, and the inside of the waste rubber powder still is in a three-dimensional cross-linked state. Therefore, even if photocatalytic degradation is carried out in a non-supercritical carbon dioxide state, the degradation efficiency and degree are low, sufficient desulfurization degradation of the crosslinked waste rubber component cannot be realized, and the basically fully uncrosslinked linearized rubber cannot be prepared;
2. as can be seen from the comparison of the data in the above examples and comparative examples 1 and 2, the method of the present invention provides a higher degree of desulfurization of the waste rubber crumb and a higher degree of linearization of the devulcanized rubber. In particular, the twin-screw mechanical devulcanization used in example 21 was carried out without differential chain scission of the three-dimensional crosslinked network in the waste rubber powder, and therefore, the gel content was relatively low, but at the same time, the small molecules content was high, the large molecules content was low, and the molecular weight of the large molecular chains was relatively low. The preparation methods adopted in examples 1 to 20 have the advantage of selective chain scission for S-S bonds and S-C bonds in the three-dimensional cross-linked network of the waste rubber powder, so that the desulfurization linearized active rubbers prepared in examples 1 to 20 of the present invention have higher macromolecular content than that of example 21. In example 22, the rubber powder is degraded by a high-temperature boiling method, but the preparation method of the rubber powder is added with a large amount of small molecule softeners (paraffin oil and solid coumarone), so that the content of the gradient small molecules in the linearized active rubber is high, and the content of the linearized large molecules is low.
3. More particularly, as can be seen from the comparison of the data in examples 1 to 17 above, the optimization of the swelling step and the photocatalytic desulfurization step using the composite inorganic photocatalyst enables the desulfurization regeneration degree of the waste rubber powder to be significantly improved, and the substantially fully uncrosslinked, linearized rubber to be obtained. And the process is optimized, and the prepared fully-desulfurized de-crosslinked linearized rubber has high macromolecular polymer (rubber) content, large molecular weight and narrow macromolecular chain distribution coefficient (polydispersity index PDI).
4. When photocatalytic degradation is performed under supercritical carbon dioxide, the requirements on the wavelength of ultraviolet light are not strict, and the photocatalytic degradation can be realized within the wavelength range of 350-420.
Preparing a cold-patch rubber asphalt mixed solution:
examples 23 to 44, comparative examples 3 and 4(D3 and D4)
Examples 23 to 44, comparative examples 3 and 4 cold-patch rubber-asphalt mixtures were prepared by the following methods:
heating the asphalt to 185 ℃, adding the olefin polymer and optional petroleum resin, and stirring for 30-60 min at a stirring speed of 2000rpm to form a first mixture;
adding the linearized active rubber, the optional elastomer polymer and the optional anti-stripping agent into the first mixture, and stirring for 60min at 185 ℃ and 2000rpm to form a second mixture;
and cooling the second mixture to 130 ℃, adding a diluent into the second mixture, and stirring the mixture for 30min at the stirring speed of 2000rpm to obtain the cold patch rubber asphalt mixed solution.
The formulations are given in table 3 below: (Note: the following olefin polymers have a molecular weight of 3000 to 7000 and a melting point of 90 to 125 ℃ C.) Table 3
Figure BDA0001978975370000151
Figure BDA0001978975370000161
Note: the raw material sources are as follows: polyethylene wax: new materials, inc, luo land, jun; oxidized polyethylene wax: the science and technology of new Jiangsu Helong materials are according to the company; sasolbit wax: shanghai Kaiyn chemical Co., Ltd; SBR: shandong Qiangli Industrial science, Inc.; SIS: medium petro-chemicals barling petro-chemicals limited 1105; EVA: dupont 265, usa.
And (3) performance characterization: the properties of the cold patch rubber asphalt mixtures and the corresponding cold patch rubber asphalt mixtures prepared in the above examples 23 to 37 and comparative examples 3 and 4 are characterized as follows:
the performance of the cold-patch rubber asphalt mixed solution is characterized by: (a) standard viscosity at 60 ℃; (b) resistance to flaking (poaching), characterized as follows: standard viscosity at 60 ℃: JTG E20-2011 road engineering asphalt and asphalt mixture test procedure T0621-1993 asphalt standard viscosity test; resistance to flaking (boiling method): JTG E20-2011 Highway engineering asphalt and asphalt mix test protocol T0616-1993 adhesion tests of asphalt to coarse aggregate. The characterization results are detailed in table 4.
TABLE 4
Standard viscosity(s) at 60 ℃ Resistance to flaking (Water boiling method)
Example 23 78 Grade 4
Example 24 70 Grade 4
Example 25 68 4 stage
Example 26 82 4 stage
Example 27 75 4 stage
Example 28 64.3 Grade 4
Example 29 65 Grade 5
Example 30 80 Grade 4
Example 31 73 4 stage
Example 32 85 Grade 5
Example 33 67 Grade 3
Example 34 56 Grade 3
Example 35 72 Grade 5
Example 36 68 Grade 3
Example 37 65 Grade 3
Comparative example 3 124 Stage 2
Comparative example 4 126 Stage 2
Preparing a cold-patch rubber asphalt mixture:
examples 38 to 52, comparative example 5 and comparative example 6
Cold-patch rubber asphalt mixtures were prepared by using the respective cold-patch rubber asphalt mixed solutions prepared in the above examples 23 to 37 and comparative examples 3 and 4 as raw materials, and the cold-patch rubber asphalt mixtures corresponding to the examples 23 to 37 and comparative examples 3 and 4 were respectively as shown in examples 38 to 52, comparative example 5 and comparative example 6 shown in the following table:
the preparation method comprises the following steps:
heating the cold-patch rubber asphalt mixed solution to 80 ℃, and stirring for 30min at the stirring speed of 1000 rpm; according to the weight ratio of aggregate to filler to cold-patch rubber asphalt mixed solution of 100:7:8 (the aggregate is basalt granules and the filler is lime powder), putting the aggregate and the filler into a stirring cylinder, stirring for 90s, and stirring at the speed: 300 rpm; and then further adding the cold-patch rubber asphalt mixed solution, stirring for 240s at a stirring speed of 500rpm to obtain a cold-patch rubber asphalt mixture, metering, sealing, filling and storing.
Characterizing various performances of the cold-patch rubber asphalt mixture, (c) operating at low temperature and workability; (d) cohesiveness; (e) marshall stability. Several methods of performance characterization are based on the following: JTG F40-2004 Highway asphalt pavement construction technical specification-Cold mix asphalt mixture pavement, the characterization results are detailed in Table 5.
TABLE 5
Figure BDA0001978975370000181
Figure BDA0001978975370000191
Example 53
The difference from example 44 is that the weight ratio of aggregate to filler to cold-patch rubber asphalt mixture is 100:2:4, and the performance results are shown in Table 6.
Example 54
The difference from example 44 is that the weight ratio of aggregate to filler to cold-patch rubber asphalt mixture is 100:5:10, and the performance results are shown in Table 6.
Example 55
The difference from example 44 is that the aggregate is limestone granules and the filler is ground slag and the performance results are shown in Table 6.
TABLE 6
Workability at Low temperature Cohesiveness (less than or equal to 40 percent) Marshall stability (not less than 3KN)
Example 53 Less caking, easier mixing (-10 ℃ C.) 26 5.5
Example 54 No caking, easy mixing (-10 ℃ C.) 19 6.3
Example 55 No caking, easy mixing (-10 ℃ C.) 17 6.6
From the data, the standard viscosity of the cold patch asphalt mixed solution at 60 ℃ and the low-temperature mixability of the mixture are increased along with the increase of the desulfurization degradation degree of the rubber powder, and the two indexes reflect the construction workability of the cold patch asphalt mixed solution, which indicates that the desulfurization degradation degree of the rubber powder is increased and the capability of absorbing asphalt and a diluent is weakened; in addition, as the desulfurization degradation degree of the rubber powder is increased, the amount of the diluent which needs to be additionally added in the cold patch asphalt mixed solution can be reduced, which is related to that a small amount of small molecular components generated in the degradation process of the rubber powder can replace the additional diluent. It can be seen from the examples and comparative examples that, as the amount of the anti-stripping agent and the content of the macromolecular component in the linearized active rubber are increased, the anti-stripping performance and the cohesiveness of the cold patch asphalt mixture and the cold patch asphalt mixture are increased, and the content of the macromolecular component in the linearized active rubber is increased, the winding and wrapping capacity between the cold patch asphalt and the aggregate can be effectively improved, so that the anti-stripping performance is increased. The strength of the cold-patch asphalt mixture is improved along with the increase of the dosage of the elastomer polymer, the dosage of the olefin polymer and the content of the macromolecular components in the linearized active rubber, which is related to the improvement of the wrapping strength of the macromolecular components and the aggregates; the addition proportion of the macromolecular polymer is too small, and the intensity of the cold-patch asphalt mixture is greatly influenced. When the addition proportion of the linear active rubber is too high/the proportion of the diluent is too low, the low-temperature operability and the standard viscosity at 60 ℃ of the cold-patch asphalt mixed solution are changed rapidly, so that the construction workability is influenced, and in addition, when the desulfurization degradation degree of the rubber powder is low, the capability of the rubber powder for absorbing light components and the diluent of the asphalt is greatly increased, so that the low-temperature construction workability and the standard viscosity at 60 ℃ are greatly increased.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The cold-patch rubber asphalt mixture is characterized by comprising 100 parts by weight of aggregate, 2-7 parts by weight of filler and 1-8 parts by weight of cold-patch rubber asphalt mixed solution; the cold-patch rubber asphalt mixed solution comprises, by weight, 100 parts of asphalt, 20-30 parts of linearized active rubber, 1-2 parts of olefin polymer, 2-5 parts of diluent, 0.05-1.5 parts of elastomer polymer, 0.05-2 parts of petroleum resin and 0.1-3 parts of anti-stripping agent; wherein the olefin polymer has a molecular weight of 3000-7000 and a melting point of 90-125 ℃, and is selected from one or more of polyethylene wax, oxidized polyethylene wax, sasobit wax and polyamide wax; the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75 percent; the linearized active rubber is prepared by the following method: in supercritical carbon dioxide, placing a mixture of waste rubber powder and a photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber; the linearized molecules in the linearized active rubber comprise gradient micromolecules and macromolecular polymers, the molecular weight of the gradient micromolecules is 500-10000, and the molecular weight of the macromolecular polymers is more than 10000; in the linearized molecules, the weight percentage of the gradient small molecules is 10-20%, and the weight percentage of the macromolecular polymers is 80-90%.
2. A cold-patch rubber asphalt mixture according to claim 1, wherein said elastomeric polymer is selected from one or more of SBS, SEBS, SIS, SBR, EVA and POE; the petroleum resin is selected from one or more of C5 petroleum resin, C9 petroleum resin, phenolic resin and terpene resin; the anti-stripping agent is selected from one or more of p-aminobenzamide, m-aminobenzylamine, a silane coupling agent and sodium lignosulfonate.
3. A cold-patch rubber asphalt mixture according to claim 1 or 2, wherein said diluent is selected from diesel and/or kerosene.
4. A cold-patch rubber-asphalt mixture according to claim 1 or 2, wherein said aggregate is selected from basalt and/or limestone; the filler is selected from lime powder and/or slag powder.
5. A method for preparing a cold-patch rubber asphalt mixture according to any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing and dispersing asphalt, linearized active rubber, olefin polymer and a diluent to obtain a cold-patch rubber asphalt mixed solution; the rubber composition is characterized by comprising a linearization active rubber, a rubber powder and a rubber powder, wherein the linearization active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearization molecules in the linearization active rubber is more than or equal to 75%; the linearized active rubber is prepared by the following method: in supercritical carbon dioxide, placing a mixture of waste rubber powder and a photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber; wherein during the addition of the olefin polymer, petroleum resin is added simultaneously; adding an elastomer polymer and an anti-stripping agent simultaneously in the process of adding the linearized active rubber;
and mixing the aggregate, the filler and the cold-patch rubber asphalt mixed solution to obtain the cold-patch rubber asphalt mixture.
6. The preparation method of the cold-patch rubber asphalt mixture according to claim 5, wherein the process of mixing and dispersing to obtain the cold-patch rubber asphalt mixture comprises the following steps:
heating the asphalt to 150-185 ℃, adding the olefin polymer, and stirring for 30-60 min at a stirring speed of 1000-2000 rpm to form a first mixture;
adding the linearized active rubber into the first mixture, and stirring for 60-120 min at the conditions of the temperature of 150-185 ℃ and the stirring speed of 1000-2000 rpm to form a second mixture;
and cooling the second mixture to 110-130 ℃, adding the diluent, and stirring for 30-60 min at the stirring speed of 1000-2000 rpm to obtain the cold-patch rubber asphalt mixed solution.
7. The method for preparing a cold-patch rubber asphalt mixture according to claim 5, wherein the process of mixing the aggregate, the filler and the cold-patch rubber asphalt mixture comprises the following steps:
heating the cold-patch rubber asphalt mixed solution to 40-80 ℃, and stirring for 30-60 min at a stirring speed of 500-1000 rpm in a heat preservation manner;
putting the aggregate and the filler into a stirring cylinder, and stirring for 30-90 s under the condition that the stirring speed is 200-500 rpm;
and adding the cold-patch rubber asphalt mixed solution into the mixture of the aggregate and the filler, and stirring for 60-240 s under the condition that the stirring speed is 200-500 rpm to obtain the cold-patch rubber asphalt mixture.
8. The preparation method of the cold-patch rubber-asphalt mixture according to any one of claims 5 to 7, wherein the photocatalyst is a composite inorganic photocatalyst.
9. The method for preparing a cold-patch rubber asphalt mixture according to claim 8, wherein the photocatalyst is Co-doped TiO2、ZrO2/ZnO composite and ZrO2/TiO2One or more of the complexesAnd (4) seed preparation.
10. The preparation method of the cold-patch rubber asphalt mixture as claimed in claim 8, wherein the amount of the photocatalyst is 0.5-3% of the weight of the waste rubber powder.
CN201910142491.6A 2019-02-26 2019-02-26 Cold-patch rubber asphalt mixture and preparation method thereof Active CN111606602B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910142491.6A CN111606602B (en) 2019-02-26 2019-02-26 Cold-patch rubber asphalt mixture and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910142491.6A CN111606602B (en) 2019-02-26 2019-02-26 Cold-patch rubber asphalt mixture and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111606602A CN111606602A (en) 2020-09-01
CN111606602B true CN111606602B (en) 2022-07-15

Family

ID=72193896

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910142491.6A Active CN111606602B (en) 2019-02-26 2019-02-26 Cold-patch rubber asphalt mixture and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111606602B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112897937B (en) * 2021-02-01 2022-04-19 西安建筑科技大学 Composite modified cold-patch asphalt mixture and preparation method thereof
CN113583628A (en) * 2021-08-25 2021-11-02 上海斛卓咨询管理有限公司 Crack sealing waterproof cold-patch liquid crack pouring adhesive and preparation method thereof

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765964A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Normal temperature modification additive for pavement asphalt and its preparation method and uses
CN101100534A (en) * 2007-07-03 2008-01-09 天津市亚腾达橡塑制品发展有限公司 Plaster-shape regenerated rubber and preparation method thereof
CN101353481A (en) * 2007-07-25 2009-01-28 同济大学 Asphalt mixture for rapid repair of hot-mix-cold-laid pavement
CN102220020A (en) * 2010-04-15 2011-10-19 东莞市超逸建材有限公司 High-molecular polymer asphalt for road crack repair, manufacturing method and crack-bonding belt
CN103043962A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Mixture for normal-temperature repairing of asphalt pavement pits, and preparation method and application thereof
CN103540147A (en) * 2013-10-23 2014-01-29 潍坊市晨鸣新型防水材料有限公司 High-strength and anti-stripping elastomer modified asphalt waterproof coiled material and production process
CN103739873A (en) * 2013-12-19 2014-04-23 河北瑞威科技有限公司 Process method for recycling rubber by utilizing light energy
KR20140060038A (en) * 2012-11-09 2014-05-19 한국토지주택공사 A asphalt sealant composition, preparing method for thereof and repairing method of road
CN103804936A (en) * 2014-02-20 2014-05-21 重庆交通大学 Waste SBS asphalt regenerant and preparation method thereof
CN103881405A (en) * 2014-04-08 2014-06-25 王国清 Waste rubber powder modified asphalt and preparation method thereof
CN104387611A (en) * 2014-11-28 2015-03-04 天津海泰环保科技发展有限公司 Environment-friendly method for regenerating waste rubber
CN104693821A (en) * 2015-02-16 2015-06-10 北京路德永泰环保科技有限公司 Bituminous mixture using DVS (direct vat set) high-adhesion modifier and preparation method thereof
KR101860144B1 (en) * 2017-11-22 2018-05-21 (주)한동알앤씨 Cold Asphalt Concrete Mixture for Repairing Road
CN108793831A (en) * 2018-07-02 2018-11-13 银禧工程塑料（东莞）有限公司 A kind of high intensity cold repairing asphalt mixture and preparation method thereof
CN109053032A (en) * 2018-07-04 2018-12-21 辽宁省交通科学研究院有限责任公司 A kind of storage type asphalt pavement pit repairing material and preparation method thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765964A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Normal temperature modification additive for pavement asphalt and its preparation method and uses
CN101100534A (en) * 2007-07-03 2008-01-09 天津市亚腾达橡塑制品发展有限公司 Plaster-shape regenerated rubber and preparation method thereof
CN101353481A (en) * 2007-07-25 2009-01-28 同济大学 Asphalt mixture for rapid repair of hot-mix-cold-laid pavement
CN102220020A (en) * 2010-04-15 2011-10-19 东莞市超逸建材有限公司 High-molecular polymer asphalt for road crack repair, manufacturing method and crack-bonding belt
CN103043962A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Mixture for normal-temperature repairing of asphalt pavement pits, and preparation method and application thereof
KR20140060038A (en) * 2012-11-09 2014-05-19 한국토지주택공사 A asphalt sealant composition, preparing method for thereof and repairing method of road
CN103540147A (en) * 2013-10-23 2014-01-29 潍坊市晨鸣新型防水材料有限公司 High-strength and anti-stripping elastomer modified asphalt waterproof coiled material and production process
CN103739873A (en) * 2013-12-19 2014-04-23 河北瑞威科技有限公司 Process method for recycling rubber by utilizing light energy
CN103804936A (en) * 2014-02-20 2014-05-21 重庆交通大学 Waste SBS asphalt regenerant and preparation method thereof
CN103881405A (en) * 2014-04-08 2014-06-25 王国清 Waste rubber powder modified asphalt and preparation method thereof
CN104387611A (en) * 2014-11-28 2015-03-04 天津海泰环保科技发展有限公司 Environment-friendly method for regenerating waste rubber
CN104693821A (en) * 2015-02-16 2015-06-10 北京路德永泰环保科技有限公司 Bituminous mixture using DVS (direct vat set) high-adhesion modifier and preparation method thereof
KR101860144B1 (en) * 2017-11-22 2018-05-21 (주)한동알앤씨 Cold Asphalt Concrete Mixture for Repairing Road
CN108793831A (en) * 2018-07-02 2018-11-13 银禧工程塑料（东莞）有限公司 A kind of high intensity cold repairing asphalt mixture and preparation method thereof
CN109053032A (en) * 2018-07-04 2018-12-21 辽宁省交通科学研究院有限责任公司 A kind of storage type asphalt pavement pit repairing material and preparation method thereof

Also Published As

Publication number Publication date
CN111606602A (en) 2020-09-01

Similar Documents

Publication Publication Date Title
CN110724386B (en) High-viscosity rubber asphalt and preparation method thereof
Sienkiewicz et al. Development of methods improving storage stability of bitumen modified with ground tire rubber: A review
Wang et al. Recent developments in the application of chemical approaches to rubberized asphalt
CN110054903B (en) Elastomer modified asphalt waterproof coiled material and preparation method thereof
CA2152774C (en) Treatment of rubber to form bituminous compositions
CN110723928A (en) High-performance rubber asphalt mixture, preparation method and application thereof
CN109776856B (en) Method for preparing linearized active rubber from waste rubber
CN109705365B (en) Preparation method of environment-friendly composite modified asphalt
CN101817946A (en) Activated waste rubber powder and preparation method thereof as well as modified asphalt and preparation method thereof
CN111606602B (en) Cold-patch rubber asphalt mixture and preparation method thereof
CN107446364A (en) A kind of rubber asphalt and preparation method thereof
CN110724385B (en) High-viscosity rubber asphalt modifier and preparation method thereof
CN105482474B (en) Low-viscosity rubber powder modified asphalt and preparation method thereof
CN111057383B (en) Rubber modified emulsified asphalt and preparation method thereof
CN104356407A (en) Method for preventing packing in rubber blend from migration
CN105733275B (en) A kind of rubber asphalt and preparation method thereof
CN114058097B (en) High-performance uncrosslinked rubber asphalt and preparation method thereof
CN104693822A (en) Low-temperature ductility and high-temperature-resistant storage stability auxiliaries for modified asphalt as well as preparation method for low-temperature ductility and high-temperature-resistant storage stability auxiliaries and modified asphalt
CN109971349B (en) Non-curing rubber asphalt waterproof coating and preparation method thereof
WO2019214097A1 (en) Low-temperature environmental-friendly high-rubber asphalt having high performance and production process therefor
CN109837038B (en) Self-adhesive polymer modified asphalt waterproof coiled material modifier and preparation method thereof
CN111607239B (en) Cold-patch rubber asphalt mixed solution and preparation method thereof
CN109837767B (en) Self-adhesive polymer modified asphalt waterproof coiled material and preparation method thereof
CN110198974A (en) For make rubber regeneration method and thus obtained renovation rubber composition
CN109810521B (en) High-rubber asphalt master batch and low-temperature environment-friendly production process thereof

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