CN113214666B - Functionalized solution-polymerized styrene-butadiene rubber composite C9 petroleum resin modified asphalt and preparation method thereof - Google Patents
Functionalized solution-polymerized styrene-butadiene rubber composite C9 petroleum resin modified asphalt and preparation method thereof Download PDFInfo
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- 239000010426 asphalt Substances 0.000 title claims abstract description 129
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 79
- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 239000003208 petroleum Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims description 39
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 16
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 15
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 4
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- 230000005855 radiation Effects 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 8
- 239000003607 modifier Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011384 asphalt concrete Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 terpene compounds Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
-
- 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
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- 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
- C08J2457/00—Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08J2457/02—Copolymers of mineral oil hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to functionalized solution polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt and a preparation method thereof. The invention is mainly used for improving the low-temperature cracking problem of asphalt, and mainly uses functionalized solution polymerized styrene-butadiene rubber, C9 petroleum resin and matrix asphalt to carry out composite modification on the matrix asphalt in a mixing and dissolving way so as to obtain the modified asphalt. The composite modified asphalt not only can remarkably improve the low-temperature resistance, but also can well keep the high-temperature resistance advantage of the asphalt and has better cohesive force. In engineering, the asphalt can improve the service performance of the pavement, prolong the service life of the pavement and reduce the maintenance cost; the preparation process is simple, the product performance is stable, and the asphalt pavement material is suitable for areas with high altitude, low annual average temperature and serious ultraviolet radiation.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to functionalized solution polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt and a preparation method thereof.
Background
The C9 petroleum resin is a thermoplastic resin obtained by polymerizing a C9 fraction, which is a by-product of a cracking ethylene production plant, as a main raw material in the presence of a catalyst or copolymerizing the fraction with aldehydes, aromatic hydrocarbons, and terpene compounds. The C9 petroleum resin has partial double bonds and aromatic rings in the structure, does not contain polar groups, has good water resistance, acid and alkali resistance, weather resistance and light aging resistance, is mainly used in the fields of coatings, rubber auxiliaries, paper additives, printing ink, adhesives and the like, and has large market demand. However, the molecular structure of the C9 petroleum resin does not contain polar or functional groups, has no chemical activity, is poor in compatibility with polar polymers, and is generally not used alone because the C9 petroleum resin has poor mechanical properties and high brittleness.
Asphalt pavement often has problems such as cracking in a low temperature environment in winter due to limitations in physical properties of asphalt itself. Relevant researches at home and abroad show that the low-temperature performance of the asphalt can be optimized through asphalt modification. The modified asphalt can be used with a plurality of modifiers, and different modifiers are selected according to modification purposes, so that the low-temperature crack resistance in winter can be improved, or the modified asphalt can be used as a stress digestion layer to resist reflection cracks, or the high-temperature flow deformation resistance can be improved. In practical situations, in the process of modifying asphalt, when certain performance of the asphalt is improved, other performances of the asphalt are often affected. Therefore, the improvement of the target performance index of asphalt modification is improved, and other performances are not reduced or improved, so that the problem to be solved by researchers is solved.
The modifiers commonly used in asphalt, such as rubber, resin, high molecular polymer, ground rubber powder or other fillers, are generally classified into three categories, depending on the modifier used: (1) thermoplastic rubbers: representative varieties are styrene-butadiene-styrene block copolymers (SBS); (2) rubber type: representative varieties are styrene butadiene rubber and emulsion thereof; (3) thermoplastic resins: representative varieties are ethylene-vinyl acetate copolymers (EVA), Low Density Polyethylene (LDPE), and polyolefins. Thermoplastic rubber-based modified asphalt, the most widely used polymer is a styrene block copolymer, particularly an SBS block copolymer. There is a problem in that the mixing of the asphalt with SBS is often not uniform enough and two-phase separation easily occurs at the time of low-temperature cooling. The rubber-based modified asphalt is, in most cases, styrene-butadiene rubber and chloroprene rubber.
In fact, it is a very technical task to select the variety and dosage of the modifier, and it is hard to say that which variety of modifier is good or bad, and it is necessary to comprehensively consider the road modification purpose and the like according to the climate conditions, traffic conditions, modified asphalt equipment conditions, damage forms of asphalt pavements, and different climate conditions in different regions, and it is best to compare the effects of different modifiers and determine the effects by technical and economic analysis. Wherein, the technical requirements of different modified asphalt grades are regulated according to the technical Specification of asphalt pavement construction, and the technical requirements are selected according to different climatic regions. The requirements on high-temperature stability in hot areas in summer in the south are high, and the modification effects of SBS, PE, EVA and the like are good; and the requirement on the crack resistance of low-temperature cold areas is high, and the modification effect of SBS and styrene butadiene rubber is good.
The method aims at a series of problems caused by low-temperature cracking and ultraviolet aging of asphalt concrete pavements in high-altitude areas with low annual average temperature, long duration of extremely cold temperature and serious ultraviolet radiation. Therefore, for asphalt pavements in low-temperature cold regions, SBS and styrene butadiene rubber modified asphalt are often selected to meet the requirement of crack resistance. The modification mechanism of the styrene butadiene rubber to the asphalt is mainly that the styrene butadiene rubber and the asphalt are subjected to a cross-linking reaction to generate a space network and absorb polar aromatic phenol in the asphalt, so that the temperature sensitivity of the asphalt can be improved, and the temperature sensitivity of the asphalt is further reduced along with the increase of the doping amount. Compared with SBS modified asphalt, the styrene butadiene rubber can obviously improve the low temperature ductility of the modified asphalt, reduce the temperature sensitivity of the asphalt, has certain anti-ultraviolet aging effect, and is more suitable for road construction in cold areas. Because rubber modified asphalt has a limited bonding ability with stone no matter how high the rubber content is. Therefore, it is an urgent problem to solve how to provide a high-performance modified asphalt, which changes the current situation that the modified asphalt in the prior art has poor low-temperature performance and insufficient adhesiveness.
Disclosure of Invention
In order to solve the problems of low-temperature cracking, insufficient adhesion and the like of styrene-butadiene rubber modified asphalt in the prior art, the invention aims to provide the functionalized rubber composite C9 petroleum resin modified asphalt and the preparation method thereof, the functionalized solution polymerized styrene-butadiene rubber is combined with C9 petroleum resin to carry out composite modification on the matrix asphalt, and the method has mild preparation conditions, simple process and stable product performance and is suitable for industrial production. The prepared modified asphalt has greatly improved low-temperature cracking resistance and pavement adhesion, effectively improves the phenomena of easy falling, easy cracking and the like commonly existing in asphalt pavements, and effectively prolongs the service life of the pavements.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the invention provides a functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt, which is a ternary blend of functionalized solution-polymerized styrene-butadiene rubber, C9 petroleum resin and matrix asphalt, wherein the mass part of the matrix asphalt is 100 parts, the amount of the C9 petroleum resin is 1-15 parts, and the amount of the functionalized solution-polymerized styrene-butadiene rubber is 1-15 parts;
the C9 petroleum resin is thermoplastic resin prepared by using a byproduct C9 fraction of a cracking ethylene preparation device as a main raw material; the molecular weight of the C9 petroleum resin is 200-11000;
the functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functional groups; the number average molecular weight of the functionalized solution polymerized styrene-butadiene rubber is 500-30000; the terpolymer contains 0.1-10 wt% of diphenylethylene derivatives containing functional groups, 50-90 wt% of butadiene and the balance of styrene;
the diphenylethylene derivative containing functional groups comprises at least one of a silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative, an amino group-containing monomer 1, 1-diphenylethylene derivative and a silicon-oxygen group-and amino group-containing monomer 1, 1-diphenylethylene derivative.
Further, the amount of the functionalized solution-polymerized styrene-butadiene rubber is 2-5 parts and the amount of the C9 resin is 5-10 parts based on 100 parts of the matrix asphalt.
Further, the molecular weight of the C9 petroleum resin is 500-10000.
Further, the number average molecular weight of the functionalized solution polymerized styrene-butadiene rubber is 10000-15000.
Further, the functionalized solution-polymerized styrene-butadiene rubber can be of a random structure, a gradual change structure or a block structure.
Furthermore, the chain end and chain of the functionalized solution-polymerized styrene-butadiene rubber at least contain 1 diphenylethylene derivative containing functional groups.
Further, the diphenylethylene derivatives containing functional groups are uniformly or gradually distributed in the solution polymerized styrene-butadiene rubber chain.
Furthermore, the functional solution polymerized styrene-butadiene rubber contains 0.5-7 wt% of diphenylethylene derivatives containing functional groups and 55-80 wt% of butadiene.
Furthermore, the content of the diphenylethylene derivative containing functional groups in the functionalized solution-polymerized styrene-butadiene rubber is 3-5 wt%, and the content of butadiene is 60-70 wt%.
Furthermore, the functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functional groups, and the glass transition temperature of the terpolymer is-100 ℃ to-50 ℃.
On the other hand, the invention provides a preparation method of the functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt, which comprises the following steps of: (1-15): 100, then shearing for 0.5-2 hours at 120-180 ℃ at 3000-6000r/min by using a high-speed shearing machine, and developing the sheared modified asphalt for 1-2 hours at 160-180 ℃ to obtain the modified asphalt.
Further, the functionalized solution polymerized styrene-butadiene rubber, C9 petroleum resin and matrix asphalt are mixed according to the mass fraction of (2-10): (3-10): 100, shearing the mixture at the temperature of 120-160 ℃ for 0.5-1.5 hours at the speed of 3500-5000 r/min by a high-speed shearing machine, and developing the sheared modified asphalt for 1-2 hours at the temperature of 160-170 ℃ to obtain the modified asphalt.
Further, the functionalized solution polymerized styrene-butadiene rubber, the C9 petroleum resin and the matrix asphalt are (3-5) in mass fraction: (5-9): 100, then shearing for 0.5-1.5 hours at 140-160 ℃ at a speed of 3500-5000 r/min by using a high-speed shearing machine, and developing the sheared modified asphalt for 1-2 hours at 165 ℃ to obtain the modified asphalt.
Further, the preparation method of the functionalized solution polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt comprises the following steps of firstly mixing the matrix asphalt and the C9 petroleum resin according to the mass ratio of 100: (1-15) and melting at a temperature of 100-180 ℃; then adding 1-15 parts of functionalized solution polymerized styrene-butadiene rubber sheets or powder, shearing for 0.5-2 hours at the temperature of 120-180 ℃ at the speed of 3000-6000r/min by adopting a high-speed shearing machine, and finally developing for 1-2 hours at the temperature of 160-180 ℃ to prepare the modified asphalt.
Further, the matrix asphalt and the C9 petroleum resin are mixed according to the mass ratio of 100: (3-10), and mixing and melting at the temperature of 100-180 ℃; then adding 2-10 parts of functionalized solution polymerized styrene-butadiene rubber sheets or powder, shearing at the temperature of 120-160 ℃ for 0.5-2 hours at the speed of 3500-5000 r/min by using a high-speed shearing machine, and finally developing at the temperature of 160-170 ℃ for 1-2 hours to prepare the modified asphalt.
Further, the matrix asphalt and the C9 petroleum resin are mixed according to the mass fraction of 100: (5-10) and melting at the temperature of 100-180 ℃; then adding 1-5 parts of functionalized solution polymerized styrene-butadiene rubber sheets or powder, shearing at 140-160 ℃ for 0.5-2 hours at 3500-5000 r/min by using a high-speed shearing machine, and finally developing at 165 ℃ for 1-2 hours to prepare the modified asphalt.
The preparation method of the functional solution polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt comprises the following steps of: 100, adding the functionalized solution polymerized styrene-butadiene rubber into 100 parts of matrix asphalt which is heated to 100-180 ℃ in advance, shearing at the temperature of 120-180 ℃ for 0.5-1 hour at the speed of 3500-6000r/min by adopting a high-speed shearing machine, then adding 1-15 parts of C9 petroleum resin, continuing shearing for 20-60 minutes, and then developing the sheared modified asphalt for 1-2 hours at the temperature of 160 ℃ to prepare the modified asphalt.
Further, adding 1-10 parts by mass of the functionalized solution polymerized styrene-butadiene rubber into 100 parts of matrix asphalt which is heated to 120-180 ℃ in advance, shearing at the speed of 3500-5000 r/min for 0.5-1 hour at the temperature of 120-160 ℃ by adopting a high-speed shearing machine, then adding 3-10 parts of C9 petroleum resin, continuing to shear for 20-60 minutes, and then developing the sheared modified asphalt for 1-2 hours at the temperature of 160-180 ℃ to prepare the modified asphalt.
Further, 2-5 parts of the functionalized solution polymerized styrene-butadiene rubber is added into 100 parts of matrix asphalt which is heated to 120-160 ℃ in advance, a high-speed shearing machine is adopted to shear for 0.5-1 hour at the temperature of 140-160 ℃ at the speed of 3500-5000 r/min, then 5-10 parts of C9 petroleum resin is added, the shearing is continued for 20-60 minutes, and then the sheared modified asphalt is developed for 1-2 hours at the temperature of 160-170 ℃ to prepare the modified asphalt.
Further, the C9 petroleum resin is a thermoplastic resin obtained by polymerizing a by-product C9 fraction obtained from a cracking ethylene production plant as a main raw material under a catalyst condition or copolymerizing the by-product C9 fraction with an aldehyde, an aromatic hydrocarbon or a terpene compound.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The invention has the beneficial effects that:
the matrix asphalt is modified by adopting the functionalized solution polymerized styrene-butadiene rubber and the C9 petroleum resin, and the prepared modified asphalt not only can keep the advantage of low-temperature resistance of the asphalt, but also can improve the binding power of the modified asphalt. In engineering, the modified asphalt can obviously improve the low-temperature ductility of an asphalt pavement under a low-temperature condition, and improve the bonding performance of an asphalt and sand rock interface and an asphalt concrete base surface and a steel plate base surface, so that the service performance of the pavement is improved, the service life of the pavement is prolonged, and the maintenance cost is reduced; the preparation process has the advantages of simple preparation process and stable performance, and can provide a suitable asphalt pavement material for areas with high altitude, low annual average temperature and serious ultraviolet radiation.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments. Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The penetration, softening point and ductility of the modified asphalt in the embodiment of the invention are measured according to T0604, T006 and T0605 in JTG E20-2011 road engineering asphalt and asphalt mixture test specification. Analyzing the composition sequence distribution and microstructure of the copolymer by a nuclear magnetic resonance spectrometer and an infrared spectrometer, and analyzing the molecular weight and molecular weight distribution index of the copolymer by a gel permeation chromatograph.
Example 1:
functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 10000, wherein the content of butadiene is 55 wt%, the content of silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative is 3 wt%, and the glass transition temperature of the functionalized solution polymerized styrene-butadiene rubber is-55 ℃. C9 petroleum resin (self-made in laboratory): the molecular weight is 5000, and the softening point is 110 ℃. Adding 4 parts of functionalized solution-polymerized styrene-butadiene rubber powder into 100 parts of 170 ℃ hot-melt matrix asphalt, shearing for 1 hour at the rotating speed of 5500r/min at 170 ℃ by using a high-speed shearing machine, then adding 5 parts of C9 petroleum resin, continuing to shear for 30 minutes, and finally placing at 160 ℃ for constant-temperature development for 60 minutes to obtain the composite modified resin, wherein the softening point of the composite modified resin is 59 ℃, the ductility of the composite modified resin at 5 ℃ is 56cm, and the penetration of the composite modified resin at 25 ℃ is 8.5 cm.
Example 2:
functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 5000, wherein the content of butadiene is 90 wt%, the content of the monomer 1, 1-diphenylethylene derivative containing the silicon-oxygen group and the amino group is 0.1 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-90 ℃. C9 petroleum resin (self-made in laboratory): the molecular weight is 2000 and the softening point is 90 ℃. Adding 5 parts of functionalized solution-polymerized styrene-butadiene rubber sheet into 100 parts of matrix asphalt at the temperature of 130 ℃, shearing for 0.5 hour at the temperature of 120-130 ℃ at the speed of 3500r/min by adopting a high-speed shearing machine, adding 8 parts of C9 petroleum resin, continuously shearing for 20 minutes at the temperature of 120 ℃ at the speed of 3500r/min, and then developing the sheared modified asphalt for 2 hours at the temperature of 160 ℃ to obtain the modified asphalt. The softening point of the obtained composite modified asphalt is 62 ℃, and the penetration at 25 ℃ is 7.8 cm.
Example 3:
functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of the silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C9 petroleum resin (self-made in laboratory): the molecular weight is 5000, and the softening point is 120 ℃. Mixing and melting 100 parts of matrix asphalt and 15 parts of C9 petroleum resin at the temperature of 155-160 ℃, then adding 5 parts of functionalized solution polymerized styrene-butadiene rubber powder, shearing at the temperature of 140-160 ℃ for 1 hour at the speed of 5000r/min by using a high-speed shearing machine, and finally developing for 2 hours at the temperature of 160 ℃. The softening point of the obtained composite modified asphalt is 61 ℃, and the penetration at 25 ℃ is 8.1 cm.
Example 4:
functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of the silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C9 petroleum resin (self-made in laboratory): the molecular weight is 5000, and the softening point is 120 ℃. Adding 4 parts of functional solution-polymerized styrene-butadiene rubber and 1 part of C9 petroleum resin into 100 parts of 150 ℃ matrix asphalt, shearing by adopting a high-speed shearing machine at the speed of 4500-5500 r/min and at the temperature of 165-175 ℃, and developing in a 170 ℃ oven for 2 hours after shearing for 60 minutes to obtain the composite modified asphalt. The softening point of the obtained composite modified asphalt is 62 ℃, and the penetration at 25 ℃ is 7.7 cm.
Example 5
Functionalized solution polymerized styrene-butadiene rubber (self-made in laboratory): the molecular weight is 15000, wherein the content of butadiene is 70 wt%, the content of the amino group-containing monomer 1, 1-diphenylethylene derivative is 5 wt%, and the glass transition temperature of the functionalized solution-polymerized styrene-butadiene rubber is-70 ℃. C9 petroleum resin (self-made in laboratory): the molecular weight is 2000 and the softening point is 90 ℃. Adding 5 parts of functionalized solution polymerized styrene-butadiene rubber powder and 15 parts of C9 petroleum resin into 100 parts of matrix asphalt, mixing and melting at the temperature of 155-160 ℃, shearing at the speed of 40-5000 r/min for 1 hour at the temperature of 140-160 ℃ by using a high-speed shearing machine, and finally developing for 2 hours at the temperature of 160 ℃. The softening point of the obtained composite modified asphalt is 64 ℃, and the penetration at 25 ℃ is 8.6 cm.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The functional solution polymerized styrene-butadiene rubber composite C9 petroleum resin modified asphalt is characterized in that the modified asphalt is a ternary blend of functional solution polymerized styrene-butadiene rubber, C9 petroleum resin and matrix asphalt, and the ternary blend comprises 100 parts of matrix asphalt, 1-15 parts of C9 petroleum resin and 1-15 parts of functional solution polymerized styrene-butadiene rubber in parts by mass;
the C9 petroleum resin is thermoplastic resin prepared by using a byproduct C9 fraction of a cracking ethylene preparation device as a main raw material; the number average molecular weight of the C9 petroleum resin is 200-11000;
the functionalized solution polymerized styrene-butadiene rubber is a terpolymer of butadiene, styrene and diphenylethylene derivatives containing functional groups; the number average molecular weight of the functionalized solution polymerized styrene-butadiene rubber is 500-30000; the terpolymer contains 0.1-10 wt% of diphenylethylene derivatives containing functional groups, 50-90 wt% of butadiene and the balance of styrene;
the diphenylethylene derivative containing functional groups comprises at least one of a silicon-oxygen group-containing monomer 1, 1-diphenylethylene derivative, an amino group-containing monomer 1, 1-diphenylethylene derivative and a silicon-oxygen group-and amino group-containing monomer 1, 1-diphenylethylene derivative;
the functionalized solution polymerized styrene-butadiene rubber is in one of a random structure, a gradual change structure or a block structure; the chain end and chain of the functionalized solution polymerized styrene-butadiene rubber at least contain 1 diphenylethylene derivative containing functional groups; the diphenylethylene derivatives containing functional groups are uniformly distributed or gradually distributed in the solution polymerized styrene-butadiene rubber chain.
2. The functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt according to claim 1, wherein the ternary blend of the modified asphalt comprises 100 parts by mass of matrix asphalt, 5-10 parts by mass of C9 petroleum resin and 2-5 parts by mass of functionalized solution-polymerized styrene-butadiene rubber.
3. The functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt according to claim 2, wherein the molecular weight of the C9 petroleum resin is 500-10000; the functionalized solution polymerized styrene-butadiene rubber has the number average molecular weight of 10000-15000.
4. The functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt according to claim 1, wherein the functionalized solution-polymerized styrene-butadiene rubber contains 0.5-7 wt% of diphenylethylene derivatives containing functional groups and 55-80 wt% of butadiene.
5. The functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt according to claim 4, wherein the functionalized solution-polymerized styrene-butadiene rubber contains 3-5 wt% of diphenylethylene derivatives containing functional groups and 60-70 wt% of butadiene.
6. The preparation method of the functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt as claimed in any one of claims 1 to 5, wherein the functionalized solution-polymerized styrene-butadiene rubber, the C9 petroleum resin and the matrix asphalt are mixed according to the mass parts of (1-15): (1-15): 100, then shearing for 0.5-2 hours at the temperature of 120-180 ℃ at the speed of 3000-6000r/min by a high-speed shearing machine, and developing the sheared modified asphalt for 1-2 hours at the temperature of 160-180 ℃ to prepare the modified asphalt.
7. The preparation method of the functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt as claimed in any one of claims 1 to 5, wherein the mass ratio of the matrix asphalt to the C9 petroleum resin is 100: (1-15), mixing and melting at 100-180 ℃, then adding 1-15 parts of functionalized solution polymerized styrene-butadiene rubber sheets or powder, shearing at the temperature of 120-180 ℃ at the speed of 3000-6000r/min for 0.5-2 hours by adopting a high-speed shearing machine, and finally developing for 1-2 hours at the temperature of 160-180 ℃ to prepare the composite modified asphalt.
8. The preparation method of the functionalized solution-polymerized styrene-butadiene rubber compounded C9 petroleum resin modified asphalt as claimed in any one of claims 1 to 5, characterized in that, by mass, 1 to 15 parts of the functionalized solution-polymerized styrene-butadiene rubber is added into 100 parts of the base asphalt which is heated to 100 to 180 ℃ in advance, a high-speed shearing machine is adopted to shear the base asphalt at the temperature of 120 to 180 ℃ at the speed of 3500-6000r/min for 0.5 to 1 hour, then 1 to 15 parts of C9 petroleum resin is added, the shearing is continued for 20 to 60 minutes, and then the sheared modified asphalt is developed for 1 to 2 hours at the temperature of 160 to 180 ℃ to prepare the modified asphalt.
9. The preparation method of the modified asphalt of claim 8, wherein the modified asphalt is prepared by adding 1-10 parts by mass of the functionalized solution-polymerized styrene-butadiene rubber to 100 parts by mass of base asphalt previously heated to 120-180 ℃, shearing at 120-160 ℃ for 0.5-1 hour at 3500-5000 r/min by using a high-speed shearing machine, adding 3-10 parts by mass of C9 petroleum resin, continuing to shear for 20-60 minutes, and developing the sheared modified asphalt at 160-170 ℃ for 1-2 hours.
10. The preparation method of the functionalized solution-polymerized styrene-butadiene rubber compounded with C9 petroleum resin modified asphalt according to claim 7, wherein the mass ratio of the functionalized solution-polymerized styrene-butadiene rubber, the C9 petroleum resin and the matrix asphalt is (2-10): (3-10): 100.
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