CN115028784A - Preparation method of bio-based elastomer and preparation method of bio-based elastomer modified asphalt mixture - Google Patents
Preparation method of bio-based elastomer and preparation method of bio-based elastomer modified asphalt mixture Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
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- 150000002148 esters Chemical class 0.000 claims description 3
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 3
- JEAVBVKAYUCPAQ-UHFFFAOYSA-N ethyl 2-chloropropanoate Chemical compound CCOC(=O)C(C)Cl JEAVBVKAYUCPAQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 claims description 3
- FVAZJUHWWXJXGV-UHFFFAOYSA-N n,n-diethylethanamine;n,n-dimethyl-1-phenylmethanamine Chemical compound CCN(CC)CC.CN(C)CC1=CC=CC=C1 FVAZJUHWWXJXGV-UHFFFAOYSA-N 0.000 claims description 3
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000011276 wood tar Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
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Abstract
The invention discloses a preparation method of a bio-based elastomer and a preparation method of a bio-based elastomer modified asphalt mixture, wherein the preparation method of the bio-based elastomer comprises the steps of (1) providing 100 parts of epoxy vegetable oil and 0.2-0.3 part of polymerization inhibitor, dropwise adding 0.4-1 part of catalyst and 25-40 parts of graft when heating in an oil bath to 80-120 ℃, wherein the graft is a mixture of acid or anhydride containing active carbon-carbon double bonds, and reacting for 2-4h to obtain a modified epoxy vegetable oil monomer A; (2) adding 100 parts of modified epoxy vegetable oil monomer A, 0.01-0.05 part of catalyst and 0.01-0.05 part of ligand into an organic solvent, sealing and purging with inert gas for 15-20 minutes, adding 0.6-1.2 parts of initiator and 0.1-0.5 part of accelerator, uniformly mixing, and reacting at the constant temperature of 60-90 ℃ for 2-6 hours to obtain the bio-based elastomer. The novel bio-based elastomer disclosed by the invention is simple in preparation method, the performance of the novel bio-based elastomer is close to that of the traditional petroleum-based elastomer, but the raw materials are cheaper and environment-friendly.
Description
Technical Field
The invention relates to preparation of modified asphalt, in particular to a preparation method of a bio-based elastomer and a preparation method of a bio-based elastomer modified asphalt mixture.
Background
The strong power of the social economy development drives the construction of road traffic career. The asphalt pavement has obvious natural advantages such as short construction period, smooth surface without joints, simple maintenance, recyclability and the like, but related technical problems and quality problems often occur in the actual use process, such as severe early damage of the pavement, failure in reaching the expected service life, poor surface performance of the pavement, easy occurrence of severe rutting and cracking problems and the like.
The modification of asphalt by using the modifier is an effective method for improving the performance of asphalt. Among the numerous modifiers, polymers are sought after by researchers due to abundant types and different properties, polymer modified asphalt is also most abundantly researched, and a relatively perfect modification system is formed. However, petroleum-based polymers typified by SBS have significant disadvantages such as high price, environmental pollution, and the like. Biobased materials are gradually moving into the field of researchers because of their unique advantages. The bio-based material has the advantage of compatibility with asphalt, so the bio-based material is also widely applied to asphalt. At present, the application of the bio-based materials in asphalt at home and abroad mainly comprises the following aspects. Firstly, the application of bio-based materials in regenerated asphalt, the main component of bio-oil is aromatic light component, the property of which is similar to the saturation component and the aromatic component in asphalt, namely the main component required by the regeneration of aged asphalt, and currently, the asphalt regenerant is prepared by adopting soybean oil, biodiesel, wood tar, orange peel extract and the like; secondly, the application of the bio-based material in warm-mixed asphalt adopts the bio-based material as a warm-mixing agent, can effectively reduce the high-temperature viscosity of the asphalt, directly shows that the mixing temperature is reduced, meets the technical conditions of warm mixing, and adopts the bio-oil prepared from isosorbide, soybean oil, illegal cooking oil, pine, rice hulls and the like as the warm-mixing agent of the asphalt at present. And thirdly, the application of the bio-based material in the modified asphalt is mainly divided into two aspects, namely the bio-based material is used as a stabilizer of the asphalt and a modifier in the modified asphalt, and the bio-based material is directly used as the modifier. Most of the bio-based raw materials serving as the modifier are still at the monomer molecular level, and the development and application of the biopolymer are less. Further investigation is needed to enable the use of biopolymers instead of petroleum-based polymers. The bio-based elastomer synthesized by the bio-based material and the application thereof in the asphalt are still in the beginning stage at home and abroad, and the bio-based elastomer asphalt modifier based on the bio-based material is urgently needed to be developed at present and is in the lead of the industrial level. The modified epoxy vegetable oil is synthesized by using an epoxy vegetable oil modified grafting technology, the bio-based elastomer with excellent performance is developed by using the modified epoxy vegetable oil and an atom transfer radical polymerization technology, the high-temperature performance and the fatigue resistance are improved on the premise of ensuring the low-temperature performance of the modified asphalt, and the problems of environment pollution, high price and the like of the traditional petroleum-based product are solved.
Disclosure of Invention
The invention mainly aims to solve the problems of environmental pollution, high price and the like in the production of the traditional petroleum-based asphalt modifier, provides a preparation method of a bio-based elastomer based on a bio-based material and application of the bio-based elastomer in asphalt, and improves the high-temperature performance and the fatigue resistance of the modified asphalt.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
A method for preparing a bio-based elastomer,
(1) providing 100 parts of epoxy vegetable oil and 0.2-0.3 part of polymerization inhibitor, heating in an oil bath to 80-120 ℃, dropwise adding 0.4-1 part of catalyst and 25-40 parts of graft, wherein the graft is a mixture of acid or acid anhydride containing active carbon-carbon double bonds, and reacting for 2-4h to obtain a modified epoxy vegetable oil monomer A;
(2) adding 100 parts of modified epoxy vegetable oil monomer A, 0.01-0.05 part of catalyst and 0.01-0.05 part of ligand into an organic solvent, sealing and purging with inert gas for 15-20 minutes, adding 0.6-1.2 parts of initiator and 0.1-0.5 part of accelerator, uniformly mixing, and reacting at the constant temperature of 60-90 ℃ for 2-6 hours to obtain the bio-based elastomer.
Furthermore, the epoxidized vegetable oil is one or more of epoxidized soybean oil, high oleic epoxidized soybean oil, epoxidized peanut oil, epoxidized castor oil, epoxidized rapeseed oil, epoxidized corn oil and epoxidized cottonseed oil.
Furthermore, the graft in the preparation of the modified epoxy vegetable oil is one or more of acrylic acid, methacrylic acid, crotonic acid, 3-methyl crotonic acid, maleic anhydride, fumaric anhydride, acrylamide and N, N-dimethylacrylamide, and the dosage of the graft is 25-40% of that of the epoxy vegetable oil.
Furthermore, the catalyst in the preparation of the modified epoxy vegetable oil is triphenylphosphine, N, N-dimethylaniline, N, N-dimethylbenzylamine triethylamine, 1, 4-diazabicyclo [2.2.2] octane, and the doping amount of the catalyst is 0.4-1% of that of the epoxy vegetable oil.
Furthermore, the catalyst in the preparation of the bio-based elastomer is a Cu-XX halogen atom catalyst, and the mixing amount of the catalyst is 0.01-0.05% of that of the modified epoxy vegetable oil.
Furthermore, the ligand in the preparation of the bio-based elastomer is bipyridine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tris- ((N, N-dimethylamino) ethyl) amine, N, N, N ', N' -tetrakis- (2-pyridylmethyl) ethylenediamine nitrogenous ligand, and the doping amount of the ligand is 0.01% -0.05% of that of the modified epoxy vegetable oil.
Further, the initiator in the preparation of the bio-based elastomer is alkyl halide initiator oil comprising CHCl 3 、CCl 4 Or the alpha-halogenated ester initiator comprises 2-methyl chloropropionate, 2-ethyl chloropropionate, 2-methyl bromopropionate, 2-ethyl bromoisobutyrate and the like, and the addition amount of the initiator is 0.6-1.2 percent of that of the modified epoxy vegetable oil.
Furthermore, the accelerant in the preparation of the bio-based elastomer is one of urea, N-dimethylformamide, urotropine, triethanolamine, acetonitrile, p-hydroxybenzaldehyde and formamide, and the mixing amount of the accelerant is 0.1-0.5% of the modified epoxy vegetable oil.
A method for preparing bio-based elastomer modified asphalt mixture,
(1) adding 3.4-6.5 parts of the bio-based elastomer prepared by the preparation method of the novel bio-based elastomer as a modifier into 100 parts of the matrix asphalt, and preparing the biopolymer modified asphalt by a high-speed shearing machine, wherein the shearing temperature is 120-3000 ℃, the shearing time is 15-45min, and the shearing speed is 1000-3000 r/min.
(2) And heating 100 parts of aggregate to 170 ℃, mixing for 90s, adding 4-6 parts of 160 ℃ bio-based elastomer modified asphalt, and mixing for 90s to obtain the bio-based elastomer modified asphalt mixture.
Furthermore, the mixing amount of the bio-based elastomer in the bio-based elastomer modified asphalt obtained after the shearing is finished is 3.4% -6.5%; in the step (2), the oilstone ratio is 4-6%.
By adopting the technical scheme, the following technical effects can be realized:
the invention uses the epoxy vegetable oil modified grafting technology to graft a material containing carbonyl and carbon-carbon double bonds to the epoxy vegetable oil to obtain a biological monomer A. The biomonomer A is polymerized to form a homopolymer, namely a biobased elastomer by an atom transfer radical polymerization technology. The bio-based elastomer is used as a modifier and is mixed with matrix asphalt through a high-speed shearing machine to prepare modified asphalt. And mixing the bio-based elastomer modified asphalt with aggregate to prepare the bio-based elastomer modified asphalt mixture. The bio-based elastomer modified asphalt has excellent high-temperature performance and fatigue resistance, and the cost is obviously reduced.
The preparation and performance detection methods of the bio-based elastomer modified asphalt and the preparation and performance detection methods of the mixture refer to the technical Specification for road asphalt pavement construction (the industry Standard of the people's republic of China, JTG F40-2004).
Description of the drawings:
FIG. 1 is a flow chart of a method of making a bio-based elastomer of the present invention;
FIG. 2 is a flow chart of the preparation method of the bio-based elastomer modified asphalt mixture of the invention.
Detailed Description
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a bio-based elastomer,
(1) providing 100 parts of epoxy vegetable oil and 0.2-0.3 part of polymerization inhibitor, heating in an oil bath to 80-120 ℃, dropwise adding 0.4-1 part of catalyst and 25-40 parts of graft, wherein the graft is a mixture of acid or acid anhydride containing active carbon-carbon double bonds, and reacting for 2-4h to obtain a modified epoxy vegetable oil monomer A;
(2) adding 100 parts of modified epoxy vegetable oil monomer A, 0.01-0.05 part of catalyst and 0.01-0.05 part of ligand into an organic solvent, sealing and purging with inert gas for 15-20 minutes, adding 0.6-1.2 parts of initiator and 0.1-0.5 part of accelerator, mixing uniformly, and reacting at a constant temperature of 60-90 ℃ for 2-6 hours to obtain the bio-based elastomer.
Furthermore, the epoxidized vegetable oil is one or more of epoxidized soybean oil, high oleic epoxidized soybean oil, epoxidized peanut oil, epoxidized castor oil, epoxidized rapeseed oil, epoxidized corn oil and epoxidized cottonseed oil.
Furthermore, the graft in the preparation of the modified epoxy vegetable oil is one or more of acrylic acid, methacrylic acid, crotonic acid, 3-methyl crotonic acid, maleic anhydride, fumaric anhydride, acrylamide and N, N-dimethylacrylamide, and the dosage of the graft is 25-40% of that of the epoxy vegetable oil.
Furthermore, the catalyst in the preparation of the modified epoxy vegetable oil is triphenylphosphine, N, N-dimethylaniline, N, N-dimethylbenzylamine triethylamine, 1, 4-diazabicyclo [2.2.2] octane, and the doping amount of the catalyst is 0.4-1% of that of the epoxy vegetable oil.
Furthermore, the catalyst in the preparation of the bio-based elastomer is a Cu-XX halogen atom catalyst, and the doping amount of the catalyst is 0.01-0.05% of that of the modified epoxy vegetable oil.
Furthermore, the ligand in the preparation of the bio-based elastomer is bipyridine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tris- ((N, N-dimethylamino) ethyl) amine, N, N, N ', N' -tetrakis- (2-pyridylmethyl) ethylenediamine nitrogenous ligand, and the doping amount of the ligand is 0.01% -0.05% of that of the modified epoxy vegetable oil.
Further, the initiator in the preparation of the bio-based elastomer is alkyl halide initiator oil comprising CHCl 3 、CCl 4 Or the alpha-halogenated ester initiator comprises 2-methyl chloropropionate, 2-ethyl chloropropionate, 2-methyl bromopropionate, 2-ethyl bromoisobutyrate and the like, and the addition amount of the initiator is 0.6-1.2 percent of that of the modified epoxy vegetable oil.
Furthermore, the accelerator in the preparation of the bio-based elastomer is one of urea, N-dimethylformamide, urotropine, triethanolamine, acetonitrile, p-hydroxybenzaldehyde and formamide, and the mixing amount of the accelerator is 0.1-0.5% of that of the modified epoxy vegetable oil.
Referring to fig. 2, another embodiment provides a method for preparing a bio-based elastomer modified asphalt mixture,
(1) adding 3.4-6.5 parts of the bio-based elastomer prepared by the preparation method of the novel bio-based elastomer as a modifier into 100 parts of the matrix asphalt, and preparing the biopolymer modified asphalt by a high-speed shearing machine, wherein the shearing temperature is 120-3000 ℃, the shearing time is 15-45min, and the shearing speed is 1000-3000 r/min.
(2) And heating 100 parts of aggregate to 170 ℃, mixing for 90s, adding 4-6 parts of 160 ℃ bio-based elastomer modified asphalt, and mixing for 90s to obtain the bio-based elastomer modified asphalt mixture.
Furthermore, the mixing amount of the bio-based elastomer in the bio-based elastomer modified asphalt obtained after the shearing is finished is 3.4% -6.5%; in the step (2), the oilstone ratio is 4-6%.
The present invention is explained in detail below with reference to some specific examples.
The composition of the mixes in the following examples is shown in table 1 below.
Table 1 grading of the aggregates used in examples 1-7
Remarking: the example uses the gradation to mean that the gradation is used in the gradation in examples 1 to 7.
Example 1
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add a mixture of the catalyst and the graft when the three-neck flask is heated to 100 ℃ in an oil bath, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating No. 70 matrix asphalt to 150 ℃, adding a bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after leaving at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 1 experimental method:
the formula of SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: 100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, 5 parts of SBS modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the SBS modified asphalt mixture is tested.
Table 2 basic parameters of the bio-based elastomer prepared in example 1
| Detecting items | Unit of | Example 1 | Test method |
| Weight average molecular weight | Da | 52873 | Gel chromatography |
| Glass transition temperature | ℃ | -7.43 | Differential scanning calorimetry |
Table 3 main performance parameters of bio-based elastomer modified bitumen prepared in example 1
Table 4 road performance parameters of bio-based elastomer modified asphalt mixture prepared in example 1
| Detecting items | Unit of | Test method | Comparative example 1 | Example 1 | Technical index |
| Dynamic stability of rut test | Order/mm | T 0719 | 3537 | 6532 | ≥1800 |
| Immersion Marshall test residual stability | ％ | T 0709 | 85.9 | 86.2 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 84.8 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3120 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 12.3 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.4 | 1.5-4 |
The raw material of the bio-based elastomer is epoxidized soybean oil, compared with the raw material of the petroleum-based elastomer such as butadiene, the bio-based elastomer is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 1, the high-temperature performance and the fatigue resistance of the bio-based elastomer modified asphalt of the example 1 are improved under the condition of the same mixing amount, and the PG classification is also improved from the PG70-22 to PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 1, the bio-based elastomer modified asphalt mixture of the example 1 has more excellent road performance, especially high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 2
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparation of modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add the mixture of the catalyst and the graft when the oil bath is heated to 100 ℃, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating No. 70 matrix asphalt to 150 ℃, adding a bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 2 experimental method:
the formula of the SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: taking 100 parts (parts by weight, the same below) of the graded aggregate shown in the table 1, placing the graded aggregate in a mixing bar, heating the graded aggregate to 170 ℃, mixing the graded aggregate for 90s, adding 5 parts of SBS modified asphalt, mixing the SBS modified asphalt at 170 ℃ for 120s, discharging the SBS modified asphalt, wherein the discharging temperature is 160 ℃, placing the SBS modified asphalt for one day at normal temperature, and testing the performance of the SBS modified asphalt mixture.
Table 5 basic parameters of the bio-based elastomer prepared in example 2
| Detecting items | Unit of | Example 2 | Test method |
| Weight average molecular weight | Da | 57248 | Gel chromatography |
| Glass transition temperature | ℃ | -6.89 | Differential scanning calorimetry |
Table 6 main performance parameters of bio-based elastomer modified bitumen prepared in example 2
Table 7 road performance parameters for bio-based elastomer modified asphalt mix prepared in example 2
| Detecting items | Unit of | Test method | Comparative example 2 | Example 2 | Technical index |
| Dynamic stability of rut test | Sub/mm | T 0719 | 3537 | 6498 | ≥1800 |
| Residual stability of immersion Marshall test | ％ | T 0709 | 85.9 | 87.1 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 83.8 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3145 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 11.9 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.1 | 1.5-4 |
The raw material of the bio-based elastomer is high-oleic acid epoxidized soybean oil, and compared with the raw material of petroleum-based elastomer such as butadiene, the bio-based elastomer is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 2, the high-temperature performance and the fatigue resistance of the bio-based elastomer modified asphalt of the example 2 are improved under the condition of the same mixing amount, and the PG classification is also improved from the PG70-22 to PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 2, the bio-based elastomer modified asphalt mixture of the example 2 has more excellent road performance, particularly high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 3
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add a mixture of the catalyst and the graft when the three-neck flask is heated to 100 ℃ in an oil bath, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating the No. 70 matrix asphalt to 150 ℃, adding the bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by using a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 3 experimental method:
the formula of SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: 100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, 5 parts of SBS modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the SBS modified asphalt mixture is tested.
Table 8 basic parameters of bio-based elastomer prepared in example 3
| Detecting items | Unit of | Example 3 | Test method |
| Weight average molecular weight | Da | 62748 | Gel chromatography |
| Glass transition temperature | ℃ | -6.69 | Differential scanning calorimetry |
TABLE 9 Main Performance parameters of the Bio-based elastomer-modified bitumen prepared in example 3
TABLE 10 road performance parameters for bio-based elastomer modified asphalt mixes prepared in example 3
| Detecting items | Unit of | Test method | Comparative example 3 | Example 3 | Technical index |
| Dynamic stability of rut test | Sub/mm | T 0719 | 3537 | 6487 | ≥1800 |
| Residual stability of immersion Marshall test | ％ | T 0709 | 85.9 | 86.4 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 84.9 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3098 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 12.8 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.6 | 1.5-4 |
The bio-based elastomer raw material is epoxy peanut oil, so that compared with petroleum-based elastomer raw materials such as butadiene, the bio-based elastomer raw material is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 3, the bio-based elastomer modified asphalt of the example 3 has the advantages that the high-temperature performance and the fatigue resistance are improved under the condition of the same mixing amount, and the PG classification is also improved from the PG70-22 to the PG 76-22; compared with the SBS modified asphalt mixture in the comparative example 3, the bio-based elastomer modified asphalt mixture in the example 3 has more excellent road performance, particularly high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 4
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add a mixture of the catalyst and the graft when the three-neck flask is heated to 100 ℃ in an oil bath, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating the No. 70 matrix asphalt to 150 ℃, adding the bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by using a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (parts by weight, the same below) of the graded aggregate shown in the table 1 are taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, 5 parts of bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃ and discharged, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 4 experimental method:
the formula of the SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: taking 100 parts (parts by weight, the same below) of the graded aggregate shown in the table 1, placing the graded aggregate in a mixing bar, heating the graded aggregate to 170 ℃, mixing the graded aggregate for 90s, adding 5 parts of SBS modified asphalt, mixing the SBS modified asphalt at 170 ℃ for 120s, discharging the SBS modified asphalt, wherein the discharging temperature is 160 ℃, placing the SBS modified asphalt for one day at normal temperature, and testing the performance of the SBS modified asphalt mixture.
Table 11 basic parameters of bio-based elastomer prepared in example 4
| Detecting items | Unit of | Example 4 | Test method |
| Weight average molecular weight | Da | 62475 | Gel chromatography |
| Glass transition temperature | ℃ | -6.98 | Differential scanning calorimetry |
Table 12 main performance parameters of bio-based elastomer modified bitumen prepared in example 4
TABLE 13 road performance parameters for bio-based elastomer modified asphalt mixes prepared in example 4
| Detecting items | Unit of | Test method | Comparative example 4 | Example 4 | Technical index |
| Dynamic stability of rut test | Sub/mm | T 0719 | 3537 | 6745 | ≥1800 |
| Residual stability of immersion Marshall test | ％ | T 0709 | 85.9 | 88.1 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 84.5 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3148 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 12.5 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.2 | 1.5-4 |
The bio-based elastomer raw material is epoxy rapeseed oil, compared with petroleum-based elastomer raw materials such as butadiene, the bio-based elastomer raw material is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 4, the high-temperature performance and the fatigue resistance of the bio-based elastomer modified asphalt of the example 4 are improved under the condition of the same mixing amount, and the PG classification is also improved from the PG70-22 to the PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 4, the bio-based elastomer modified asphalt mixture of the example 4 has more excellent road performance, particularly high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 5
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add the mixture of the catalyst and the graft when the oil bath is heated to 100 ℃, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating No. 70 matrix asphalt to 150 ℃, adding a bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 5 experimental method:
the formula of SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: 100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, 5 parts of SBS modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the SBS modified asphalt mixture is tested.
Table 14 basic parameters of bio-based elastomer prepared in example 5
| Detecting items | Unit of | Example 5 | Test method |
| Weight average molecular weight | Da | 65930 | Gel chromatography |
| Glass transition temperature | ℃ | -6.43 | Differential scanning calorimetry |
TABLE 15 Main Performance parameters of the Bio-based elastomer-modified bitumen prepared in example 5
TABLE 16 road performance parameters for bio-based elastomer modified asphalt mixes prepared in example 5
| Detecting items | Unit of | Test method | Comparative example 5 | Example 5 | Technical index |
| Dynamic stability of rut test | Sub/mm | T 0719 | 3537 | 6654 | ≥1800 |
| Immersion Marshall test residual stability | ％ | T 0709 | 85.9 | 87.2 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 82.8 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3028 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 12.8 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.5 | 1.5-4 |
The raw material of the bio-based elastomer is epoxy cottonseed oil, so that compared with the raw material of petroleum-based elastomer such as butadiene, the bio-based elastomer is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 5, the bio-based elastomer modified asphalt of the example 5 has the advantages that the high-temperature performance and the fatigue resistance are improved under the condition of the same doping amount, and the PG classification is also improved from the PG70-22 to the PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 5, the bio-based elastomer modified asphalt mixture of the example 5 has more excellent road performance, particularly high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 6
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add the mixture of the catalyst and the graft when the oil bath is heated to 100 ℃, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating No. 70 matrix asphalt to 150 ℃, adding a bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 6 experimental method:
the formula of SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises: taking 100 parts (parts by weight, the same below) of the graded aggregate shown in the table 1, placing the graded aggregate in a mixing bar, heating the graded aggregate to 170 ℃, mixing the graded aggregate for 90s, adding 5 parts of SBS modified asphalt, mixing the SBS modified asphalt at 170 ℃ for 120s, discharging the SBS modified asphalt, wherein the discharging temperature is 160 ℃, placing the SBS modified asphalt for one day at normal temperature, and testing the performance of the SBS modified asphalt mixture.
Table 17 basic parameters of bio-based elastomer prepared in example 6
| Detecting items | Unit of | Example 6 | Test method |
| Weight average molecular weight | Da | 62235 | Gel chromatography |
| Glass transition temperature | ℃ | -6.58 | Differential scanning calorimetry |
Table 18 main performance parameters of bio-based elastomer modified bitumen prepared in example 6
TABLE 19 road Performance parameters for bio-based elastomer modified asphalt mixes prepared in example 6
| Detecting items | Unit | Test method | Comparative example 6 | Example 6 | Technical index |
| Dynamic stability of rut test | Sub/mm | T 0719 | 3537 | 6625 | ≥1800 |
| Immersion Marshall test residual stability | ％ | T 0709 | 85.9 | 86.1 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 84.2 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3184 | ≥2800 |
| Marshall test (60 ℃ C.) for stability | kN | T 0709 | 11.2 | 11.8 | ≥8 |
| Flow number in Marshall test (60 ℃ C.) | 1mm | T 0709 | 3.3 | 2.4 | 1.5-4 |
The raw material of the bio-based elastomer is epoxy castor oil, compared with the raw material of petroleum-based elastomer such as butadiene, the bio-based elastomer is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 6, the bio-based elastomer modified asphalt of the example 6 has the advantages that the high-temperature performance and the fatigue resistance are improved under the condition of the same doping amount, and the PG classification is also improved from the PG70-22 to the PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 6, the bio-based elastomer modified asphalt mixture of the example 6 has more excellent road performance, especially high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
Example 7
The proportion of the modified epoxy vegetable oil monomer A is as follows:
the proportion of the bio-based elastomer is as follows:
preparing a modified epoxy vegetable oil monomer A:
and adding the epoxy vegetable oil and the polymerization inhibitor into a three-neck flask provided with a snake-shaped condenser pipe, a stirrer and a dropping funnel, starting to dropwise add the mixture of the catalyst and the graft when the oil bath is heated to 100 ℃, controlling the dropwise adding speed, and measuring the initial acid value after the dropwise adding is finished. And then heating to 120 ℃, reacting at a constant temperature for 6 hours, extracting the reaction product by using n-hexane, spin-drying on a rotary evaporator, and removing the n-hexane to obtain the required modified epoxy vegetable oil monomer.
Preparation of bio-based elastomer:
adding the modified epoxy vegetable oil monomer, the catalyst and the ligand in the ratio into a reaction tube provided with a magnetic stirrer, uniformly mixing, sealing and purging with nitrogen for 20 minutes, then placing the reaction tube into an oil bath at 70 ℃ for heating for 2 minutes, adding the initiator in the ratio, adding the accelerator in the ratio after reacting for 3 minutes, reacting for 4 hours at constant temperature of 70 ℃, purifying by using absolute ethyl alcohol to obtain the bio-based elastomer, and testing the basic performance of the bio-based elastomer.
Preparing bio-based elastomer modified asphalt:
heating the No. 70 matrix asphalt to 150 ℃, adding the bio-based elastomer with the amount of 5.0 percent of the weight of the modified asphalt, and shearing for 40min by using a high-speed shearing machine at the shearing speed of 2800 r/min. And naturally cooling the asphalt to room temperature to obtain the bio-based elastomer modified asphalt. The test was carried out after standing at room temperature for 1 day.
Preparing a bio-based elastomer modified asphalt mixture:
100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, then 5 parts of the bio-based elastomer modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the bio-based elastomer modified asphalt mixture is tested.
Comparative example 7 experimental method:
the formula of the SBS modified asphalt comprises: heating the Bilong No. 70 base asphalt to 170 ℃, adding SBS with the amount of 5% of the modified asphalt weight, and shearing for 1h by a high-speed shearing machine at the shearing speed of 3000 r/min. Then 2 percent of No. 8-24 rubber oil is added, the temperature is raised to 180 ℃, the sulfur stabilizer with the SBS mass fraction of 1/30 is added within 1 hour, and after the addition of the sulfur is finished, the mixture is stirred and developed for 5 hours at 175 ℃ to obtain the stable SBS modified asphalt. The test was carried out after standing at room temperature for 1 day.
The formula of the SBS modified asphalt mixture comprises the following components: 100 parts (by weight, the same below) of the graded aggregate shown in the table 1 is taken and placed in a mixing bar to be heated to 170 ℃ and mixed for 90s, 5 parts of SBS modified asphalt is added, the mixture is mixed for 120s at 170 ℃, the discharging temperature is 160 ℃, the mixture is placed for one day at normal temperature, and the performance of the SBS modified asphalt mixture is tested.
Table 20 basic parameters of bio-based elastomer prepared in example 7
| Detecting items | Unit of | Example 7 | Test method |
| Weight average molecular weight | Da | 65873 | Gel chromatography |
| Glass transition temperature | ℃ | -7.08 | Differential scanning calorimetry |
TABLE 21 Main Performance parameters of the Bio-based elastomer-modified bitumen prepared in example 7
TABLE 22 road Performance parameters for the bio-based elastomer modified asphalt mixture prepared in example 7
| Detecting items | Unit of | Test method | Comparative example 7 | Example 7 | Technical index |
| Dynamic stability of rut test | Order/mm | T 0719 | 3537 | 6658 | ≥1800 |
| Residual stability of immersion Marshall test | ％ | T 0709 | 85.9 | 87.1 | ≥85 |
| Residual strength ratio of freeze-thaw split test | ％ | T 0729 | 82.4 | 84.3 | ≥80 |
| Low temperature bending test strain to failure | μ ε | T 0715 | 2615 | 3145 | ≥2800 |
| Stability in Marshall test (60 ℃ C.) | kN | T 0709 | 11.2 | 12.6 | ≥8 |
| Marshall test (60 ℃ C.) flow number | 1mm | T 0709 | 3.3 | 2.1 | 1.5-4 |
The bio-based elastomer raw material is epoxy corn oil, compared with petroleum-based elastomer raw materials such as butadiene, the bio-based elastomer raw material is more environment-friendly and lower in cost, and the cost is saved by more than 20%; as can be seen from the parameters of the examples and the comparative examples, compared with the SBS modified asphalt of the comparative example 7, the bio-based elastomer modified asphalt of the example 7 has the advantages that the high-temperature performance and the fatigue resistance are improved under the condition of the same doping amount, and the PG classification is also improved from the PG70-22 to the PG 76-22; compared with the SBS modified asphalt mixture of the comparative example 7, the bio-based elastomer modified asphalt mixture of the example 7 has more excellent road performance, especially high-temperature stability and remarkable improvement under the condition of the same mixing amount; in summary, the various performances of the application of the bio-based elastomer in the asphalt are superior to those of the traditional SBS modifier.
According to the detection data of the specific examples given in examples 1 to 7, the bio-based elastomer modified asphalt prepared by using the bio-based elastomer as the modifier disclosed by the invention has the advantages that the high-temperature performance, the fatigue resistance and the pavement performance are all improved, and the bio-based material is cheaper and more environment-friendly. The technical implementation can help break the technical monopoly of the preparation of the bio-based elastomer in China.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method of preparing a bio-based elastomer, comprising:
(1) providing 100 parts of epoxy vegetable oil and 0.2-0.3 part of polymerization inhibitor, dropwise adding 0.4-1 part of catalyst and 25-40 parts of graft when heating to 80-120 ℃ in an oil bath, wherein the graft is a mixture of acid or anhydride containing active carbon-carbon double bonds, and reacting for 2-4h to obtain a modified epoxy vegetable oil monomer A;
(2) adding 100 parts of modified epoxy vegetable oil monomer A, 0.01-0.05 part of catalyst and 0.01-0.05 part of ligand into an organic solvent, sealing and purging with inert gas for 15-20 minutes, adding 0.6-1.2 parts of initiator and 0.1-0.5 part of accelerator, uniformly mixing, and reacting at the constant temperature of 60-90 ℃ for 2-6 hours to obtain the bio-based elastomer.
2. The method of claim 1, wherein the epoxidized vegetable oil is one or more of epoxidized soybean oil, high oleic epoxidized soybean oil, epoxidized peanut oil, epoxidized castor oil, epoxidized rapeseed oil, epoxidized corn oil, and epoxidized cottonseed oil.
3. The method for preparing the bio-based elastomer according to claim 1, wherein the graft in the preparation of the modified epoxy vegetable oil is one or more of acrylic acid, methacrylic acid, crotonic acid, 3-methyl crotonic acid, maleic anhydride, fumaric anhydride, acrylamide and N, N-dimethylacrylamide, and the amount of the graft is 25% -40% of that of the epoxy vegetable oil.
4. The method for preparing the bio-based elastomer according to claim 1, wherein the catalyst used in the preparation of the modified epoxy vegetable oil is triphenylphosphine, N, N-dimethylaniline, N, N-dimethylbenzylamine triethylamine, 1, 4-diazabicyclo [2.2.2] octane, and the mixing amount of the catalyst is 0.4-1% of the epoxy vegetable oil.
5. The method for preparing the bio-based elastomer according to claim 1, wherein the catalyst used in the preparation of the bio-based elastomer is a Cu-XX halogen atom catalyst, and the doping amount of the catalyst is 0.01-0.05% of that of the modified epoxy vegetable oil.
6. The method of claim 1, wherein the ligand in the bio-based elastomer preparation is bipyridine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tris- ((N, N-dimethylamino) ethyl) amine, N' -tetrakis- (2-pyridylmethyl) ethylenediamine nitrogenous ligand in an amount of 0.01% to 0.05% of the modified epoxy vegetable oil.
7. A process for the preparation of a bio-based elastomer as claimed in claim 1 wherein said initiator in said bio-based elastomer preparation is an alkyl halide initiator oil comprising CHCl 3 、CCl 4 Or the alpha-halogenated ester initiator comprises 2-methyl chloropropionate, 2-ethyl chloropropionate, 2-methyl bromopropionate, 2-ethyl bromoisobutyrate and the like, and the addition amount of the initiator is 0.6-1.2 percent of that of the modified epoxy vegetable oil.
8. The method for preparing a bio-based elastomer according to claim 1, wherein the accelerator used in the preparation of the bio-based elastomer is one of urea, N-dimethylformamide, urotropin, triethanolamine, acetonitrile, p-hydroxybenzaldehyde and formamide, and the mixing amount of the accelerator is 0.1-0.5% of the modified epoxidized vegetable oil.
9. A preparation method of a bio-based elastomer modified asphalt mixture is characterized by comprising the following steps:
(1) adding 3.4-6.5 parts of the bio-based elastomer prepared by the preparation method of the novel bio-based elastomer as claimed in claim 1 as a modifier into 100 parts of the base asphalt, and preparing the biopolymer modified asphalt by a high-speed shearing machine, wherein the shearing temperature is 120-150 ℃, the shearing time is 15-45min, and the shearing speed is 1000-3000 r/min;
(2) and heating 100 parts of aggregate to 170 ℃, mixing for 90s, adding 4-6 parts of 160 ℃ bio-based elastomer modified asphalt, and mixing for 90s to obtain the bio-based elastomer modified asphalt mixture.
10. The method for preparing the bio-based elastomer modified asphalt mixture according to claim 9, wherein the bio-based elastomer is added in the bio-based elastomer modified asphalt obtained after the shearing is finished, wherein the content of the bio-based elastomer is 3.4-6.5%; in the step (2), the oilstone ratio is 4-6%.
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| CN108623762A (en) * | 2012-01-18 | 2018-10-09 | 爱荷华州立大学研究基金会有限公司 | Via the thermoplastic elastomer (TPE) of the atom transfer radical polymerization of vegetable oil |
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