CN111978677A - Bio-based epoxy asphalt and preparation method thereof - Google Patents
Bio-based epoxy asphalt and preparation method thereof Download PDFInfo
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- CN111978677A CN111978677A CN202010800971.XA CN202010800971A CN111978677A CN 111978677 A CN111978677 A CN 111978677A CN 202010800971 A CN202010800971 A CN 202010800971A CN 111978677 A CN111978677 A CN 111978677A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- 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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Abstract
The invention discloses a bio-based epoxy asphalt and a preparation method thereof, wherein the asphalt is prepared by modifying asphalt with lignin-based epoxy resin and a curing agent under the action of a catalyst; the catalyst is 2-ethyl 1, 4-methylimidazole; the curing agent is tung oil fatty acid. The mass ratio of the lignin-based epoxy resin to the tung oil fatty acid is 100: 80; the mass ratio of the total mass of the lignin-based epoxy resin and the curing agent to the mass of the asphalt is 100: (7.5-22.5); the mass ratio of the total mass of the lignin-based epoxy resin, the asphalt and the curing agent to the catalyst is 189: 1. The obtained bio-based epoxy asphalt is low in price and non-toxic, reduces the precipitation and oxidation of light components of bio-oil, and slows down the aging phenomenon. Fundamentally changes the low-temperature brittleness and high-temperature softness of the traditional asphalt.
Description
Technical Field
The invention relates to the technical field of buildings, in particular to bio-based epoxy asphalt and a preparation method thereof.
Background
The modified asphalt is an asphalt binder prepared by adding external additives (modifiers) such as rubber, resin, high molecular polymer, ground rubber powder or other fillers or by adopting measures such as mild oxidation processing of the asphalt and the like, so that the performance of the asphalt or the asphalt mixture is improved. The modified asphalt has two mechanisms, namely, the chemical composition of the asphalt is changed, and the modifier is uniformly distributed in the asphalt to form a certain space network structure. The types of modified asphalt at present are mainly: (1) rubber and thermoplastic elastomer modified asphalt: the method comprises the following steps: natural rubber modified asphalt, SBS modified asphalt (most widely used), styrene butadiene rubber modified asphalt, chloroprene rubber modified asphalt, butadiene rubber modified asphalt, butyl rubber modified asphalt, waste rubber and reclaimed rubber modified asphalt, and other rubber modified asphalt (such as ethylene propylene rubber, nitrile rubber, etc.). (2) Plastic and synthetic resin modified asphalt: the method comprises the following steps: polyethylene modified asphalt, ethylene-vinyl acetate polymer modified asphalt, polystyrene modified asphalt, coumaras resin modified asphalt, epoxy resin modified asphalt and alpha-olefin random polymer modified asphalt. (3) Blending type high molecular polymer modified asphalt: two or more polymers are added into asphalt at the same time to modify the asphalt. The two or more polymers may be two separate high molecular polymers or may be a so-called high molecular alloy which is blended in advance to form a high molecular interpenetrating network.
However, the epoxy resins currently used for asphalt modification are all derived from petroleum, mainly bisphenol a type epoxy resins. The disadvantages of such epoxy resins are mainly: petroleum belongs to non-renewable resources, and the source of raw materials is limited; the price is high, so that the application of the road material in common road engineering is limited; has toxicity, releases more volatile organic compounds, and is not beneficial to environmental protection and human health. The bio-based polymer material takes renewable resources as a main raw material, reduces the consumption of petrochemical products in the plastic industry, reduces the pollution of the petrochemical raw materials to the environment in the production process, has the dual effects of saving petroleum resources and protecting the environment, and is an important development direction of the current polymer material.
The patent with the application number of CN200710028748.2 discloses asphalt modified by epoxy resin and rubber powder, wherein the rubber powder, the epoxy resin and a curing agent are added into the asphalt; the curing agent is a heat curing type anhydride curing agent, such as methyl hexahydrophthalic anhydride; the modified asphalt has excellent performance, and four technical indexes of penetration degree, softening point, low-temperature ductility, torsional springback and the like are superior to those of common asphalt. An authorized patent with the application number of CN201910678552.0 discloses a preparation method of epoxy resin modified emulsified asphalt, which is characterized in that epoxy resin is mixed with heated matrix asphalt and then emulsified according to a conventional asphalt emulsification method; the epoxy resin is not required to be subjected to water-based processing independently only through one emulsification processing process, and has extremely low viscosity when being heated to about 130 ℃, so that the viscosity of the hot asphalt can be reduced by adding the epoxy resin, the emulsification implementation is facilitated, the particle size of emulsion particles can be effectively reduced, and the emulsion is favorable for the storage stability and the film forming uniformity of the emulsion and the uniform coating of the aggregate in the mixing process; the single emulsion particle is a mixture of asphalt and epoxy, and the emulsion breaking process of the emulsion particle is simultaneous, so that the epoxy resin can be uniformly distributed in the asphalt after emulsion breaking and film forming, the modification effect is improved, and more excellent performance can be obtained.
An authorized patent with the application number of CN201010569487.7 discloses thermosetting emulsified epoxy resin modified emulsified asphalt, which is prepared by emulsifying double A-type epoxy resin with alkylphenol polyoxyethylene, and mixing and synthesizing to form epoxy resin water emulsion; and mixing the prepared epoxy resin water emulsion into the emulsified asphalt, and fully mixing to prepare the thermosetting epoxy resin modified emulsified asphalt. The epoxy resin curing agent is prepared by mixing one or more mixed amines of modified aliphatic amine, phenolic amine, aromatic amine and the like with an aqueous solution of alkylphenol polyoxyethylene, and the epoxy resin curing agent is mixed with thermosetting epoxy resin modified emulsified asphalt according to a proportion for use. The epoxy resin curing agent and the thermosetting epoxy resin modified emulsified asphalt are subjected to reactive crosslinking, so that the performance is completely changed, and the epoxy resin curing agent is dissolved from 60 ℃ of the common emulsified asphalt and is converted into the characteristic of insolubilization at 160 ℃.
Disclosure of Invention
In order to overcome the problems of high material price and toxicity caused by using bisphenol A type epoxy resin during asphalt modification in the prior art, the invention aims to provide the bio-based epoxy asphalt and the preparation method thereof.
In order to realize the technical problem, the invention provides the following technical scheme:
the biological epoxy asphalt is characterized in that the asphalt is modified by lignin-based epoxy resin and a curing agent under the action of a catalyst;
the catalyst is 2-ethyl 1, 4-methylimidazole;
the curing agent is tung oil fatty acid;
the mass ratio of the total mass of the lignin-based epoxy resin, the catalyst and the bio-based curing agent to the asphalt is 100: (7.5-22.5);
the mass ratio of the total mass of the lignin-based epoxy resin, the catalyst and the bio-based curing agent to the catalyst is 189: 1.
The asphalt is No. 70 road petroleum asphalt.
The preparation method of the bio-based epoxy asphalt comprises the following steps:
step 1, preparing lignin-based epoxy resin: adding 5g of depolymerized enzymatic lignin, 30g of epichlorohydrin, 75mg of benzyltriethylammonium chloride and 50g of dimethyl sulfoxide into a flask, raising the temperature to 70 ℃, and continuously reacting for 3 hours; after cooling the reaction mixture to 60 ℃, 1.23g of sodium hydroxide was added; the mixture was stirred at 60 ℃ for 4 hours; washing the crude product with diethyl ether twice, and then washing with deionized water twice; drying the product by freeze drying to obtain lignin-based epoxy resin;
step 2, preparing tung oil fatty acid: heating tung oil and maleic anhydride to 15 ℃ under the condition of taking acetic acid as a catalyst, refluxing for 48 hours, and obtaining a reaction product, namely tung oil fatty acid;
and 3, respectively heating the lignin-based epoxy resin obtained in the step 1 and the tung oil fatty acid obtained in the step 2 to 70 ℃, uniformly mixing and stirring by adopting high-speed stirring and shearing equipment, pouring into asphalt heated to 90 +/-5 ℃, adding a catalyst, continuously mixing and stirring uniformly by adopting high-speed stirring and shearing equipment, and curing to obtain the biological epoxy asphalt. Curing at 150 deg.C for 2 hr, and then at 200 deg.C for 1 hr
Compared with the prior art, the invention has the following advantages:
1. tung acid and maleic anhydride generate tung oil fatty acid through a Diels-Alder reaction, the tung oil fatty acid is used as a curing agent, lignin-based epoxy resin is used for replacing the traditional epoxy resin, the prepared biological epoxy asphalt reduces the precipitation and oxidation of light components of the biological oil, and the aging phenomenon of the biological asphalt is effectively slowed down.
2. The lignin-based epoxy resin is used for replacing the traditional epoxy resin, so that the material cost of the epoxy asphalt mixture can be effectively reduced, and the popularization and the use of the epoxy asphalt in road engineering are facilitated.
3. Compared with the traditional petroleum asphalt, the bio-based epoxy asphalt fundamentally changes the low-temperature brittle and high-temperature soft thermoplastic properties, and has excellent high-temperature and low-temperature and anti-aging characteristics.
4. The construction time of the warm-mixed epoxy asphalt is not more than 90min at most, and the construction time of the hot-mixed epoxy asphalt is 30-120 min (see the existing document 'Nanjing iron core bridge steel bridge deck hot-mixed epoxy asphalt concrete paving technology', the author: Zhoujin Xia), compared with the construction holding time of the biological epoxy asphalt is longer and can reach 3h, the operation time from mixing, transportation, paving to rolling completion is longer, and the construction quality of the pavement is effectively ensured.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
The present invention is described in detail below by way of examples, and in the following examples, the parts of each component are parts by mass.
The preparation method of the biological epoxy asphalt A component comprises the following steps:
example 1:
the preparation method of the bio-based epoxy asphalt comprises the following steps:
step 1, preparing lignin-based epoxy resin (Wang Fang, Kuai you, Hu Gao, etc.. Synthesis and Properties of phenolate enzymatic hydrolysis lignin-epoxy resin/epoxy resin composite material [ J ]. Purchase on composite material, 2017, 34(12): 2681-2688): adding 5g of depolymerized enzymatic lignin, 30g of epichlorohydrin, 75mg of benzyltriethylammonium chloride and 50g of dimethyl sulfoxide into a flask, raising the temperature to 70 ℃, and continuously reacting for 3 hours; after cooling the reaction mixture to 60 ℃, 1.23g of sodium hydroxide was added; the mixture was stirred at 60 ℃ for 4 hours; washing the crude product with diethyl ether twice, and then washing with deionized water twice; and drying the product by freeze drying to obtain the lignin-based epoxy resin.
Step 2, preparing tung oil fatty acid (fuweichang, guohong, champion, etc.. tung oil fatty acid component analysis and triglyceride structure determination [ J ]. natural product research and development, 2008, 20(6): 964-968, 982): heating tung oil and maleic anhydride to 15 ℃ under the condition of taking acetic acid as a catalyst, refluxing for 48 hours, and obtaining a reaction product, namely tung oil fatty acid;
and 3, sampling the lignin-based epoxy resin obtained in the step 1 and the tung oil fatty acid obtained in the step 2 according to a mass ratio of 100:80, respectively heating to 70 ℃, uniformly mixing and stirring by adopting high-speed stirring and shearing equipment, pouring into asphalt heated to 90 +/-5 ℃ (the mass of the asphalt is calculated according to the total mass of the lignin-based epoxy resin and the tung oil fatty acid: the mass of the asphalt =100: 7.5), adding a catalyst (the dosage of the catalyst is calculated according to the mass ratio of 189:1 of the total mass of the lignin-based epoxy resin, the asphalt and the curing agent to the catalyst), continuously mixing and stirring uniformly by adopting the high-speed stirring and shearing equipment, and curing to obtain the biological epoxy asphalt.
The curing conditions were 150 ℃ for 2h, followed by 200 ℃ for 1 h.
Example 2
The difference from the example 1 is that in the step (3), the mass of the asphalt is calculated according to the total mass of the lignin-based epoxy resin and the tung oil fatty acid: asphalt mass =100: 22.5 meter.
Example 3
The difference from the example 1 is that in the step (3), the mass of the asphalt is calculated according to the total mass of the lignin-based epoxy resin and the tung oil fatty acid: asphalt mass =100: 10 counts.
Example 4
The difference from the example 1 is that in the step (3), the mass of the asphalt is calculated according to the total mass of the lignin-based epoxy resin and the tung oil fatty acid: asphalt mass =100: 15 meters.
Example 5 Performance testing
And cutting the cured bio-based epoxy asphalt material into a tensile test sample strip for mechanical property test, wherein the test temperature is 23 ℃, and the tensile speed is 500 mm/min. The test results are shown in Table 1.
Comparative example
Modified asphalt (Jingjing, Qianzhongdong, luosisan. epoxy asphalt chemical rheological property research [ J ]. highway, 2012, (8): 198-201) is prepared by using bisphenol A type epoxy resin as a raw material according to the prior method.
TABLE 1 mechanical Properties of Bio-based epoxy asphalt materials
| Example 1 | Example 2 | Example 3 | Example 4 | Technical requirements | Comparative example | |
| Tensile strength/MPa | 7.64 | 6.23 | 5.56 | 6.12 | ≥2.5 | 2.6 |
| Elongation at break/% | 331 | 366 | 389 | 390 | ≥100 | 220 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The biological epoxy asphalt is characterized in that the asphalt is modified by lignin-based epoxy resin and a curing agent under the action of a catalyst;
the catalyst is 2-ethyl 1, 4-methylimidazole;
the curing agent is tung oil fatty acid.
2. The bio-based epoxy asphalt according to claim 1, wherein the asphalt is No. 70 road petroleum asphalt.
3. The bio-based epoxy asphalt according to claim 1, wherein the mass ratio of the lignin-based epoxy resin to the tung oil fatty acid is 100: 80;
the mass ratio of the total mass of the lignin-based epoxy resin and the curing agent to the mass of the asphalt is 100: (7.5-22.5);
the mass ratio of the total mass of the lignin-based epoxy resin, the asphalt and the curing agent to the catalyst is 189: 1.
4. The method for preparing bio-based epoxy asphalt according to claim 1, characterized by comprising the steps of:
step 1, preparing lignin-based epoxy resin: adding 5g of depolymerized enzymatic lignin, 30g of epichlorohydrin, 75mg of benzyltriethylammonium chloride and 50g of dimethyl sulfoxide into a flask, raising the temperature to 70 ℃, and continuously reacting for 3 hours; after cooling the reaction mixture to 60 ℃, 1.23g of sodium hydroxide was added; the mixture was stirred at 60 ℃ for 4 hours; washing the crude product with diethyl ether twice, and then washing with deionized water twice; drying the product by freeze drying to obtain lignin-based epoxy resin;
step 2, preparing tung oil fatty acid: heating tung oil and maleic anhydride to 15 ℃ under the condition of taking acetic acid as a catalyst, refluxing for 48 hours, and obtaining a reaction product, namely tung oil fatty acid;
and 3, respectively heating the lignin-based epoxy resin obtained in the step 1 and the tung oil fatty acid obtained in the step 2 to 70 ℃, uniformly mixing and stirring by adopting high-speed stirring and shearing equipment, pouring into asphalt heated to 90 +/-5 ℃, adding a catalyst, continuously mixing and stirring uniformly by adopting high-speed stirring and shearing equipment, and curing to obtain the biological epoxy asphalt.
5. The method for preparing bio-based epoxy asphalt according to claim 4, wherein the curing condition of step (3) is 150 ℃ for 2h, and then 200 ℃ for 1 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744953A (en) * | 2015-04-01 | 2015-07-01 | 武汉工程大学 | Thermosetting eleostearic acid ester epoxy asphalt compatibilizer and preparation method thereof |
| CN105038274A (en) * | 2015-07-28 | 2015-11-11 | 蚌埠南自仪表有限公司 | Tung oil modified bituminous waterproof sheet material |
| CN106750374A (en) * | 2016-12-15 | 2017-05-31 | 天津康泽威科技有限公司 | A kind of asphalt emulsifier and preparation method thereof and emulsified asphalt product |
-
2020
- 2020-08-11 CN CN202010800971.XA patent/CN111978677A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744953A (en) * | 2015-04-01 | 2015-07-01 | 武汉工程大学 | Thermosetting eleostearic acid ester epoxy asphalt compatibilizer and preparation method thereof |
| CN105038274A (en) * | 2015-07-28 | 2015-11-11 | 蚌埠南自仪表有限公司 | Tung oil modified bituminous waterproof sheet material |
| CN106750374A (en) * | 2016-12-15 | 2017-05-31 | 天津康泽威科技有限公司 | A kind of asphalt emulsifier and preparation method thereof and emulsified asphalt product |
Non-Patent Citations (2)
| Title |
|---|
| HUANG, KUN ET AL.: ""Preparation of biobased epoxies using tung oil fatty acid-derived C21 diacid and C22 triacid and study of epoxy properties"", 《GREEN CHEMISTRY》 * |
| XIN JUNNA ET AL.: ""Green Epoxy Resin System Based on Lignin and Tung Oil and Its Application in Epoxy Asphalt"", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
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