WO2019223201A1 - Biological epoxy asphalt and preparation method therefor and application thereof - Google Patents

Abstract

Disclosed by the present invention is a biological epoxy asphalt, comprising a component A, a component B and a component C. The component A includes epoxidized soybean oil and a diluent, the component B includes a curing agent, an accelerant and a defoaming agent, and the component C includes asphalt. The mass ratio of the component A to the component B is (105~126) : 45, and the mass ratio of the sum of the component A and the component B to the component C is 100 : (57~520). Compared with the prior art, the biological epoxy asphalt disclosed by the present invention can be used to replace the traditional petroleum asphalt; by utilizing the materials such as epoxidized soybean oil and biological curing agent, the cost is remarkably lowered, and the thermoplastic property of the traditional asphalt material can be effectively improved, so that the biological epoxy asphalt has excellent high-and-low temperature performance and anti-aging property and can be widely applied to the pavements of highways, tunnels and the like and bridge deck pavement. Further disclosed by the present invention is a preparation method for the biological epoxy asphalt.

Description

Biological epoxy asphalt and preparation method and application thereof Technical field

The invention belongs to the field of construction, and particularly relates to a biological epoxy asphalt and a preparation method and application thereof.

Background technique

Epoxy pitch is a three-dimensional continuous phase thermosetting material formed by irreversible chemical cross-linking curing reaction of epoxy resin, curing agent and petroleum pitch. As the temperature rises, epoxy asphalt will not soften like traditional asphalt, and has good aging resistance and chemical resistance. The fatigue performance of epoxy asphalt concrete is three orders of magnitude greater than that of Superpave polymer modified asphalt concrete. Good for heavy traffic and wide area air temperature, greatly improving road performance. On the other hand, bio-asphalt, as an alternative product of traditional petroleum pitch, can be obtained from a variety of biomass materials, such as wheat straw, waste wood chips, trench oil, etc., to a certain extent, it can be "turned into treasure" as petroleum. Effective addition of asphalt and performance modification of petroleum asphalt. In addition, people are paying more and more attention to the environment, climate, and the depletion of non-renewable resources. Therefore, the use of biomaterials to replace petroleum materials to achieve sustainable development of transportation infrastructure has become the hotspot of global transportation infrastructure technology research.

At present, the application of epoxy asphalt and bio-asphalt often faces the following problems: the high cost of petroleum epoxy resin and curing agent, the brittleness of epoxy resin after curing reaction, and the patented product properties of existing epoxy asphalt on the market As a result, epoxy asphalt is only used in special pavement structures such as long-span steel bridge decks and airport runways, which limits its use in road pavements. The bio-asphalt has a higher content of light components due to the rapid heating and rapid cooling manufacturing process in high-temperature cracking, and the raw material biomass generally contains higher oxygen elements, which leads to the oxygen content in the finished product (> 15 %) Is much higher than the content of oxygen in petroleum asphalt (<1%). During high-temperature construction, light components are liable to precipitate, which causes the mechanical properties of the remaining asphalt mixture to decrease. At the same time, many chemical components in the bio-asphalt are susceptible to oxidation at high temperatures, which makes the bio-asphalt appear to be rapidly hardened. Degraded performance.

Summary of the Invention

The technical problem to be solved by the present invention is to provide a biological epoxy asphalt to solve the problems such as poor effect existing in the prior art.

To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

A biological epoxy asphalt, including three components A, B and C, component A includes epoxy soybean oil and diluent, component B includes curing agent, accelerator and defoamer, and component C includes asphalt;

Among them, the mass ratio of the A component and the B component is 105 to 126: 45, and the ratio of the sum of the masses of the A component and the B component to the mass of the C component is 100: 57 to 520;

Among them, in the component A, the mass ratio of the epoxy soybean oil and the diluent is 100: 10 to 30; in the component B, the mass ratio of the curing agent, the accelerator and the defoaming agent is 45: 0.5 to 1: 0.6 to 1.

Wherein, the diluent is an epoxy resin reactive diluent, preferably phenyl glycidyl ether or benzyl glycidyl ether.

Wherein, the curing agent is a long-chain aliphatic primary amine, preferably octadecyl primary amine or tallow amine.

The promoter is an aromatic amine or a base; wherein the aromatic amine is a benzylamine and the base is a strong base, preferably potassium hydroxide.

The defoamer is a low-molecular-weight polyether having a molecular weight of 2000 or less, preferably a copolymer of ethylene oxide and propylene oxide.

Wherein, the asphalt is road petroleum asphalt No. 70 or road petroleum asphalt No. 90.

The method for preparing the above-mentioned bio-epoxy asphalt includes the following steps:

(1) Preparation of component A: After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ± 2 ℃, stir for 100 ～ 140min, and then cool for 23 ～ 25h at room temperature to obtain the biological ring. A component of oxygen pitch;

(2) Preparation of component B: After mixing the formulating amount of curing agent, accelerator and defoaming agent uniformly, heating to 98-102 ° C, fully reacting for 27-33min, and then cooling to room temperature to obtain biological epoxy Asphalt B component;

(3) Pour component A prepared in step (1) heated to 58-62 ° C into component B prepared in step (2) heated to 58-62 ° C, and use high-speed stirring and shearing equipment Mix and stir at a speed of 2000 ± 200r / min for 2 ~ 3min, mix well and pour into component C heated to 148 ～ 152 ℃, continue to use a high-speed stirring shearing device to mix and stir at a speed of 2000 ± 200r / min ～ 2min. After mixing evenly, the epoxy epoxy pitch is obtained after curing.

In step (3), the curing is performed at 60 ± 2 ° C for 70-74 hours.

The application of the above-mentioned biological epoxy asphalt in preparing epoxy asphalt mixture is also within the protection scope of the present invention.

Wherein, the application method is as follows: the aggregate and mineral powder prepared according to the grading requirements are kept at 150 ± 2 ° C for 4 hours, and the bio-epoxy asphalt material prepared above is heated to 150 ± 2 ° C, Take out the aggregate and pour it into a mixing pot at 150 ± 2 ℃ and mix for 30 ± 2s, then pour the bio-epoxy asphalt material and mineral powder into the mixing pot at the same time and mix at a speed of 50 ± 5r / min. 2 ～ 3 minutes, until the asphalt mixture is mixed uniformly with no white matter, to obtain a high-performance biological epoxy asphalt mixture.

Beneficial effects:

Compared with the prior art, the present invention has the following advantages:

1. The present invention uses epoxy soybean oil instead of traditional epoxy resin to prepare bio-epoxy pitch, which can effectively slow the aging phenomenon of bio-asphalt, reduce the precipitation and oxidation of light components of bio-oil, and to a certain extent break through bio-asphalt in Barriers applied in the transportation infrastructure industry;

2. The current price of traditional epoxy resin in the market is about 27,000 yuan / ton, and the price of epoxy soybean oil is about 7,000 yuan / ton. Using epoxy soybean oil instead of traditional epoxy resin can effectively reduce the epoxy asphalt mixture. Material cost of materials is beneficial to the popularization and use of epoxy asphalt in road engineering;

3. Compared with traditional petroleum asphalt, bio-epoxy asphalt fundamentally changes its low-temperature brittle, high-temperature soft thermoplastic properties, has excellent high-low temperature and anti-aging characteristics, and satisfies the road and bridge paving requirements. Demand for use

4. The construction time of warm-mixed epoxy asphalt can't exceed 90min at the longest, and the construction time of hot-mixed epoxy asphalt can be 30 ～ 120min technology ", author: Zhou Jinxia), by contrast, shelter construction time biological epoxy asphalt up to 3h, from mixing, transportation, rolling to complete the paving has longer operating time, effectively ensuring the road Construction Quality;

5. The production process of epoxy soybean oil has the characteristics of bio-renewable, environmental protection, and cheap, which greatly reduces the energy consumption during the production of epoxy asphalt. As a pavement layer of transportation infrastructure, it is more green, environmentally friendly and consistent with sustainable development idea.

Detailed ways

The invention can be better understood from the following examples. However, those skilled in the art can easily understand that the content described in the embodiments is only used to illustrate the present invention, and should not and should not limit the present invention described in detail in the claims.

The present invention is described in detail below by examples. In the following examples, the parts of each component are all parts by mass.

The preparation method of the biological epoxy asphalt A component is as follows:

Example 1: Weigh 100 parts of epoxy soybean oil, add 20 parts of phenyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.

Example 2: Weigh 100 parts of epoxy soybean oil, add 20 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C., and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.

Example 3: Weigh 100 parts of epoxy soybean oil, add 30 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain the A component of the biological epoxy material.

The preparation method of the component B of the epoxy epoxy asphalt is as follows:

Example 4: Weigh 45 parts of octadecyl primary amine, 1 part of aromatic amine, 1 part of low molecular weight polyether, heat to 100 ° C, mechanically stir for 30 min, and cool to room temperature to obtain the B component of biological epoxy asphalt .

Example 5: Weigh 45 parts of tallow amine, 1 part of KOH, and 1 part of low molecular weight polyether, heat to 100 ° C, mechanically stir for 30 minutes, and then cool to room temperature to obtain the B component of biological epoxy asphalt.

The following are examples and test results of the preparation of the biological epoxy asphalt material A, B and C components of the biological epoxy asphalt provided by the present invention:

Example 6: 110 parts of the A component of the bio-epoxy asphalt material obtained in Example 1 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 4 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, mix and stir at 2000 r / min using a high-speed stirring and shearing device for 3 minutes. Pour the mixture into 150 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The cured bio-epoxy asphalt material was punched into tensile test strips for mechanical property testing. The test temperature was 23 ° C and the tensile speed was 500 mm / min. The above test results are shown in Schedule 1.

Example 7: 120 parts of the A component of the bio-epoxy asphalt material obtained in Example 2 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 5 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, and use a high-speed stirring and shearing device to mix and stir at a speed of 2000 r / min for 3 minutes. Pour the mixture of the two into 300 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The tensile test conditions are the same as in Example 6. The test results are shown in Table 1.

Example 8: 130 parts of the A component of the bio-epoxy asphalt material obtained in Example 1 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 5 were heated to 60 ° C. respectively, and then Group A Slowly pour into component B, and use a high-speed stirring and shearing device to mix and stir at a speed of 2000 r / min for 3 minutes. Pour the mixture of the two into 300 parts of component C (90 pitch) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The tensile test conditions are the same as in Example 6. The test results are shown in Table 1.

Table 1 Mechanical properties of bio-epoxy asphalt materials

Examples and test results of the bio-epoxy asphalt prepared by using the bio-epoxy asphalt A component, B-component, C-component, and appropriate amount of aggregate and mineral powder are provided below:

Example 9: Six parts of the epoxy asphalt mixture obtained in Example 6 and 94 parts of a certain gradation aggregate were heated to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After the actual forming, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The obtained epoxy asphalt mixture was subjected to a Marshall test, a -15 ° C low-temperature bending test, and a rutting test. The results of the above tests are shown in Table 3.

Example 10: 6.5 parts of the epoxy asphalt mixture obtained in Example 7 and 93.5 parts of a certain gradation aggregate were heated to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After the actual forming, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The road performance test is the same as that in Example 9. The test results are shown in Table 3.

Example 11: Heat 7 parts of the epoxy asphalt mixture obtained in Example 8 and 93 parts of a certain gradation aggregate to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After compaction and molding, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The road performance test is the same as that in Example 9. The test results are shown in Table 3.

Table 2 Aggregate grading

Sieve hole size (mm)	13.2	9.5	4.75	2.36	1.18	0.6	0.3	0.15	0.075
Pass percentage (%)	100	97.2	32.4	27.3	19.5	13.5	9.9	8.2	6.5

Table 3 Performance of biological epoxy asphalt mixture

Pilot projects	experiment method	Example 9	Example 10	Example 11
Marshall stability / kN	JTG E20-2011	93	89	86
Current value / 0.1mm	JTG E20-2011	31	33	36
Void ratio /%	JTG E20-2011	1.8	1.9	1.8
Bending stiffness modulus / Mpa	JTG E20-2011	14032	13542	13028
Bending strain / 10 -3	JTG E20-2011	3.21	3.12	3.01
Dynamic stability / times / mm	JTG E20-2011	24532	24512	22318

Example 12: The bio-epoxy asphalt mixture prepared in Example 9 was used for paving the actual road surface. The length of the test section was 300m, the width was 4m, and the thickness of the upper layer was 4cm. According to the calculation, the required mass of epoxy soybean oil is 2.54t, and the material cost is 177.8 thousand yuan. If the epoxy resin under the same conditions is used as the raw material, the required material cost is 68.58 million yuan. Therefore, it can be seen that the cost of materials can be reduced by nearly 50,800 yuan only by laying a test section of 300m in length, and the economic benefits are significant.

Comparative Example 1:

The preparation method is the same as that in Example 6, except that the A component of the bio-epoxy asphalt material is obtained by the following method: 100 parts of epoxy soybean oil is weighed, 20 parts of phenyl glycidyl ether is added, stirring is started, and heating is gradually performed The temperature was raised to 110-120 ° C, and the reaction was cooled to room temperature after 2 hours to obtain the A component of the biological epoxy material. The obtained bio-epoxy asphalt material was reference product 1.

Comparative Example 2:

The preparation method is the same as that in Example 6, except that the A component of the bio-epoxy asphalt material is obtained by the following method: 100 parts of epoxy soybean oil is weighed, 20 parts of phenyl glycidyl ether is added, stirring is started, and heating is gradually performed The temperature was raised to 170-190 ° C, and the reaction was cooled to room temperature after 2 hours to obtain the A component of the biological epoxy material. The obtained bio-epoxy asphalt material was reference product 2.

The performance comparison between the product in Example 6 and Control 1 and Control 2 is as follows:

Table 4 Mechanical properties of bio-epoxy asphalt materials

Comparative example	Tensile strength (MPa, 23 ℃)	Elongation at break (%, 23 ° C)
4	1.75	82
5	3.2	146
6	5.84	352
skills requirement	≥2.5	≥100

Claims (9)

1. A biological epoxy asphalt, which is characterized in that it includes three components: A, B, and C; component A includes epoxy soybean oil and diluent; component B includes a curing agent, an accelerator, and an antifoaming agent; and group C Points include asphalt;

   Among them, the mass ratio of the A component and the B component is 105 to 126: 45, and the ratio of the sum of the masses of the A component and the B component to the mass of the C component is 100: 57 to 520;

   Among them, in the component A, the mass ratio of the epoxy soybean oil and the diluent is 100: 10 to 30; in the component B, the mass ratio of the curing agent, the accelerator and the defoaming agent is 45: 0.5 to 1: 0.6 to 1.
2. The bio-epoxy asphalt according to claim 1, wherein the diluent is an epoxy resin reactive diluent.
3. The bio-epoxy pitch according to claim 1, wherein the curing agent is a long-chain aliphatic primary amine.
4. The biological epoxy asphalt according to claim 1, wherein the accelerator is an aromatic amine or a base.
5. The biological epoxy asphalt according to claim 1, wherein the defoaming agent is a low molecular weight polyether.
6. The bio-epoxy asphalt according to claim 1, wherein the asphalt is road petroleum asphalt No. 70 or road petroleum asphalt No. 90.
7. The method for preparing biological epoxy asphalt according to claim 1, characterized in that it comprises the following steps:

   (1) Preparation of component A: After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ± 2 ℃, stir for 100 ～ 140min, and then cool for 23 ～ 25h at room temperature to obtain the biological ring. A component of oxygen pitch;

   (2) Preparation of component B: After mixing the formulating amount of curing agent, accelerator and defoaming agent uniformly, heating to 98-102 ° C, fully reacting for 27-33min, and then cooling to room temperature to obtain biological epoxy Asphalt B component;

   (3) Pour component A prepared in step (1) heated to 58-62 ° C into component B prepared in step (2) heated to 58-62 ° C, mix well and pour into heat In the component C to 148 to 152 ° C, after being mixed uniformly, the epoxy epoxy asphalt is obtained by curing.
8. The preparation method according to claim 7, characterized in that, in step (3), the curing conditions are curing at 58-62 ° C for 70-74h.
9. The use of the biological epoxy asphalt according to claim 1 in preparing an epoxy asphalt mixture.