Epoxy asphalt mixture and preparation process thereof

Abstract

The invention relates to the technical field of building materials, and discloses an epoxy asphalt mixture and a preparation process thereof. The preparation method comprises the following steps: carrying out polymerization reaction on an esterification product of 1, 2-dodecanediol and acrylic acid and ethylene glycol dimercaptoacetate, carrying out end capping reaction with mercaptoethylamine to prepare a compatibilizer, and stirring and mixing the compatibilizer with matrix asphalt and other materials to finally prepare the epoxy asphalt mixture. The compatibilizer contains amido and a non-polar aliphatic carbon chain structure, the amido can react with an epoxy group of epoxy resin, and the non-polar aliphatic carbon chain structure is similar to asphalt in structure and can be well compatible with the asphalt. The difunctional compatibilizer enhances the interface bonding force of epoxy resin and asphalt, improves the tensile strength and elongation at break of the mixture, reduces the softening point difference value, and effectively improves the compatibility of epoxy resin and asphalt.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to an epoxy asphalt mixture and its preparation process. Background Technology

[0002] Epoxy asphalt mixtures, as a high-performance road construction material, are widely used in engineering fields such as steel bridge deck paving and highway pavement due to their excellent durability and fatigue resistance. They combine the high strength and high adhesion of epoxy resin with the flexibility of asphalt, achieving a balance of rigidity and flexibility. However, epoxy resin is a polar substance, while asphalt is a non-polar or weakly polar substance, making it difficult for them to become a homogeneous and stable system. To improve their compatibility, methods such as adding compatibilizers and modifying asphalt are mainly employed. Compatibilizers containing non-polar aliphatic carbon chains are highly compatible with asphalt; amine-based curing agent compatibilizers can react with the epoxy groups of epoxy resin, enhancing the interfacial bonding between epoxy resin and asphalt. Developing bifunctional compatibilizers with both non-polar aliphatic carbon chains and amine groups to solve the compatibility problem between epoxy resin and asphalt and improve the mechanical properties of the mixture is currently a research hotspot. Patent CN115594443B discloses a warm-mix epoxy asphalt mixture and its preparation method. The epoxy resin component, curing agent component, asphalt component and mineral powder are mixed evenly to obtain an epoxy asphalt mixture with good dynamic stability. However, this patent does not solve the problem of poor compatibility between epoxy resin and asphalt. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides an epoxy asphalt mixture and its preparation process, which solves the compatibility problem between epoxy resin and asphalt.

[0004] The preparation process of an epoxy asphalt mixture is as follows: In step S1, toluene, 1,2-dodecanediol, acrylic acid, p-toluenesulfonic acid, and hydroquinone were added to a flask to initiate an esterification reaction. The mixture was then filtered, washed with water, and decolorized with activated carbon to obtain 1,2-dodecanediacrylate. The reaction for preparation was as follows: .

[0005] In step S2, tetrahydrofuran, 1,2-dodecanediacrylate, ethylene glycol dimercaptoacetate, and triethylamine were added to a flask. The mixture was stirred under a nitrogen atmosphere to carry out the reaction. Acetonitrile was added dropwise to wash away the triethylamine, and the mixture was allowed to settle and filtered. Mercaptoethylamine was then added to the filter cake, and the reaction continued. The mixture was then distilled under reduced pressure, washed with ethanol, and dried to obtain the compatibilizer. The reaction formula for the preparation is as follows: .

[0006] S3 adds base asphalt to the mixing tank, stirs and melts it, then adds curing agent and compatibilizer, stirs it, then adds epoxy resin, mixes and stirs it to obtain epoxy asphalt mixture.

[0007] Preferably, the ratio of 1,2-dodecanediol, acrylic acid, p-toluenesulfonic acid, and hydroquinone in S1 is 1 mol: (2-2.5) mol: (0.1-0.16) mol: (1.5-2) mmol.

[0008] Preferably, the esterification reaction in S1 is carried out at a temperature of 110-120℃ and the reaction is carried out under reflux for 12-18 hours.

[0009] Preferably, the ratio of 1,2-dodecanediacrylate, ethylene glycol dimercaptoacetate, triethylamine, and mercaptoethylamine in S2 is (1.1-1.16) mol: 1 mol: (0.07-0.09) mol: (0.3-0.4) mol.

[0010] Preferably, the temperature of the first reaction in S2 is 20-30℃ and the reaction time is 24-36h; the temperature of the second reaction is 20-28℃ and the reaction time is 2-3h.

[0011] Preferably, the mass ratio of matrix asphalt, compatibilizer, curing agent and epoxy resin in S3 is 100:(4-8):(3-16):(20-28).

[0012] Preferably, the curing agent in S3 is methyltetrahydrophthalic anhydride or tung oil anhydride.

[0013] Preferably, the melting temperature in S3 is 150-160℃.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention involves polymerizing 1,2-dodecanediol and the esterification product of acrylic acid with ethylene glycol dimercaptoacetate, followed by end-capping with mercaptoethylamine to prepare a compatibilizer. This compatibilizer is then blended with base asphalt, a curing agent, and epoxy resin to ultimately prepare an epoxy asphalt mixture. This compatibilizer contains bi-terminated amine groups and nonpolar aliphatic carbon chains. The former reacts with the epoxy groups of the epoxy resin, while the latter, similar in structure to asphalt, exhibits good compatibility. This bifunctional compatibilizer enhances the interfacial bonding between epoxy resin and asphalt, improves the tensile strength and elongation at break of the mixture, and reduces the softening point difference, effectively improving the compatibility between epoxy resin and asphalt. Detailed Implementation

[0015] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0016] The following base asphalt, grade 70# and 90#, is sourced from Jiangxi Xunyang Building Materials Co., Ltd. The epoxy resin, grade E51, is sourced from Shandong Suihua Biotechnology Co., Ltd. The CAS number for ethylene glycol dimercaptoacetate is 123-81-9, sourced from Hubei Jiahuixingcheng Biotechnology Co., Ltd. The CAS number for methyltetrahydrophthalic anhydride is 11070-44-3, sourced from Wuhan Jixin Yibang Biotechnology Co., Ltd. The grade for tung oil anhydride is GREAT8218, sourced from Hubei Greete Biomedical Technology Co., Ltd.

[0017] Example 1: The preparation process of an epoxy asphalt mixture is as follows: S1. Add 400 mL of toluene, 0.5 mol of 1,2-dodecanediol, 1.25 mol of acrylic acid, 0.05 mol of p-toluenesulfonic acid, and 0.75 mmol of hydroquinone to a flask. Reflux at 120 °C for 12 h. Filter, wash with water, and decolorize with activated carbon to obtain 1,2-dodecanediacrylate.

[0018] S2 added 800 mL of tetrahydrofuran, 0.22 mol of 1,2-dodecanediacrylate, 0.5 mol of ethylene glycol dimercaptoacetate, and 0.035 mol of triethylamine to a flask. The mixture was stirred and reacted at 25 °C for 24 h under a nitrogen atmosphere. Acetonitrile was added dropwise to wash away the triethylamine, and the mixture was filtered after sedimentation. 0.2 mol of mercaptoethylamine was then added to the filter cake, and the reaction was continued at 20 °C for 3 h. The mixture was then distilled under reduced pressure, washed with ethanol, and dried to obtain the compatibilizer.

[0019] S3 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 160°C, then adds 200 g of compatibilizer and 150 g of methyltetrahydrophthalic anhydride, stirs, then adds 1.4 kg of epoxy resin, mixes and stirs to obtain epoxy asphalt mixture.

[0020] Example 2: The preparation process of an epoxy asphalt mixture is as follows: S1. Add 500 mL of toluene, 0.5 mol of 1,2-dodecanediol, 1 mol of acrylic acid, 0.065 mol of p-toluenesulfonic acid, and 1 mmol of hydroquinone to a flask. Reflux at 110 °C for 18 h. Filter, wash with water, and decolorize with activated carbon to obtain 1,2-dodecanediacrylate.

[0021] S2 added 600 mol tetrahydrofuran, 0.226 mol 1,2-dodecanediacrylate, 0.5 mol ethylene glycol dimercaptoacetate, and 0.045 mol triethylamine to a flask. Under a nitrogen atmosphere, the mixture was stirred at 30°C for 24 h. Acetonitrile was added dropwise to wash away the triethylamine, and the mixture was filtered after sedimentation. 0.15 mol mercaptoethylamine was then added to the filter cake, and the reaction was continued at 24°C for 1.5 h. The mixture was then distilled under reduced pressure, washed with ethanol, and dried to obtain the compatibilizer.

[0022] S3 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 150°C, then adds 300 g of compatibilizer and 475 g of tung oil anhydride, stirs, then adds 1 kg of epoxy resin, mixes and stirs to obtain epoxy asphalt mixture.

[0023] Example 3: The preparation process of an epoxy asphalt mixture is as follows: S1. Add 450 mL of toluene, 0.5 mol of 1,2-dodecanediol, 1.125 mol of acrylic acid, 0.08 mol of p-toluenesulfonic acid, and 0.875 mmol of hydroquinone to a flask. Reflux at 115 °C for 18 h. Filter, wash with water, and decolorize with activated carbon to obtain 1,2-dodecanediacrylate.

[0024] S2 added 700 mL of tetrahydrofuran, 0.232 mol of 1,2-dodecanediacrylate, 0.5 mol of ethylene glycol dimercaptoacetate, and 0.04 mol of triethylamine to a flask. The mixture was stirred at 20 °C for 36 h under a nitrogen atmosphere. Acetonitrile was added dropwise to wash away the triethylamine, and the mixture was filtered after sedimentation. 0.175 mol of mercaptoethylamine was then added to the filter cake, and the reaction was continued at 28 °C for 2 h. The mixture was then distilled under reduced pressure, washed with ethanol, and dried to obtain the compatibilizer.

[0025] S3 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 155℃, then adds 400 g of compatibilizer and 150 g of tung oil anhydride, stirs, then adds 1.2 kg of epoxy resin, mixes and stirs to obtain epoxy asphalt mixture.

[0026] Example 4: The preparation process of an epoxy asphalt mixture is as follows: S1. Add 400 mL of toluene, 0.5 mol of 1,2-dodecanediol, 1 mol of acrylic acid, 0.08 mol of p-toluenesulfonic acid, and 1 mmol of hydroquinone to a flask. Reflux at 110 °C for 15 h. Filter, wash with water, and decolorize with activated carbon to obtain 1,2-dodecanediacrylate.

[0027] S2 added 600 mL of tetrahydrofuran, 0.232 mol of 1,2-dodecanediacrylate, 0.5 mol of ethylene glycol dimercaptoacetate, and 0.035 mol of triethylamine to a flask. The mixture was stirred at 30 °C for 30 h under a nitrogen atmosphere. Acetonitrile was added dropwise to wash away the triethylamine, and the mixture was filtered after sedimentation. 0.2 mol of mercaptoethylamine was added to the filter cake, and the reaction was continued at 20 °C for 2 h. The mixture was then distilled under reduced pressure, washed with ethanol, and dried to obtain the compatibilizer.

[0028] S3 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 150°C, then adds 400 g of compatibilizer and 800 g of methyltetrahydrophthalic anhydride, stirs, then adds 1 kg of epoxy resin, mixes and stirs to obtain epoxy asphalt mixture.

[0029] The difference between Comparative Example 1 and Example 1 is that no compatibilizer is added: S1 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 160°C, then adds 150 g of methyltetrahydrophthalic anhydride, stirs, and then adds 1.4 kg of epoxy resin. After mixing, epoxy asphalt mixture is obtained.

[0030] The difference between Comparative Example 2 and Example 1 is that mercaptoethylamine is not added: S1. Add 400 mL of toluene, 0.5 mol of 1,2-dodecanediol, 1.25 mol of acrylic acid, 0.05 mol of p-toluenesulfonic acid, and 0.75 mmol of hydroquinone to a flask. Reflux at 120 °C for 12 h. Filter, wash with water, and decolorize with activated carbon to obtain 1,2-dodecanediacrylate.

[0031] S2 added 800 mL of tetrahydrofuran, 0.22 mol of 1,2-dodecanediacrylate, 0.5 mol of ethylene glycol dimercaptoacetate, and 0.035 mol of triethylamine to a flask. The mixture was stirred at 25 °C for 24 h under a nitrogen atmosphere. Acetonitrile was added dropwise to wash away the triethylamine. The mixture was then filtered after sedimentation and dried to obtain the compatibilizer.

[0032] S3 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 160°C, then adds 200 g of compatibilizer and 150 g of methyltetrahydrophthalic anhydride, stirs, then adds 1.4 kg of epoxy resin, mixes and stirs to obtain epoxy asphalt mixture.

[0033] The difference between Comparative Example 3 and Example 1 is that ethylene glycol diacrylate (CAS No. 2274-11-5) is used instead of 1,2-dodecane diacrylate. S1. Add 800 mL of tetrahydrofuran, 0.22 mol of ethylene glycol diacrylate, 0.5 mol of ethylene glycol dimercaptoacetate, and 0.035 mol of triethylamine to a flask. Stir and react for 24 h at 25 °C under a nitrogen atmosphere. Wash with acetonitrile to remove triethylamine, filter after sedimentation, add 0.2 mol of mercaptoethylamine to the filter cake, and continue the reaction at 20 °C for 3 h. Distill under reduced pressure, wash with ethanol, and dry to obtain the compatibilizer.

[0034] S2 adds 5 kg of base asphalt to the mixing tank, stirs and melts it at 160°C, then adds 200 g of compatibilizer and 150 g of methyltetrahydrophthalic anhydride, stirs, and then adds 1.4 kg of epoxy resin. After mixing, epoxy asphalt mixture is obtained.

[0035] The tensile properties of epoxy asphalt mixtures were tested according to ASTM D638-22. The difference in softening points between the upper and lower sections of the epoxy asphalt mixture was tested according to standards JTG E20-2011 and GB / T 4507-2014. The smaller the difference in softening points, the better the compatibility between epoxy resin and asphalt.

[0036] Table 1 Tensile properties and compatibility of epoxy asphalt mixtures

[0037] Example 1 uses the esterification product of 1,2-dodecanediol and acrylic acid, which is polymerized with ethylene glycol dimercaptoacetate and then capped with mercaptoethylamine to prepare a compatibilizer. This compatibilizer is then mixed with base asphalt and other materials to prepare an epoxy asphalt mixture. This compatibilizer acts as a bridge between epoxy resin and asphalt. On the one hand, it contains nonpolar aliphatic carbon chains similar to asphalt, allowing for good compatibility with asphalt. On the other hand, its two ends are amine groups, which can react with the epoxy groups of epoxy resin. This compatibilizer enhances the interfacial bonding between epoxy resin and asphalt, effectively reduces the softening point difference of epoxy asphalt, and the two exhibit good compatibility, resulting in significant improvements in tensile strength and elongation at break.

[0038] Compared to Example 1, Comparative Example 1 did not add compatibilizer, and the compatibility between epoxy resin and asphalt was very poor, resulting in a larger difference in softening point of the mixture than in all examples, and lower mechanical properties than in all examples.

[0039] Comparative Example 2, without the addition of mercaptoethylamine, produced a compatibilizer with alkenyl groups at both ends, which did not react with the epoxy groups of the epoxy resin. This resulted in weak interfacial bonding of the epoxy asphalt, a large difference in softening point, and poor compatibility.

[0040] Comparative Example 3 used ethylene glycol diacrylate instead of 1,2-dodecyl acrylate and reacted it with ethylene glycol dimercaptoacetate and mercaptoethylamine. The compatibilizer prepared lacked a nonpolar aliphatic carbon chain similar to asphalt, resulting in a larger difference in the softening point of the mixture than in all examples, indicating poor compatibility.

[0041] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of them. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention. Although the specific embodiments of the present invention have been described above, they are not intended to limit the protection scope of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A preparation process for epoxy asphalt mixture, characterized in that, The preparation process is as follows: Step (1) Add tetrahydrofuran, 1,2-dodecanediacrylate, ethylene glycol dimercaptoacetate and triethylamine to a flask. Stir and react under a nitrogen atmosphere. Wash with acetonitrile to remove triethylamine, filter by sedimentation, add mercaptoethylamine to the filter cake and continue the reaction. Distill under reduced pressure, wash with ethanol and dry to obtain compatibilizer. Step (2) Add base asphalt to the mixing tank, stir and melt it, then add curing agent and compatibilizer, stir and then add epoxy resin, mix and stir to obtain epoxy asphalt mixture.

2. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, In step (1), the ratio of 1,2-dodecanediacrylate, ethylene glycol dimercaptoacetate, triethylamine, and mercaptoethylamine is (1.1-1.16) mol: 1 mol: (0.07-0.09) mol: (0.3-0.4) mol.

3. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, In step (1), the temperature of the first reaction is 20-30℃ and the reaction time is 24-36h; the temperature of the second reaction is 20-28℃ and the reaction time is 2-3h.

4. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, The preparation method of 1,2-dodecanediacrylate in step (1) is as follows: Toluene, 1,2-dodecanediol, acrylic acid, p-toluenesulfonic acid and hydroquinone are added to a flask for esterification reaction, filtered, washed with water, and decolorized with activated carbon to obtain 1,2-dodecanediacrylate.

5. The preparation process of epoxy asphalt mixture according to claim 4, characterized in that, The ratio of 1,2-dodecanediol, acrylic acid, p-toluenesulfonic acid, and hydroquinone is 1 mol: (2-2.5) mol: (0.1-0.16) mol: (1.5-2) mmol.

6. The preparation process of epoxy asphalt mixture according to claim 4, characterized in that, The esterification reaction was carried out at a temperature of 110-120℃ and under reflux for 12-18 hours.

7. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, In step (2), the mass ratio of matrix asphalt, compatibilizer, curing agent and epoxy resin is 100:(4-8):(3-16):(20-28).

8. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, The curing agent in step (2) is methyltetrahydrophthalic anhydride or tung oil anhydride.

9. The preparation process of epoxy asphalt mixture according to claim 1, characterized in that, The melting temperature in step (2) is 150-160℃.

10. An epoxy asphalt mixture prepared by the preparation process according to any one of claims 1-9.

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