An epoxy asphalt binder and a method of making the same

Abstract

The application discloses an epoxy asphalt binder and a preparation method thereof, and belongs to the technical field of asphalt preparation, in particular relates to the binder which is composed of modified asphalt, epoxy resin material, compatilizer and anti-aging agent, and the mass ratio of the modified asphalt, the epoxy resin material, the compatilizer and the anti-aging agent is 100:15-60:5-10:0.1-0.5.The epoxy asphalt binder prepared by the application has excellent bonding performance and flexibility, in particular, the bonding performance at high temperature is significantly better than that of modified emulsified asphalt or polymer modified asphalt, and the flexibility is better than that of epoxy resin binder.

Description

Technical Field

[0001] This invention belongs to the field of asphalt preparation technology, specifically relating to an epoxy asphalt binder and its preparation method. Background Technology

[0002] Currently, bridge deck paving mainly uses emulsified asphalt, modified asphalt, and epoxy resin as interlayer binders. Emulsified asphalt is produced by adding polymer latex during the emulsification process, mixing polymer latex with finished emulsified asphalt, or emulsifying polymer-modified asphalt. Modified asphalt refers to asphalt mixtures with added modifiers such as rubber, resin, high-molecular polymers, and finely ground rubber powder, or by lightly oxidizing the asphalt to improve its properties. However, both emulsified and modified asphalt suffer from low adhesion, poor aging resistance, high temperature sensitivity, and insufficient strength, making them prone to defects such as shoving. Meanwhile, current epoxy resin binders are relatively expensive and unsuitable for general concrete bridge deck paving or road engineering. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide an epoxy asphalt binder and a method for preparing the same.

[0004] To achieve the above objectives, the present invention provides the following technical solution: an epoxy asphalt binder, wherein the binder is composed of modified asphalt, epoxy resin material, compatibilizer and anti-aging agent, and the mass ratio of the modified asphalt, epoxy resin material, compatibilizer and anti-aging agent is 100:15-60:5-10:0.1-0.5.

[0005] Further, the epoxy resin material is composed of a main agent, a curing agent, and a curing accelerator in a mass ratio of 80-120:65-105:5-15; the curing agent includes a compound of a primary amine curing agent, a polythiol rubber curing agent, and an amino-terminated urethane prepolymer in a mass ratio of 60-100:15-30:5-20; the primary amine curing agent is one or more of cis-oil-based primary amines, octadecyl primary amines, and hexadecyl primary amines in any combination; the polythiol rubber curing agent is composed of liquid polythiol rubber with thiol-terminated ends and a polysulfide compound with thiol-terminated ends; the curing accelerator is one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, and boron trifluoride amine complex in any combination.

[0006] Furthermore, the molecular structure of the compound of the terminal amino carbamate prepolymer is shown below:

[0007]

[0008] Where R is a diisocyanate residue, R' is an alkylene group, and n is a natural number from 2 to 10.

[0009] Further, the main agent is composed of epoxy resin, liquid nitrile rubber, and diglycidyl ether in a mass ratio of 100:5-25:10-25; the epoxy resin is bisphenol epoxy resin with a Brookfield viscosity of 5000-15000 mPa·s at 25°C and an epoxy value of 0.4-0.6 eq / 100g; the liquid nitrile rubber is one or a combination of several of the following: carboxyl-terminated nitrile rubber, epoxy-terminated nitrile rubber, vinyl-terminated nitrile rubber, and hydroxyl-terminated nitrile rubber; the diglycidyl ether is one or a combination of several of the following: 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0010] Further, the modified asphalt, by mass fraction, comprises 100 parts maleic anhydride asphalt, 2-6 parts thermoplastic elastomer, 1-4 parts tackifying resin, 1-4 parts mineral oil, and 0.1-0.25 parts sulfur stabilizer; the thermoplastic elastomer is a blend of thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in a mass ratio of 1-3:1-5; the tackifying resin is a solid coumarone resin.

[0011] Furthermore, the anti-aging agent is any combination of one or more of the following: dithiodipropionate diester, dodecyl alcohol ester, 2,6-di-tert-butyl-p-methylphenol, and tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ester; the compatibilizer is epoxidized soybean oil with oleic acid and linoleic acid content ≥90%, acid value ≤0.5mgKOH / g, and epoxy value 0.07-0.09eq / 100g.

[0012] Furthermore, it also includes a method for preparing an epoxy asphalt binder, characterized by comprising the following steps.

[0013] S1. After heating the maleic anhydride-modified asphalt to 170-180℃, thermoplastic elastomer, tackifying resin, and mineral oil are added and sheared. Then, sulfur stabilizer is added and stirred continuously while maintaining the temperature at 170-185℃ to obtain modified asphalt.

[0014] S2. Mix epoxy resin, liquid nitrile rubber and diglycidyl ether in proportion to obtain the main agent; mix primary amine curing agent, polythiol rubber curing agent and amino-terminated urethane prepolymer in proportion to obtain the curing agent.

[0015] S3. Heat the main agent, curing agent and curing accelerator to 50-60℃, then mix the three in proportion and stir to make epoxy resin material.

[0016] S4. Heat the modified asphalt to 170-185℃, then mix it with epoxy resin material in proportion, add compatibilizer and anti-aging agent and stir, keeping the temperature at 155-170℃ during the process to obtain epoxy asphalt binder.

[0017] Furthermore, the shearing time in step S1 is 60-120 min, the shearing machine speed is 3000-4000 r / min, and the stirring time after adding the sulfur stabilizer is 30-60 min.

[0018] Furthermore, the mixing and stirring time of the main agent, curing agent and curing accelerator in step S3 is 3-5 minutes.

[0019] Furthermore, in step S4, the stirring time for adding epoxy resin material, compatibilizer and anti-aging agent is 5-20 minutes.

[0020] The beneficial effects of this invention are as follows:

[0021] 1. The epoxy asphalt binder prepared by this invention exhibits superior bonding performance, particularly at high temperatures, significantly outperforming modified emulsified asphalt or polymer-modified asphalt. The use of liquid nitrile rubber, polysulfide rubber curing agent, and amino-terminated urethane prepolymer synergistically enhances the flexibility of the epoxy resin material, resulting in superior flexibility compared to ordinary epoxy resin materials. Simultaneously, it can form a non-stick tire with a certain strength at room temperature within a short time, subsequently remelting and completing the curing process at high temperatures. Under compaction, large aggregate particles embed into the epoxy asphalt binder, strengthening the interlayer bond of the pavement.

[0022] 2. The epoxy asphalt binder prepared by this invention has low cost, simple preparation method, and excellent effect, and can be widely used in road construction in my country.

[0023] Other advantages, objectives, and features of the invention will be set forth in the following description and will be apparent to those skilled in the art in some respects, or may be learned by practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Detailed Implementation

[0024] This invention provides a method for preparing an epoxy asphalt binder.

[0025] Example 1

[0026] The thermoplastic elastomer is a blend of thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in a 1:1 mass ratio; the epoxy resin is bisphenol epoxy resin with a Brookfield viscosity of 12500 mPa·s at 25℃ and an epoxy value of 0.45 eq / 100g; the liquid nitrile rubber is carboxyl-terminated nitrile rubber; the diglycidyl ether is 1,4-butanediol diglycidyl ether; the primary amine curing agent is cis-oil-based primary amine; the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol; the anti-aging agent is thiodipropionic acid diester; and the compatibilizer is epoxidized soybean oil with oleic acid and linoleic acid content ≥90%, acid value ≤0.5 mgKOH / g, and epoxy value 0.07 eq / 100g.

[0027] S1. Heat 100 parts of maleic anhydride asphalt to 170°C, then add 3 parts of thermoplastic elastomer, 1 part of tackifying resin and 1 part of mineral oil in sequence. Shear the mixture at 3000 r / min for 70 min, then add 0.1 parts of sulfur stabilizer and stir continuously for 30 min, keeping the temperature at 170°C during the process, to obtain modified asphalt.

[0028] S2. Mix epoxy resin, liquid nitrile rubber and diglycidyl ether in a mass ratio of 100:5:10 to obtain the main agent; then mix a compound of primary amine curing agent, polythiol rubber curing agent and amino-terminated urethane prepolymer in a mass ratio of 60:15:5 to obtain the curing agent.

[0029] S3. Heat the main agent, curing agent and curing accelerator to 50°C, then mix and stir them in a mass ratio of 80:70:10 to make an epoxy resin material.

[0030] S4. Heat the modified asphalt to 170℃, then mix it with epoxy resin material. After mixing, add compatibilizer and anti-aging agent and stir. The mass ratio of modified asphalt, epoxy resin material, compatibilizer and anti-aging agent is 100:30:6:0.1. Keep the temperature at 160℃ to obtain epoxy asphalt binder.

[0031] Example 2

[0032] The thermoplastic elastomer is a blend of thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in a mass ratio of 2:3; the epoxy resin is bisphenol epoxy resin with a Brookfield viscosity of 11100 mPa·s at 25℃ and an epoxy value of 0.49 eq / 100g; the liquid nitrile rubber is hydroxyl-terminated nitrile rubber; the diglycidyl ether is neopentyl glycol diglycidyl ether; the primary amine curing agent is a blend of cis-oleoyl primary amine and octadecyl primary amine in a mass ratio of 3:1; the curing accelerator is benzyl dimethylamine; the anti-aging agent is 2,6-di-tert-butyl-p-methylphenol; the compatibilizer is epoxidized soybean oil with oleic acid and linoleic acid content ≥90%, acid value ≤0.5 mg KOH / g, and epoxy value 0.08 eq / 100g.

[0033] S1. Heat 100 parts of maleic anhydride asphalt to 175°C, then add 4 parts of thermoplastic elastomer, 2 parts of tackifying resin and 2 parts of mineral oil in sequence. Shear the mixture at 3500 r / min for 90 min, then add 0.15 parts of sulfur stabilizer and stir continuously for 40 min, keeping the temperature at 175°C during the process, to obtain modified asphalt.

[0034] S2. Mix epoxy resin, liquid nitrile rubber and diglycidyl ether in a mass ratio of 100:15:15 to obtain the main agent; then mix a compound of primary amine curing agent, polythiol rubber curing agent and amino-terminated urethane prepolymer in a mass ratio of 70:20:10 to obtain the curing agent.

[0035] S3. Heat the main agent, curing agent and curing accelerator to 55°C, then mix and stir them in a mass ratio of 90:85:8 to make an epoxy resin material.

[0036] S4. Heat the modified asphalt to 175℃, then mix it with epoxy resin material. After mixing, add compatibilizer and anti-aging agent and stir. The mass ratio of modified asphalt, epoxy resin material, compatibilizer and anti-aging agent is 100:40:7:0.2. Keep the temperature at 165℃ to obtain epoxy asphalt binder.

[0037] Example 3

[0038] The thermoplastic elastomer is a blend of thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in a mass ratio of 3:5; the epoxy resin is bisphenol epoxy resin with a Brookfield viscosity of 8000 mPa·s at 25℃ and an epoxy value of 0.53 eq / 100g; the liquid nitrile rubber is terminally epoxy-terminated nitrile rubber; the diglycidyl ether is 1,6-hexanediol diglycidyl ether; the primary amine curing agent is a blend of cis-oil-based primary amine, octadecyl primary amine, and hexadecyl primary amine in a mass ratio of 3:2:1; the curing accelerator is boron trifluoride amine complex; the anti-aging agent is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ester; the compatibilizer is epoxidized soybean oil with oleic acid and linoleic acid content ≥90%, acid value ≤0.5 mgKOH / g, and epoxy value 0.09 eq / 100g.

[0039] S1. Heat 100 parts of maleic anhydride asphalt to 180°C, then add 5 parts of thermoplastic elastomer, 3 parts of tackifying resin and 3 parts of mineral oil in sequence. Shear the mixture at 3800 r / min for 110 min, then add 0.2 parts of sulfur stabilizer and stir continuously for 55 min, keeping the temperature at 180°C during the process, to obtain modified asphalt.

[0040] S2. Mix epoxy resin, liquid nitrile rubber and diglycidyl ether in a mass ratio of 100:20:20 to obtain the main agent; then mix a compound of primary amine curing agent, polythiol rubber curing agent and amino-terminated urethane prepolymer in a mass ratio of 100:30:20 to obtain the curing agent.

[0041] S3. Heat the main agent, curing agent and curing accelerator to 60°C, then mix and stir them in a mass ratio of 115:100:13 to make an epoxy resin material.

[0042] S4. Heat the modified asphalt to 180℃, then mix it with epoxy resin material. After mixing, add compatibilizer and anti-aging agent and stir. The mass ratio of modified asphalt, epoxy resin material, compatibilizer and anti-aging agent is 100:50:9:0.4. Keep the temperature at 170℃ to obtain epoxy asphalt binder.

[0043] To demonstrate the superiority of this application, the inventors have also provided comparative examples 1 and 2:

[0044] Comparative Example 1

[0045] Comparative Example 1 is the same as Example 3, except that no epoxy resin material is added.

[0046] Comparative Example 2

[0047] Comparative Example 2 is the same as Example 3, except that liquid nitrile rubber is not added to the main agent, and polythiol rubber curing agent and amino-terminated urethane prepolymer are not added to the curing agent.

[0048] According to the requirements of the "Test Methods for Waterproof Coatings for Buildings" (GB / T 16777-2008) and other standard documents, the performance indicators of the epoxy asphalt binders prepared in Examples 1-3, as well as traditional modified emulsified asphalt, polymer-modified asphalt and epoxy resin binders were tested. The results are shown in Table 1.

[0049] Table 1. Technical Specifications of Epoxy Asphalt Adhesive

[0050] Inspection items Low temperature performance (10℃) Bond strength at 25℃ (MPa) Bond strength at 60℃ (MPa) Example 1 No cracks 2.11 0.41 Example 2 No cracks 2.26 0.44 Example 3 No cracks 2.53 0.50 Comparative Example 1 No cracks 1.27 <0.1 Comparative Example 2 Cracks 2.34 0.43 Modified emulsified asphalt No cracks 0.78 <0.1 Polymer-modified asphalt No cracks 1.16 <0.1 Epoxy resin adhesive Cracks 3.31 1.20

[0051] The table above shows that the epoxy asphalt adhesives prepared in Examples 1-3 exhibit no surface cracks at low temperatures, a bond strength exceeding 2.0 MPa at 25°C, and a bond strength exceeding 0.4 MPa at 60°C. This indicates that the epoxy asphalt adhesives prepared according to this method have excellent performance in all aspects, and their bonding properties are suitable for bridge deck paving under both 25°C and 60°C conditions, demonstrating excellent bonding effect. Comparative Example 1 and Example 3 show that the epoxy resin material significantly improves the bond strength of the adhesive. Comparative Example 2 and Example 3 show that liquid nitrile rubber, polysulfide rubber curing agent, and amino-terminated urethane prepolymer can synergistically improve the flexibility of the adhesive.

[0052] Traditional modified emulsified asphalt and polymer-modified asphalt, although showing no surface cracks at low temperatures, have bond strengths of less than 1.2 MPa at 25°C and as low as 0.1 MPa at 60°C, making them prone to delamination and loss of adhesion under high temperature and heavy loads. While epoxy resin adhesives have high bond strength, they develop surface cracks at low temperatures, making them susceptible to fatigue cracking. More importantly, they are costly and difficult to use for ordinary cement concrete bridge deck paving.

[0053] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. An epoxy asphalt binder, characterized in that: The binder is composed of modified asphalt, epoxy resin material, compatibilizer and anti-aging agent, and the mass ratio of the modified asphalt, epoxy resin material, compatibilizer and anti-aging agent is 100:15-60:5-10:0.1-0.

5. The epoxy resin material is composed of a main agent, a curing agent, and a curing accelerator in a mass ratio of 80-120:65-105:5-15. The curing agent comprises a compound of a primary amine curing agent, a polysulfide rubber curing agent, and an amino-terminated urethane prepolymer in a mass ratio of 60-100:15-30:5-20. The primary amine curing agent is one or more of cis-oil-based primary amines, octadecyl primary amines, and hexadecyl primary amines, or any combination thereof. The polysulfide rubber curing agent is composed of liquid polysulfide rubber with thiol-terminated ends and a polysulfide compound with thiol-terminated ends. The molecular structure of the compound of the terminal amino carbamate prepolymer is shown below: Where: R is a diisocyanate residue, R' is an alkylene group, and n is a natural number from 2 to 10; The main component is composed of epoxy resin, liquid nitrile rubber, and diglycidyl ether in a mass ratio of 100:5-25:10-25. The liquid nitrile rubber is one or more of the following: carboxyl-terminated nitrile rubber, epoxy-terminated nitrile rubber, vinyl-terminated nitrile rubber, and hydroxyl-terminated nitrile rubber. The modified asphalt, by mass fraction, consists of 100 parts maleic anhydride asphalt, 2-6 parts thermoplastic elastomer, 1-4 parts tackifying resin, 1-4 parts mineral oil, and 0.1-0.25 parts sulfur stabilizer; the thermoplastic elastomer is a blend of thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene-butadiene-styrene block copolymer (SEBS) in a mass ratio of 1-3:1-5.

2. The epoxy asphalt binder according to claim 1, characterized in that: The curing accelerator is one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, and boron trifluoride amine complex, or any combination thereof.

3. The epoxy asphalt binder according to claim 2, characterized in that: The epoxy resin is a bisphenol epoxy resin with a Brookfield viscosity of 5000-15000 mPa·s at 25°C and an epoxy value of 0.4-0.6 eq / 100g; the diglycidyl ether is one or a combination of several of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

4. The epoxy asphalt binder according to claim 3, characterized in that: The tackifying resin is a solid coumarone resin.

5. The epoxy asphalt binder according to claim 4, characterized in that: The anti-aging agent is any combination of one or more of the following: dithiodipropionate diester, dodecyl alcohol ester, 2,6-di-tert-butyl-p-methylphenol, and tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ester; the compatibilizer is epoxidized soybean oil with oleic acid and linoleic acid content ≥90%, acid value ≤0.5mgKOH / g, and epoxy value 0.07-0.09eq / 100g.

6. A method for preparing the epoxy asphalt binder according to any one of claims 1 to 5, characterized in that: Includes the following steps: S1. After heating the maleic anhydride-modified asphalt to 170-180℃, thermoplastic elastomer, tackifying resin, and mineral oil are added and sheared. Then, sulfur stabilizer is added and stirred continuously while maintaining the temperature at 170-185℃ to obtain modified asphalt. S2. Mix epoxy resin, liquid nitrile rubber and diglycidyl ether in proportion to obtain the main agent; mix primary amine curing agent, polysulfide rubber curing agent and amino-terminated urethane prepolymer in proportion to obtain the curing agent. S3. Heat the main agent, curing agent and curing accelerator to 50-60℃, then mix the three in proportion and stir to make epoxy resin material. S4. Heat the modified asphalt to 170-185℃, then mix it with epoxy resin material in proportion, add compatibilizer and anti-aging agent and stir, keeping the temperature at 155-170℃ during the process to obtain epoxy asphalt binder.

7. The method for preparing the epoxy asphalt binder according to claim 6, characterized in that: The shearing time in step S1 is 60-120 min, the shearing speed is 3000-4000 r / min, and the stirring time after adding the sulfur stabilizer is 30-60 min.

8. The method for preparing the epoxy asphalt binder according to claim 7, characterized in that: The mixing time for the main agent, curing agent and curing accelerator in step S3 is 3-5 minutes.

9. The method for preparing the epoxy asphalt binder according to claim 8, characterized in that: In step S4, the epoxy resin material, compatibilizer, and anti-aging agent are added and stirred for 5-20 minutes.

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