Anti-rutting agent with ultraviolet aging resistance and preparation method thereof
Technical Field
The invention relates to an anti-rutting agent and a preparation method thereof, in particular to an anti-rutting agent with ultraviolet aging resistance and a preparation method thereof.
Background
With the increasing of the traffic flow of high-grade highways, the increasing heavy load of transport vehicles and the canalization of the traffic flow, rutting becomes the main form of road surface damage, and the comfort of road driving and the service life of roads are seriously influenced. The research and application of high-performance modified asphalt become urgent requirements for the current pavement construction.
At present, the method for improving the stiffness modulus of the asphalt mixture to prevent the rutting is an effective means. The technology mainly adopts several methods of using high-viscosity hard asphalt cement, adding natural asphalt or polyolefin additive into asphalt mixture, etc. Because the polyolefin additive has the advantages of simple construction process, convenient use, obvious improvement on the high-temperature performance of the mixture and the like, the application of the polyolefin additive to the base course and the bottom layer of the highway pavement is continuously and stably increased in recent years. But has certain limitations, which are mainly shown in that (1) the polymer has poor aging resistance to oxygen, ozone and ultraviolet light, particularly under the radiation of ultraviolet light, asphalt and the polymer can generate a series of physical and chemical changes, so that the asphalt and the polymer are hardened and embrittled, the damage strain is reduced, the asphalt and the polymer are easy to crack and age gradually, and the service life of the asphalt pavement is greatly shortened; (2) the high-temperature performance of the asphalt mixture is improved, and the low-temperature performance of the asphalt mixture is reduced.
CN101357835A discloses a high modulus asphalt concrete additive. The high-modulus asphalt concrete additive comprises, by weight, polyethylene PE20-70%, polyester PES0.9-10%, polypropylene PP15-60%, polyvinyl chloride PVC 20-50%, chlorinated polypropylene PP-C5-10%, rubber 3-5%, asphalt 1-6%, cellulose 1-4.5% and an auxiliary agent 0.1-0.5%. The polymerization temperature is T, T is more than or equal to 130 ℃ and less than or equal to 190 ℃, and the particle size specification of the product is that D is more than or equal to 1MM and less than or equal to 6MM and is in a granular shape (90 percent of the product). The additive can obviously improve the high-temperature anti-rutting performance of the asphalt concrete, but does not consider the ultraviolet aging resistance of the asphalt concrete, so that the service life of the asphalt concrete is influenced.
CN102964525A discloses a road asphalt mixture anti-rutting additive and a preparation method thereof, wherein the preparation method comprises the following steps: the composite material is prepared by mixing the raw materials, and performing melt extrusion, grain cutting and drying, wherein the raw materials comprise the following components in parts by weight: 100 parts of polyolefin, 3-30 parts of waste rubber powder, 0.5-2 parts of maleic anhydride and 0.05-0.2 part of dicumyl peroxide. The additive prepared by the method can obviously improve the anti-rutting performance of the asphalt concrete, but weakens the low-temperature performance of the asphalt mixture to a certain extent, and simultaneously has the problem of insufficient anti-ultraviolet aging performance.
In conclusion, although the prior art can improve the anti-rutting performance of the asphalt concrete to a certain extent, the low-temperature performance of the asphalt concrete is reduced, and the anti-ultraviolet aging performance is insufficient.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an anti-rutting agent with ultraviolet aging resistance and a preparation method thereof. The anti-rutting agent not only obviously improves the anti-rutting performance and the low-temperature performance of the asphalt concrete, but also greatly improves the anti-ultraviolet aging performance of the asphalt concrete.
The invention provides an anti-rutting agent with ultraviolet aging resistance, which comprises the following raw material components in parts by weight:
100 parts of low-density polyethylene;
10-30 parts of styrene butadiene rubber;
10-30 parts of polypropylene;
5-10 parts of an organic-inorganic composite material;
wherein the organic-inorganic composite material is formed by cohydrolysis and polycondensation reaction of tetraethoxysilane and organic silane containing triazinetrione groups.
The organic silane containing the triazinetrione group is 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and can be represented by the following chemical formula:
formula (I).
The organic-inorganic composite material comprises raw materials of a polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer, hydrochloric acid, ethyl orthosilicate, organic silane containing a triazinetrione group and water, wherein the weight ratio of the polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer to the hydrochloric acid to the ethyl orthosilicate to the organic silane containing the triazinetrione group to the water is (25-35): 130-200): 35-55): 30-50): 1000, preferably (28-32): 150-180): 85-X): X1000, wherein X = 30-50, and the concentration of the hydrochloric acid is 8-12 mol/L.
The temperature of the cohydrolysis and polycondensation reaction is 90-120 ℃, preferably 100-110 ℃, and the time is 36-48 h.
The low-density polyethylene can be a recycled waste material, and the melt flow index is 2-30 g/10 min.
The polypropylene can be a recycled waste material, and the melt flow index is 10-30 g/10 min.
The styrene butadiene rubber can be an industrial product and has the molecular weight of 2 multiplied by 105~8×105。
The invention also provides a preparation method of the anti-rutting agent with the ultraviolet aging resistance, which comprises the following steps:
(1) dissolving a polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer and hydrochloric acid in water, continuously stirring until the polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer and the hydrochloric acid are completely dissolved, adding tetraethoxysilane and organic silane containing triazinetrione groups, uniformly stirring, carrying out cohydrolysis and polycondensation reaction, filtering, washing and carrying out first drying after the reaction is finished, then adding a mixed solution of ethanol and hydrochloric acid, heating and refluxing, then washing and carrying out second drying to obtain the organic-inorganic composite material;
(2) uniformly mixing low-density polyethylene, styrene butadiene rubber, polypropylene and an organic-inorganic composite material, and then blending, extruding and granulating by an extruder to obtain the anti-rutting agent with the ultraviolet aging resistance.
In the step (1), the weight ratio of the polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer, hydrochloric acid, ethyl orthosilicate, organic silane containing triazinetrione groups and water is (25-35): (130-200): (35-55): (30-50): 1000, preferably (28-32): (150-180): (85-X): X:1000, wherein X = 30-50, and the concentration of hydrochloric acid is 8-12 mol/L.
In the step (1), the stirring temperature is 30-50 ℃, and the stirring time is 18-24 hours.
In the step (1), the temperature of the cohydrolysis and polycondensation reaction is 90-120 ℃, preferably 100-110 ℃, and the time is 36-48 h.
In step (1), the filtration, washing and drying can adopt the conventional method. Drying to volatilize the solvent, wherein the first drying temperature can be 80-120 ℃ and the time is 5-12 h. The temperature of the second drying can be 80-120 ℃, and the time is 5-12 h.
In the step (1), the heating reflux temperature is 60-90 ℃, preferably 70-80 ℃, and the time is 6-10 hours.
In the step (2), the extruder can be a conventionally used extruder, preferably a screw extruder, the extrusion temperature is 130-160 ℃, and the screw rotation speed is 30-150 r/min. The twin-screw extruder is further preferred, the two screws are parallel to each other in the barrel, the temperature in the barrel can be controlled in multiple sections, for example, the barrel of the extruder can be divided into eight temperature sections, and the specific operating conditions are as follows: a first section is 130-150 ℃; the second section is 135-155 ℃; three sections are 140-160 ℃; 140-160 ℃ in the fourth section; five sections are 150-160 ℃; six sections are 150-160 ℃; the seven sections are 145-160 ℃; eight sections are 150-160 ℃.
Compared with the prior art, the anti-rutting agent with the ultraviolet aging resistance and the preparation method thereof have the following advantages:
(1) the invention introduces organic groups of organic silane into the organic-inorganic composite material through copolycondensation-hydrolysis reaction of tetraethoxysilane and organic silane containing triazinetrione groups, and the organic groups are uniformly distributed in the organic-inorganic composite material, thereby preventing physical migration or volatilization loss of the organic groups, so that the organic groups have the functions of absorbing ultraviolet rays, capturing free radicals, decomposing hydroperoxide and the like, inorganic components have stronger shielding function on the ultraviolet rays, the two functions are coordinated and mutually influenced, the comprehensive function greatly improves the ultraviolet aging resistance, and obviously improves the anti-rutting performance and the low-temperature performance of the asphalt concrete. Therefore, the track is not easy to appear in summer and is not easy to frost crack in winter.
(2) The organic-inorganic composite material has the characteristics of organic groups and inorganic nano materials, breaks the boundary between organic matters and inorganic matters and ensures that the anti-rutting agent and the asphalt have excellent compatibility.
(3) The organic-inorganic composite material is in a granular (or powder) shape, and is convenient to store and transport.
(4) The invention can take recycled waste plastics (such as low-density polyethylene, polypropylene and the like) and waste rubber (such as styrene butadiene rubber and the like) as raw materials, has lower production cost, outstanding environmental benefit, convenient construction and simple use.
Detailed Description
The technical features of the present invention will be further described below by way of examples, which are not intended to limit the present invention.
The co-hydrolysis and polycondensation are that organic silane and ethyl orthosilicate jointly undergo hydrolysis reaction and polycondensation reaction, so that organic-inorganic composite materials containing different organic groups are synthesized in one step.
Example 1
(1) Dissolving 29.14 parts by weight of polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer (P123) and 168.40 parts by weight of concentrated hydrochloric acid (12 mol/L) in 1000 parts by weight of water, continuously stirring until the mixture is completely dissolved, measuring 35 parts by weight of ethyl orthosilicate and 50 parts by weight of 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, adding the ethyl orthosilicate and the 1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione into the solution, continuously stirring for 24 hours at 40 ℃, then placing the solution into a reaction kettle, standing for 48 hours at 100 ℃ in an oven to complete the cohydrolysis and polycondensation reactions, filtering and washing with water, drying for 12 hours at 100 ℃, adding the solution into a mixed solution of 600 parts by weight of anhydrous ethanol and 10 parts by weight of concentrated hydrochloric acid (12 mol/L), heating and refluxing for 8 hours at 80 ℃, then washing the mixture to be neutral, washing the mixture by using ethanol, and drying the mixture for 8 hours at 100 ℃ to obtain the organic-inorganic composite material.
(2) 100 parts by weight of low-density polyethylene (melt flow index: 20 g/10 min), 30 parts by weight of polypropylene (melt flow index: 10 g/10 min), 30 parts by weight of a polypropylene (melt flow index: 10 g/10 min) were mixedStyrene butadiene rubber (molecular weight 8X 10)5) And after uniformly mixing 10 parts by weight of the organic-inorganic composite material, co-mixing, extruding and granulating by a double-screw extruder to obtain the anti-rutting agent with the ultraviolet aging resistance. The extruder operating conditions were: the first section is 150 ℃; the second section is 155 ℃; the third section is 160 ℃; the fourth section is 160 ℃; the fifth section is 160 ℃; the six sections are 160 ℃; the seven sections are 160 ℃; the eight sections are 160 ℃. The screw speed was 120 r/min.
Example 2
(1) Dissolving 29.14 parts by weight of polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer (P123) and 168.40 parts by weight of concentrated hydrochloric acid (12 mol/L) in 1000 parts by weight of water, continuously stirring until the mixture is completely dissolved, measuring 45 parts by weight of ethyl orthosilicate and 40 parts by weight of 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, adding the ethyl orthosilicate and the 1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione into the solution, continuously stirring for 20 hours at 40 ℃, then placing the solution into a reaction kettle, standing for 48 hours at 100 ℃ in an oven, cooling, carrying out suction filtration, washing with water, drying for 12 hours at 100 ℃, adding the solution into a mixed solution of 540 parts by weight of anhydrous ethanol and 9 parts by weight of concentrated hydrochloric acid (12 mol/L), heating and refluxing for 8 hours at 80 ℃, then washing, washing with ethanol, and drying at 100 deg.C for 8 hr to obtain the organic-inorganic composite material.
(2) 100 parts by weight of low density polyethylene (melt flow index of 10 g/10 min), 20 parts by weight of polypropylene (melt flow index of 15 g/10 min) and 20 parts by weight of styrene butadiene rubber (molecular weight 6 x 10)5) And 7 parts by weight of organic-inorganic composite material are uniformly mixed, and then are subjected to blending extrusion and granulation by a double-screw extruder to obtain the anti-rutting agent with the ultraviolet aging resistance. The extruder operating conditions were: the first section is 140 ℃; the second section is 145 ℃; the third section is 150 ℃; the fourth section is 150 ℃; the fifth section is 155 ℃; the six sections are 155 ℃; the seven sections are 155 ℃; the eight sections are 155 ℃. The screw speed was 80 r/min.
Example 3
(1) Dissolving 31 parts by weight of polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer (P123) and 160 parts by weight of concentrated hydrochloric acid (12 mol/L) in 1000 parts by weight of water, continuously stirring until the copolymer is completely dissolved, weighing 55 parts by weight of ethyl orthosilicate and 30 parts by weight of 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, adding the ethyl orthosilicate and the 1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione into the solution, continuously stirring for 18 hours at 40 ℃, then putting the mixture into a reaction kettle, standing the mixture in an oven at 100 ℃ for 36 hours, cooling and carrying out suction filtration, drying the mixture for 12 hours at 100 ℃, adding the dried mixture into a mixed solution of 480 parts by weight of anhydrous ethanol and 8 parts by weight of concentrated hydrochloric acid (12 mol/L), heating and refluxing the mixture for 8 hours at 80, washing with ethanol, and drying at 100 deg.C for 8 hr to obtain the organic-inorganic composite material.
(2) 100 parts by weight of low density polyethylene (melt flow index of 5 g/10 min), 10 parts by weight of polypropylene (melt flow index of 10 g/10 min) and 10 parts by weight of styrene-butadiene rubber (molecular weight 2X 10)5) And 5 parts by weight of organic-inorganic composite material are uniformly mixed, and then are subjected to blending extrusion and granulation by a double-screw extruder to obtain the anti-rutting agent with the ultraviolet aging resistance. The extruder operating conditions were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃. The screw speed was 50 r/min.
Comparative example 1
(1) Dissolving 29.14 parts by weight of polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer (P123) and 168.40 parts by weight of concentrated hydrochloric acid (12 mol/L) in 1000 parts by weight of water, continuously stirring until the polyvinyl ether-polypropylene ether-polyvinyl ether triblock copolymer is completely dissolved, measuring 45 parts by weight of ethyl orthosilicate, adding the ethyl orthosilicate into the solution, continuously stirring for 20 hours at 40 ℃, then placing the solution into a reaction kettle, standing for 48 hours at 100 ℃ in an oven, cooling, carrying out suction filtration, washing with water, drying for 12 hours at 100 ℃, adding the ethyl orthosilicate into a mixed solution of 540 parts by weight of anhydrous ethanol and 9 parts by weight of concentrated hydrochloric acid (12 mol/L), heating and refluxing for 8 hours at 80 ℃, then washing with water to be neutral, washing with ethanol, and drying for 8 hours at 100 ℃ to obtain the inorganic material.
(2) 100 parts by weight of low density polyethylene (melt flow index of 5 g/10 min), 10 parts by weight of polypropylene (melt flow index of 10 g/10 min) and 10 parts by weight of styrene-butadiene rubber (molecular weight 2X 10)5) 1.43 parts by weight of an inorganic material, and 3.57 parts by weight of 1,3, 5-tris [3- (trimethoxysilyl) propyl group]-1,3,5Uniformly mixing the triazine-2, 4,6(1H,3H,5H) -trione, blending, extruding and granulating by a double-screw extruder to obtain the anti-rutting agent with the ultraviolet aging resistance. The extruder operating conditions were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃. The screw speed was 50 r/min.
Comparative example 2
100 parts by weight of low density polyethylene (melt flow index of 5 g/10 min), 10 parts by weight of polypropylene (melt flow index of 10 g/10 min) and 10 parts by weight of styrene-butadiene rubber (molecular weight 2X 10)5) Uniformly mixing 1.43 parts of titanium dioxide and 3.57 parts of ultraviolet resistant absorbent UV-531 (2-hydroxy-4-n-octoxy benzophenone), blending, extruding and granulating by a double-screw extruder to obtain the anti-rutting agent with ultraviolet aging resistance. The operating conditions of the extruder were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃. The screw speed was 50 r/min.
Comparative example 3
100 parts by weight of low density polyethylene (melt flow index of 5 g/10 min), 10 parts by weight of polypropylene (melt flow index of 10 g/10 min) and 10 parts by weight of styrene-butadiene rubber (molecular weight 2X 10)5) And after uniformly mixing, co-blending, extruding and granulating by a double-screw extruder to obtain the anti-rutting agent. The extruder operating conditions were: the first section is 130 ℃; the second section is 135 ℃; the third section is 140 ℃; the fourth section is 140 ℃; the fifth section is 150 ℃; the six sections are 150 ℃; the seven sections are 145 ℃; the eight sections are 150 ℃. The screw speed was 50 r/min.
Test example
The ultraviolet aging test is carried out in an ultraviolet aging box, and the ultraviolet intensity is 210W/m2The aging temperature is 60 ℃, and the aging time is 6 days. The asphalt concrete samples prepared by the anti-rutting agents of examples 1 to 3 and comparative examples 1 to 3 were tested, and the results are shown in table 1.
TABLE 1 asphalt concrete sample Performance test results
|
Base asphalt
|
Example 1
|
Example 2
|
Example 3
|
Comparative example 1
|
Comparative example 2
|
Comparative example 3
|
Rut dynamic stability (time/mm)
|
875
|
3513
|
3098
|
2837
|
2697
|
2651
|
2645
|
Freeze-thaw split tensile strength ratio TSR (%)
|
69.0
|
81.2
|
80.6
|
79.8
|
79.6
|
79.2
|
79.1
|
Low temperature bending failure strain (mu epsilon)
|
2316
|
2769
|
2682
|
2642
|
2592
|
2583
|
2581
|
After ultraviolet aging test
|
|
|
|
|
|
|
|
Rut dynamic stability (time/mm)
|
692
|
3232
|
2823
|
2553
|
2346
|
2281
|
2250
|
Freeze-thaw split tensile strength ratio TSR (%)
|
62.0
|
75.3
|
74.3
|
73.0
|
72.7
|
72.2
|
72.0
|
Low temperature bending failure strain (mu epsilon)
|
1788
|
2511
|
2415
|
2365
|
2276
|
2247
|
2238 |
As can be seen from table 1, the anti-rutting agent with ultraviolet aging resistance prepared in the examples can significantly improve the anti-rutting performance of the asphalt concrete and improve the low temperature performance of the asphalt concrete, compared with the base asphalt.
In examples 1 to 3, the dynamic stability of rutting was reduced by 8% to 10%, the freeze-thaw cleavage tensile strength was reduced by 7.2% to 8.5% as compared with TSR, and the low-temperature bending failure strain was reduced by 9.3% to 10.5%. In comparative example 3, the rut dynamic stability was reduced by 15%, the freeze-thaw split tensile strength was reduced by 9.0% compared to TSR, and the low temperature bending failure strain was reduced by 13.3%. The comparison shows that the anti-rutting agent with the anti-ultraviolet aging performance can effectively improve the anti-ultraviolet aging performance of the asphalt concrete.
As can be seen from comparative examples 1 and 2, the UV aging resistance effect is inferior to that of examples 1 to 3, mainly because: comparative examples 1 and 2 are simply to add inorganic materials, titanium dioxide, and uv absorbers, and there are phenomena of volatilization, physical migration, etc. of uv absorbers, causing loss. Therefore, the anti-ultraviolet aging effect is not as good as that of the anti-rutting agent with anti-ultraviolet aging performance of the invention.