CN117866447A - Preparation method of uvioresistant aging-resistant weather-resistant asphalt - Google Patents
Preparation method of uvioresistant aging-resistant weather-resistant asphalt Download PDFInfo
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- CN117866447A CN117866447A CN202310050412.5A CN202310050412A CN117866447A CN 117866447 A CN117866447 A CN 117866447A CN 202310050412 A CN202310050412 A CN 202310050412A CN 117866447 A CN117866447 A CN 117866447A
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- 239000010426 asphalt Substances 0.000 title claims abstract description 115
- 230000032683 aging Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003822 epoxy resin Substances 0.000 claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 15
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 15
- 229960004853 betadex Drugs 0.000 claims abstract description 15
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 41
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 238000010008 shearing Methods 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 16
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 16
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005639 Lauric acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 230000000630 rising effect Effects 0.000 abstract description 4
- 230000006750 UV protection Effects 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 29
- 230000035515 penetration Effects 0.000 description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 229920006150 hyperbranched polyester Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Abstract
The invention discloses a preparation method of ultraviolet aging resistant weather resistant asphalt, and relates to the technical field of road asphalt. When the ultraviolet aging resistant weather resistant asphalt is prepared, the ultraviolet aging resistant asphalt is prepared by using modified epoxy resin and modified matrix asphalt; introducing a conjugated macromolecular structure of s-triazine on the modified epoxy resin, and adding modified nano zinc oxide to the modified epoxy resin to adsorb the modified nano zinc oxide on the s-triazine structure due to the coordination effect of the s-triazine, so that the heat resistance of asphalt is enhanced; under high-temperature irradiation, the temperature of the modified epoxy resin taking the s-triazine as the center is rapidly dispersed along the tetrapod-like nano zinc oxide, so that the temperature rising rate is reduced, and the asphalt has better high-temperature resistance; the monochloro-s-triazine-beta-cyclodextrin is added into the matrix asphalt, so that the aging of the asphalt can be delayed, the ultraviolet resistance of the asphalt can be improved, and the modified nano zinc oxide on the modified epoxy resin can pass through the hydrophobic cavity in the monochloro-s-triazine-beta-cyclodextrin, so that the mechanical property of the asphalt can be improved.
Description
Technical Field
The invention relates to the technical field of road asphalt, in particular to a preparation method of ultraviolet aging resistant weather resistant asphalt.
Background
Aging of asphalt is generally classified into thermal aging caused by high temperature and ultraviolet aging caused by ultraviolet irradiation contained in sunlight. Photo-oxidative aging is a major cause of long-term aging of asphalt roads. Ultraviolet energy exceeds the breaking energy of carbon-carbon bond and hydrocarbon bond, and weaker chemical bond inside asphalt molecule is broken, so that chemical reaction occurs, and the molecular structure is changed, so that the performance is reduced. The asphalt mixture is made of black materials, and the effects of the ultraviolet-resistant absorbers such as cerium dioxide, titanium dioxide, zinc dioxide, carbon black and the like which are commonly used in rubber and plastic products are not obvious.
In northwest China, the altitude is high, the air is thin, and the ultraviolet radiation is strong; meanwhile, the areas have the characteristics of wide regions, complex geological features and diversification, and the strong ultraviolet radiation easily causes the rapid aging of asphalt pavement; in addition, the temperature difference is larger, the temperature change is quicker, and the service life of the asphalt pavement is seriously influenced. Therefore, the application researches and prepares the ultraviolet aging resistant weather-resistant asphalt with slower temperature rising rate, ultraviolet aging resistance and better viscosity.
Disclosure of Invention
The invention aims to provide ultraviolet aging resistant weather resistant asphalt and a preparation method thereof, which are used for solving the problems in the background technology.
An ultraviolet aging resistant weather resistant asphalt comprises a component A and a component B; the component A is modified epoxy resin; the component B comprises modified matrix asphalt and a curing agent.
Preferably, the modified epoxy resin is prepared by blending hyperbranched epoxy resin with modified zinc oxide; the hyperbranched epoxy resin is prepared by preparing hyperbranched polyester with triazine ring as a center by using triazine ring and phthalic anhydride, and then reacting the hyperbranched polyester with glycidol.
Preferably, the modified zinc oxide is prepared by coating tetrapod-like zinc oxide with lauric acid.
Preferably, the modified matrix asphalt is prepared by adding monochloro-s-triazine-beta-cyclodextrin into the matrix asphalt.
Preferably, the curing agent is one or two of diethylenetriamine and phthalic anhydride.
Preferably, the preparation method of the ultraviolet aging resistant weather resistant asphalt comprises the following steps: and (3) preparing a component A, preparing a component B and preparing the ultraviolet-aging-resistant weather-resistant asphalt.
Preferably, the preparation method of the anti-ultraviolet aging weather-resistant asphalt comprises the following specific steps:
(1) Triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.4 to 1:3.8, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of that of a triazine ring and acetone with the mass fraction of 10-15 times of that of the triazine ring, heating to 25-30 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare hyperbranched epoxy resin;
(2) Adding 0.1-0.18 times of modified zinc oxide into hyperbranched epoxy resin, stirring at 150-180 rpm, dripping 3-5% ammonia water with the mass fraction of 0.05-0.1 times of hyperbranched epoxy resin at 1-2 ml/min, stirring and reacting for 12-14 h after dripping is completed, and filtering to obtain modified epoxy resin, namely component A;
(3) Heating matrix asphalt to 140-160 ℃, adding monochloro-s-triazine-beta-cyclodextrin with the mass of 0.05-0.12 times of that of the matrix asphalt, and stirring at 400-800 rpm for 15-20 min to prepare modified matrix asphalt; adding a curing agent with the mass of 0.08-0.12 times that of the matrix asphalt, and continuously stirring for 8-12 min to prepare a component B;
(4) The component A and the component B are mixed according to the mass ratio of 2: 3-2: 4, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture at 50-80 kHz for 10-20 min, and then transferring the mixture to a high-speed shearing instrument for shearing to obtain the anti-ultraviolet aging weather-resistant asphalt.
Preferably, in the step (1): the preparation method of the triazine ring comprises the following steps: dispersing the o-aminobenzyl alcohol in acetone with the mass of 10-15 times of that of the o-aminobenzyl alcohol, heating to 85-95 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass of 10-15 times of that of the o-aminobenzyl alcohol and the mass fraction of 15-20% in a nitrogen atmosphere at 3-6 ml/min, standing for 12-18 h after the dropwise adding is finished to obtain an upper layered solution and a lower layered solution, rotationally steaming to remove the upper layered solution, blending the upper layered solution with silica gel powder with the mass of 20-30 times of that of the o-aminobenzyl alcohol, and separating the mixture by chromatography to obtain a triazine ring.
Preferably, in the step (3): the preparation method of the modified zinc oxide comprises the following steps: adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with 5-8 times of the mass of the tetrapod-like nano zinc oxide, adding lauric acid with 0.02 time of the mass of the tetrapod-like nano zinc oxide, stirring at 400-800 rpm for 12 hours at room temperature, centrifuging to take out a lower layer of mud, washing the mud with absolute ethyl alcohol again, centrifuging again, washing and centrifuging for 3 times repeatedly, drying the centrifugate in an oven at 80 ℃ for 1-2 hours, grinding and sieving with a 100-mesh sieve to obtain the modified zinc oxide.
Preferably, in the step (3): during shearing, the shearing is performed for 60-80 min at 3000-5000 rpm, the shearing temperature is 170-200 ℃, the rotating speed is regulated to 400-800 rpm, and stirring and shearing are continued for 30min.
Compared with the prior art, the invention has the following beneficial effects:
when the ultraviolet aging resistant weather resistant asphalt is prepared, the ultraviolet aging resistant asphalt is prepared by using modified epoxy resin and modified matrix asphalt;
the modified epoxy resin is prepared by blending hyperbranched epoxy resin and modified nano zinc oxide; the hyperbranched epoxy resin is prepared by preparing hyperbranched polyester with triazine ring as a center by using triazine ring and phthalic anhydride, and then reacting the hyperbranched polyester with glycidol; the conjugated macromolecular structure of the sym-triazine is introduced into the modified epoxy resin, and the modified nano zinc oxide is adsorbed on the sym-triazine structure due to the coordination effect of the sym-triazine, so that a continuous phase formed by the modified epoxy resin is more stable, and the high temperature resistance of asphalt is enhanced; the modified epoxy resin is used as a continuous phase to be subjected to ring opening and crosslinking under the action of a curing agent to form a three-dimensional space network structure, and the modified matrix asphalt is used as a disperse phase to form a two-phase three-dimensional crosslinking network, so that the rigidity and strength of the asphalt are enhanced, and the curing shrinkage rate is reduced; under high-temperature irradiation, the temperature of the modified epoxy resin taking the sym-triazine as the center is rapidly dispersed along the tetrapod-like nano zinc oxide, so that the temperature rising rate is reduced, and the asphalt has better high-temperature resistance.
The modified matrix asphalt is prepared by adding monochloro-s-triazine-beta-cyclodextrin into the matrix asphalt; the monochloro-s-triazine-beta-cyclodextrin forms a covalent bond with active hydroxyl and sulfhydryl groups in matrix asphalt, so that an asphaltene cluster is broken to form a stable space network, and the generation of carbonyl and sulfonyl groups can be reduced, so that the aging of asphalt is delayed; the monochloro-s-triazine-beta-cyclodextrin connected to the matrix asphalt can also react with free radicals generated by active groups in the asphalt autoxidation process, so that the cracking of carbon-hydrogen bonds, carbon-carbon double bonds and the like on an asphalt molecular chain caused by ultraviolet light is avoided, and the ultraviolet resistance of the asphalt is improved; when the modified matrix asphalt and the modified epoxy resin are blended and the modified epoxy resin of the continuous phase form a three-position network structure, the modified nano zinc oxide is prepared by coating four-needle-shaped nano zinc oxide with lauric acid, the surface of the four-needle-shaped nano zinc oxide is changed from hydrophilic to hydrophobic, and the four-needle-shaped nano zinc oxide can pass through a hydrophobic cavity in the monochlorotriazine-beta-cyclodextrin to fix the continuous phase in the disperse phase, so that the compatibility of the modified matrix asphalt and the modified epoxy resin is enhanced, the formed two-phase three-dimensional crosslinked network is more stable, and the viscosity of the asphalt is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the method for testing each index of the ultraviolet aging resistant weather resistant asphalt prepared in the examples and the comparative examples as follows:
ultraviolet aging resistance: the ultraviolet aging resistant asphalt prepared in the examples and the comparative examples is placed in an ultraviolet aging box for ultraviolet aging test, and the ultraviolet intensity is 1200 mu w/cm 2 The aging temperature was 60℃and the aging time was 6 days.
High temperature resistance: drying the UV aging resistant asphalt prepared in the examples and comparative examples, and standing at 80deg.C for 24 hr to observe whether deformation occurs
Softening point: the high temperature resistant road asphalt prepared in examples and comparative examples was subjected to softening point testing in accordance with the relevant regulations of asphalt for highway engineering asphalt and asphalt mixture test procedure (JTJE 20).
Penetration degree: the high temperature resistant road asphalt prepared in examples and comparative examples was subjected to penetration test at 25℃according to the relevant regulations of asphalt mixture test procedure for Highway engineering (JTJE 20).
Rate of temperature rise: the anti-ultraviolet aging weather-resistant asphalt prepared in the examples and the comparative examples was dried and then placed in a high temperature environment of 80 ℃ to record the temperature change of the asphalt before and after 1 hour.
Example 1
The preparation method of the ultraviolet-aging-resistant weather-resistant asphalt comprises the following steps:
(1) Dispersing the o-aminobenzyl alcohol in acetone with the mass being 10 times that of the o-aminobenzyl alcohol, heating to 85 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass being 10 times that of the o-aminobenzyl alcohol and the mass fraction being 15-20% in a nitrogen atmosphere at the speed of 3ml/min, standing for 12 hours after the dropwise adding is finished, obtaining an upper-lower layered solution, rotationally steaming to remove the upper-layer solution, blending the upper-layer solution with silica gel powder with the mass being 20 times that of the o-aminobenzyl alcohol, and separating the mixture through chromatography to obtain a triazine ring; triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.4, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of triazine ring and acetone with the mass fraction of 10 times of triazine ring, heating to 25 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare hyperbranched epoxy resin;
(2) Adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with the mass being 5 times that of the tetrapod-like nano zinc oxide, adding lauric acid with the mass being 0.02 time that of the tetrapod-like nano zinc oxide, stirring for 12 hours at 400rpm at room temperature, centrifuging to take out a lower layer of mud, washing the mud with absolute ethyl alcohol again, centrifuging again, washing and centrifuging for 3 times repeatedly, drying the centrifugate in an oven at 80 ℃ for 1 hour, grinding and sieving with a 100-mesh sieve to obtain modified zinc oxide; adding 0.1 times of modified zinc oxide of hyperbranched epoxy resin into hyperbranched epoxy resin, stirring at 150rpm, dropwise adding 3% ammonia water of which the mass is 0.05 times of that of the hyperbranched epoxy resin at 1ml/min, stirring for reaction for 12 hours after dropwise adding, and filtering to obtain modified epoxy resin, namely component A;
(3) Heating matrix asphalt to 140 ℃, adding monochloro-s-triazine-beta-cyclodextrin with the mass of 0.05 times of that of the matrix asphalt, and stirring at 400rpm for 150min to prepare modified matrix asphalt; adding a curing agent diethylenetriamine with the mass of 0.08 times that of the matrix asphalt, and continuously stirring for 8min to prepare a component B;
(4) The component A and the component B are mixed according to the mass ratio of 2:3, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 10min at 50kHz, transferring to a high-speed shearing instrument for shearing, shearing for 60min at 3000rpm, adjusting the shearing temperature to 170 ℃, adjusting the rotating speed to 400rpm, and continuously stirring and shearing for 30min to obtain the anti-ultraviolet aging weather-resistant asphalt.
Example 2
The preparation method of the ultraviolet-aging-resistant weather-resistant asphalt comprises the following steps:
(1) Dispersing the o-aminobenzyl alcohol in acetone with the mass of 13 times of that of the o-aminobenzyl alcohol, heating to 90 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass of 13 times of that of the o-aminobenzyl alcohol and the mass fraction of 17% in a nitrogen atmosphere at the speed of 4ml/min, standing for 15 hours after the dropwise adding is finished, obtaining an upper-lower layered solution, rotationally steaming to remove the upper-layer solution, blending the upper-layer solution with silica gel powder with the mass of 25 times of that of the o-aminobenzyl alcohol, and separating the mixture by chromatography to obtain a triazine ring; triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.6, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of triazine ring and acetone with the mass fraction of 13% of triazine ring, heating to 27 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare hyperbranched epoxy resin;
(2) Adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with the mass of 6 times of that of the tetrapod-like nano zinc oxide, adding lauric acid with the mass of 0.02 time of that of the tetrapod-like nano zinc oxide, stirring at 600rpm for 12 hours at room temperature, centrifuging to take out a lower layer of mud, washing the mud with absolute ethyl alcohol again, centrifuging again, washing and centrifuging for 3 times repeatedly, drying the centrifugate in an oven at 80 ℃ for 1.5 hours, grinding and sieving with a 100-mesh sieve to obtain modified zinc oxide; adding 0.15 times of modified zinc oxide of hyperbranched epoxy resin into hyperbranched epoxy resin, stirring at 170rpm, dropwise adding 4% ammonia water of which the mass is 0.08 times of that of the hyperbranched epoxy resin at 1ml/min, stirring for reaction for 13 hours after dropwise adding, and filtering to obtain modified epoxy resin, namely component A;
(3) Heating matrix asphalt to 150 ℃, adding monochloro-s-triazine-beta-cyclodextrin with the mass of 0.09 times of that of the matrix asphalt, and stirring at 600rpm for 17min to prepare modified matrix asphalt; adding a curing agent diethylenetriamine with the mass of 0.1 time of that of the matrix asphalt, and continuously stirring for 10min to prepare a component B;
(4) The component A and the component B are mixed according to the mass ratio of 2:3.5, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 15min at 70kHz, transferring to a high-speed shearing instrument for shearing, shearing at 4000rpm for 60-80 min at 185 ℃ and regulating the rotating speed to 600rpm, and continuously stirring and shearing for 30min to obtain the anti-ultraviolet aging weather-resistant asphalt.
Example 3
The preparation method of the ultraviolet-aging-resistant weather-resistant asphalt comprises the following steps:
(1) Dispersing the o-aminobenzyl alcohol in acetone with the mass being 15 times that of the o-aminobenzyl alcohol, heating to 95 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass being 15 times that of the o-aminobenzyl alcohol and the mass fraction being 20% in a nitrogen atmosphere at the speed of 6ml/min, standing for 18 hours after the dropwise adding is finished, obtaining an upper-lower layered solution, rotationally steaming to remove the upper-layer solution, blending the upper-layer solution with silica gel powder with the mass being 30 times that of the o-aminobenzyl alcohol, and separating the mixture through chromatography to obtain a triazine ring; triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.8, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of triazine ring and acetone with the mass fraction of 15% of triazine ring, heating to 30 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare hyperbranched epoxy resin;
(2) Adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with the mass of 8 times of that of the tetrapod-like nano zinc oxide, adding lauric acid with the mass of 0.02 time of that of the tetrapod-like nano zinc oxide, stirring at 800rpm for 12 hours at room temperature, centrifuging to take out a lower layer of mud, washing the mud with absolute ethyl alcohol again, centrifuging again, washing and centrifuging for 3 times repeatedly, drying the centrifugate in an oven at 80 ℃ for 2 hours, grinding and sieving with a 100-mesh sieve to obtain modified zinc oxide; adding modified zinc oxide with the mass of 0.18 times of that of the hyperbranched epoxy resin into the hyperbranched epoxy resin, stirring at 180rpm, dropwise adding ammonia water with the mass of 0.1 time of that of the hyperbranched epoxy resin and the mass fraction of 5% at 2ml/min, stirring for reaction for 14 hours after the dropwise adding is finished, and filtering to obtain modified epoxy resin, namely a component A;
(3) Heating matrix asphalt to 160 ℃, adding monochloro-s-triazine-beta-cyclodextrin with the mass of 0.12 times of that of the matrix asphalt, and stirring at 800rpm for 20min to prepare modified matrix asphalt; adding phthalic anhydride serving as a curing agent with the mass 0.12 times of that of the matrix asphalt, and continuously stirring for 12min to obtain a component B;
(4) The component A and the component B are mixed according to the mass ratio of 2:4, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 20min at 80kHz, transferring to a high-speed shearing instrument for shearing, shearing for 80min at 5000rpm, adjusting the shearing temperature to z 1' 200 ℃ and the rotating speed to 800rpm, and continuously stirring and shearing for 30min to obtain the ultraviolet aging-resistant weather-resistant asphalt.
Comparative example 1
The recipe of comparative example 1 was the same as in example 2. The preparation method of the anti-ultraviolet aging weather-resistant asphalt is different from the preparation method of the example 2 only in that the treatment of the step (2) is not carried out, and the step (1) is modified as follows: dispersing the o-aminobenzyl alcohol in acetone with the mass of 13 times of that of the o-aminobenzyl alcohol, heating to 90 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass of 13 times of that of the o-aminobenzyl alcohol and the mass fraction of 17% in a nitrogen atmosphere at the speed of 4ml/min, standing for 15 hours after the dropwise adding is finished, obtaining an upper-lower layered solution, rotationally steaming to remove the upper-layer solution, blending the upper-layer solution with silica gel powder with the mass of 25 times of that of the o-aminobenzyl alcohol, and separating the mixture by chromatography to obtain a triazine ring; triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.6, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of triazine ring and acetone with the mass fraction of 13% of triazine ring, heating to 27 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare the hyperbranched epoxy resin, namely the component A. The remaining preparation steps were the same as in example 2.
Comparative example 2
The recipe for comparative example 2 was the same as that of example 2. The preparation method of the anti-ultraviolet aging weather-resistant asphalt is different from that of the example 2 only in that the treatment of the step (1) is not carried out, and the step (2) is modified as follows: (adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with the mass of 6 times of tetrapod-like nano zinc oxide, adding lauric acid with the mass of 0.02 times of tetrapod-like nano zinc oxide, stirring at 600rpm for 12h at room temperature, centrifuging to obtain a lower layer of paste, washing the paste with absolute ethyl alcohol again, centrifuging again, washing and centrifuging again for 3 times, drying the centrifuged product in an oven at 80 ℃ for 1.5h, grinding and sieving with a 100-mesh sieve to obtain modified zinc oxide, adding modified zinc oxide with the mass of 0.15 times of bisphenol A epoxy resin into bisphenol A epoxy resin, stirring at 170rpm, dripping ammonia with the mass of 0.08 times of 4% of bisphenol A epoxy resin at 1ml/min, stirring for 13h after the dripping is completed, and filtering to obtain modified epoxy resin, namely component A; the rest preparation steps are the same as in example 2.
Comparative example 3
The recipe for comparative example 3 was the same as in example 2. The preparation method of the anti-ultraviolet aging weather-resistant asphalt is different from that of the embodiment 2 only in the step (3), and the step (3) is modified as follows: adding the curing agent diethylenetriamine with the mass of 0.1 time of that of the matrix asphalt into the matrix asphalt, and continuously stirring for 10 minutes to obtain the component B. The remaining preparation steps were the same as in example 2.
Comparative example 4
The preparation method of the ultraviolet-aging-resistant weather-resistant asphalt comprises the following steps:
the bisphenol A epoxy resin and the matrix asphalt of the component B are mixed according to the mass ratio of 2:3.5, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 15min at 70kHz, transferring to a high-speed shearing instrument for shearing, shearing at 4000rpm for 60-80 min at 185 ℃ and regulating the rotating speed to 600rpm, and continuously stirring and shearing for 30min to obtain the anti-ultraviolet aging weather-resistant asphalt.
Effect example 1
The following Table 1 shows the results of the high temperature resistance, penetration and softening point analysis of the weathering asphalt of the UV-resistant aging using examples 1, 2, 3 and comparative examples 1, 2, 3, 4 of the present invention.
TABLE 1
| Softening point (. Degree. C.) | Penetration (dmm) at 25 DEG C | High temperature resistance | |
| Matrix asphalt | 80.0 | 74 | Deformation of |
| Example 1 | 92.3 | 46 | No variation |
| Example 2 | 93.0 | 48 | No variation |
| Example 3 | 92.7 | 49 | No variation |
| Comparative example 1 | 88.6 | 56 | Deformation of |
| Comparative example 2 | 85.5 | 69 | Deformation of |
| Comparative example 3 | 90.4 | 62 | No variation |
| Comparative example 4 | 81.6 | 71 | Deformation of |
As is evident from the comparison of the experimental data of the examples in Table 1 and the comparative examples, the ultraviolet aging resistant weather resistant asphalt prepared in examples 1 and 2 has higher softening point, lower penetration at 25 ℃ and no deformation at 80 ℃ under high-temperature environment for 24 hours, thus showing better viscosity and better high-temperature resistance;
from comparison of experimental data of examples 1, 2, 3 and comparative examples 1 and 2, it can be found that hyperbranched epoxy resin is used and modified zinc oxide is added in preparation of modified epoxy resin, and s-triazine on the modified epoxy resin adsorbs the modified zinc oxide, so that asphalt performance can be improved, softening point is improved, penetration at 25 ℃ is reduced, and asphalt has excellent high temperature resistance; from comparison of experimental data of examples 1, 2, 3 and comparative examples 3 and 4, it can be found that the addition of the monochlorotriazine-beta-cyclodextrin to the matrix asphalt allows the modified zinc oxide to pass through the hydrophobic cavity inside the monochlorotriazine-beta-cyclodextrin, fix the continuous phase in the dispersed phase, enhance the compatibility of the modified matrix asphalt with the modified epoxy resin, make the formed two-phase three-dimensional crosslinked network more stable, and enhance the viscosity of the asphalt.
Effect example 2
The following Table 2 shows the results of the ultraviolet aging resistance and the temperature rise rate analysis of the ultraviolet aging resistant weatherable asphalt of examples 1, 2, 3 and comparative examples 1, 2, 3, 4 according to the present invention.
TABLE 2
| Penetration ratio (%) | Softening point increment (. Degree. C.) | Rate of temperature rise (. Degree. C./h) | |
| Matrix asphalt | 55 | 17 | 64 |
| Example 1 | 61 | 6 | 46 |
| Example 2 | 60 | 7 | 41 |
| Example 3 | 59 | 6 | 44 |
| Comparative example 1 | 59 | 8 | 61 |
| Comparative example 2 | 60 | 9 | 62 |
| Comparative example 3 | 57 | 13 | 51 |
| Comparative example 4 | 56 | 15 | 63 |
As is evident from the comparison of the experimental data of the examples and the comparative examples in Table 2, the penetration of the anti-ultraviolet aging weatherproof asphalt prepared in examples 1 and 2 is higher, the increment of softening point and the heating rate are lower, and the anti-ultraviolet aging weatherproof asphalt has excellent anti-ultraviolet aging property and high temperature resistance;
from comparison of experimental data of example 1, example 2, example 3 and comparative examples 1 and 2, it can be found that hyperbranched epoxy resin is used and modified zinc oxide is added in preparation of modified epoxy resin, and the modified epoxy resin with s-triazine as a center is rapidly dispersed along four-needle-shaped nano zinc oxide at high temperature irradiation, so that the temperature rising rate is reduced, and asphalt has better high temperature resistance; from the experimental data of examples 1, 2, 3 and comparative examples 3 and 4, it can be found that the monochlorotriazine-beta-cyclodextrin is added into the matrix asphalt, and forms a covalent bond with the hydroxyl and sulfhydryl groups of the active groups in the matrix asphalt, so that the asphaltene clusters are broken, the generation of carbonyl and sulfonyl groups is reduced, the aging of the asphalt is delayed, the monochlorotriazine-beta-cyclodextrin can react with free radicals generated by the active groups in the autoxidation process of the asphalt, and the ultraviolet resistance is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (1)
1. A preparation method of anti-ultraviolet aging weather-resistant asphalt is characterized by comprising the following steps: the preparation method of the anti-ultraviolet aging weather-resistant asphalt comprises the following steps: preparing a component A, preparing a component B and preparing ultraviolet-aging-resistant weather-resistant asphalt;
the method comprises the following specific steps:
(1) Dispersing the o-aminobenzyl alcohol in acetone with the mass of 13 times of that of the o-aminobenzyl alcohol, heating to 90 ℃, stirring until the o-aminobenzyl alcohol is dissolved, dropwise adding the o-aminobenzyl alcohol into a formaldehyde aqueous solution with the mass of 13 times of that of the o-aminobenzyl alcohol and the mass fraction of 17% in a nitrogen atmosphere at the speed of 4ml/min, standing for 15 hours after the dropwise adding is finished, obtaining an upper-lower layered solution, rotationally steaming to remove the upper-layer solution, blending the upper-layer solution with silica gel powder with the mass of 25 times of that of the o-aminobenzyl alcohol, and separating the mixture by chromatography to obtain a triazine ring; triazine ring and phthalic anhydride are mixed according to the mass ratio of 1:3.6, mixing and placing the mixture into a three-mouth bottle, adding concentrated sulfuric acid with the mass fraction of 98% of triazine ring and acetone with the mass fraction of 13% of triazine ring, heating to 27 ℃ in a nitrogen atmosphere, reacting for 24 hours, adding glycidol with the mass of phthalic anhydride and the like, and continuously reacting for 24 hours to prepare hyperbranched epoxy resin;
(2) Adding tetrapod-like nano zinc oxide into absolute ethyl alcohol with the mass of 6 times of that of the tetrapod-like nano zinc oxide, adding lauric acid with the mass of 0.02 time of that of the tetrapod-like nano zinc oxide, stirring at 600rpm for 12 hours at room temperature, centrifuging to take out a lower layer of mud, washing the mud with absolute ethyl alcohol again, centrifuging again, washing and centrifuging for 3 times repeatedly, drying the centrifugate in an oven at 80 ℃ for 1.5 hours, grinding and sieving with a 100-mesh sieve to obtain modified zinc oxide; adding 0.15 times of modified zinc oxide of hyperbranched epoxy resin into hyperbranched epoxy resin, stirring at 170rpm, dropwise adding 4% ammonia water of which the mass is 0.08 times of that of the hyperbranched epoxy resin at 1ml/min, stirring for reaction for 13 hours after dropwise adding, and filtering to obtain modified epoxy resin, namely component A;
(3) Heating matrix asphalt to 150 ℃, adding monochloro-s-triazine-beta-cyclodextrin with the mass of 0.09 times of that of the matrix asphalt, and stirring at 600rpm for 17min to prepare modified matrix asphalt; adding a curing agent diethylenetriamine with the mass of 0.1 time of that of the matrix asphalt, and continuously stirring for 10min to prepare a component B;
(4) The component A and the component B are mixed according to the mass ratio of 2:3.5, uniformly mixing to obtain a mixture; and (3) carrying out ultrasonic treatment on the mixture for 15min at 70kHz, transferring to a high-speed shearing instrument for shearing, shearing at 4000rpm for 60-80 min at 185 ℃ and regulating the rotating speed to 600rpm, and continuously stirring and shearing for 30min to obtain the anti-ultraviolet aging weather-resistant asphalt.
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| CN105754074A (en) * | 2016-04-22 | 2016-07-13 | 长安大学 | Method for preparing high-temperature blending epoxy asphalt curing agent for paving |
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