CN113150569A - Wear-resistant SBS (styrene butadiene styrene) modified asphalt and preparation method thereof - Google Patents
Wear-resistant SBS (styrene butadiene styrene) modified asphalt and preparation method thereof Download PDFInfo
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- CN113150569A CN113150569A CN202110434700.1A CN202110434700A CN113150569A CN 113150569 A CN113150569 A CN 113150569A CN 202110434700 A CN202110434700 A CN 202110434700A CN 113150569 A CN113150569 A CN 113150569A
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- 239000010426 asphalt Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title description 143
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 title description 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002105 nanoparticle Substances 0.000 claims abstract description 65
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 26
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- QXOXHPTYHCESTD-UHFFFAOYSA-N SBS Chemical compound SBS QXOXHPTYHCESTD-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000047 product Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- HRPBJVKCKVPICO-UHFFFAOYSA-N OC1(CCCCC1)CC(CCCC)=O Chemical compound OC1(CCCCC1)CC(CCCC)=O HRPBJVKCKVPICO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 2
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
- C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
The invention discloses wear-resistant SBS modified asphalt and a preparation method thereof, wherein the wear-resistant SBS modified asphalt comprises the following components in parts by weight: 90-100 parts of asphalt, 2-6 parts of modified SBS and 7-13 parts of modified nano particles, wherein the modified SBS comprises the following components: SBS, chloroethylene, vinyl acetate, methanol, a photoinitiator, a catalyst and diisocyanate. According to the invention, through the blending reaction of the modified SBS blocked by the isocyanuric acid, the modified nano particles containing the epoxy group and the asphalt, the compatibility of the SBS in the asphalt is improved, the phenomenon of phase separation is prevented, the stability is improved, the SBS modified asphalt forms a three-dimensional network structure, the nano particles are coated, the limitation on molecular chains is enhanced, the internal stress is weakened, and the wear resistance and the mechanical property are improved.
Description
Technical Field
The invention relates to the technical field of asphalt, in particular to wear-resistant SBS modified asphalt and a preparation method thereof.
Background
The asphalt is black on the surface, mostly exists in a liquid state or a semi-solid state, is composed of hydrocarbons with different molecular weights and non-metallic derivatives thereof, has high viscosity, and is widely applied to the industrial fields of coatings, plastics, rubber and the like and pavement and the like. SBS is a styrene-butadiene-styrene block copolymer and is a thermoplastic elastomer with the highest worldwide production and the most similar properties to rubber. The SBS modified asphalt adopts methods of shearing, stirring and the like to uniformly disperse a certain amount of SBS in the raw material matrix asphalt to form an SBS blending material, and the good physical properties of SBS are utilized to modify the asphalt, so that the high and low temperature resistance of the asphalt can be improved, and the elastic toughness, the bearing capacity and the like of the asphalt are improved. The asphalt and SBS are mixed to form micro mixed compatible state, the styrene area in SBS is swelled by the hydrocarbon in asphalt, the chain segment of polybutadiene is swelled and stretched to be used as elastic bond, phase transfer occurs, and mixed phase is formed with asphalt. However, compared with asphalt, SBS has smaller density, larger molecular weight and larger viscosity, and is a non-polar substance, so that it is easy to gather on the top of asphalt after blending, and asphalt sinks on the bottom to generate phase separation phenomenon, and when applied to friction plane, it has some defects in wear resistance. Therefore, the wear-resistant SBS modified asphalt and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide wear-resistant SBS modified asphalt and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the wear-resistant SBS modified asphalt comprises the following components in parts by weight: 90-100 parts of asphalt, 2-6 parts of modified SBS and 7-13 parts of modified nano particles, wherein the modified SBS comprises the following components: SBS, chloroethylene, vinyl acetate, methanol, a photoinitiator, a catalyst and diisocyanate.
Further, the modified nano particle comprises the following components in parts by weight: nano silicon dioxide and gamma-glycidol ether oxygen propyl trimethoxy silane.
Further, the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is (3-7): (7-3).
Furthermore, the mass ratio of the SBS to the vinyl chloride to the catalyst is (1.0-2.8): (1.0-1.4): 0.08-0.14), and the mass ratio of the vinyl chloride to the vinyl acetate is (1.0-4.2): 1.0-1.8).
Further, the photoinitiator is one of 1-hydroxycyclohexyl hexanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, azobisisoheptonitrile and azobisisobutyronitrile, and the catalyst is one of anhydrous aluminum chloride, anhydrous ferric chloride and anhydrous tin chloride.
A preparation method of wear-resistant SBS modified asphalt comprises the following steps:
(1) preparing modified SBS:
taking vinyl chloride and vinyl acetate, adding a photoinitiator, and radiating by ultraviolet light to obtain a product A;
taking the product A, and carrying out alcoholysis to obtain a product B;
taking SBS and product B, adding catalyst, microwave reacting to obtain product C;
taking the product C, heating, adding diisocyanate, and reacting to obtain modified SBS;
(2) preparing modified nano particles:
adding gamma-glycidol ether oxypropyl trimethoxy silane into the nano particles, and reacting to prepare modified nano particles;
(3) preparing modified asphalt:
and (3) adding the modified SBS and the modified nano particles into the asphalt, heating and stirring to obtain the SBS modified asphalt.
Further, the method comprises the following steps:
(1) preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding a photoinitiator, and performing nitrogen atmosphere at a speed of 20-300 mu W/cm2The ultraviolet light with the light intensity is radiated for 20-60 min; crushing the reaction product, adding acetone to soak for 45-54 h, stirring to dissolve, adding deionized water, taking the precipitate, and drying at the temperature of 75-85 ℃ for 45-50 h to obtain a product A; under the radiation of ultraviolet light, the photoinitiator absorbs the radiation energy of the ultraviolet light to initiate chloroethylene and vinyl acetate to form free radicals and polymerize to form a chloroethylene-vinyl acetate copolymer, the molecular weight is higher, the sliding difficulty between molecular chains is increased, and the interaction between molecules is enhanced due to the existence of polar bonds, so that the improvement of mechanical properties is facilitated.
Adding methanol into the product A, heating to dissolve the product A, adjusting the temperature of the system to 35-45 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 20-40 min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing to stir for 60-90 min; washing the solid product, and drying at the temperature of 75-85 ℃ for 10-15 h to obtain a product B; vinyl chloride-vinyl acetate copolymer reacts with methanol under the alkaline action to prepare vinyl chloride-vinyl alcohol copolymer, the intermolecular hydrogen bond is increased, the intermolecular interaction is enhanced, and the strength is improved; the subsequent hydrogen bond interaction force with other materials is enhanced, the compatibility is good, and the reaction effect is better; the polarity is increased, the compatibility between the prepared modified SBS and the asphalt is enhanced, the dispersion degree of the modified SBS in the asphalt is improved, the stability of the prepared SBS modified asphalt is improved, and the phase separation phenomenon is prevented.
Respectively dissolving SBS and the product B in a solvent, dissolving a catalyst in absolute ethyl alcohol, blending the SBS and the product B, and carrying out microwave reaction for 40-90 min at the power of 200-800W to obtain a product C; the chloroethylene in the chloroethylene-vinyl alcohol copolymer reacts with the styrene in the SBS, so that the SBS is grafted with the chloroethylene-vinyl alcohol copolymer, the molecular weight and the density of the prepared modified SBS are improved, the prepared modified SBS is favorably dispersed in the asphalt, and the mechanical property and the stability of the SBS modified asphalt are improved. The SBS is a compound of star-shaped SBS and linear SBS, so that the modification effect of the modified SBS in the asphalt can be improved, and the processing performance of the modified SBS is improved.
Taking the product C, dehydrating in vacuum at the temperature of 90-120 ℃, preserving heat at the temperature of 80-100 ℃, adding diisocyanate, and fully stirring and dispersing to obtain modified SBS; the vinyl alcohol in the product C reacts with diisocyanate, wherein the diisocyanate is excessive, the isocyanate-terminated urethane-containing polymer is prepared, the polarity is improved, the compatibility of the prepared modified SBS in the asphalt is improved, the thermal storage stability is good, the segregation is avoided, and the mechanical property and the wear resistance of the SBS modified asphalt are improved.
(2) Preparing modified nano particles:
adding toluene into nanoparticles, performing ultrasonic dispersion, adding gamma-glycidyl ether oxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 70-110 ℃ for 4-8 h, performing centrifugal separation, and drying at normal temperature for 8-10 h to obtain modified nanoparticles; the modified nano particles containing epoxy groups are prepared by the blending reaction of the nano particles gamma-glycidyl ether oxypropyl trimethoxy silane, and a coating film with reaction activity is formed on the surface of the nano particles, so that the dispersion degree of the nano particles in asphalt can be improved, the bonding property between the nano particles and the asphalt is enhanced, and the epoxy groups are introduced to prepare for the blending reaction of modified SBS, the modified nano particles and the asphalt.
(3) Preparing modified asphalt:
heating the asphalt to 180-190 ℃, stirring, adding the modified SBS and the modified nano particles, stirring and shearing for 2-4 h to obtain the SBS modified asphalt. The isocyanate group and the asphaltene in the modified SBS react with the epoxy group in the modified nano particles to prepare a blending system with a three-dimensional network structure, the nano particles are wrapped, the limitation on molecular chains is enhanced, the internal stress is weakened, the wear resistance and the mechanical property are improved, and the water resistance, the oil resistance, the high-temperature stability, the low-temperature crack resistance and the ageing resistance of the prepared SBS modified asphalt are improved.
Further, the concentration of the photoinitiator in the reaction system in the step (1) is 1 x 10 < -5 > to 5 x 10 < -3 > mol/L.
Furthermore, the mass ratio of the vinyl acetate, the methanol and the sodium hydroxide in the step (1) is (1-2): (2.0-2.3): 0.01-0.02).
Further, the concentration of the nano particles in the reaction system in the step (2) is 3-5%, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 0.1-1%.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the wear-resistant SBS modified asphalt and the preparation method thereof, the compatibility of SBS in asphalt is improved, the phenomenon of phase separation is prevented, the stability is improved, the SBS modified asphalt forms a three-dimensional network structure, the nano particles are coated, the limitation on molecular chains is enhanced, the internal stress is weakened, and the wear resistance and the mechanical property are improved through the blending reaction of the modified SBS blocked by the isocyanuric acid, the modified nano particles containing the epoxy group and the asphalt.
2. The wear-resistant SBS modified asphalt and the preparation method thereof have the advantages that the chloroethylene-vinyl alcohol copolymer is mixed with the SBS, chloropropene in the mixture is grafted with styrene under the action of microwaves, the molecular weight and the density of the modified SBS are improved, the prepared modified SBS is favorably dispersed in the asphalt, the storage stability of the SBS in the asphalt is improved, and the mechanical property of the SBS modified asphalt is improved.
3. According to the wear-resistant SBS modified asphalt and the preparation method thereof, the polarity of the modified SBS is improved through alcoholysis of the chloroethylene-vinyl acetate copolymer, the full compatibility of the SBS and the asphalt is facilitated, the stability of the SBS modified asphalt is improved, the segregation phenomenon is avoided, hydrogen bonds among molecules are increased, the interaction among the molecules is enhanced, and the mechanics of the SBS modified asphalt is improved.
4. The wear-resistant SBS modified asphalt and the preparation method thereof provided by the invention have the advantages that polymerization of vinyl chloride and vinyl acetate is initiated by the photoinitiator to prepare the vinyl chloride-vinyl acetate copolymer, the molecular weight is higher, the molecular weight and the density of the prepared modified SBS are improved, and a foundation is provided for compatibility of the modified SBS in the asphalt; the sliding difficulty among molecular chains is increased, and the existence of polar bonds enhances the interaction among molecules, thereby being beneficial to improving the mechanical property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding photoinitiator 1-hydroxy cyclohexyl hexanone, and stirring at 150 μ W/cm in nitrogen atmosphere2The light intensity of the ultraviolet ray is radiated for 40 min; crushing the reaction product, adding acetone to soak for 48h, stirring to dissolve, adding deionized water, taking the precipitate, and drying at the temperature of 80 ℃ for 48h to obtain a product A; wherein the mass ratio of the chloroethylene to the vinyl acetate is 4.2:1.0, and the concentration of the photoinitiator in the reaction system is 3 multiplied by 10-3mol/L；
Taking the product A, adding methanol, heating to dissolve, adjusting the temperature of the system to 40 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 30min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing to stir for 75 min; washing the solid product, and drying at 80 ℃ for 12h to obtain a product B;
respectively dissolving SBS and the product B in a solvent, dissolving catalyst anhydrous aluminum chloride in absolute ethyl alcohol, blending the three, and carrying out microwave reaction for 60min at the power of 500W to obtain a product C;
wherein the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is 7: 3; the mass ratio of styrene in SBS to chloroethylene in product B and catalyst is 2.8:1.0: 0.1;
taking the product C, dehydrating in vacuum at 105 ℃, preserving heat at 90 ℃, adding diisocyanate, and fully stirring and dispersing to prepare modified SBS;
(2) preparing modified nano particles:
adding toluene into the nanoparticles, performing ultrasonic dispersion, adding gamma-glycidoxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 90 ℃ for 6 hours, performing centrifugal separation, and drying at normal temperature for 9 hours to obtain modified nanoparticles; wherein the concentration of the nano particles is 4 percent, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 0.5 percent;
(3) preparing modified asphalt:
heating asphalt to 185 ℃, stirring, adding the modified SBS and the modified nano particles, stirring and shearing for 3 hours to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 95 parts of asphalt, 4 parts of modified SBS and 10 parts of modified nano particles.
Example 2
(1) Preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl]-1-propanone, under nitrogen atmosphere, at 20 μ W/cm2The ultraviolet light with the light intensity is radiated for 60 min; pulverizing the reaction product, adding acetone, soaking for 45 hr, stirring for dissolving, adding deionized water, collecting precipitate, and drying at 75 deg.CDrying for 45 hours to obtain a product A; wherein the mass ratio of the chloroethylene to the vinyl acetate is 1.0:1.8), and the concentration of the photoinitiator in the reaction system is 1 x 10-5mol/L；
Taking the product A, adding methanol, heating to dissolve, adjusting the temperature of the system to 35 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 20min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing stirring for 60 min; washing the solid product, and drying at 75 ℃ for 10h to obtain a product B;
respectively dissolving SBS and the product B in a solvent, dissolving catalyst anhydrous ferric chloride in absolute ethyl alcohol, blending the three, and carrying out microwave reaction for 40min at the power of 800W to obtain a product C;
wherein the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is 5: 5; the mass ratio of styrene in SBS to chloroethylene in product B and catalyst is 1.0:1.0: 0.08;
taking the product C, dehydrating in vacuum at the temperature of 90 ℃, preserving heat at the temperature of 80 ℃, adding diisocyanate, and fully stirring and dispersing to prepare modified SBS;
(2) preparing modified nano particles:
adding toluene into the nanoparticles, performing ultrasonic dispersion, adding gamma-glycidoxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 70 ℃ for 4 hours, performing centrifugal separation, and drying at normal temperature for 8 hours to obtain modified nanoparticles; wherein the concentration of the nano particles is 3 percent, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 0.1 percent;
(3) preparing modified asphalt:
heating asphalt to 180 ℃, stirring, adding the modified SBS and the modified nano particles, stirring and shearing for 2 hours to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 100 parts of asphalt, 6 parts of modified SBS and 7 parts of modified nano particles.
Example 3
(1) Preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding photoinitiator azobisisoheptonitrile, and stirring at 300 μ W/cm in nitrogen atmosphere2The ultraviolet light with the light intensity is radiated for 20 min; pulverizing the reaction productCrushing, adding acetone to soak for 54h, stirring for dissolving, adding deionized water, taking precipitate, and drying at 85 ℃ for 50h to obtain a product A; wherein the mass ratio of the chloroethylene to the vinyl acetate is 2.6:1.4, and the concentration of the photoinitiator in the reaction system is 5 multiplied by 10-3mol/L；
Taking the product A, adding methanol, heating to dissolve, adjusting the temperature of the system to 45 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 40min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing stirring for 90 min; washing the solid product, and drying at 85 ℃ for 15h to obtain a product B;
respectively dissolving SBS and the product B in a solvent, dissolving catalyst anhydrous stannic chloride in absolute ethyl alcohol, blending the three, and carrying out microwave reaction for 90min at the power of 200W to obtain a product C;
wherein the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is 3: 7; the mass ratio of styrene in SBS to chloroethylene in product B and catalyst is 2.8:1.4: 0.14;
taking the product C, dehydrating in vacuum at the temperature of 120 ℃, preserving heat at the temperature of 100 ℃, adding diisocyanate, and fully stirring and dispersing to prepare modified SBS;
(2) preparing modified nano particles:
adding toluene into the nanoparticles, performing ultrasonic dispersion, adding gamma-glycidoxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 110 ℃ for 8 hours, performing centrifugal separation, and drying at normal temperature for 10 hours to obtain modified nanoparticles; wherein the concentration of the nano particles is 5 percent, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 1 percent;
(3) preparing modified asphalt:
heating asphalt to 190 ℃, stirring, adding the modified SBS and the modified nano particles, stirring and shearing for 4 hours to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 100 parts of asphalt, 2 parts of modified SBS and 7 parts of modified nano particles.
Comparative example 1
(1) Preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding photoinitiator 1-hydroxycyclohexanePhenylhexanone, in a nitrogen atmosphere at 150. mu.W/cm2The light intensity of the ultraviolet ray is radiated for 40 min; crushing the reaction product, adding acetone to soak for 48h, stirring to dissolve, adding deionized water, taking the precipitate, and drying at the temperature of 80 ℃ for 48h to obtain a product A; wherein the mass ratio of the chloroethylene to the vinyl acetate is 4.2:1.0, and the concentration of the photoinitiator in the reaction system is 3 multiplied by 10-3mol/L；
Taking the product A, adding methanol, heating to dissolve, adjusting the temperature of the system to 40 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 30min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing to stir for 75 min; washing the solid product, and drying at 80 ℃ for 12h to obtain a product B;
respectively dissolving SBS and the product B in a solvent, dissolving catalyst anhydrous aluminum chloride in absolute ethyl alcohol, blending the three, and carrying out microwave reaction for 60min at the power of 500W to obtain a product C;
wherein the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is 7: 3; the mass ratio of styrene in SBS to chloroethylene in product B and catalyst is 2.8:1.0: 0.1;
taking the product C, dehydrating in vacuum at 105 ℃, preserving heat at 90 ℃, adding diisocyanate, and fully stirring and dispersing to prepare modified SBS;
(2) preparing modified asphalt:
heating asphalt to 185 ℃, stirring, adding the modified SBS and the nano particles, stirring and shearing for 3 hours to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 95 parts of asphalt, 4 parts of modified SBS and 10 parts of nano particles.
Comparative example 2
(1) Preparing modified nano particles:
adding toluene into the nanoparticles, performing ultrasonic dispersion, adding gamma-glycidoxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 90 ℃ for 6 hours, performing centrifugal separation, and drying at normal temperature for 9 hours to obtain modified nanoparticles; wherein the concentration of the nano particles is 4 percent, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 0.5 percent;
(2) preparing modified asphalt:
heating asphalt to 185 ℃, stirring, adding SBS and modified nano particles, stirring and shearing for 3h to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 95 parts of asphalt, 4 parts of SBS and 10 parts of modified nano particles.
Comparative example 3
Heating asphalt to 185 ℃, stirring, adding SBS and nano particles, stirring and shearing for 3 hours to prepare SBS modified asphalt; wherein the SBS modified asphalt comprises the following components in parts by weight: 95 parts of asphalt, 4 parts of SBS and 10 parts of nano particles.
The nanoparticles in examples 1-3 and comparative examples 1-3 are all nano-silica.
Experiment of
Taking the SBS modified asphalt obtained in the examples 1-3 and the comparative examples 1-3 to prepare samples, respectively detecting the wear resistance, the stability and the mechanical property of the samples and recording the detection results:
1. and (3) testing the high-temperature stability: testing the softening point of the sample by using a ring-and-ball method by taking GB/T0606-2000 as an experimental standard;
the experimental steps are as follows: the sample was poured into a 19mm inner diameter ring, a steel ball weighing 3.5g was placed on the ring, the sample was gradually softened by heating at a rate of 5 ℃/min using water as a medium, and the temperature at which the asphalt settled down to a predetermined distance (25.4mm) under the load of the steel ball was taken as the softening point.
2. And (3) testing mechanical properties:
ductility: testing the ductility of a sample at the temperature of 5 ℃ by taking GB/T0605-1993 as an experimental standard; (resistance to deformation)
Elastic recovery: the percentage of recoverable deformation of the specimen was measured by pulling the specimen to 10cm at 25 ℃ at a pull rate of 5 ℃/min, cutting the specimen from the middle, and maintaining the water temperature for 1h, using GB/T0661-1998 as the experimental standard.
3. Isolation experiment: the samples were placed in an oven at 163 ℃ for 48h by taking GB/T0661-2000 as an experimental standard, and the difference between the softening points of the samples was measured by a ring and ball method by taking the samples at the upper and lower 1/3 ends.
4. And (3) wear resistance test: the mass loss of the test sample is determined by using an Akron abrasion-resistant tester by taking GB 1689-1998 as an experimental standard.
From the data in the table above, it is clear that the following conclusions can be drawn:
the SBS modified asphalt obtained in the examples 1-3 is compared with the SBS modified asphalt obtained in the comparative examples 1-3, and the detection result shows that:
1. compared with the SBS modified asphalt obtained in the comparative example 3, the SBS modified asphalt obtained in the examples 1-3 has the advantages that the softening point, the ductility and the elastic recovery data are obviously improved, the segregation temperature difference and the quality loss data are obviously reduced, and the high-temperature stability, the low-temperature performance, the crack resistance, the storage stability and the wear resistance of the SBS modified asphalt in the examples 1-3 are obviously improved, so that the improvement of the stability, the wear resistance and the high-low temperature performance of the SBS modified asphalt is fully realized;
2. compared with the SBS modified asphalt obtained in the example 1, the SBS modified asphalt obtained in the comparative examples 1-3 has the advantages that the nano particles in the comparative example 1 are not modified, the SBS in the comparative example 2 is not modified, the softening point, the ductility, the elastic recovery, the segregation temperature difference and the mass loss data are obviously changed, and the change trend is deterioration.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The wear-resistant SBS modified asphalt is characterized by comprising the following components in parts by weight: 90-100 parts of asphalt, 2-6 parts of modified SBS and 7-13 parts of modified nano particles, wherein the modified SBS comprises the following components: SBS, chloroethylene, vinyl acetate, methanol, a photoinitiator, a catalyst and diisocyanate.
2. The wear-resistant SBS modified asphalt of claim 1, wherein: the modified nanoparticles comprise the following components in parts by weight: nano silicon dioxide and gamma-glycidol ether oxygen propyl trimethoxy silane.
3. The wear-resistant SBS modified asphalt of claim 1, wherein: the SBS comprises a star-shaped SBS and a linear SBS, and the mass ratio of the star-shaped SBS to the linear SBS is (3-7): (7-3).
4. The wear-resistant SBS modified asphalt of claim 1, wherein: the mass ratio of the SBS to the chloroethylene to the catalyst is (1.0-2.8): (1.0-1.4): 0.08-0.14), and the mass ratio of the chloroethylene to the vinyl acetate is (1.0-4.2): 1.0-1.8).
5. The wear-resistant SBS modified asphalt of claim 1, wherein: the photoinitiator is one of 1-hydroxycyclohexyl hexanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, azobisisoheptonitrile and azobisisobutyronitrile, and the catalyst is one of anhydrous aluminum chloride, anhydrous ferric chloride and anhydrous tin chloride.
6. A preparation method of wear-resistant SBS modified asphalt is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing modified SBS:
taking vinyl chloride and vinyl acetate, adding a photoinitiator, and radiating by ultraviolet light to obtain a product A;
taking the product A, and carrying out alcoholysis to obtain a product B;
taking SBS and product B, adding catalyst, microwave reacting to obtain product C;
taking the product C, heating, adding diisocyanate, and reacting to obtain modified SBS;
(2) preparing modified nano particles:
adding gamma-glycidol ether oxypropyl trimethoxy silane into the nano particles, and reacting to prepare modified nano particles;
(3) preparing modified asphalt:
and (3) adding the modified SBS and the modified nano particles into the asphalt, heating and stirring to obtain the SBS modified asphalt.
7. The method for preparing wear-resistant SBS modified asphalt according to claim 6, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparing modified SBS:
mixing vinyl chloride and vinyl acetate, adding a photoinitiator, and performing nitrogen atmosphere at a speed of 20-300 mu W/cm2The ultraviolet light with the light intensity is radiated for 20-60 min; crushing the reaction product, adding acetone to soak for 45-54 h, stirring to dissolve, adding deionized water, taking the precipitate, and drying at the temperature of 75-85 ℃ for 45-50 h to obtain a product A;
adding methanol into the product A, heating to dissolve the product A, adjusting the temperature of the system to 35-45 ℃, adding a sodium hydroxide solution and methanol, stirring to react for 20-40 min, adding the sodium hydroxide solution and the methanol, increasing the stirring speed, and continuing to stir for 60-90 min; washing the solid product, and drying at the temperature of 75-85 ℃ for 10-15 h to obtain a product B;
respectively dissolving SBS and the product B in a solvent, dissolving a catalyst in absolute ethyl alcohol, blending the SBS and the product B, and carrying out microwave reaction for 40-90 min at the power of 200-800W to obtain a product C;
taking the product C, dehydrating in vacuum at the temperature of 90-120 ℃, preserving heat at the temperature of 80-100 ℃, adding diisocyanate, and fully stirring and dispersing to obtain modified SBS;
(2) preparing modified nano particles:
adding toluene into nanoparticles, performing ultrasonic dispersion, adding gamma-glycidyl ether oxypropyltrimethoxysilane, performing ultrasonic dispersion, stirring and reacting at 70-110 ℃ for 4-8 h, performing centrifugal separation, and drying at normal temperature for 8-10 h to obtain modified nanoparticles;
(3) preparing modified asphalt:
heating the asphalt to 180-190 ℃, stirring, adding the modified SBS and the modified nano particles, stirring and shearing for 2-4 h to obtain the SBS modified asphalt.
8. The method for preparing wear-resistant SBS modified asphalt according to claim 7, wherein the method comprises the following steps: the concentration of the photoinitiator in the reaction system in the step (1) is 1 x 10-5～5×10-3mol/L。
9. The method for preparing wear-resistant SBS modified asphalt according to claim 7, wherein the method comprises the following steps: in the step (1), the mass ratio of vinyl acetate, methanol and sodium hydroxide is (1-2): (2.0-2.3): 0.01-0.02).
10. The method for preparing wear-resistant SBS modified asphalt according to claim 7, wherein the method comprises the following steps: the concentration of the nano particles in the reaction system in the step (2) is 3-5%, and the concentration of the gamma-glycidoxypropyltrimethoxysilane is 0.1-1%.
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