CN116925558B - SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof - Google Patents
SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof Download PDFInfo
- Publication number
- CN116925558B CN116925558B CN202311187141.4A CN202311187141A CN116925558B CN 116925558 B CN116925558 B CN 116925558B CN 202311187141 A CN202311187141 A CN 202311187141A CN 116925558 B CN116925558 B CN 116925558B
- Authority
- CN
- China
- Prior art keywords
- sbs
- parts
- asphalt
- silver
- polyphosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010426 asphalt Substances 0.000 title claims abstract description 145
- 229920000137 polyphosphoric acid Polymers 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229960000892 attapulgite Drugs 0.000 claims abstract description 60
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 claims abstract description 43
- 239000004332 silver Substances 0.000 claims abstract description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- -1 silver ions Chemical class 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000001629 suppression Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 38
- 239000003517 fume Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- 239000007787 solid Substances 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000011068 loading method Methods 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
- 229920001601 polyetherimide Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012855 volatile organic compound 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- 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)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of polymer modified asphalt, in particular to SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and a preparation method thereof. The SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt comprises the following raw materials in parts by weight: 90-110 parts of matrix asphalt, 8-12 parts of modified SBS, 4-6 parts of polyphosphoric acid and 2-4 parts of silver-loaded attapulgite, wherein the silver-loaded attapulgite is loaded with silver ions and nano titanium dioxide. The SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt has excellent high-temperature resistance and asphalt smoke suppression effect.
Description
Technical Field
The application relates to the technical field of polymer modified asphalt, in particular to SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and a preparation method thereof.
Background
The polymer modified asphalt is a novel high-quality road construction material with higher technical content and added value, improves the service performance by doping the polymer into the road asphalt, can obviously prolong the service life of the road, reduce noise and improve the driving comfort and safety.
The SBS modified asphalt has excellent high-temperature rutting resistance, low-temperature cracking resistance, fatigue resistance and excellent elastic recovery capability, is mainly applied to high-grade pavements such as upper layers of highways, road sections with heavy traffic and more overload vehicles, and the like, and becomes a main stream product in the modified asphalt based on the excellent road performance. However, the addition amount of SBS is too large, the cost is too high, and the high-temperature rutting resistance of SBS modified asphalt still needs to be improved.
Disclosure of Invention
The application provides SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and a preparation method thereof, in order to improve the high-temperature rutting resistance of SBS modified asphalt.
In a first aspect, the application provides SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt, which adopts the following technical scheme:
the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt comprises the following raw materials in parts by weight: 90-110 parts of matrix asphalt, 8-12 parts of modified SBS, 4-6 parts of polyphosphoric acid and 2-4 parts of silver-loaded attapulgite, wherein the silver-loaded attapulgite is loaded with silver ions and nano titanium dioxide.
The SBS and the matrix asphalt are modified into physical blending, and no obvious chemical reaction occurs, so that the SBS modified asphalt has the defects of insufficient stability and poor dispersibility. The polyphosphoric acid belongs to an acidic chemical modifier, and can generate salt with active groups in asphalt or generate esterification reaction, so that asphalt components are promoted to be converted in form, quantity and dispersion state, an internal network structure is constructed, the elastic behavior of asphalt is improved, SBS is replaced partially, and more excellent high-temperature rutting resistance and stability are realized.
In addition, the silver-carrying attapulgite is added into the asphalt matrix, so that the high-temperature rutting resistance and stability of asphalt can be effectively improved, and the silver-carrying attapulgite can form a network structure in the asphalt to play a role in supporting a framework.
In addition, asphalt is easy to volatilize to generate asphalt smoke which mainly consists of sulfur dioxide and volatile organic compounds in the asphalt mixing and paving process and in a high-temperature environment, and the asphalt smoke has great harm to human bodies. The silver-loaded attapulgite has extremely large specific surface area and extremely strong adsorption capacity, so that the silver-loaded attapulgite can effectively adsorb asphalt smoke.
Silver ions and nano titanium dioxide are loaded on the silver-loaded attapulgite, and the silver ions have a removal effect on benzene series substances which are main components of volatile organic gases. The nano titanium dioxide can excite electrons in the valence band to cross into the forbidden band and form holes in the valence band after being irradiated, and the holes have obvious electron obtaining capability and can react with oxygen element to generate OH - Thereby effectively eliminating sulfur dioxide.
Preferably, the silver-loaded attapulgite comprises the following raw materials in parts by weight: 8-12 parts of attapulgite, 2-4 parts of nano titanium dioxide, 4-8 parts of ammonia water and 3-6 parts of silver nitrate.
Preferably, the preparation method of the silver-loaded attapulgite comprises the following steps: dispersing attapulgite in deionized water, centrifuging to remove impurities, adding the attapulgite and nano titanium dioxide into ammonia water, mixing and stirring uniformly, adding silver nitrate, heating to 60-80 ℃ and continuously stirring for 1-2h to obtain the silver-loaded attapulgite.
Preferably, the modified SBS comprises the following raw materials in parts by weight: 10-20 parts of SBS, 6-10 parts of polyetherimide-benzophenone solution and 2-4 parts of copper nitrate aqueous solution.
The asphalt flue gas also contains solid particles, and the modified SBS is formed by mixing and reacting SBS, polyetherimide-diphenyl ketone solution and copper nitrate aqueous solution, so that the modified SBS is the SBS grafted with primary amine, at the moment, the modified SBS contains negative electricity, and the negative electrode is easy to adsorb the solid particles with positive electricity, so that the solid particles with small particle size are aggregated into large particles, and the large particles are settled under the action of gravity, thereby realizing the effect of eliminating the solid particles in the asphalt flue gas.
Preferably, the preparation method of the modified SBS comprises the following steps:
s1, crushing, cutting and soaking SBS in absolute ethyl alcohol, removing impurities on the surface of the SBS by adopting an ultrasonic cleaning method, and drying to obtain the pre-processed SBS;
s2, fully mixing the pre-processed SBS, the polyetherimide-diphenyl ketone solution and the copper nitrate aqueous solution, transferring the mixture into a sealed bag, removing oxygen in the sealed bag by using nitrogen, and finally discharging bubbles in the bag and sealing a bag opening;
s3, standing and ultraviolet irradiation treatment is carried out on the sealed bag, each side is irradiated for 5-15min, and finally deionized water and absolute ethyl alcohol are used for cleaning in sequence, so that the modified SBS is obtained.
Preferably, the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt further comprises 10-16 parts of silane coupling agent and 1-3 parts of active carbon, wherein the silane coupling agent contains polyethoxy.
All molecules have mutual attraction, and the porous structure of the activated carbon provides a large amount of surface area, so that strong attraction is generated, and the adsorption effect on asphalt smoke is achieved. In addition, the surface of the activated carbon also contains a small amount of oxide or complex, and the oxide or complex can chemically react with organic substances in the asphalt fume, so that the adsorption effect on the asphalt fume is further improved.
However, the dispersibility of the activated carbon is relatively poor, and the silane coupling agent can play a bridging role at the interface of the inorganic material and the organic material, thereby connecting the two different materials. The silane coupling agent disclosed by the application contains a plurality of ethoxy groups, so that the silane coupling agent also has more silicon-oxygen bond sites, and further, the polyethoxy silane coupling agent can act on silver-loaded attapulgite, activated carbon and nano titanium dioxide at the same time, so that the cross-linked network structure of asphalt is more stable and perfect, and the asphalt has more excellent high-temperature rutting resistance and stability.
Preferably, the silane coupling agent is one of vinyl triethoxysilane, 3-aminopropyl triethoxysilane and dimethyl diethoxysilane.
Preferably, the silane coupling agent is 3-aminopropyl triethoxysilane.
Compared with dimethyl diethoxy silane, vinyl triethoxy silane and 3-amino propyl triethoxy silane have more ethoxy groups, so that the silane coupling agent has more silicon-oxygen bond sites, and the connection of silver-carrying attapulgite, activated carbon and nano titanium dioxide is more stable.
In addition, the 3-aminopropyl triethoxy silane also contains amino groups, and the amino groups can react with organic materials containing active hydroxyl groups to form hydrogen bonds or covalent bonds, so that the compatibility and the adhesiveness of the components of the asphalt are further improved.
In a second aspect, the application provides a preparation method of SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt, which adopts the following technical scheme:
a preparation method of SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt comprises the following steps:
heating matrix asphalt to 160-170 ℃, then adding modified SBS, mixing and stirring for 20-40min, then raising the temperature to 165-175 ℃, and shearing for 60-80min to obtain SBS modified asphalt;
adding polyphosphoric acid, a silane coupling agent, active carbon and silver-loaded attapulgite into the SBS modified asphalt, heating to 170-190 ℃ and shearing for 80-100min, and finally developing for 30-40min at 170-180 ℃ to obtain the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt.
In summary, the application has the following beneficial effects:
1. polyphosphoric acid belongs to an acidic chemical modifier, and can generate salt with active groups in asphalt or generate esterification reaction, so that asphalt components are converted in form, quantity and dispersion state, an internal network structure is constructed, the elastic behavior of asphalt is improved, and SBS is replaced partially.
2. The silver-carrying attapulgite can also effectively improve the high-temperature rutting resistance and stability of asphalt by adding the silver-carrying attapulgite into the asphalt matrix, and the silver-carrying attapulgite has a network structure inside the asphalt to play a role in supporting a framework.
3. Silver ions and nano titanium dioxide are loaded on the silver-loaded attapulgite, and the silver ions have a removal effect on benzene series substances which are main components of volatile organic gases. The nano titanium dioxide can excite electrons in the valence band to enter the conduction band after being irradiated, and simultaneously form holes on the valence band, and the holes have obvious electron obtaining capability and can react with oxygen elements to generate OH-, so that sulfur dioxide is effectively eliminated.
4. The asphalt flue gas also contains solid particles, and the modified SBS is formed by mixing and reacting SBS, polyetherimide-diphenyl ketone solution and copper nitrate aqueous solution, so that the modified SBS is the SBS grafted with primary amine, at the moment, the modified SBS contains negative electricity, and the negative electrode is easy to adsorb the solid particles with positive electricity, so that the solid particles with small particle size are aggregated into large particles, and the large particles are settled under the action of gravity, thereby realizing the effect of eliminating the solid particles in the asphalt flue gas.
Detailed Description
The present application will be described in further detail with reference to examples 1 to 13 and comparative examples 1 to 6.
Raw materials: matrix asphalt SK-90 # The method comprises the steps of carrying out a first treatment on the surface of the Polyphosphoric acid CAS:8017-16-1; 200 meshes of attapulgite; nano titanium dioxide 1000 mesh; aqueous ammonia CAS:1336-21-6; silver nitrate CAS:7761-88-8; petrochemical YH-1401 in SBS; polyetherimide CAS:61128-46-9; benzophenone CAS:119-61-9; copper nitrate CAS:10402-29-6; ethanol CAS:64-17-5; 1000 meshes of active carbon; vinyl triethoxysilane CAS:78-08-0; 3-aminopropyl triethoxysilane CAS:919-30-2; dimethyl diethoxysilane CAS:2031-62-1; polyetherimide-benzophenone solution polyetherimide comprises 40wt% of the total mass of the solution; the copper nitrate aqueous solution contains copper nitrate 10wt% of the total mass of the solution.
Example 1
The SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt is prepared by mixing the following raw materials in mass: 100kg of matrix asphalt, 10kg of modified SBS, 5kg of polyphosphoric acid and 3kg of silver-loaded attapulgite;
the preparation method of the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt comprises the following steps:
heating matrix asphalt to 165 ℃, then adding modified SBS, mixing and stirring for 30min, then raising the temperature to 170 ℃, and shearing for 70min to obtain SBS modified asphalt;
and secondly, adding polyphosphoric acid and silver-loaded attapulgite into the SBS modified asphalt, heating to 180 ℃, shearing for 90min, and finally developing for 35min at the temperature of 175 ℃ to obtain the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt.
The modified SBS is prepared from the following raw materials in mass: 15kg SBS, 8kg 40wt% polyetherimide-benzophenone solution and 3kg 10wt% copper nitrate aqueous solution;
the preparation method of the modified SBS comprises the following steps:
s1, crushing, cutting and soaking SBS in absolute ethyl alcohol, removing impurities on the surface of the SBS by adopting an ultrasonic cleaning method, and drying to obtain the pre-processed SBS;
s2, fully mixing the pre-processed SBS, the polyetherimide-diphenyl ketone solution and the copper nitrate aqueous solution, transferring the mixture into a sealed bag, removing oxygen in the sealed bag by using nitrogen, and finally discharging bubbles in the bag and sealing a bag opening;
s3, adopting ultraviolet radiation crosslinking line UV-6000 to carry out static ultraviolet radiation treatment on the sealing bag, irradiating each surface for 10min, and finally cleaning with deionized water and absolute ethyl alcohol in sequence to obtain the modified SBS.
The silver-carrying attapulgite is prepared from the following raw materials in mass: 10kg of attapulgite, 3kg of nano titanium dioxide, 6kg of ammonia water and 4.5kg of silver nitrate;
the preparation method of the silver-loaded attapulgite comprises the following steps: dispersing attapulgite in deionized water, centrifuging to remove impurities, adding the attapulgite and nano titanium dioxide into ammonia water, mixing and stirring uniformly, adding silver nitrate, heating to 70 ℃ and continuously stirring for 1.5 hours to obtain the silver-loaded attapulgite.
Examples 2 to 3
The difference from example 1 is that the addition amounts of the components of the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt are different, as shown in Table 1.
Table 1 the additive amount/kg of each component of SBS polyphosphoric acid composite high-viscosity high-elastic modified asphalt in examples 1-3
Examples 4 to 5
The difference from example 1 is that the amounts of each component of the modified SBS added are different, as shown in Table 2.
TABLE 2 additive levels of the respective components of modified SBS in example 1, examples 4 to 5/kg
Examples 6 to 7
The difference from example 1 is that the addition amounts of the components of the silver-loaded attapulgite clay are different, as shown in table 3.
TABLE 3 addition amount of each component of silver-loaded attapulgite in example 1, examples 6 to 7/kg
Example 8
The difference from example 1 is that in the second step, 2kg of activated carbon was added while adding polyphosphoric acid and silver-loaded attapulgite to the SBS modified asphalt.
Example 9
The difference from example 8 is that in the second step, 13kg of vinyltriethoxysilane was added to SBS modified asphalt while polyphosphoric acid, activated carbon, and silver-loaded attapulgite were added.
Example 10
The difference from example 9 is that vinyltriethoxysilane is replaced by 3-aminopropyl triethoxysilane in the same addition.
Example 11
The difference from example 9 is that vinyltriethoxysilane is replaced by dimethyldiethoxysilane in the same addition.
Examples 12 to 13
The difference from example 10 is that the amounts of activated carbon and 3-aminopropyl triethoxysilane added are different, as shown in Table 4.
Table 4 the amounts of activated carbon and 3-aminopropyl triethoxysilane added per kg in examples 9, 12-13
Comparative example 1
The difference from example 1 is that the SBS polyphosphoric acid and silver-loaded attapulgite are not added in the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt, and the modified SBS is replaced by SBS with the same addition amount.
Comparative example 2
The difference from example 1 is that polyphosphoric acid and silver-loaded attapulgite are not added to the SBS polyphosphoric acid composite high-viscosity high-elastic modified asphalt.
Comparative example 3
The difference from example 1 is that the silver-loaded attapulgite is not added to the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt, and the modified SBS is replaced with SBS with the same addition amount.
Comparative example 4
The difference from example 1 is that the modified SBS was replaced with SBS of the same addition and the silver-loaded attapulgite was replaced with attapulgite of the same addition.
Comparative example 5
The difference with the embodiment 1 is that the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt is not added with polyphosphoric acid any more, and the silver-loaded attapulgite is replaced by the attapulgite with the same addition amount.
Comparative example 6
The difference with the embodiment 1 is that the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt is not added with polyphosphoric acid, and the silver-loaded attapulgite is not added with nano titanium dioxide.
Comparative example 7
The difference from example 1 is that no polyphosphoric acid is added to the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt.
Performance test: the detection method comprises the following steps: 1. high temperature resistance test
Six samples were taken from examples 1 to 3, examples 8 to 13, comparative example 1 and comparative examples 3 to 4, respectively, and three of the samples were then tested for pitch rutting factor by reference to JTG E20-2011, highway engineering asphalt and asphalt mixture test procedure, and the average value was taken to obtain the original pitch rutting factor;
then carrying out high-temperature treatment on the other three samples at 65 ℃ for 2 hours, then carrying out asphalt rutting factor test on the samples again by referring to JTG E20-2011, namely, highway engineering asphalt and asphalt mixture test procedure, and taking an average value to obtain asphalt rutting factor after high temperature;
finally, the high temperature resistance of the asphalt is represented by adopting a rutting factor high temperature index, and the higher the rutting factor high temperature index is, the worse the high temperature resistance of the asphalt is;
rutting factor high temperature index= (high temperature post asphalt rutting factor-raw asphalt rutting factor)/raw asphalt rutting factor x 100%.
The test results are shown in Table 5.
2. Asphalt smoke inhibition effect test
Three 20kg samples were taken from examples 1 to 13, comparative examples 1 to 2 and comparative examples 5 to 7, respectively, and then asphalt fumes released during sample preparation were collected through glass filter papers, after which the glass filter papers were dried to promote complete evaporation of water on the glass filter papers, and then weight differences before and after the glass filter papers were calculated, and the average value was taken to obtain asphalt fumes production.
The test results are shown in Table 6.
TABLE 5 high temperature resistance Properties Table of examples 1-3, 8-13 and comparative examples 1, 3-4
Referring to comparative examples 1 and 3 in combination with Table 5, it can be seen that comparative example 3 additionally adds polyphosphoric acid with respect to comparative example 1, resulting in comparative example 3 having a rutting factor high temperature index significantly lower than that of comparative example 1, thereby demonstrating that polyphosphoric acid has an effect of improving high temperature resistance of asphalt.
The reason is that polyphosphoric acid belongs to an acidic chemical modifier, and can generate salt or generate esterification reaction with active groups in asphalt to promote the asphalt components to be converted in form, quantity and dispersion state, thereby helping to construct an internal network structure, improving the elastic behavior of asphalt and further improving the high temperature resistance of asphalt.
Referring to comparative examples 3 and 4 in combination with Table 5, it can be seen that comparative example 4 additionally incorporates attapulgite clay relative to comparative example 3, thereby promoting a rutting factor high temperature index of comparative example 4 that is significantly lower than that of comparative example 3, thus demonstrating that attapulgite clay can also improve the high temperature resistance of asphalt. The reason for this is that the silver-loaded attapulgite can form a network structure inside asphalt, thereby playing a role of framework support and indirectly improving the high temperature resistance of asphalt.
Referring to examples 1-3 and comparative example 4 in combination with Table 5, it can be seen that the rutting factor high temperature index of example 1 is substantially unchanged from that of comparative example 4, thus demonstrating that silver ion loading, titanium dioxide loading and SBS modification have no significant improvement effect on the high temperature resistance of asphalt.
Compared with the embodiment 1, the rutting factor high temperature index of the embodiments 2-3 is slightly improved, so that the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt has better high temperature resistance when the components of the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt adopt the addition amount of the embodiment 1.
Referring to examples 1 and 8 in combination with Table 5, it can be seen that the rutting factor high temperature index of example 8 is slightly lowered compared with example 1, because the activated carbon can form a cross-linked network structure with the attapulgite clay simultaneously, thereby improving the high temperature resistance of asphalt.
Referring to examples 8-11 in combination with Table 5, it can be seen that the rutting factor high temperature index of examples 9-11 is significantly reduced relative to example 8, wherein the rutting factor high temperature index of example 10 is relatively lowest.
The main reason is that the vinyl triethoxysilane, the 3-aminopropyl triethoxysilane and the dimethyl diethoxysilane all contain a plurality of ethoxy groups, so that the asphalt has more silicon-oxygen bond sites, and further the polyethoxy silane coupling agent can act on silver-loaded attapulgite, activated carbon and nano titanium dioxide at the same time, so that the cross-linked network structure of the asphalt is more stable and perfect, and the asphalt has more excellent high-temperature rutting resistance and stability.
Compared with dimethyl diethoxy silane, vinyl triethoxy silane and 3-amino propyl triethoxy silane have more ethoxy groups, so that the silane coupling agent has more silicon-oxygen bond sites, and the connection of silver-carrying attapulgite, activated carbon and nano titanium dioxide is promoted to be more stable. In addition, the 3-aminopropyl triethoxy silane also contains amino groups, and the amino groups can react with organic materials containing active hydroxyl groups to form hydrogen bonds or covalent bonds, so that the compatibility and the adhesiveness of the components of the asphalt are further improved.
Referring to examples 10 and examples 12-13 in combination with Table 5, it can be seen that the rutting factor high temperature index of examples 12-13 is relatively higher than that of example 10, thus indicating that the prepared SBS polyphosphate composite high-viscosity high-elasticity modified asphalt has better high temperature resistance when the addition amount of example 10 is used for activated carbon and 3-aminopropyl triethoxysilane.
TABLE 6 asphalt fume inhibition effect tables of examples 1-13 and comparative examples 1-2, 5-7
Referring to comparative examples 1 to 2 in combination with Table 6, it can be seen that the amount of asphalt fume produced in comparative example 2 is significantly reduced compared to comparative example 1, because asphalt fume also contains solid particles, and because the modified SBS is formed by mixing SBS, a polyetherimide-benzophenone solution and a copper nitrate aqueous solution, the modified SBS is SBS grafted with primary amine, and at this time, the modified SBS contains negative electricity.
The negative electrode is easy to adsorb solid particles with positive electricity, so that the solid particles with small particle size are aggregated into large particles, and the large particles are settled under the action of gravity, thereby realizing the effect of eliminating the solid particles in asphalt flue gas.
As can be seen from the comparison of comparative examples 2 and 5 in combination with table 6, the asphalt fume generation amount of comparative example 5 is further reduced compared to comparative example 2, which is because the attapulgite has a very large specific surface area and the surface thereof has a very strong adsorption capacity, and thus it can effectively adsorb asphalt fume.
Referring to comparative examples 5 to 7 in combination with Table 6, it can be seen that the asphalt fume generation amount of comparative example 6 is significantly reduced, and that the asphalt fume generation amount of comparative example 7 is further reduced, relative to comparative example 5. The reason for this is that silver ions have an effect of removing benzene-based substances which are main components of volatile organic gases. The nano titanium dioxide can excite electrons in the valence band to cross into the forbidden band and form holes in the valence band after being irradiated, and the holes have obvious electron obtaining capabilityCan react with oxygen element to generate OH - Thereby effectively eliminating sulfur dioxide.
Referring to comparative example 7, examples 1 to 3, and Table 6, it can be seen that the asphalt fume generation amount of example 1 was substantially unchanged from that of comparative example 7, thereby indicating that polyphosphoric acid had no inhibitory effect on asphalt fume.
Compared with the embodiment 1, the asphalt fume generation amount of the embodiments 2-3 is relatively more, so that the prepared SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt has better asphalt fume inhibition effect when the addition amount of the embodiment 1 is adopted for each component of the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt.
Referring to examples 1 and 4-5 in combination with Table 6, it can be seen that the asphalt fume generation amounts of examples 4-5 are relatively more than those of example 1, thus demonstrating that the prepared SBS polyphosphate composite high-viscosity high-elasticity modified asphalt has more excellent asphalt fume inhibition effect when the additive amount of each component of the modified SBS is used in example 1.
Referring to examples 1, examples 6-7 and Table 6, it can be seen that the asphalt fume generation amount of examples 4-5 is relatively more than that of example 1, thus demonstrating that the prepared SBS polyphosphate composite high-viscosity high-elasticity modified asphalt has more excellent asphalt fume inhibition effect when the additive amount of example 1 is used as each component of the silver-loaded attapulgite.
Referring to example 1, example 8, and table 6, it can be seen that the asphalt fume generation amount of example 8 is further reduced compared to example 1, owing to the mutual attraction between all molecules, and the porous structure of activated carbon provides a large amount of surface area, thereby generating a strong attraction force, thereby playing an adsorption effect on asphalt fume. In addition, the surface of the activated carbon also contains a small amount of oxide or complex, and the oxide or complex can chemically react with organic substances of asphalt fume, so that the adsorption effect on the asphalt fume is further improved.
Referring to examples 8 to 11 in combination with Table 6, it can be seen that the asphalt fume production amounts of examples 9 to 11 were reduced compared with example 8, wherein the asphalt fume production amount of example 10 was the lowest, due to the relatively poor dispersibility of activated carbon, and the silane coupling agent was able to bridge the interface between the inorganic material and the organic material, thereby connecting the two different materials and indirectly reducing the asphalt fume inhibition effect of the SBS polyphosphoric acid composite high-viscosity high-elastic modified asphalt.
Referring to examples 10 and examples 12 to 13 in combination with Table 6, it can be seen that the asphalt fume generation amount of examples 12 to 13 is relatively high compared with example 10, thereby demonstrating that the prepared SBS polyphosphate composite high-viscosity high-elasticity modified asphalt has more excellent asphalt fume inhibition effect when the addition amount of the activated carbon and 3-aminopropyl triethoxysilane is adopted in example 10.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (4)
1. The SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt is characterized by comprising the following raw materials in parts by weight: 90-110 parts of matrix asphalt, 8-12 parts of modified SBS, 4-6 parts of polyphosphoric acid, 2-4 parts of silver-loaded attapulgite, 10-16 parts of silane coupling agent and 1-3 parts of active carbon, wherein the silver-loaded attapulgite is loaded with silver ions and nano titanium dioxide, and the silane coupling agent contains polyethoxy groups;
the silver-carrying attapulgite comprises the following raw materials in parts by weight: 8-12 parts of attapulgite, 2-4 parts of nano titanium dioxide, 4-8 parts of ammonia water and 3-6 parts of silver nitrate;
the preparation method of the silver-loaded attapulgite comprises the following steps: dispersing attapulgite in deionized water, centrifuging to remove impurities, adding the attapulgite and nano titanium dioxide into ammonia water, mixing and stirring uniformly, adding silver nitrate, heating to 60-80 ℃ and continuously stirring for 1-2h to obtain silver-loaded attapulgite;
the modified SBS comprises the following raw materials in parts by weight: 10-20 parts of SBS, 6-10 parts of polyetherimide-benzophenone solution and 2-4 parts of copper nitrate aqueous solution;
the preparation method of the modified SBS comprises the following steps:
s1, crushing, cutting and soaking SBS in absolute ethyl alcohol, removing impurities on the surface of the SBS by adopting an ultrasonic cleaning method, and drying to obtain the pre-processed SBS;
s2, fully mixing the pre-processed SBS, the polyetherimide-diphenyl ketone solution and the copper nitrate aqueous solution, transferring the mixture into a sealed bag, removing oxygen in the sealed bag by using nitrogen, and finally discharging bubbles in the bag and sealing a bag opening;
s3, standing and ultraviolet irradiation treatment is carried out on the sealed bag, each side is irradiated for 5-15min, and finally deionized water and absolute ethyl alcohol are used for cleaning in sequence, so that the modified SBS is obtained.
2. The SBS polyphosphoric acid composite high viscosity high elastic modified asphalt according to claim 1, wherein: the silane coupling agent is one of vinyl triethoxysilane, 3-aminopropyl triethoxysilane and dimethyl diethoxysilane.
3. The SBS polyphosphoric acid composite high viscosity high elastic modified asphalt according to claim 2, wherein: the silane coupling agent is 3-aminopropyl triethoxysilane.
4. A method for preparing the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt according to any one of claims 1 to 3, comprising the following steps:
heating matrix asphalt to 160-170 ℃, then adding modified SBS, mixing and stirring for 20-40min, then raising the temperature to 165-175 ℃, and shearing for 60-80min to obtain SBS modified asphalt;
adding polyphosphoric acid, a silane coupling agent, active carbon and silver-loaded attapulgite into the SBS modified asphalt, heating to 170-190 ℃ and shearing for 80-100min, and finally developing for 30-40min at 170-180 ℃ to obtain the SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311187141.4A CN116925558B (en) | 2023-09-14 | 2023-09-14 | SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311187141.4A CN116925558B (en) | 2023-09-14 | 2023-09-14 | SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116925558A CN116925558A (en) | 2023-10-24 |
| CN116925558B true CN116925558B (en) | 2023-11-21 |
Family
ID=88386380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311187141.4A Active CN116925558B (en) | 2023-09-14 | 2023-09-14 | SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116925558B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788668A (en) * | 2013-12-30 | 2014-05-14 | 长沙理工大学 | Composite modified asphalt and preparation method thereof |
| CN105038280A (en) * | 2015-09-22 | 2015-11-11 | 长安大学 | SBS modified asphalt and preparation method thereof |
| CN108641386A (en) * | 2018-05-30 | 2018-10-12 | 广东华路交通科技有限公司 | A kind of environment-friendly type anti-rutting modified asphalt and preparation method thereof |
| CN110041720A (en) * | 2019-05-07 | 2019-07-23 | 无锡市城市道桥科技有限公司 | A kind of high adhered modification asphalt material and preparation method thereof |
| CN111978750A (en) * | 2020-09-08 | 2020-11-24 | 福州大学 | High-toughness SBS/SBR polyphosphoric acid composite modified asphalt and preparation method thereof |
| CN114479500A (en) * | 2022-03-18 | 2022-05-13 | 陕西国琳建设工程有限公司 | Environment-friendly modified asphalt and preparation method thereof |
-
2023
- 2023-09-14 CN CN202311187141.4A patent/CN116925558B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788668A (en) * | 2013-12-30 | 2014-05-14 | 长沙理工大学 | Composite modified asphalt and preparation method thereof |
| CN105038280A (en) * | 2015-09-22 | 2015-11-11 | 长安大学 | SBS modified asphalt and preparation method thereof |
| CN108641386A (en) * | 2018-05-30 | 2018-10-12 | 广东华路交通科技有限公司 | A kind of environment-friendly type anti-rutting modified asphalt and preparation method thereof |
| CN110041720A (en) * | 2019-05-07 | 2019-07-23 | 无锡市城市道桥科技有限公司 | A kind of high adhered modification asphalt material and preparation method thereof |
| CN111978750A (en) * | 2020-09-08 | 2020-11-24 | 福州大学 | High-toughness SBS/SBR polyphosphoric acid composite modified asphalt and preparation method thereof |
| CN114479500A (en) * | 2022-03-18 | 2022-05-13 | 陕西国琳建设工程有限公司 | Environment-friendly modified asphalt and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116925558A (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112159597A (en) | Low-viscosity modified rubber asphalt and preparation method thereof | |
| CN110697855A (en) | Flocculating agent and preparation method and application thereof | |
| CN114409997A (en) | High-flame-retardance photoelectric composite cable sheath material with good processability and preparation method thereof | |
| CN116925558B (en) | SBS polyphosphoric acid composite high-viscosity high-elasticity modified asphalt and preparation method thereof | |
| CN109054849A (en) | A kind of agent for fixing for heavy-metal contaminated soil reparation | |
| CN115124838B (en) | Polysulfone/modified filler composite dielectric film material and preparation method thereof | |
| CN114213140B (en) | Coal gangue-based ceramsite for phosphorus adsorption, preparation method thereof and water treatment equipment | |
| CN109486219A (en) | A kind of organic coating nano-titanium dioxide grafting SBS modified asphalt and preparation method thereof | |
| WO2021036093A1 (en) | High-performance sulfur-based modified asphalt and preparation method therefor | |
| CN111747685A (en) | Environment-friendly odorless asphalt mixture and preparation method thereof | |
| CN111040769B (en) | Soil restoration improving agent and soil restoration improving method | |
| CN115710112B (en) | Composite curing agent for dredging sludge and preparation method and application thereof | |
| CN114560637B (en) | Basalt fiber modified slurry, basalt modified fiber and preparation method | |
| CN113368833B (en) | Inorganic-organic flocculant and preparation method thereof | |
| CN115109423A (en) | Anti-aging durable asphalt and preparation method thereof | |
| CN111233362A (en) | Preparation method and application of concrete toughening material | |
| CN112592105A (en) | Anti-rutting drainage asphalt mixture and preparation method thereof | |
| CN108636353B (en) | domestic sewage sludge/rectorite compound and preparation method and application thereof | |
| CN113908805B (en) | Carbon nano tube reinforced inorganic adsorbent, preparation method and application thereof | |
| Lu et al. | The surface modification by carboxyl ionic liquid for mesoporous silica and the preparation of composite polymer electrolyte with the modified mesoporous silica | |
| CN111019404A (en) | Modified attapulgite for rubber reinforcement and preparation method thereof | |
| CN110564236B (en) | Haze-removing sand-in-water multicolor paint and preparation method thereof | |
| CN117801126B (en) | Cellulose-based multiple binding site heavy metal sewage treatment agent and preparation method and application thereof | |
| CN113045247B (en) | Light asphalt mixture capable of being degraded by photocatalysis and preparation method thereof | |
| CN116218275B (en) | Putty powder for removing formaldehyde and indoor tvoc and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |