CN117866494A - Pavement marking paint and preparation method thereof - Google Patents
Pavement marking paint and preparation method thereof Download PDFInfo
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- CN117866494A CN117866494A CN202311842841.2A CN202311842841A CN117866494A CN 117866494 A CN117866494 A CN 117866494A CN 202311842841 A CN202311842841 A CN 202311842841A CN 117866494 A CN117866494 A CN 117866494A
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- silicon dioxide
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- 239000003973 paint Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 31
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- 239000006247 magnetic powder Substances 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004925 Acrylic resin Substances 0.000 abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 abstract description 8
- 239000011325 microbead Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000003480 eluent Substances 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a pavement marking paint and a preparation method thereof, and belongs to the technical field of pavement marking paint. The pavement marking paint provided by the invention is water-based paint, and is environment-friendly; the acrylic resin is used as a main body, has better glossiness and weather resistance, and is safe and low in production cost; the rutile type titanium dioxide is added, so that the marked line paint can be endowed with weather resistance and light reflection to a certain extent; the hollow all-weather rainy night reflecting microbeads are added, so that the all-weather reflecting effect of the marked lines can be realized, the discrimination is improved, and the recognition effect of the automatic driving automobile in a severe environment can be improved; in addition, fe 3 O 4 The magnetic powder can be added corresponding to the radar of the automatic driving automobile, so that the identification effect of the automatic driving automobile on the marked line is enhancedThe safety is improved; in addition, the modified nano silicon dioxide has better compatibility with the paint, also endows the paint with good wear resistance, hardness and waterproof performance, and improves the stability and service life of the paint.
Description
Technical Field
The invention belongs to the technical field of pavement marking paint, and particularly relates to pavement marking paint and a preparation method thereof.
Background
With the rapid growth of the economy in China, the road traffic marking has increasingly remarkable effects in guiding, controlling and warning traffic participants while the road industry and the vehicle industry are getting sudden and rapid progress. The marking has important functions for guiding traffic and is very important for application in various countries. Among the numerous road marking materials, the coating is considered as the most potential road marking material by virtue of its ease of application to the road surface and its ability to be firmly attached to the road surface in the form of a thin film.
Common coatings include acrylic resin coatings, polyurethane coatings, epoxy resin coatings and polyurea coatings, wherein the acrylic resin has good glossiness, weather resistance and chemical resistance, is safe and low in production cost, and has wide application in the field of coatings. However, the pavement marking has strict requirements on the paint, the paint is subjected to factors such as blowing, sun, rain, rolling of automobiles and the like, the service life of the paint can be seriously influenced, and the wear resistance, the water resistance, the weather resistance and the stability of the paint are all high, so that the common acrylic resin paint is obviously difficult to meet the requirements.
The conventional acrylic resin coating is solvent type, a large amount of organic matters can be volatilized after the coating, and the organic matters have certain influence on the health of the human body and pollute the environment. Therefore, the environment-friendly aqueous acrylic resin coating is paid attention to, the aqueous coating takes water as a solvent, and the aqueous emulsion replaces solvent type resin. The paint has good paint film stability, skid resistance and cohesiveness in a short period, but has shorter wear-resistant service life, needs repeated coating every year, has higher maintenance cost, and limits the use of the water-based acrylic resin paint in the field of pavement marking paint.
Moreover, in recent years, the field of autopilot develops heat, the general reflectivity of the marking is poor, and in rainy and snowy weather, the radar of the autopilot is difficult to identify, and the running safety of the autopilot is affected, so that the problem needs to be solved to meet the higher demands of the field of marking paint.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a pavement marking paint and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a method of preparing a pavement marking coating comprising the steps of:
a1, mixing and stirring acrylic acid, butyl acrylate, methacrylic acid, styrene and nonylphenol polyoxyethylene (4) ether ammonium sulfate (emulsifier) uniformly, adding the mixture into deionized water, and dispersing the mixture at a high speed to obtain a pre-emulsion;
a2, uniformly stirring and mixing the pre-emulsion, sodium dodecyl sulfate (emulsifier), sodium bicarbonate (PH buffer) and ammonium persulfate (initiator) in a reaction kettle, heating to 80 ℃, preserving heat and reacting for 2 hours, cooling to room temperature, and regulating the pH value between 7 and 8 by using ammonia water to obtain acrylic emulsion;
a3, acrylic emulsion, glass beads and Fe 3 O 4 Magnetic powder, rutile type titanium dioxide, a defoaming agent, modified nano silicon dioxide and azodiisopropyl imidazoline (water-soluble initiator) are added into deionized water, and are stirred strongly, dispersed for 30min by ultrasound, heated to 85 ℃, and reacted for 3h under heat preservation, thus obtaining the pavement marking paint.
Further, in the step A1, the dosage ratio of the acrylic acid, the butyl acrylate, the methacrylic acid, the styrene, the nonylphenol polyoxyethylene (4) ether ammonium sulfate and the deionized water is 10g:10g:3g:4g:0.5g:200mL.
Further, the ratio of the pre-emulsion, sodium dodecyl sulfate, sodium bicarbonate and ammonium persulfate in the step A2 is 40g:4g:8g:0.2g.
Further, in the step A3, acrylic emulsion, glass beads and Fe 3 O 4 The ratio of the dosages of the magnetic powder, the rutile type titanium dioxide, the defoamer, the modified nano silicon dioxide, the azodiisopropylimidazoline and the deionized water is 40g to 20g to 4g to 8g to 2g to 5-15g to 1g to 30g.
Further, the defoaming agent in the step A3 is an organosilicon defoaming agent.
Further, the glass beads in the step A3 are hollow all-weather rainy night reflecting beads with the particle size of 40-60 mu m and the rounding rate of more than 85 percentThe spreading amount is 350-450g/m 3 。
The solvent is water, and the prepared marking paint is environment-friendly; the rutile type titanium dioxide is used, compared with the common titanium dioxide, the titanium dioxide has high refractive index and high whiteness, and can endow the marked line paint with a certain degree of weather resistance and light reflection; the hollow all-weather rainy night reflecting microbeads are used, so that the hollow all-weather rainy night reflecting microbeads can reflect light normally at rainy night, the all-weather reflecting effect of marked lines can be realized, the number of reflecting lines is increased, the discrimination is improved, and the recognition effect of an automatic driving automobile is also improved; in addition Fe 3 O 4 The magnetic powder can be added corresponding to the radar of the automatic driving automobile, so that the identification effect of the automatic driving automobile on the marked line is further enhanced.
Further, the modified nano-silica is prepared by the steps of:
s1, adding 1, 3-acetone dicarboxylic acid, DAST (diethylaminosulfur trifluoride, fluoridation reagent) and methylene dichloride into a beaker, stirring and mixing uniformly at room temperature, reacting for 40min, suction filtering, taking a filter cake, washing 3 times with absolute ethyl alcohol, and drying to obtain an intermediate 1; the dosage ratio of the 1, 3-acetone dicarboxylic acid, DAST and methylene dichloride is 14.6g to 8.5g to 50mL;
under the action of a fluorination reagent, carbonyl on the 1, 3-acetone dicarboxylic acid is converted into a difluoro compound, the fluorination reagent has selectivity, and carboxyl is not affected, so that an intermediate 1 is obtained; the specific reaction process is as follows:
s2, mixing the intermediate 1, hydroxyethyl acrylate and ethyl acetate in a three-neck flask with a stirring device, slowly adding concentrated sulfuric acid solution (catalyst and dehydrating agent) into the solution while stirring, reacting for 4 hours at 75 ℃, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of methanol/acetone, the volume ratio of the methanol to the acetone is 3:2), and removing the eluent by rotary evaporation to obtain an intermediate 2; the dosage ratio of the intermediate 1 to the hydroxyethyl acrylate to the ethyl acetate to the concentrated sulfuric acid solution is 18.7g to 11.6g to 100mL to 20mL;
under the catalysis of concentrated sulfuric acid, carboxyl on the intermediate 1 and hydroxyl on hydroxyethyl acrylate are subjected to esterification reaction, and only one carboxyl on the intermediate 1 participates in the reaction by controlling the molar ratio of the carboxyl to the hydroxyl to be close to 1:1 and slightly excessive intermediate 1, so that an intermediate 2 is obtained; the specific reaction process is as follows:
s3, mixing nano silicon dioxide with toluene, adding the mixture into a magnetic stirring device, adding magnetite, starting stirring, dispersing for 30min to uniformly disperse the silicon dioxide in toluene solution, vacuumizing the device, introducing nitrogen, adding gamma-aminopropyl triethoxysilane (silane coupling agent KH-550), starting oil bath heating, setting 50 ℃, starting condensed water, setting 80 ℃, heating to 80 ℃, reacting for 4h, filtering, washing the toluene, and drying in a vacuum drying oven for 2h to obtain an intermediate 3; the dosage ratio of the nano silicon dioxide, toluene and gamma-aminopropyl triethoxysilane is 10.0g to 100mL to 6.5g;
the nano silicon dioxide has a plurality of-OH on the surface, and can be introduced into-NH by reacting with KH-550 2 Reactive groups to give intermediate 3; the specific reaction process is as follows:
s4, carrying out ultrasonic treatment on the intermediate 3 in ethyl acetate for 30min, dispersing uniformly, adding the intermediate 2 and benzenesulfonic acid (dehydrating agent), mixing and stirring uniformly, slowly heating to 65 ℃, using magnetic stirring (rotating speed 1000 r/min), stopping heating after stirring for 3h, carrying out suction filtration after the temperature in a reaction bottle is reduced to 30 ℃, taking filter residues, washing with absolute ethyl alcohol, drying, and grinding to obtain modified nano silicon dioxide; the dosage ratio of the intermediate 3 to the ethyl acetate to the intermediate 2 to the benzenesulfonic acid is 10.0g to 100mL to 26.6g to 8.8g;
the amino group of the intermediate 3 and the carboxyl group of the intermediate 2 are subjected to amidation reaction, and can react under milder conditions with the help of a dehydrating agent to obtain modified nano silicon dioxide; the specific reaction process is as follows:
the prepared modified nano silicon dioxide grafts an organic molecular chain through chemical bonding, namely, an organic layer is formed on the surface of the modified nano silicon dioxide, so that the interfacial compatibility of the nano silicon dioxide and acrylic acid can be greatly improved, and the nano silicon dioxide is promoted to be uniformly dispersed in the marking paint; in addition, nano silicon dioxide belongs to inorganic filler, and organic molecular chains are dispersed in the coating through grafting on the surface of the nano silicon dioxide, so that exudation and migration are difficult, and the durability of various performances is ensured; from the structural point of view of the organic molecular chain itself, contains C-F bonds and carbon-carbon double bonds; the C-F bond has high chemical bond and good stability, and can also endow marked line paint with remarkable water resistance; moreover, the C-F bond can gradually migrate to the surface layer of the marking paint, so that the surface energy of the marking paint is reduced; in addition, the C-F bond can well coat the C-C main chain, shield the C-C main chain, play a role in protection, and greatly enhance the stability and the service life of the marking paint; finally, the carbon-carbon double bond contained at the tail end of the modified nano silicon dioxide is polymerized to the tail end of the acrylic resin main chain through free radicals under the action of a micro initiator, so that the compatibility of the modified nano silicon dioxide and acrylic acid is improved, and the stability is also improved.
The invention has the beneficial effects that:
the pavement marking paint provided by the invention is water-based paint, and is environment-friendly; the rutile type titanium dioxide is added, so that the marked line paint can be endowed with weather resistance and light reflection to a certain extent; the hollow all-weather rainy night reflecting microbeads are added, so that the all-weather reflecting effect of the marked lines can be realized, the discrimination is improved, and the recognition effect of the automatic driving automobile in a severe environment can be improved; in addition, fe 3 O 4 The magnetic powder can be added and automatically drivenThe radar of the automobile is corresponding, so that the identification effect of the automatic driving automobile on the marked line is further enhanced, and the safety is improved; in addition, the modified nano silicon dioxide has better compatibility with the paint, also endows the paint with good wear resistance, hardness and waterproof performance, and improves the stability and service life of the paint. Therefore, the prepared pavement marking paint has stable and efficient light reflection, wear resistance, waterproof performance and weather resistance, is environment-friendly, long in service life and easy to identify by an automatic driving automobile, and has important application value in the field of pavement marking paint.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of modified nanosilicon dioxide
S1, adding 14.6g of 1, 3-acetone dicarboxylic acid, 8.5g of DAST and 50mL of dichloromethane into a beaker, stirring and mixing uniformly at room temperature, reacting for 40min, suction filtering, taking a filter cake, washing 3 times with absolute ethyl alcohol, and drying to obtain an intermediate 1;
s2, mixing 18.7g of intermediate 1, 11.6g of hydroxyethyl acrylate and 100mL of ethyl acetate in a three-neck flask with a stirring device, slowly adding 20mL of concentrated sulfuric acid solution into the solution while stirring, reacting for 4 hours at 75 ℃, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of methanol/acetone with the volume ratio of 3:2), and removing the eluent by rotary evaporation to obtain intermediate 2;
s3, mixing 10.0g of nano silicon dioxide with 100mL of toluene, adding the mixture into a magnetic stirring device, adding magnetite, starting stirring, dispersing for 30min to uniformly disperse the silicon dioxide in toluene solution, vacuumizing the device, introducing nitrogen, adding 6.5g of silane coupling agent KH-550, starting oil bath heating, setting 50 ℃, opening condensed water, setting 80 ℃, heating to 80 ℃, reacting for 4h, filtering, washing with toluene, and drying in a vacuum drying oven for 2h to obtain an intermediate 3;
s4, carrying out ultrasonic treatment on 10.0g of the intermediate 3 in 100mL of ethyl acetate for 30min, dispersing uniformly, adding 26.6g of the intermediate 2 and 8.8g of benzenesulfonic acid, mixing and stirring uniformly, slowly heating to 65 ℃, using magnetic stirring, stopping heating after stirring for 3h, carrying out suction filtration after the temperature in a reaction bottle is reduced to 30 ℃, taking filter residues, washing with absolute ethyl alcohol, drying, and grinding to obtain the modified nano silicon dioxide.
Example 2
Preparation of modified nanosilicon dioxide
S1, adding 29.2g of 1, 3-acetone dicarboxylic acid, 17.0g of DAST and 100mL of dichloromethane into a beaker, stirring and mixing uniformly at room temperature, reacting for 40min, suction filtering, taking a filter cake, washing 3 times with absolute ethyl alcohol, and drying to obtain an intermediate 1;
s2, mixing 37.4g of intermediate 1, 23.2g of hydroxyethyl acrylate and 200mL of ethyl acetate in a three-neck flask with a stirring device, slowly adding 40mL of concentrated sulfuric acid solution into the solution while stirring, reacting for 4 hours at 75 ℃, removing most of the solvent by rotary evaporation after the reaction is finished, purifying by column chromatography (eluent adopts a mixed solvent of methanol/acetone with the volume ratio of 3:2), and removing the eluent by rotary evaporation to obtain intermediate 2;
s3, mixing 20g of nano silicon dioxide with 200mL of toluene, adding the mixture into a magnetic stirring device, adding a magnet, starting stirring, dispersing for 30min to uniformly disperse the silicon dioxide in a toluene solution, vacuumizing the device, introducing nitrogen, adding 13g of silane coupling agent KH-550, starting oil bath heating, setting 50 ℃, opening condensed water, setting 80 ℃, heating to 80 ℃, reacting for 4h, filtering, washing the toluene, and drying in a vacuum drying oven for 2h to obtain an intermediate 3;
s4, ultrasonically dispersing 20g of intermediate 3 in 200mL of ethyl acetate for 30min, uniformly dispersing, adding 53.2g of intermediate 2 and 17.6g of benzenesulfonic acid, uniformly mixing and stirring, slowly heating to 65 ℃, using magnetic stirring, stopping heating after stirring for 3h, carrying out suction filtration after the temperature in a reaction bottle is reduced to 30 ℃, taking filter residues, washing with absolute ethyl alcohol, drying, and grinding to obtain the modified nano silicon dioxide.
Example 3
A1, mixing and stirring 10g of acrylic acid, 10g of butyl acrylate, 3g of methacrylic acid, 4g of styrene and 0.5g of nonylphenol polyoxyethylene (4) ether ammonium sulfate uniformly, adding the mixture into 200mL of deionized water, and dispersing at a high speed to obtain a pre-emulsion;
a2, uniformly stirring and mixing 40g of pre-emulsion, 4g of sodium dodecyl sulfate, 8g of sodium bicarbonate and 0.2g of ammonium persulfate in a reaction kettle, heating to 80 ℃, preserving heat for 2 hours, cooling to room temperature, and regulating the pH between 7 and 8 by using ammonia water to obtain acrylic emulsion;
a3, 40g of acrylic emulsion, 20g of hollow all-weather rainy night reflective microbeads and 4g of Fe 3 O 4 Magnetic powder, 8g of rutile type titanium dioxide, 2g of organosilicon defoamer (manufactured by Shandong energy-accumulating chemical Co., ltd.), 5g of modified nano silicon dioxide and 1g of azo diisopropyl imidazoline are added into 30g of deionized water, the mixture is stirred strongly, dispersed for 30min by ultrasonic, heated to 85 ℃, and reacted for 3h under heat preservation, thus obtaining the pavement marking paint.
Example 4
A1, mixing and stirring 10g of acrylic acid, 10g of butyl acrylate, 3g of methacrylic acid, 4g of styrene and 0.5g of nonylphenol polyoxyethylene (4) ether ammonium sulfate uniformly, adding the mixture into 200mL of deionized water, and dispersing at a high speed to obtain a pre-emulsion;
a2, uniformly stirring and mixing 40g of pre-emulsion, 4g of sodium dodecyl sulfate, 8g of sodium bicarbonate and 0.2g of ammonium persulfate in a reaction kettle, heating to 80 ℃, preserving heat for 2 hours, cooling to room temperature, and regulating the pH between 7 and 8 by using ammonia water to obtain acrylic emulsion;
a3, 40g of acrylic emulsion, 20g of hollow all-weather rainy night reflective microbeads and 4g of Fe 3 O 4 Magnetic powder, 8g of rutile type titanium dioxide, 2g of organosilicon defoamer (manufactured by Shandong energy-accumulating chemical Co., ltd.), 10g of modified nano silicon dioxide and 1g of azo diisopropyl imidazoline are added into 30g of deionized water, and the mixture is stirred vigorously, dispersed for 30min by ultrasound, heated to 85 ℃, and reacted for 3h under heat preservation, thus obtaining the pavement marking paint.
Example 5
A1, mixing and stirring 10g of acrylic acid, 10g of butyl acrylate, 3g of methacrylic acid, 4g of styrene and 0.5g of nonylphenol polyoxyethylene (4) ether ammonium sulfate uniformly, adding the mixture into 200mL of deionized water, and dispersing at a high speed to obtain a pre-emulsion;
a2, uniformly stirring and mixing 40g of pre-emulsion, 4g of sodium dodecyl sulfate, 8g of sodium bicarbonate and 0.2g of ammonium persulfate in a reaction kettle, heating to 80 ℃, preserving heat for 2 hours, cooling to room temperature, and regulating the pH between 7 and 8 by using ammonia water to obtain acrylic emulsion;
a3, 40g of acrylic emulsion, 20g of hollow all-weather rainy night reflective microbeads and 4g of Fe 3 O 4 Magnetic powder, 8g of rutile type titanium dioxide, 2g of organosilicon defoamer (manufactured by Shandong energy-accumulating chemical Co., ltd.), 15g of modified nano silicon dioxide and 1g of azo diisopropyl imidazoline are added into 30g of deionized water, the mixture is stirred strongly, dispersed for 30min by ultrasonic, heated to 85 ℃, and reacted for 3h under heat preservation, thus obtaining the pavement marking paint.
Comparative example 1
The modified nanosilica of example 5 was replaced with a common nanosilica of the same quality, the remainder of the procedure being the same as example 5.
Comparative example 2
Road marking paint waterborne acrylic paint manufactured by Kaiger paint Co., ltd. In Guangzhou was used.
The coatings of examples 3 to 5 and comparative examples 1 to 2 were heated to 180℃and then applied to the treated base plate with a total thickness of about 2mm, and the resulting coating film was subjected to the following performance test according to GB/T1727-92 general preparation for paint film:
hardness (pencil hardness is 6B-6H) is measured by using national standard GB/T6739-1996 pencil hardness determination method of film coating;
the appearance, water resistance, alkali resistance, wear resistance and retroreflection coefficient of a coating film are measured by JT/T280-2004 pavement marking paint;
the measured results are shown in Table 1:
TABLE 1
Using the same test criteria, the results are shown in table 2 after the coating film was left outdoors for 60 days:
TABLE 2
As can be seen from the comparison of the table 1 and the table 2, the prepared pavement marking paint has stable and efficient light reflection, wear resistance, waterproof performance and weather resistance, is environment-friendly, has long service life, can improve the automatic driving recognition effect, and has important application value in the field of pavement marking paint.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. A method of preparing a pavement marking coating comprising the steps of:
a1, mixing and stirring acrylic acid, butyl acrylate, methacrylic acid, styrene and ammonium nonylphenol polyoxyethylene (4) ether sulfate uniformly, adding the mixture into deionized water, and dispersing the mixture at a high speed to obtain a pre-emulsion;
a2, uniformly stirring and mixing the pre-emulsion, sodium dodecyl sulfate, sodium bicarbonate and ammonium persulfate, heating to 80 ℃, preserving heat for 2 hours, cooling to room temperature, and regulating the pH value to 7-8 by using ammonia water to obtain acrylic emulsion;
a3, acrylic emulsion, glass beads and Fe 3 O 4 Adding magnetic powder, rutile type titanium dioxide, a defoaming agent, modified nano silicon dioxide and azodiisopropyl imidazoline into deionized water, stirring strongly, dispersing ultrasonically for 30min, heating to 85 ℃, and reacting for 3h under heat preservation to obtain the pavement marking paint.
2. The method for preparing pavement marking paint according to claim 1, wherein in step A3, the acrylic emulsion, the glass beads, the Fe are as follows 3 O 4 The ratio of the dosages of the magnetic powder, the rutile type titanium dioxide, the defoamer, the modified nano silicon dioxide, the azodiisopropylimidazoline and the deionized water is 40g to 20g to 4g to 8g to 2g to 5-15g to 1g to 30g.
3. The method for preparing pavement marking paint according to claim 1, wherein in the step A3, the glass beads are hollow all-weather rainy night reflective beads with a particle size of 40-60 μm, a rounding rate of more than 85% and a spreading amount of 350-450g/m 3 。
4. The method of preparing a pavement marking coating of claim 1, wherein the modified nano-silica is prepared by:
s1, stirring and mixing 1, 3-acetone dicarboxylic acid, DAST and methylene dichloride at room temperature uniformly, reacting for 40min, filtering, taking a filter cake, washing with absolute ethyl alcohol for 3 times, and drying to obtain an intermediate 1;
s2, mixing the intermediate 1, hydroxyethyl acrylate and ethyl acetate, adding a concentrated sulfuric acid solution, reacting for 4 hours at 75 ℃, performing rotary evaporation, purifying by column chromatography, and performing rotary evaporation to obtain an intermediate 2;
s3, mixing nano silicon dioxide with toluene, adding the mixture into a magnetic stirring device, stirring and dispersing for 30min, vacuumizing the device, introducing nitrogen, adding gamma-aminopropyl triethoxysilane, starting oil bath heating, setting 50 ℃, opening condensed water, setting 80 ℃, heating to 80 ℃, reacting for 4h, filtering, washing the toluene, and drying in a vacuum drying oven for 2h to obtain an intermediate 3;
s4, carrying out ultrasonic treatment on the intermediate 3 in ethyl acetate for 30min, uniformly dispersing, adding the intermediate 2 and benzenesulfonic acid, mixing and stirring uniformly, slowly heating to 65 ℃, using magnetic stirring, stirring for 3h, after the temperature in a reaction bottle is reduced to 30 ℃, carrying out suction filtration, taking filter residues, washing with absolute ethyl alcohol, drying, and grinding to obtain the modified nano silicon dioxide.
5. The method of claim 4, wherein the ratio of 1, 3-acetone dicarboxylic acid, DAST, and methylene chloride in step S1 is 14.6g:8.5g:50mL.
6. The method of claim 4, wherein the ratio of the amounts of intermediate 1, hydroxyethyl acrylate, ethyl acetate, and concentrated sulfuric acid solution in step S2 is 18.7g to 11.6g to 100ml to 20ml.
7. The method of claim 4, wherein the ratio of nano silica, toluene, gamma-aminopropyl triethoxysilane in step S3 is 10.0g to 100ml to 6.5g.
8. The method of claim 4, wherein the ratio of the amounts of intermediate 3, ethyl acetate, intermediate 2, and benzenesulfonic acid used in step S4 is 10.0 g/100 ml/26.6 g/8.8 g.
9. A pavement marking coating prepared according to the method of any one of claims 1-8.
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