CN106634137A - Preparation method of glass micro-beads used for road marking line - Google Patents
Preparation method of glass micro-beads used for road marking line Download PDFInfo
- Publication number
- CN106634137A CN106634137A CN201611252639.4A CN201611252639A CN106634137A CN 106634137 A CN106634137 A CN 106634137A CN 201611252639 A CN201611252639 A CN 201611252639A CN 106634137 A CN106634137 A CN 106634137A
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- Prior art keywords
- glass microballoon
- preparation
- roadmarking
- beads
- glass micro
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- 239000011521 glass Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011325 microbead Substances 0.000 title abstract 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical class CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 7
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical class CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- -1 methacryloxypropyl Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003973 paint Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Road Signs Or Road Markings (AREA)
Abstract
The invention discloses a preparation method of glass micro-beads used for road marking lines. The preparation method includes the steps of: acidically activating glass micro-beads and pre-treating the glass micro-beads with a first coupling agent; spraying an alcohol-water mixed solution containing an antistatic agent and a second coupling agent to perform after-treatment, and drying the glass micro-beads to produce the glass micro-beads used for road marking lines. Through the multistep treatment, attachment and adhesion effect between the glass micro-beads and marking line paint and the dispersibility of the glass micro-beads in the marking line paint, thereby reducing surface tension of and adsorption to pollutants by the glass micro-beads and increasing antifouling capability and light reflecting effect of the glass micro-beads. Meanwhile, the glass micro-beads have a catalytic effect and can quickly initiate a reaction of surrounding monomers, thereby reducing settlement and improving mechanical performance and light reflecting effect of the marking line paint. The glass micro-beads can prolong service life of the marking line paint and improves safety of road traffic.
Description
Technical field
The present invention relates to the surface treatment of glass microballoon, the more particularly to surface treatment of roadmarking glass microballoon,
Glass microballoon after processing in the process of the present invention is adapted to the interior mixed face in road mark paint and spreads use.
Background technology
The roadmarking retroreflective energy of glass microballoon energy road improvement gage mark coating, improves the safety of driving at night
Property, it is reflectorized material the most frequently used in road mark paint.But in actual use, due to glass microballoon and road mark paint
Cohesive it is bad, the glass microballoon on roadmarking surface easily comes off in use, cause roadmarking reflecting effect decline.
Simultaneously as glass microballoon surface is in polarity, easily adsorb polluter, can also cause the reduction of roadmarking reflecting effect.
CN 103571234A disclose a kind of preparation method of reflective membrane modified glass microspheres, and it is in preparation process
Glass microballoon is not pre-processed, is directly changed with coupling agent, surfactant and film forming agent in acid modification solution
Property process, processing speed is slower, and the continuous heating of long period is needed in processing procedure, in addition, the method using larger
The coupling agent of amount, certainly will cause unnecessary waste.
The content of the invention
It is an object of the invention to provide a kind of preparation method of roadmarking glass microballoon, prepares in the process of the present invention
Glass microballoon is strong with the caking property of road mark paint, and glass microballoon surface tension is little, can reduce the absorption to pollutant.
The preparation method of roadmarking glass microballoon of the present invention includes：
Add the first coupling agent to be well mixed in the alkaline aqueous solution of pH value 8～10, pH value is adjusted afterwards to 4～6, prepare the
The surface processing solution of one coupling agent mass concentration 1～5%；
Glass microballoon is boiled in the acidic aqueous solution of pH value 4～6 and obtains activating glass microballoon；
Activation glass microballoon is added and is processed in the surface processing solution, obtain pretreated glass microballon；
Antistatic additive and the second coupling agent are added in alcohol water mixed solution, be configured to antistatic additive mass concentration 0.5～2%, the
The post-treatment solution of two coupling agent mass concentrations 1～5%；
The post-treatment solution is sprayed after pretreated glass microballon is washed, the roadmarking is obtained after 70～80 DEG C of dryings
Use glass microballoon.
Wherein, the first described coupling agent is 3- glycydoxy trimethoxy silanes, 3- (methacryls
Oxygen) propyl trimethoxy silicane, the one kind in dodecyltrimethoxysilane, or several arbitrary proportion mixture；It is described
The second coupling agent be 3- mercaptopropyl trimethoxysilanes or 3- mercaptopropyltriethoxysilanes.
Heretofore described alcohol water mixed solution is conventional alcohol solution, and alcohol therein is methyl alcohol or ethanol.Make
For preferred, the volume ratio of alcohol to water in alcohol water mixed solution of the present invention is 1: 1.
Equally, antistatic additive used in the present invention is also the conventional product with antistatic property.It is of the invention preferred
Using ammonium chloride.
First coupling agent can be mixed with the alkaline aqueous solution by any way.Preferably, the present invention be with
The mode of dropwise addition adds first coupling agent in the alkaline aqueous solution under stirring, and then, it is highly preferred that the present invention is in drop
After adding the first coupling agent, the alkaline aqueous solution is continued to stir 5～15min.
Before activation glass microballoon is added, the pH value of the surface processing solution is adjusted to 4～6 by needs.It is any not with
First coupling agent reacts and can use with the material for adjusting pH value effect.Preferably, the present invention is with acetic acid or lemon
Lemon acid adjusts the surface processing solution.
The present invention be glass microballoon is boiled into 10～30min in the acidic aqueous solution after reach the activation of glass microballoon
Effect.After glass microballoon after activation is filtered off, it is not necessary to be dried process, the surface processing solution can be directly added into
In pre-processed.
Further, activate process time of the glass microballoon in the surface processing solution and be preferably 15～45min, process
Simultaneously stirring should be imposed, suitable mixing speed is set as 500～1500 revs/min.
Equally, being sprayed with the pretreated glass microballon of aftertreatment fluid should impose stirring when being thermally dried, also.
In the way of the roadmarking glass microballoon prepared with said method of the present invention can be mixed within or face is spread with
Road mark paint is used cooperatively, for applying road plan marking lines.
The preparation method process is simple of the roadmarking glass microballoon that the present invention is provided, it is not necessary to special installation, is adapted to
Large-scale production, environmental friendliness in preparation process, production efficiency is high.
The inventive method first carries out activation process to glass microballoon, is lived with the reaction for improving glass microballoon surface functional group
Property, and remove the impurity being mixed with glass microballoon.It is micro- to glass using different silane couplers afterwards by the way of substep
Pearl is surface-treated, wherein, the effect of the first coupling agent mainly improves the compatibility of glass microballoon and gage mark coating matrix,
And the quantity of grafted functional group on glass microballoon is controlled, is reduced because gage mark coating becomes fragile caused by excessive crosslinking；Second is even
The effect of connection agent is the functional group for having catalytic action to part gage mark coating in glass microballoon surface grafting, is mixed into gage mark coating
Afterwards, can possess the effect for improving reaction rate, reducing sedimentation etc..
Glass microballoon prepared by said method interior the mixing in road mark paint uses, and glass microballoon is in gage mark coating base
There is in vivo good dispersion and caking property；Face is spread and have again when using low surface tension, reduces the absorption to pollutant,
Improve the stain resistance and reflecting effect of glass microballoon.Therefore, the use of glass microballoon of the present invention, it is possible to increase roadmarking
The mechanical property and reflective function of coating, extends the active time of gage mark coating.
Glass microballoon after present invention surface treatment is mixed in road mark paint with untreated glass microballon is interior respectively
Apply road plan marking lines and carry out experiment test.As a result show, using the roadmarking any surface finish of glass microballoon after surface treatment,
Reflecting effect is good, and is compared using the roadmarking of untreated glass microballon, and mechanical property improves 20～35%.
Preparation method of the present invention is not only greatly decreased by the multistep reaction for being pre-processed to glass microballoon and being post-processed
The process time of glass microballoon and raw materials consumption, and be grafted different functional groups, by the control of order and consumption,
Make it to environmental condition etc. with higher adaptability.Preparation method of the present invention is improving glass microballoon and gage mark coating compatibility
While, the activation energy of curing reaction of resin in coating can be reduced, in resinite to play catalytic action in coating system
It is quick in system to cause surrounding monomer to be reacted, accelerate reaction process, to reduce sedimentation, lift the security of road traffic.
Specific embodiment
Carry out further citing description to the present invention below by way of specific embodiment, but following embodiments do not constitute it is right
Any restriction of the present invention.On the premise of without departing substantially from the technology of the present invention solution, this area made for the present invention is common
Any change or change that technical staff easily realizes, fall within scope of the presently claimed invention.
The mesh of particle size of glass microspheres scope 30～100 used in the embodiment of the present invention, 2.4～2.6g/cm of density3, refraction
Rate >=1.50.
Embodiment 1
By glass microballoon add pH value 4 aqueous hydrochloric acid solution in, heating boil 10min, leach do not dry it is stand-by.
Take 500mL methyl alcohol to mix with 500mL water, add 5g ammonium chlorides, 10g 3- mercaptopropyl trimethoxysilanes, stirring is equal
It is even to obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 8,5g 3- glycydoxy trimethoxies are added dropwise under stirring with NaOH
Base silane and 5g dodecyltrimethoxysilanes, continue to stir 5min, with the pH value of second acid-conditioning solution to 4.Addition is not dried
Dry glass microballoon, with 500 revs/min of speed 15min is stirred, and leaches glass microballoon, is rinsed 2 times with water.By post-treatment solution
The surface of glass microballoon is uniformly sprayed at, 70 DEG C are warming up to, is heated while stirring, taken out after glass microballoon is dried and obtain road
Graticule glass microballoon.
Embodiment 2
By glass microballoon add pH value 4 aqueous hydrochloric acid solution in, heating boil 20min, leach do not dry it is stand-by.
Take 500mL methyl alcohol to mix with 500mL water, add 5g ammonium chlorides, 30g 3- mercaptopropyl trimethoxysilanes, stirring is equal
It is even to obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 8,10g 3- glycydoxy front threes are added dropwise under stirring with NaOH
TMOS and 20g dodecyltrimethoxysilanes, continue to stir 10min, the pH value of second acid-conditioning solution to 4.Add not
The glass microballoon of drying, with 1000 revs/min of stirring 30min, leaches glass microballoon, is rinsed 2 times with water.Post-treatment solution is uniform
The surface of glass microballoon is sprayed at, 70 DEG C are warming up to, is heated while stirring, taken out after glass microballoon is dried and obtain roadmarking
Use glass microballoon.
Embodiment 3
By glass microballoon add pH value 4 aqueous hydrochloric acid solution in, heating boil 30min, leach do not dry it is stand-by.
Take 500mL methyl alcohol to mix with 500mL water, add 5g ammonium chlorides, 50g 3- mercaptopropyl trimethoxysilanes, stirring is equal
It is even to obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 8,12.5g 3- glycydoxies three are added dropwise under stirring with NaOH
Methoxy silane and 37.5g dodecyltrimethoxysilanes, continue to stir 15min, with the pH value of second acid-conditioning solution to 4.
The glass microballoon that addition is not dried, with 1500 revs/min of speed 45min is stirred, and leaches glass microballoon, is rinsed 2 times with water, by after
Processing solution is uniformly sprayed at the surface of glass microballoon, is warming up to 70 DEG C, heats while stirring, takes out after glass microballoon is dried
Obtain roadmarking glass microballoon.
Embodiment 4
By glass microballoon add pH value 5 aqueous hydrochloric acid solution in, heating boil 10min, leach do not dry it is stand-by.
Take 500mL ethanol to mix with 500mL water, add 15g ammonium chlorides, 10g 3- mercaptopropyltriethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 9,5g 3- (methacryloxypropyl) propyl group trimethoxy is added dropwise under stirring with NaOH
Base silane and 5g dodecyltrimethoxysilanes, continue to stir 10min, the pH value of citric acid regulating solution to 5.Addition is not dried
Dry glass microballoon, with 500 revs/min of speed 30min is stirred, and leaches glass microballoon, is rinsed 2 times with water, by post-treatment solution
The surface of glass microballoon is uniformly sprayed at, 75 DEG C are warming up to, is heated while stirring, taken out after glass microballoon is dried and obtain road
Graticule glass microballoon.
Embodiment 5
By glass microballoon add pH value 5 aqueous hydrochloric acid solution in, heating boil 20min, leach do not dry it is stand-by.
Take 500mL ethanol to mix with 500mL water, add 15g ammonium chlorides, 30g 3- mercaptopropyltriethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 9,20g 3- (methacryloxypropyl) propyl group trimethoxy is added dropwise under stirring with KOH
Base silane and 10g dodecyltrimethoxysilanes, continue to stir 15min, with lemon acid for adjusting pH value to 4.Addition is not dried
Glass microballoon, 45min is stirred with 1000 revs/min of speed, leach glass microballoon, rinsed 2 times with water, post-treatment solution is equal
The even surface for being sprayed at glass microballoon, is warming up to 75 DEG C, heats while stirring, takes out after glass microballoon is dried and obtains road sign
Line glass microballoon.
Embodiment 6
By glass microballoon add pH value 5 aqueous hydrochloric acid solution in, heating boil 30min, leach do not dry it is stand-by.
Take 500mL ethanol to mix with 500mL water, add 15g ammonium chlorides, 50g 3- mercaptopropyltriethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 9,37.5g 3- (methyl-propyl acyl-oxygen) propyl group front three is added dropwise under stirring with KOH
TMOS and 12.5g dodecyltrimethoxysilanes, continue to stir 5min, with the pH value of citric acid regulating solution to 5.Plus
Enter the glass microballoon do not dried, 15min is stirred with 1500 revs/min of speed, leach glass microballoon, rinsed 2 times with water, by rear place
Reason solution is uniformly sprayed at the surface of glass microballoon, is warming up to 75 DEG C, heats while stirring, takes out after glass microballoon is dried
To roadmarking glass microballoon.
Embodiment 7
By glass microballoon add pH value 6 aqueous hydrochloric acid solution in, heating boil 10min, leach do not dry it is stand-by.
Take 500mL methyl alcohol to mix with 500mL water, add 20g ammonium chlorides, 10g 3- mercaptopropyl trimethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 10,7.5g 3- glycydoxy front threes are added dropwise under stirring with KOH
TMOS and 2.5g dodecyltrimethoxysilanes, continue to stir 15min, with the pH value of second acid-conditioning solution to 6.Add
The glass microballoon do not dried, with 500 revs/min of speed 45min is stirred, and leaches glass microballoon, is rinsed 2 times with water, will be post-processed
Solution is uniformly sprayed at the surface of glass microballoon, is warming up to 80 DEG C, heats while stirring, takes out after glass microballoon is dried and obtains
Roadmarking glass microballoon.
Embodiment 8
By glass microballoon add pH value 6 aqueous hydrochloric acid solution in, heating boil 20min, leach do not dry it is stand-by.
Take 500mL ethanol to mix with 500mL water, add 20g ammonium chlorides, 30g 3- mercaptopropyltriethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 10,18g 3- glycydoxy front threes are added dropwise under stirring with NaOH
TMOS and 12g dodecyltrimethoxysilanes, continue to stir 5min, with second acid for adjusting pH value to 6.What addition was not dried
Glass microballoon, with 1000 revs/min of speed 15min is stirred, and leaches glass microballoon, is rinsed 2 times with water, and post-treatment solution is uniform
The surface of glass microballoon is sprayed at, 80 DEG C are warming up to, is heated while stirring, taken out after glass microballoon is dried and obtain roadmarking
Use glass microballoon.
Embodiment 9
By glass microballoon add pH value 6 aqueous hydrochloric acid solution in, heating boil 30min, leach do not dry it is stand-by.
Take 500mL methyl alcohol to mix with 500mL water, add 20g ammonium chlorides, 50g 3- mercaptopropyl trimethoxysilanes, stirring
Uniformly obtain post-treatment solution.
The pH value of 1000mL water is adjusted to 10,37.5g 3- (methacryloxypropyl) propyl group three is added dropwise under stirring with NaOH
Methoxy silane and 12.5g dodecyltrimethoxysilanes, continue to stir 10min, with the pH value of citric acid regulating solution extremely
6.The glass microballoon that addition is not dried, with 1500 revs/min of speed 30min is stirred, and leaches glass microballoon, is rinsed 2 times with water, will
Post-treatment solution is uniformly sprayed at the surface of glass microballoon, is warming up to 80 DEG C, heats while stirring, takes after glass microballoon is dried
Go out to obtain roadmarking glass microballoon.
Claims (10)
1. a kind of preparation method of roadmarking glass microballoon, methods described includes：
Add the first coupling agent to be well mixed in the alkaline aqueous solution of pH value 8～10, pH value is adjusted afterwards to 4～6, prepare the
The surface processing solution of one coupling agent mass concentration 1～5%；
Glass microballoon is boiled in the acidic aqueous solution of pH value 4～6 and obtains activating glass microballoon；
Activation glass microballoon is added and is processed in the surface processing solution, obtain pretreated glass microballon；
Antistatic additive and the second coupling agent are added in alcohol water mixed solution, be configured to antistatic additive mass concentration 0.5～2%, the
The post-treatment solution of two coupling agent mass concentrations 1～5%；
The post-treatment solution is sprayed after pretreated glass microballon is washed, the roadmarking is obtained after 70～80 DEG C of dryings
Use glass microballoon；
Wherein, the first described coupling agent is 3- glycydoxy trimethoxy silanes, 3- (methacryloxypropyl)
One kind in propyl trimethoxy silicane, dodecyltrimethoxysilane, or several arbitrary proportion mixtures；Described
Two coupling agents are 3- mercaptopropyl trimethoxysilanes or 3- mercaptopropyltriethoxysilanes.
2. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that the alcohol water mixing is molten
Alcohol used in liquid is methyl alcohol or ethanol.
3. the preparation method of roadmarking glass microballoon according to claim 1 and 2, is characterized in that the alcohol water mixing
Volume ratio of alcohol to water in solution is 1: 1.
4. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that described antistatic additive
For ammonium chloride.
5. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that being coupled described first
Agent is added dropwise in the alkaline aqueous solution under stirring, continues to stir 5～15min preparation surface processing solutions after completion of dropping.
6. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that with acetic acid or citric acid
The pH value of the surface processing solution is adjusted to 4～6.
7. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that glass microballoon in institute
State and boil in acidic aqueous solution 10～30min.
8. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that glass microballoon will be activated
Add 15～45min of stir process in the surface processing solution.
9. the preparation method of roadmarking glass microballoon according to claim 8, is characterized in that the mixing speed is
500～1500 revs/min.
10. the preparation method of roadmarking glass microballoon according to claim 1, is characterized in that post processing will be sprayed with
The pretreated glass microballon of liquid is thermally dried under agitation.
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| CN111234682A (en) * | 2020-01-17 | 2020-06-05 | 成都迪泰化工有限公司 | Photosensitive graphene oxide UV (ultraviolet) photocuring building coating and preparation method thereof |
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| CN114410144A (en) * | 2022-02-25 | 2022-04-29 | 山西中涂交通科技股份有限公司 | Anti-settling glass bead for hot-melt marking paint |
| CN114410144B (en) * | 2022-02-25 | 2023-03-10 | 山西中涂交通科技股份有限公司 | Anti-settling glass bead for hot-melt marking paint |
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