CN106634137B - A kind of preparation method of roadmarking glass microballoon - Google Patents
A kind of preparation method of roadmarking glass microballoon Download PDFInfo
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- CN106634137B CN106634137B CN201611252639.4A CN201611252639A CN106634137B CN 106634137 B CN106634137 B CN 106634137B CN 201611252639 A CN201611252639 A CN 201611252639A CN 106634137 B CN106634137 B CN 106634137B
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- glass microballoon
- roadmarking
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- glass
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- 239000011521 glass Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002216 antistatic agent Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 17
- 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
- 230000004913 activation Effects 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 7
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound 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 5
- -1 methacryloxypropyl Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture 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
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000012805 post-processing Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 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
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 230000001070 adhesive effect Effects 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
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 244000248349 Citrus limon Species 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DUUSWXBAUSDNRJ-UHFFFAOYSA-N CC(=C)C([O])=O Chemical compound CC(=C)C([O])=O DUUSWXBAUSDNRJ-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000000126 substance Substances 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
Abstract
The invention discloses a kind of preparation methods of roadmarking glass microballoon, it is to pre-process the acidic activated elder generation afterwards of glass microballoon with the first coupling agent, the alcohol water mixed solution for spraying antistatic agent and the second coupling agent again is post-processed, and obtains roadmarking glass microballoon after dry.The present invention passes through multi step strategy mode, the attachment adhesive effect for improving glass microballoon and gage mark coating and the dispersibility in gage mark coating, reduce the surface tension of glass microballoon and the absorption to pollutant, improve the stain resistance and reflecting effect of glass microballoon, catalytic action can also be played simultaneously, monomer reaction around quickly causing in resin system, reduce sedimentation, improve the mechanical property and reflective function of gage mark coating, the active time for extending gage mark coating improves the safety of road traffic.
Description
Technical field
The present invention relates to the surface treatment of glass microballoon, more particularly to the surface treatment of roadmarking glass microballoon,
Treated in the process of the present invention, and glass microballoon is suitble to the interior mixed face in road mark paint to spread use.
Background technique
The roadmarking retroreflective energy of glass microballoon energy road improvement gage mark coating, improves the safety of driving at night
Property, it is most common reflectorized material in road mark paint.But in actual use, due to glass microballoon and road mark paint
Adhesiveness it is bad, the glass microballoon on roadmarking surface is easy to fall off in use, cause roadmarking reflecting effect decline.
Simultaneously as glass microballoon surface is in polarity, it is easy absorption polluter, can also cause the reduction of roadmarking reflecting effect.
CN 103571234A discloses a kind of preparation method of reflective membrane modified glass microspheres, during the preparation process
Glass microballoon is not pre-processed, is directly changed in acid modification solution with coupling agent, surfactant and film forming agent
Property processing, processing speed is slower, and the continuous heating of long period is needed in treatment process, in addition, the method use larger
The coupling agent of amount is bound to cause unnecessary waste.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of roadmarking glass microballoon, prepare in the process of the present invention
The caking property of glass microballoon and road mark paint is strong, and glass microballoon surface tension is small, can be reduced the absorption to pollutant.
The preparation method of roadmarking glass microballoon of the present invention includes:
The first coupling agent is added in the alkaline aqueous solution of pH value 8~10 to be uniformly mixed, adjusts pH value later to 4~6, matches
Make the surface processing solution of the first coupling agent mass concentration 1~5%；
Glass microballoon is boiled to obtain activation glass microballoon in the acidic aqueous solution of pH value 4~6；
Activation glass microballoon is added in the surface processing solution and is handled, pretreated glass microballon is obtained；
Antistatic agent and the second coupling agent are added into alcohol water mixed solution, be configured to antistatic agent mass concentration 0.5~
2%, the post-treatment solution of the second coupling agent mass concentration 1~5%；
The post-treatment solution will be sprayed after the washing of pretreated glass microballon, obtains the road after dry in 70~80 DEG C
Graticule glass microballoon.
Wherein, first coupling agent is 3- glycidyl ether oxypropyltrimethoxysilane, 3- (methacryl
Oxygen) propyl trimethoxy silicane, one of dodecyltrimethoxysilane or several arbitrary proportion mixtures；It is described
The second coupling agent be 3- mercaptopropyl trimethoxysilane or 3- mercaptopropyltriethoxysilane.
Heretofore described alcohol water mixed solution is conventional alcohol solution, and alcohol therein is methanol or ethyl alcohol.Make
To be preferred, the volume ratio of alcohol to water in alcohol water mixed solution of the present invention is 1: 1.
Equally, antistatic agent used in the present invention is also the conventional product with antistatic property.The present invention is preferred
Using ammonium chloride.
First coupling agent can be mixed with the alkaline aqueous solution in any way.Preferably, the present invention be with
First coupling agent is added in the alkaline aqueous solution under stirring the mode of dropwise addition, in turn, it is highly preferred that the present invention is being dripped
After adding the first coupling agent, the alkaline aqueous solution is continued into 5~15min of stirring.
Before activation glass microballoon is added, the pH value by the surface processing solution is needed to be adjusted to 4~6.It is any not with
First coupling agent reacts and there is the substance for adjusting pH value effect can be used.Preferably, the present invention is with acetic acid or lemon
Lemon acid adjusts the surface processing solution.
The present invention is to reach the activation of glass microballoon after glass microballoon to be boiled to 10~30min in the acidic aqueous solution
Effect.It after glass microballoon after activation is filtered off, does not need to be dried, the surface processing solution can be directly added into
In pre-processed.
In turn, processing time of the activation glass microballoon in the surface processing solution is preferably 15~45min, processing
Stirring should be imposed simultaneously, suitable mixing speed is set as 500~1500 revs/min.
Equally, the pretreated glass microballon of aftertreatment fluid is sprayed with when being thermally dried, and should also impose stirring.
By the roadmarking that the above method of the present invention is prepared in such a way that glass microballoon can mix within or face is spread with
Road mark paint is used cooperatively, for applying road plan marking lines.
The preparation method simple process of roadmarking glass microballoon provided by the invention, does not need special installation, is suitble to
Large-scale production, environmental-friendly, high production efficiency in preparation process.
The method of the present invention is first activated glass microballoon, living with the reaction for improving glass microballoon surface functional group
Property, and remove the impurity being mixed in glass microballoon.It is micro- to glass using different silane coupling agents later by the way of substep
Pearl is surface-treated, wherein and 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, gage mark coating becomes fragile caused by reducing because of excessive crosslinking；Second is even
The effect of connection agent is the functional group in glass microballoon surface grafting to part gage mark coating with catalytic action, is mixed into gage mark coating
Afterwards, can have the effect improve reaction rate, reduce sedimentation etc..
Glass microballoon interior mixed use in road mark paint prepared by the above method, glass microballoon is in gage mark coating base
There is good dispersion and caking property in vivo；There is low surface tension again when use is spread in face, reduce the absorption to pollutant,
Improve the stain resistance and reflecting effect of glass microballoon.Therefore, the use of glass microballoon of the present invention, can be improved roadmarking
The mechanical property and reflective function of coating, extend the active time of gage mark coating.
By the present invention surface treatment after glass microballoon and untreated glass microballon respectively in be mixed in road mark paint
It applies road plan marking lines and carries out experiment test.The results show that using the roadmarking any surface finish of glass microballoon after surface treatment,
Reflecting effect is good, and compared with the roadmarking for using untreated glass microballon, mechanical property improves 20~35%.
Preparation method of the present invention is not only greatly decreased by the multistep reaction for being pre-processed and being post-processed to glass microballoon
The processing time of glass microballoon and raw materials consumption, and be grafted different functional groups, by the control of sequence and dosage,
Make it that there is higher adaptability to environmental condition etc..Preparation method of the present invention is improving glass microballoon and gage mark coating compatibility
While, catalytic action can also be played in coating system, the activation energy of curing reaction of resin in coating is reduced, in resinite
Quickly cause surrounding monomer in system to be reacted, accelerate reaction process, to reduce sedimentation, promotes the safety of road traffic.
Specific embodiment
Further citing description carried out to the present invention below by way of specific embodiment, but following embodiments are not constituted pair
Any restrictions of the invention.Under the premise of without departing substantially from the technology of the present invention solution, this field made for the present invention is common
Technical staff's any modifications or changes easy to accomplish, fall within scope of the presently claimed invention.
30~100 mesh of particle size of glass microspheres range used in the embodiment of the present invention, 2.4~2.6g/cm of density3, refraction
Rate >=1.50.
Embodiment 1
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 4,10min is boiled in heating, filters out and does not dry for use.
It takes 500mL methanol to mix with 500mL water, 5g ammonium chloride, 10g 3- mercaptopropyl trimethoxysilane is added, stirring is equal
It is even to obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 5g 3- glycydoxy trimethoxy to 8 under stirring
Base silane and 5g dodecyltrimethoxysilane continue to stir 5min, with the pH value of second acid-conditioning solution to 4.Addition is not dried
Dry glass microballoon stirs 15min with 500 revs/min of speed, filters out glass microballoon, be rinsed with water 2 times.By post-treatment solution
It is uniformly sprayed at the surface of glass microballoon, 70 DEG C is warming up to, heats while stirring, is taken out after glass microballoon is dry and obtains road
Graticule glass microballoon.
Embodiment 2
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 4,20min is boiled in heating, filters out and does not dry for use.
It takes 500mL methanol to mix with 500mL water, 5g ammonium chloride, 30g 3- mercaptopropyl trimethoxysilane is added, stirring is equal
It is even to obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 10g 3- glycydoxy front three to 8 under stirring
Oxysilane and 20g dodecyltrimethoxysilane continue to stir 10min, the pH value of second acid-conditioning solution to 4.It is added not
The glass microballoon of drying is filtered out glass microballoon, is rinsed with water 2 times with 1000 revs/min of stirring 30min.Post-treatment solution is uniform
It is sprayed at the surface of glass microballoon, 70 DEG C is warming up to, heats while stirring, is taken out after glass microballoon is dry and obtains roadmarking
Use glass microballoon.
Embodiment 3
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 4,30min is boiled in heating, filters out and does not dry for use.
It takes 500mL methanol to mix with 500mL water, 5g ammonium chloride, 50g 3- mercaptopropyl trimethoxysilane is added, stirring is equal
It is even to obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 12.5g 3- glycydoxy three to 8 under stirring
Methoxy silane and 37.5g dodecyltrimethoxysilane continue to stir 15min, with the pH value of second acid-conditioning solution to 4.
The glass microballoon do not dried is added, 45min is stirred with 1500 revs/min of speed, glass microballoon is filtered out, is rinsed with water 2 times, will 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 dry
Obtain roadmarking glass microballoon.
Embodiment 4
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 5,10min is boiled in heating, filters out and does not dry for use.
It takes 500mL ethyl alcohol to mix with 500mL water, 15g ammonium chloride, 10g 3- mercaptopropyltriethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 5g 3- (methacryloxypropyl) propyl trimethoxy to 9 under stirring
Base silane and 5g dodecyltrimethoxysilane continue to stir 10min, the pH value of citric acid regulating solution to 5.Addition is not dried
Dry glass microballoon stirs 30min with 500 revs/min of speed, filters out glass microballoon, be rinsed with water 2 times, by post-treatment solution
It is uniformly sprayed at the surface of glass microballoon, 75 DEG C is warming up to, heats while stirring, is taken out after glass microballoon is dry and obtains road
Graticule glass microballoon.
Embodiment 5
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 5,20min is boiled in heating, filters out and does not dry for use.
It takes 500mL ethyl alcohol to mix with 500mL water, 15g ammonium chloride, 30g 3- mercaptopropyltriethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with KOH is added dropwise to 20g 3- (methacryloxypropyl) propyl trimethoxy to 9 under stirring
Base silane and 10g dodecyltrimethoxysilane 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, glass microballoon is filtered out, is rinsed with water 2 times, 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 dry and obtains road sign
Line glass microballoon.
Embodiment 6
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 5,30min is boiled in heating, filters out and does not dry for use.
It takes 500mL ethyl alcohol to mix with 500mL water, 15g ammonium chloride, 50g 3- mercaptopropyltriethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with KOH is added dropwise to 37.5g 3- (methyl-propyl acyl-oxygen) propyl front three to 9 under stirring
Oxysilane and 12.5g dodecyltrimethoxysilane continue to stir 5min, with the pH value of citric acid regulating solution to 5.Add
Enter the glass microballoon that do not dry, 15min is stirred with 1500 revs/min of speed, glass microballoon is filtered out, is rinsed with water 2 times, by after
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 dry
To roadmarking glass microballoon.
Embodiment 7
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 6,10min is boiled in heating, filters out and does not dry for use.
It takes 500mL methanol to mix with 500mL water, 20g ammonium chloride, 10g 3- mercaptopropyl trimethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with KOH is added dropwise to 7.5g 3- glycydoxy front three to 10 under stirring
Oxysilane and 2.5g dodecyltrimethoxysilane continue to stir 15min, with the pH value of second acid-conditioning solution to 6.It is added
The glass microballoon that do not dry stirs 45min with 500 revs/min of speed, filters out glass microballoon, be rinsed with water 2 times, will post-process
Solution is uniformly sprayed at the surface of glass microballoon, is warming up to 80 DEG C, heats while stirring, takes out and obtains after glass microballoon is dry
Roadmarking glass microballoon.
Embodiment 8
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 6,20min is boiled in heating, filters out and does not dry for use.
It takes 500mL ethyl alcohol to mix with 500mL water, 20g ammonium chloride, 30g 3- mercaptopropyltriethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 18g 3- glycydoxy front three to 10 under stirring
Oxysilane and 12g dodecyltrimethoxysilane continue to stir 5min, with second acid for adjusting pH value to 6.What addition was not dried
Glass microballoon stirs 15min with 1000 revs/min of speed, filters out glass microballoon, be rinsed with water 2 times, and post-treatment solution is uniform
It is sprayed at the surface of glass microballoon, 80 DEG C is warming up to, heats while stirring, is taken out after glass microballoon is dry and obtains roadmarking
Use glass microballoon.
Embodiment 9
Glass microballoon is added in the aqueous hydrochloric acid solution of pH value 6,30min is boiled in heating, filters out and does not dry for use.
It takes 500mL methanol to mix with 500mL water, 20g ammonium chloride, 50g 3- mercaptopropyl trimethoxysilane, stirring is added
Uniformly obtain post-treatment solution.
The pH value for adjusting 1000mL water with NaOH is added dropwise to 37.5g 3- (methacryloxypropyl) propyl three to 10 under stirring
Methoxy silane and 12.5g dodecyltrimethoxysilane continue to stir 10min, extremely with the pH value of citric acid regulating solution
6.The glass microballoon that do not dry is added, 30min is stirred with 1500 revs/min of speed, glass microballoon is filtered out, is rinsed with water 2 times, it 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 dry
Roadmarking glass microballoon is obtained out.
Claims (10)
1. a kind of preparation method of roadmarking glass microballoon, which comprises
The first coupling agent is added in the alkaline aqueous solution of pH value 8~10 to be uniformly mixed, adjusts pH value later to 4~6, prepares the
The surface processing solution of one coupling agent mass concentration 1~5%；
Glass microballoon is boiled to obtain activation glass microballoon in the acidic aqueous solution of pH value 4~6；
Activation glass microballoon is added in the surface processing solution and is handled, pretreated glass microballon is obtained；
Antistatic agent and the second coupling agent are added into alcohol water mixed solution, is configured to antistatic agent mass concentration 0.5~2%, the
The post-treatment solution of two coupling agent mass concentrations 1~5%；
The post-treatment solution will be sprayed after the washing of pretreated glass microballon, obtains the roadmarking after dry in 70~80 DEG C
Use glass microballoon；
Wherein, first coupling agent is 3- glycidyl ether oxypropyltrimethoxysilane, 3- (methacryloxypropyl)
One of propyl trimethoxy silicane, dodecyltrimethoxysilane or several arbitrary proportion mixtures；Described
Two coupling agents are 3- mercaptopropyl trimethoxysilane or 3- mercaptopropyltriethoxysilane.
2. the preparation method of roadmarking glass microballoon according to claim 1, it is characterized in that alcohol water mixing is molten
Alcohol used in liquid is methanol or ethyl alcohol.
3. the preparation method of roadmarking glass microballoon according to claim 1 or 2, it is characterized in that the alcohol water mixes
Volume ratio of alcohol to water in solution is 1: 1.
4. the preparation method of roadmarking glass microballoon according to claim 1, it is characterized in that the antistatic agent
For ammonium chloride.
5. the preparation method of roadmarking glass microballoon according to claim 1, it is characterized in that described first is coupled
Agent is added dropwise in the alkaline aqueous solution under stirring, is continued 5~15min of stirring after being added dropwise and is prepared surface processing solution.
6. the preparation method of roadmarking glass microballoon according to claim 1, it 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, it is characterized in that by glass microballoon in institute
It states and boils 10~30min in acidic aqueous solution.
8. the preparation method of roadmarking glass microballoon according to claim 1, it is characterized in that glass microballoon will be activated
15~45min of stir process in the surface processing solution is added.
9. the preparation method of roadmarking glass microballoon according to claim 8, it is characterized in that the mixing speed is
500~1500 revs/min.
10. the preparation method of roadmarking glass microballoon according to claim 1, it is characterized in that post-processing will be sprayed with
The pretreated glass microballon of liquid is thermally dried under stiring.
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| CN108504240A (en) * | 2018-04-28 | 2018-09-07 | 黄旭东 | A kind of permanent seal cooling road mark paint |
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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 |
| 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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