CN111533860B - Super-hydrophobic modifier for water-based paint and preparation method thereof - Google Patents
Super-hydrophobic modifier for water-based paint and preparation method thereof Download PDFInfo
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- CN111533860B CN111533860B CN202010521305.2A CN202010521305A CN111533860B CN 111533860 B CN111533860 B CN 111533860B CN 202010521305 A CN202010521305 A CN 202010521305A CN 111533860 B CN111533860 B CN 111533860B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 31
- 239000003973 paint Substances 0.000 title claims abstract description 30
- 239000003607 modifier Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 15
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 56
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- -1 mercapto, vinyl Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000000080 wetting agent Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical group N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
-
- 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
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a super-hydrophobic modifier for a water-based coating, which is prepared by reacting polyhedral oligomeric silsesquioxane (POSS) which simultaneously contains an active group and fluoroalkyl with a surfactant with a double-bond structure to prepare POSS which simultaneously contains fluoroalkyl and a surfactant group. Through a polymerization grafting mode, a surfactant group is introduced, so that the dispersion uniformity and wettability of POSS in the water-based paint are ensured, and the film forming property and the adhesive force of a paint film are obviously improved. Compared with the traditional method for directly adding a wetting agent or a surfactant into the coating, the method directly connects the surfactant group to the super-hydrophobic modifier in a polymerization grafting manner, so that the dispersion uniformity and wettability of the super-hydrophobic modifier in the water-based coating are improved more favorably.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to a super-hydrophobic modifier for water-based paint and a preparation method thereof.
Background
Waterborne coatings are commonly used on the surfaces of various types of objects to be decorated or protected. Currently, the most studied and used water-based paints are acrylic water-based paints and polyurethane water-based paints. Generally, these waterborne coatings have some degree of hydrophobicity. Moreover, various hydrophobic modifiers can be added into the coating to enhance the hydrophobicity of the coating, so that a super-hydrophobic effect is obtained.
The super-hydrophobic effect is obtained based on the super-hydrophobic surface of the formed coating film, and the super-hydrophobic surface of the coating film can be realized by adding inorganic nano particles, such as nano silicon dioxide, nano titanium dioxide and the like, into the coating, or adding organic matters, such as fluorinated alkane, fluorinated siloxane and the like, into the coating.
However, in the case of the water-based paint, the inorganic nanoparticles are directly added thereto, and there are disadvantages that the dispersion uniformity of the inorganic nanoparticles is not good and the adhesion of the paint film is poor. Low surface energy substances such as fluoroalkanes and fluorosilicones are not added in dispersibility in aqueous coating materials, and have insufficient film-forming properties, and are difficult to use with aqueous coating materials.
Therefore, in view of the above problems of the prior art hydrophobic modifier used in water paint, the present invention aims to provide a super hydrophobic modifier suitable for water paint.
Disclosure of Invention
Aiming at the problems, the invention provides a super-hydrophobic modifier for a water-based paint, which comprises the following steps:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group;
wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R8At least one of which is fluoroalkyl and at least one of which is an active group;
the active group refers to a functional group capable of reacting with a double bond, including but not limited to mercapto, vinyl, acrylate;
wherein R is9Is C1-C10 alkyl, R10Is C1-C10 alkylene, R11Is C2-C4 alkylene, R12Is C1-C4 alkylene, and X is one of sulfonate, phosphate and benzene sulfonate.
Further, the salt in the sulfonate group, the phosphate group and the benzene sulfonate group refers to one or more of potassium salt, sodium salt and ammonium salt.
Further, the mercapto group is selected from HS- (CH)2)m-, wherein m is an integer of 1 to 5.
Further, the vinyl group is selected from CH2=CH-(CH2)n-, wherein n is an integer of 1 to 5.
Further, the acrylate group is selected from one or more of an ethyl acrylate group, a methyl methacrylate group and an ethyl methacrylate group.
Further, the fluoroalkyl is selected from one or more of C1-C10 perfluoroalkyl.
Further, R1~R8Of these, it preferably contains at least 3 fluoroalkyl groups and at least 3 reactive groups. More preferably 4 fluoroalkyl groups and 4 reactive groups.
Further, in the preparation method, the molar ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1: (3-5).
Dissolving cage type polysilsesquioxane shown in a formula (I) and provided with active groups and fluoroalkyl in a solvent, adding a catalyst, carrying out heating reaction with a surfactant shown in a formula (II) and provided with a double bond structure, wherein the reaction temperature is 40-80 ℃, the reaction time is 3-8 h, and carrying out reduced pressure distillation to remove the solvent after the reaction is finished.
Wherein the solvent is one or more selected from toluene, ethyl acetate and tetrahydrofuran.
Wherein the catalyst is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile and persulfate.
Wherein the mass ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1 (10-30).
According to the invention, the polyhedral oligomeric silsesquioxane containing both the fluoroalkyl group and the surfactant group is prepared by reacting the cage polysilsesquioxane shown in the formula (I) and having both the active group and the fluoroalkyl group with the surfactant shown in the formula (II) and having a double bond structure. The POSS still maintains the properties of the cage type polysilsesquioxane nano-compound, can ensure that the surface of the coating film has nano-scale surface roughness, and provides a nano surface structure foundation for a super-hydrophobic surface. In the POSS, the low-surface-functional fluoroalkyl group with super-hydrophobicity further ensures the super-hydrophobicity of the coating film.
In addition, in the cage-type structure, the inorganic core consisting of a large amount of Si-O frameworks is matched with the cage-type network framework, so that the POSS has a certain toughening effect on the coating film, the film forming property and the internal stress of the coating film are improved, and the adhesive force of the coating film is improved.
In addition, in the POSS, a surfactant group is introduced in a polymerization grafting mode, so that the dispersion uniformity and wettability of the POSS in the water-based paint are ensured, and the film forming property and the adhesive force of a paint film are obviously improved. Compared with the traditional method for directly adding a wetting agent or a surfactant into the coating, the method directly connects the surfactant group to the super-hydrophobic modifier in a polymerization grafting manner, so that the dispersion uniformity and wettability of the super-hydrophobic modifier in the water-based coating are improved more favorably.
Detailed Description
The present invention will be described more specifically with reference to some embodiments, which are only a part of the present invention, and not all of them. Other embodiments, which can be derived by those skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A super-hydrophobic modifier for water paint is prepared through:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group; the molar ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1: 4; dissolving cage type polysilsesquioxane shown in a formula (I) and simultaneously having an active group and fluoroalkyl into a solvent, adding a catalyst, and carrying out heating reaction with a surfactant shown in a formula (II) and having a double bond structure at the reaction temperature of 60 ℃ for 5h, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent.
Wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R8With 4 fluoroalkyl groups and 4 reactive groups.
The active group refers to a functional group capable of reacting with a double bond, is vinyl, and is specifically CH2=CH-(CH2)3-; the fluoroalkyl group is a C4 perfluoroalkyl group.
Wherein R is9Is C5 alkyl, R10Being alkylene of C5, R11Being alkylene of C2, R12Is C1 alkylene, and X is sodium sulfonate radical.
Wherein the solvent is toluene; the catalyst is tert-butyl hydroperoxide.
Wherein the mass ratio of the total mass to the solvent is 1:20 based on the total mass of the cage-type polysilsesquioxane represented by the formula (I) and having both an active group and a fluoroalkyl group and the surfactant having a double bond structure represented by the formula (II).
Example 2
A super-hydrophobic modifier for water paint is prepared through:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group; the molar ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1: 5; dissolving cage type polysilsesquioxane shown in a formula (I) and simultaneously having an active group and fluoroalkyl into a solvent, adding a catalyst, and carrying out heating reaction with a surfactant shown in a formula (II) and having a double bond structure at the reaction temperature of 70 ℃ for 4h, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent.
Wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R83 of them are fluoroalkyl groups and 5 are reactive groups.
The active group is a functional group capable of reacting with double bonds, is a sulfydryl, and is specifically HS- (CH)2)3-; the fluoroalkyl group is a C6 perfluoroalkyl group.
Wherein R is9Is C3 alkyl, R10Being alkylene of C7, R11Being alkylene of C4, R12Is C3 alkylene, and X is potassium benzenesulfonate.
Wherein the solvent is ethyl acetate, and the catalyst is azobisisobutyronitrile.
Wherein the mass ratio of the cage-type polysilsesquioxane represented by the formula (I) and having both an active group and a fluoroalkyl group to the solvent is 1:15 based on the total mass of the surfactant having a double bond structure represented by the formula (II).
Example 3
A super-hydrophobic modifier for water paint is prepared through:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group; the molar ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1: 3; dissolving cage type polysilsesquioxane shown in a formula (I) and simultaneously having an active group and fluoroalkyl into a solvent, adding a catalyst, and carrying out heating reaction with a surfactant shown in a formula (II) and having a double bond structure at the reaction temperature of 50 ℃ for 6h, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent.
Wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R85 of them are fluoroalkyl groups and 3 are reactive groups.
The active group is a functional group capable of reacting with double bonds, and is an acrylate group, specifically an ethyl acrylate group; the fluoroalkyl group is a C8 perfluoroalkyl group.
Wherein R is9Is C6 alkyl, R10Being alkylene of C4, R11Being alkylene of C3, R12Is C2 alkylene, and X is sodium phosphate radical.
Wherein, the solvent is tetrahydrofuran, and the catalyst is persulfate.
Wherein the mass ratio of the total mass to the solvent is 1:30 based on the total mass of the cage-type polysilsesquioxane represented by the formula (I) and having both an active group and a fluoroalkyl group and the surfactant having a double bond structure represented by the formula (II).
Example 4
A super-hydrophobic modifier for water paint is prepared through:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group; the molar ratio of the cage-type polysilsesquioxane shown in the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown in the formula (II) and provided with the double bond structure is 1: 4; dissolving cage type polysilsesquioxane shown in a formula (I) and simultaneously having an active group and fluoroalkyl into a solvent, adding a catalyst, and carrying out heating reaction with a surfactant shown in a formula (II) and having a double bond structure at the reaction temperature of 80 ℃ for 3h, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent.
Wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R8With 4 fluoroalkyl groups and 4 reactive groups.
The active group refers to a functional group capable of reacting with a double bond, is vinyl, and is specifically CH2=CH-(CH2)4-; the fluoroalkyl group is a C6 perfluoroalkyl group.
Wherein R is9Is C4 alkyl, R10Being alkylene of C6, R11Being alkylene of C1, R12Is C1 alkylene, and X is sodium benzenesulfonate radical.
Wherein the solvent is ethyl acetate; the catalyst is tert-butyl hydroperoxide.
Wherein the mass ratio of the total mass to the solvent is 1:20 based on the total mass of the cage-type polysilsesquioxane represented by the formula (I) and having both an active group and a fluoroalkyl group and the surfactant having a double bond structure represented by the formula (II).
Comparative example
Directly using cage type polysilsesquioxane shown as a formula (I) as a super-hydrophobic modifier, wherein R1~R8Perfluoroalkyl of all C4, in combination with the anionic surfactant sodium dodecyl sulfate.
Comparing the effects of the superhydrophobic modifiers of examples 1-4 and comparative example, which were applied to an aqueous coating material and the aqueous coating material was coated on the surface of a clean metal plate, respectively, after curing, the coating film was tested for superhydrophobicity and adhesion stability. Wherein the superhydrophobicity is measured by measuring the contact angle of the surface of the coating film to water using a contact angle measuring instrument; the adhesion stability is tested by referring to GB/T9286-1988, the test results are respectively in six grades of 0-5, 0 represents the most stable adhesion, 5 represents the least stable adhesion, and the results are shown in the following table.
| Static contact Angle (°) | Adhesion stability (grade) | |
| Example 1 | 153 | 0 |
| Example 2 | 151 | 0 |
| Example 3 | 150 | 0 |
| Example 4 | 153 | 0 |
| Comparative example | 146 | 1 |
From the above table, compared with the traditional method of directly adding a wetting agent or a surfactant into a coating, the method of the invention introduces a surfactant group into the polyhedral oligomeric silsesquioxane by a polymerization grafting method, so as to ensure the dispersion uniformity and wettability of the POSS in the water-based coating, and obviously improve the film forming property and the adhesion of the coating film. Moreover, the coating film has improved film forming property and adhesion, and in turn has a certain promotion effect on the super-hydrophobicity of the coating film.
Claims (10)
1. A preparation method of a super-hydrophobic modifier of a water-based paint comprises the following steps:
reacting cage polysilsesquioxane shown in a formula (I) and simultaneously provided with an active group and fluoroalkyl with a surfactant shown in a formula (II) and provided with a double bond structure to prepare POSS simultaneously containing fluoroalkyl and a surfactant group;
wherein R is1~R8Independently selected from fluoroalkyl or a reactive group, and R1~R8At least one of which is fluoroalkyl and at least one of which is an active group;
the active group refers to a functional group capable of reacting with a double bond, including but not limited to mercapto, vinyl, acrylate;
wherein R is9Is C1-C10 alkyl, R10Is C1-C10 alkylene, R11Is C2-C4 alkylene, R12Is an alkylene group having C1 to C4And X is one of sulfonate, phosphate and benzene sulfonate.
2. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 1, wherein: the mercapto group is selected from HS- (CH)2)m-, where m is an integer of 1 to 5; the vinyl group is selected from CH2=CH-(CH2)n-, where n is an integer of 1 to 5; the acrylate group is selected from one or more of ethyl acrylate group, methyl methacrylate group and ethyl methacrylate group.
3. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 1, wherein: the fluoroalkyl is selected from one or more of C1-C10 perfluoroalkyl.
4. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 1, wherein: r1~R8Contains at least 3 fluoroalkyl groups and at least 3 reactive groups.
5. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 1, wherein: the salt in the sulfonate group, the phosphate group and the benzene sulfonate group refers to one or more of potassium salt, sodium salt and ammonium salt.
6. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 1, wherein: in the preparation method, the molar ratio of the cage-type polysilsesquioxane shown as the formula (I) and provided with the active group and the fluoroalkyl group to the surfactant shown as the formula (II) and provided with the double bond structure is 1: (3-5); dissolving cage type polysilsesquioxane shown in a formula (I) and provided with active groups and fluoroalkyl in a solvent, adding a catalyst, carrying out heating reaction with a surfactant shown in a formula (II) and provided with a double bond structure, wherein the reaction temperature is 40-80 ℃, the reaction time is 3-8 h, and carrying out reduced pressure distillation to remove the solvent after the reaction is finished.
7. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 6, wherein: the solvent is one or more selected from toluene, ethyl acetate and tetrahydrofuran.
8. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 6, wherein: the catalyst is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile and persulfate.
9. The preparation method of the super-hydrophobic modifier for the water-based paint, as claimed in claim 6, wherein: based on the total mass of the cage-type polysilsesquioxane shown in the formula (I) and simultaneously provided with the active group and the fluoroalkyl and the surfactant shown in the formula (II) and provided with the double bond structure, the mass ratio of the total mass to the solvent is 1 (10-30).
10. A super-hydrophobic modifier for water paint prepared by the preparation method as described in any one of claims 1-9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003280207A (en) * | 2002-03-22 | 2003-10-02 | Fuji Photo Film Co Ltd | Intermediate layer material composition for three-layer resist process and pattern forming method using the same |
| WO2009110848A1 (en) * | 2008-03-04 | 2009-09-11 | Agency For Science, Technology And Research | Low shrinkage multifunctional ssq resins |
| CN103626933A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | A kind of polysilsesquioxane-polyacrylate-nanometer SiO2 composite emulsion and its preparation method and application |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN108485439A (en) * | 2018-04-26 | 2018-09-04 | 福建亿硕科技有限公司 | A kind of hydrophobic dust-protection type self-cleaning coating and preparation method thereof |
-
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- 2020-06-10 CN CN202010521305.2A patent/CN111533860B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003280207A (en) * | 2002-03-22 | 2003-10-02 | Fuji Photo Film Co Ltd | Intermediate layer material composition for three-layer resist process and pattern forming method using the same |
| WO2009110848A1 (en) * | 2008-03-04 | 2009-09-11 | Agency For Science, Technology And Research | Low shrinkage multifunctional ssq resins |
| CN103626933A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | A kind of polysilsesquioxane-polyacrylate-nanometer SiO2 composite emulsion and its preparation method and application |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN108485439A (en) * | 2018-04-26 | 2018-09-04 | 福建亿硕科技有限公司 | A kind of hydrophobic dust-protection type self-cleaning coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Protective coatings based on silsesquioxane nanocomposite films for building limestones;Simionescu, Bogdana等;《Construction and building materials》;20090718;第23卷(第11期);第3426-3430页 * |
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