CN109735144B - Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof - Google Patents
Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof Download PDFInfo
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Abstract
The invention provides a photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition, which comprises the following components in percentage by weight: a material: 40-70wt% of POSS-PA prepolymer, 15-58.9wt% of light-cured acrylate monomer UVAA, 1-10wt% of polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS and 0.1-5wt% of adhesion reinforcing agent; b, material B: 1-6wt% of photoinitiator based on the total mass of the material A. After the material A and the material B are uniformly mixed, the mixture is subjected to leveling at room temperature, prebaking at 50-60 ℃ and then curing under the action of UV light, so that the POSS/fluorocarbon siloxane modified polyacrylate coating is prepared.
Description
Technical Field
The invention belongs to the field of functional coatings and coatings, and particularly relates to a photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof.
Background
Polymethyl methacrylate (PMMA), also known as organic glass, has high light transmittance, light weight, easy coloring, easy processing and forming, weather resistance and good electrical insulation, and can be widely applied to the fields of aviation, construction, decoration, optical instruments and the like. However, the PMMA resin has low glass transition temperature and poor scratch resistance, and the application of the PMMA resin is severely limited.
Cage type oligomeric silsesquioxane (POSS) is used for hybridizing PMMA resin, so that the heat resistance stability and flame retardant property of the material can be improved, the hardness of the material is improved, and the scratch resistance of the material is endowed on the basis of keeping the original performance characteristics of PMMA; if the fluorocarbon group is continuously introduced into the PMMA structure, the water and oil repellent performance of the target material can be further endowed, and the application field of the modified polymethyl methacrylate is expected to be further expanded to the fields of functional coatings and materials (US5705276, CN1222929, CN101508755, WO2009/126467, US6126849, US5242487 and US2001/0020077), mobile phones and computer touch screens, wearable electronic products and the like.
Copolymerization of fluoro-hydrocarbon vinyl monomers and multifunctional acrylate under the action of a photoinitiator is an effective way for preparing a photo-curing fluorine-containing acrylate antifouling coating in recent years, and the points are CN102504625, CN104893542, CN102634267 and the like. For example, CN102634267 has blended UV resin, photoinitiator, acrylic acid modified fluorinated resin, solvent, etc. to make paint, then sprayed on the surface of substrate, and then cured by ultraviolet light to form antifouling coating film, which is said to have contact angle of water greater than 80 ° and contact angle of oleic acid greater than 40 ° on the surface of cured coating film, and the coating film has the functions of inhibiting the adhesion of oil stain and sweat stain, preventing scratching, and resisting friction. However, it has been found that a coating film formed by using a UV light-curable resin alone has poor hardness, unsatisfactory antifouling performance, and low adhesion. In addition, the photo-curing resin system uses a solvent (CN 102167948A), and the coating curing film-forming process releases and discharges unpleasant gas, which is not beneficial to environmental protection and needs to be improved.
Based on the method, functionalized POSS containing alkenyl and MMA are polymerized to proper viscosity in advance and are used as a base material and a solvent of polymerizable photocuring resin, and then the base material and the solvent are copolymerized with acrylate monomer modified by low-surface hydrophobic and oleophobic polymerizable fluorocarbon siloxane and multifunctional photocureable acrylate monomer under the action of a UV initiator, so that a coating and a transparent coating with good water and oil repellent effects can be prepared, and the heat resistance stability, hardness and antifouling effect of the coating can be improved beneficially.
Disclosure of Invention
The inventionAims to disclose a preparation method of POSS/fluorocarbon siloxane modified polyacrylate resin coating composition and coating which are solvent-free and can be cured by light. For this purpose, the invention firstly carries out hydrosilylation addition on perfluoroalkyl ethylene, hydrosiloxane oligomer and double-end-group acrylate to synthesize polymerizable, hydrophobic and oleophobic fluorocarbon siloxane modified acrylate monomer (FS); then, the cage octalkylene-based oligomeric silsesquioxane T was added8Preparing a POSS-PA prepolymer with certain viscosity by the free radical copolymerization of POSS and MMA; on the basis, the POSS-PA prepolymer is blended with FS, light-curable multifunctional acrylate, an adhesion reinforcing agent and a UV initiator to prepare a coating, and polymerization and curing are initiated under the action of UV light to form a coating, so that the coating with good hydrophobic and oleophobic properties, hardness and heat-resistant stability is prepared. Based on this, the invention adopts the following technical scheme:
a preparation method of a photocuring POSS/fluorosilicone co-modified polyacrylate resin coating composition is characterized by comprising the following steps:
(1) synthesis of polymerizable reactive fluorocarbon siloxane modified acrylate monomer (FS)
Weighing perfluoroalkyl ethylenes (ViR)f) Uniformly mixing the obtained product with a metered platinum catalyst, heating to 80 ℃, carrying out a coordination reaction for 60min, adding a hydrogen-containing siloxane oligomer (DH), stirring for 20min, then adding double-end-based Diacrylate (DA), controlling the temperature to be 80-100 ℃, carrying out a hydrosilylation addition reaction for 8-10h, after the reaction is finished, carrying out reduced pressure and low boiling for 30min at the absolute pressure of 60-100mmHg and the temperature of 80-100 ℃, and obtaining a product, namely a polymerizable reactive fluorocarbon siloxane modified acrylate monomer (FS); and said ViRfHydrosilylation addition reaction with DH and DA, ViRfThe molar ratio of DH to DA is 1-3.1:1: 1.
(2) Preparation of POSS-PA prepolymer
Sequentially weighing Methyl Methacrylate (MMA) and cage-shaped octalkylene oligomeric silsesquioxane (T) according to the mass ratio8POSS) and with MMA + T80.1 to 1.0 percent of free radical initiator based on the total weight of POSS, evenly stirring and ultrasonically dispersing for 10 to 30min, heating to 50-80 ℃ for prepolymerization reaction for 10-60min, and cooling to room temperature after the system reaches 130-620mPa.s to obtain a transparent viscous liquid, namely the POSS-PA prepolymer;
(3) preparation of photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application of photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition in coating
Weighing 40-70% of POSS-PA prepolymer, 15-58.9% of light-cured acrylate monomer (UVAA), 1-10% of polymerizable reactive fluorocarbon siloxane modified acrylate monomer (FS), 0.1-5% of adhesion force reinforcing agent and 1-6% of photoinitiator in total mass of the monomers in parts by mass, and fully stirring and uniformly dispersing to obtain the light-cured coating composition; and uniformly coating the photo-curing coating composition on the surface of another clean metal or glass substrate, leveling at room temperature for 3-5min, pre-drying at 50-60 ℃ for 5-10min, and then carrying out photo-curing for 1-3min by using a 1000W UV machine to obtain a solid sample loaded on the surface of the substrate, namely the photo-curing POSS/fluorocarbon siloxane modified polyacrylate coating.
The perfluoroalkyl ethylene (ViR)f) Mainly perfluorooctylethylene (also known as tridecafluorooctylene) and perfluorodecylethylene (also known as heptadecafluorodecylethylene).
The hydrogen-containing siloxane oligomer (DH) is oligosiloxane containing 2-4 Si-H bonds in the molecule, and mainly comprises tetramethyldisiloxane (D)2 H) Tetramethylcyclotetrasiloxane (D)4 H)。
The double-end-group type diacrylate is a compound with two acrylate groups respectively connected with two molecular ends, and generally comprises dihydric alcohol diacrylate, dihydric alcohol dimethacrylate, poly-condensed dihydric alcohol diacrylate (also known as poly-dihydric alcohol diacrylate) and poly-condensed dihydric alcohol dimethacrylate (also known as poly-dihydric alcohol dimethacrylate), and mainly comprises 1, 2-ethylene glycol diacrylate, 1, 2-ethylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol diacrylate, propylene, Dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and other polyethylene glycol di (meth) acrylates having a different polymerization degree [ also known as polyethylene glycol di (meth) acrylates ], polypropylene glycol di (meth) acrylates [ also known as polypropylene glycol di (meth) acrylates ], and the like.
The ViR isfHydrosilylation addition reaction with DH, DA, ViRfThe molar ratio of DH to DA is 1-3.1:1:1, the dosage of the platinum catalyst is 100-200ppm, the reaction temperature is 80-100 ℃, the reaction time is 8-10h, and the platinum catalyst is a complex platinum catalyst KP22 or hexachloroplatinic acid and the like.
The structure of the acrylate monomer FS modified by the polymerizable reactive fluorine-containing siloxane is shown as a formula (1),
CH2＝CMCOOX (1)
M＝H,CH3；A＝(CH2)y,(OC2H4)a,(OC3H6)b；Rf＝C6F13,C8F17
wherein y, a and b are positive integers of 0,1,2 and 3 … …, y is preferably selected to be in the range of 2-6, and a and b are preferably selected to be in the range of 1-10.
The cage octalkylene oligomeric silsesquioxane T8POSS, the structure of which is shown in formula (2), is a cage-shaped POSS with eight reactable alkenyl functional groups such as acrylate group (namely acryloyloxypropyl), methacrylate group (namely methacryloyloxypropyl), vinyl group, allyloxy and p-vinylbenzene methylenoxy respectively connected in the molecule.
In the formula
The cage-shaped octaacrylate POSS (namely octaacryloyloxypropyl POSS), the cage-shaped octamethacrylate POSS (namely octamethacryloyloxypropyl POSS) and the cage-shaped octavinyl POSS are directly purchased from Hybrid plastics of America or synthesized by a hydrolytic polycondensation method; the caged octaallyloxy POSS and the caged octa (p-vinylbenzene methylenoxy) POSS are prepared by a method of reference literature using caged POSS quaternary ammonium base-POSS-·8N+(CH3)4[ MS0860, caged octa (tetramethylquaternary ammonium) POSS salt, Hybrid plastics, USA]Prepared by substitution reaction with allyl chloride or p-chloromethyl styrene at low temperature of 0-10 ℃ ([ 1)]Scientific announcements, 1999, 44(17) 1817 one 1820; [2]Functionalization study of Peptilia sabdariffa, octapoly (tetramethylammonium salt) silicate [ M]Shuichi paper of Harbin Industrial university, 2008, P16-17), the amount ratio of MS0860 to allyl chloride or P-chloromethylstyrene in the reaction is 1: 8-10.
The free radical initiator is a substance which can be decomposed by heating to release free radicals and has good intersolubility with oil-soluble monomers, and mainly comprises Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), dimethyl Azobisisobutyrate (AIBME) and the like.
The methyl methacrylate MMA and the cage-shaped octaalkenyl oligomeric silsesquioxane T8Prepolymerization of POSS, MMA and T8-a ratio by mass of POSS of 100: 5-25.
The light-cured multifunctional acrylate monomer (UVAA) is generally an acrylate compound which contains 2-6 acrylate functional groups in the molecular structure and is suitable for light curing, and comprises two types of difunctional (methyl) acrylate and multifunctional (methyl) acrylate (containing 3-6 acrylate functional groups), wherein the difunctional (methyl) acrylate mainly comprises diol diacrylate, diol dimethacrylate, poly-diol diacrylate (namely poly-polyol diacrylate) and poly-diol dimethacrylate (namely poly-polyol dimethacrylate), and the difunctional (methyl) acrylate is preferably selected to be 1, 2-ethylene glycol diacrylate, 1, 2-ethylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 6-propylene glycol diacrylate, 2-propylene glycol diacrylate, 1, 2-ethylene glycol dimethacrylate, 1, 6-propylene glycol diacrylate, 2-propylene glycol diacrylate, 1, 6-propylene glycol diacrylate, 1,2-, 1, 3-propanediol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.; the multifunctional acrylate comprises glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like; can be used as a single component or as a mixture of two components. The mass ratio of the difunctional UVAA monomer to the multifunctional UVAA monomer in the photocuring acrylate monomer is 1:0-7: 3.
The adhesion force reinforcing agent is vinyl trialkoxysilane or (methyl) acryloxypropyl trialkoxysilane which can react with an acrylate monomer and can be coupled with a base material, and mainly comprises vinyl trimethoxy silane (VTMS), vinyl triethoxy silane (VTES), methacryloxypropyl trimethoxy silane (KH-570) and methacryloxypropyl triethoxy silane (KH-571), and the using amount of the adhesion force reinforcing agent is 0.1-5% of the total mass of POSS-PA + UVAA monomers;
the photoinitiator is a substance which can absorb light waves with certain wavelength in an ultraviolet-visible light region to generate free radicals and can initiate polymerization reaction of unsaturated acrylate monomers, mainly comprises 2-hydroxy-2-methyl-1-phenylpropane-1-one (1173), 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (907), benzoin dimethyl ether (651), 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide (TPO) and the like, can be used by mixing a single component or multiple components, and is generally used in an amount of 1-6%; preferably, a photoinitiator prepared by compounding 1173 and TPO (the mass ratio is about 1: 0.5-2) is selected.
The application properties of the coatings prepared from the photocurable POSS/fluorocarbon siloxane modified polyacrylate coating compositions were evaluated as follows. The light transmittance (T) is measured by a Cary 5000 type ultraviolet-visible spectrophotometer, and the T can generally reach 86 to 97 percent; the glass transition temperature (Tg) was measured by a differential scanning calorimeter of Chi-Kuh-Mi, Germany, and the temperature rise rate was 10 ℃/min. Water repellency by static contact angle (theta) of a water droplet on the surface of the coatingH2O) Represents that theta is measured by using JC2000C contact angle measuring instrument of Shanghai Zhongchen digital Co., LtdH2OTypically 85.3-113.6 deg. Scratch resistance: with reference to GB/T9279-1988 scratch test method, 0000 is used#The steel wool was rubbed on the surface of the coating layer and evaluated according to the number and depth of scratches.
The invention has the beneficial effects that: in order to improve the hardness and the water and oil repellent performance of a photocuring acrylic resin transparent coating, firstly, carrying out hydrosilylation addition on perfluoroalkyl ethylene, hydrogen-containing siloxane oligomer containing 2-4 Si-H bonds and double-end-group type diacrylate, firstly synthesizing an acrylate monomer FS modified by low-surface-energy, hydrophobic and oleophobic polymerizable fluorocarbon siloxane, and then copolymerizing methyl methacrylate MMA and octafunctional alkenyl POSS to prepare a POSS-PA prepolymer with certain viscosity; then using the prepolymer as a reaction medium and a solvent, blending POSS-PA with 2-6 functional light-cured acrylate monomers UVAA and FS, an adhesion reinforcing agent, a photoinitiator and the like to prepare a light-cured coating, and then carrying out leveling, pre-baking and light curing to prepare the POSS hybrid fluorocarbon siloxane modified polyacrylic resin coating with good waterproof and antifouling properties, overcoming the defects of low solvent, low hardness, poor antifouling property and the like of the existing light-cured transparent acrylate resin (particularly varnish) coating, obviously improving the heat resistance stability, hardness and scraping resistance of the coating, and compared with the resin which is not modified by POSS and FS, improving the Tg of the resin coating prepared by the method disclosed by the invention by 6.91-29.44 ℃, thetaH2OReaches 85.3-113.6 degrees, and the coating shows good comprehensive application effect.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Synthesis of polymerizable reactive fluorocarbon siloxane modified acrylate monomer (FS)
Sequentially adding 0.01-0.031mol of perfluoroalkyl ethylene (ViR) into a three-necked bottle provided with a thermometer, a reflux condenser and a stirrerf) And 200ppm of platinum catalyst KP22, stirring and heating to 80 ℃ to perform a coordination reaction for 60min, then adding 0.01mol of hydrogen-containing siloxane oligomer DH and stirring for 20min, then adding 0.01mol of double-end-group type diacrylate and controlling the temperature to be 80-100 ℃ to perform a continuous stirring reaction for 8h, after the reaction is finished, reducing the pressure and removing low boiling point, and obtaining a product, namely a polymerizable reactive fluorocarbon siloxane modified acrylate monomer with the structure shown in formula (1), which is recorded as FS. The raw materials and amounts used for the synthesis of FS for each example are detailed in table 1.
Table 1 synthesis of polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS raw materials and amounts used
Structure of each FS in table 1 is: FS-1, M-H, X-1 (a), y-6, a- (CH)2)6-、Rf＝C8F17；FS-2：M＝H、X＝(1)(a)、y＝2、A＝-(CH2)2-、Rf＝C6F13；FS-3：M＝CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C6F13；FS-4：M＝CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C8F17；FS-5：M＝H、X＝(1)(b)、a＝2、A＝-(OC2H4)2-、Rf＝C6F13。
(2) Preparation of prepolymer POSS-PA-1
In a 100mL three-neck flask provided with a reflux condenser, a thermometer and a stirrer, 10g of MMA and 2.5g of R ═ C represented by the formula (2) are weighed in sequence according to the mass ratio3H6OOCC(Me)＝CH2Octamethacryloxypropyl POSS (T)8POSS-1) and with MMA + T80.3 percent of POSS-1 in total mass and about 0.038g of free radical initiator AIBN, stirring and mixing uniformly, heating to 80 ℃ to react for 10min, wherein the system viscosity is about 620mPa.s, and cooling to room temperature of 30 ℃ to obtain about 10.5g of transparent viscous liquid in total, namely prepolymer POSS-PA-1.
(3) Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof in coating
According to parts by mass, 7.0 parts of POSS-PA-1, 1.5 parts of 1, 6-hexanediol diacrylate and 1.0 part of a compound represented by formula (1), wherein M is H, X is (1) (a), y is 6, and A is- (CH)2)6-、Rf＝C8F17Fully stirring and uniformly mixing the polymerizable reactive monomer FS-1, 0.5 part of adhesion enhancer VTES, 6 percent of total mass of the monomers and about 0.6 part of photoinitiator 1173 to obtain a photocuring coating composition A-1; and then taking clean tinplate, uniformly coating the coating composition A-1 on the surface of the tinplate, leveling at room temperature for 5min, baking at 50-60 ℃ for 5min, and then placing in an ultraviolet curing machine with the power of 1000W for photocuring for 3min to obtain a sample, namely the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating which is marked as FSC-1 and has the thickness of about 50.6 microns.
Example 2
(1) Synthesis of polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS-2
The synthesis method and the raw material dosage are shown in table 1, the structure of the product FS-2 is shown as formula (1), wherein M is H, X ═ 1 (a), y is 2, and A is- (CH)2)2-、Rf＝C6F13。
(2) Preparation of prepolymer POSS-PA-2
In a 100mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10g of MMA and 0.5g of R ═ C represented by the formula (2) were weighed in this order3H6OOCCH＝CH2Octaacryloyloxypropyl POSS (T)8POSS-2) and with MMA + T81% of POSS-2 based on the total mass and about 0.11g of free radical initiator BPO, stirring and uniformly mixing, heating to 50 ℃ for prepolymerization reaction for 60min to obtain a system viscosity of about 130mPa.s, and cooling to about 30 ℃ at room temperature to obtain a transparent viscous liquid with a total amount of about 10.5g, namely a prepolymer POSS-PA-2.
(3) Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof in coating
According to parts by mass, 4.0 parts of POSS-PA-1, 4.12 parts of diethylene glycol diacrylate, 1.77 parts of pentaerythritol tetramethylacrylate (difunctional UVAA: multifunctional UVAA mass ratio is 7:3), 0.1 part of compound shown as the formula (1), M is H, X (1) (a), y is 2, A is- (CH)2)2-、Rf＝C6F13The polymerizable reactive monomer FS-2, 0.01 part of adhesion enhancer VTMS, 1 percent of total mass of the monomers and about 0.1 part of photoinitiator 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide TPO are fully stirred and uniformly mixed to obtain the photocuring coating composition A-2; and then taking clean tinplate, uniformly coating the coating composition A-2 on the surface of the tinplate, leveling at room temperature for 3min, then baking at 60 ℃ for 6min, and then placing in an ultraviolet curing machine with the power of 1000W for photocuring for 1min to obtain a sample, namely the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating which is marked as FSC-2 and has the thickness of about 53.8 microns.
Example 3
(1) Synthesis of polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS-3
The synthetic method and the raw material dosage are shown in table 1, the FS-3 structure is shown as formula (1), wherein M ═ CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C6F13。
(2) Preparation of prepolymer POSS-PA-3
In a 100mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10g of MMA and 1.5g of R ═ CH represented by the formula (2) were weighed in this order in mass ratio2Octavinyl PO ofSS(T8-POSS-3), stirring, heating to dissolve the octavinyl POSS in MMA to obtain a transparent solution, and adding MMA + T80.5 percent of free radical initiator AIBME accounting for 0.5 percent of total mass of-POSS-3, uniformly stirring, heating to 60 ℃ to react for 40min, wherein the viscosity of the system is about 390mPa.s, and cooling to about 30 ℃ at room temperature to obtain transparent viscous liquid accounting for 11.5g of total mass, namely prepolymer POSS-PA-3.
(3) Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof in coating
According to the mass portion, 5.0 portions of POSS-PA-3 prepolymer, 3.0 portions of 1, 6-hexanediol dimethacrylate, 1.2 portions of dipentaerythritol pentaacrylate and 0.5 portion of dipentaerythritol pentaacrylate are weighed in sequence, the structure is shown as formula (1), and M is CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C6F13The polymerizable reactive monomer FS-3, 0.3 part of adhesion enhancer KH-570 and about 0.5 part of photoinitiator 1173+ TPO (0.2 part 1173+0.3 part of TPO) accounting for 5 percent of the total mass of the monomers are fully stirred and uniformly mixed to obtain a photo-curing coating composition A-3; and uniformly coating the coating composition A-3 on the surface of the tinplate by taking clean tinplate, leveling for 4min at room temperature, drying for 5min at 55 ℃, and performing photocuring for 2min in an ultraviolet curing machine with the power of 1000W to obtain a sample, namely the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating which is marked as FSC-3 and has the thickness of about 56 mu m.
Example 4
(1) Synthesis of polymerizable reactive fluorocarbon siloxane modified acrylates FS-4
The synthesis method and the raw material dosage are shown in table 1, the structure of the product FS-4 is shown as formula (1), wherein M ═ CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C8F17。
(2) Preparation of prepolymer POSS-PA-4
In a 100mL three-neck flask provided with a reflux condenser, a thermometer and a stirrer, 10g of MMA and 1.8g of R ═ OCH shown in a structural formula (2) are weighed in sequence according to the mass ratio2CH＝CH2Octaene ofPropoxy POSS (T)8POSS-4) and with MMA + T80.6 percent of POSS-4 in total mass and about 0.11g of free radical initiator AIBN are stirred and mixed evenly, then the mixture is heated to 70 ℃ to react for 25min, the viscosity of the system is about 430mPa.s, and then the mixture is cooled to about 30 ℃ at room temperature, so that transparent viscous liquid with the total mass of about 11.8g, namely the prepolymer POSS-PA-4, is obtained.
(3) Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof in coating
Weighing 4.5 parts of POSS-PA-4 prepolymer, 3.5 parts of 1, 4-butanediol dimethacrylate, 1.3 parts of glycerol triacrylate and 0.38 part of a compound shown as a formula (1) in sequence by mass, wherein M is CH3、X＝(1)(b)、b＝7、A＝-(OC3H6)7-、Rf＝C8F17The polymerizable reactive monomer FS-4, 0.32 part of adhesion enhancer KH-570, 3.6 percent of the total mass of the monomers and about 0.36 part of photoinitiator benzoin dimethyl ether 651 are fully stirred and uniformly mixed to obtain a photocuring coating composition A-4; taking clean tinplate, uniformly coating the coating composition A-4 on the surface of the tinplate, leveling at room temperature for 3min, then baking at 60 ℃ for 5min, and then placing in an ultraviolet curing machine with the power of 1000W for photocuring for 1.5min to obtain a sample, namely the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating which is marked as FSC-4 and has the thickness of about 55.6 microns.
Example 5
(1) Synthesis of polymerizable reactive fluorocarbon siloxane modified acrylates FS-5
The synthesis method and the raw material dosage are shown in table 1, the structure of the product FS-5 is shown as formula (1), wherein M is H, X ═ 1 (b), a is 2, A is- (OC)2H4)2-、Rf＝C6F13。
(2) Preparation of prepolymer POSS-PA-5
In a 100mL three-neck flask provided with a reflux condenser, a thermometer and a stirrer, 10g of MMA and 1.0g of R ═ OCH shown in a structural formula (2) are weighed in sequence according to the mass ratio2C6H4CH＝CH2Octa (p-vinylbenzylmethylene) POSS (T)8POSS-5) and with MMA+T80.4 percent of POSS-5 in total mass and about 0.044g of free radical initiator BPO, uniformly stirring, heating to 65 ℃ for reaction for 30min to obtain a system with viscosity of about 260mPa.s, and cooling to about 30 ℃ at room temperature to obtain a transparent viscous liquid with the total mass of about 11.0g, namely the prepolymer POSS-PA-5.
(3) Photocuring POSS/fluorocarbon siloxane modified polyacrylate composition and application thereof in coating
6.0 parts of POSS-PA-5 prepolymer, 2.0 parts of 1, 4-butanediol dimethacrylate, 0.75 part of trimethylolpropane trimethacrylate and 0.8 part of trimethylolpropane trimethacrylate are weighed in sequence according to parts by mass, wherein the structural formula is shown as formula (1), M is H, X (1) (b), a is 2, A is OC- (OC) (b)2H4)2-、Rf＝C6F13The polymerizable reactive monomer FS-5, 0.45 part of adhesion enhancer KH-571, 4.5 percent of the total mass of the monomers and about 0.45 part of photoinitiator 1173+ TPO (the mass ratio of 1173 to TPO is 2:1), and the components are fully stirred and uniformly mixed to obtain the photocuring coating composition A-5; taking clean tinplate, uniformly coating the coating composition A-5 on the surface of the tinplate, leveling at room temperature for 3min, then baking at 50 ℃ for 5min, and then placing in an ultraviolet curing machine with the power of 1000W for photocuring for 2min to obtain a sample, namely the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating which is marked as FSC-5 and has the thickness of about 58 mu m.
The photocurable POSS/fluorocarbon siloxane modified polyacrylate coatings prepared in examples 1-5 were tested for application properties as follows: the light transmittance is measured by using a Cary 5000 type ultraviolet-visible spectrophotometer, and blank glass is used as reference; glass transition temperature (Tg) as measured by a Differential Scanning Calorimeter (DSC) of Chi-Kuh-san Co., Germany, at a temperature rise rate of 10 ℃/min; water repellency by the static contact angle (theta) of water on the surface of the coatingH2O) The droplet size was 5. mu.L as measured by a contact angle measuring instrument model JC2000C1 from Shanghai, China, Ltd. Additionally, Polyacrylate (PA) resin coatings prepared in the same manner without the addition of POSS and FS monomers were used as a reference in the present invention and the results are shown in Table 2. In view of the large number of experimental data, table 2 only shows the measured data for the coating of reference PA-1 in example 1.
TABLE 2 Properties of photocured POSS/Fluoroalkylsiloxane modified polyacrylate coatings
*Reference PA resin coating-polyacrylate resin PA-1 coating prepared without POSS and FS monomers as in example 1 was measured.
**● has a large number of surface scratches, major surface scratch, minor surface scratch, major surface ═ major surface scratch, major surface mark
As can be seen from Table 2, the coatings prepared by the method of the present invention have increased glass transition temperature, increased contact angle and obviously improved scratch resistance compared with the reference, which indicates that the heat resistance stability, water and stain resistance and scratch resistance of the coatings are indeed improved.
Claims (8)
1. A photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition comprising:
a material:
40-70wt% of POSS-PA prepolymer,
15-58.9wt% of a light-curable acrylate monomer UVAA,
1-10wt% of a polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS,
0.1-5wt% of an adhesion enhancer; and the number of the first and second groups,
b, material B:
1-6wt% of photoinitiator based on the total mass of the material A;
the POSS-PA prepolymer is methyl methacrylate MMA and cage-shaped octalkylene oligomeric silsesquioxane T8-a prepolymer obtained by radical polymerization of POSS; MMA and T8-a ratio by mass of POSS of 100: (5-25);
the light-cured acrylate monomer UVAA is an acrylate compound which contains 2-6 acrylate groups in the molecular structure and is suitable for light curing;
the structural formula of the polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS is as follows:
CH2=CMCOOX （Ⅰ）；
in the formula, X =
、
；M=H，CH3；
；
(ii) a a. b and y are non-negative integers.
2. A photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition as recited in claim 1 wherein polymerizable reactive fluorocarbon siloxane modified acrylate monomer FS is obtained by a process comprising the steps of: reacting perfluoroalkyl ethylene ViR f Carrying out hydrosilylation addition reaction on the double-end-group diacrylate DA and hydrogen-containing siloxane oligomer DH to obtain polymerizable reactive fluorine-containing siloxane modified acrylate FS; ViR in the hydrosilylation addition reaction f DH and DA in a molar ratio of ViR f : DH : DA=(1~3.1) :1:1。
3. The photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition of claim 2 wherein said perfluoroalkylethylene ViR f Is one or more of perfluorooctyl ethylene and perfluorodecyl ethylene; the hydrosiloxane oligomer DH is tetramethyldisiloxane D2 HTetramethylcyclotetrasiloxane D4 HOne or more of;the double-end-group type diacrylate ester is one or more of dihydric alcohol diacrylate ester, dihydric alcohol dimethacrylate ester, poly-condensed dihydric alcohol diacrylate ester and poly-condensed dihydric alcohol dimethacrylate ester.
4. The photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition of claim 1, wherein said caged octalkylene oligomeric silsesquioxane T is characterized as8POSS is cage-shaped POSS with eight reactable alkenyl groups respectively connected in the molecule, and the structural formula is as follows:
（Ⅱ）；
in the formula, R =
，
，
，
，
。
5. The photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition of claim 4, wherein said caged octalkylene oligomeric silsesquioxane T is characterized as8POSS through caged POSS Quaternary ammonium hydroxide POSS-·8N+(CH3)4And allyl chloride or p-chloromethyl styrene.
6. The photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition of claim 1 wherein said adhesion enhancing agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, in an amount of 0.1-5% by weight of the total monomer mass.
7. The method of applying a photocurable POSS/fluorocarbon siloxane modified polyacrylate coating composition as recited in any of claims 1-6, comprising the steps of:
and fully mixing the material A and the material B of the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition, coating the mixture on the surface of a base material to be constructed, leveling at room temperature, pre-drying at 50-60 ℃, and finally photocuring by using UV light to obtain the photocuring POSS/fluorocarbon siloxane modified polyacrylate coating.
8. A photocurable POSS/fluorocarbon siloxane modified polyacrylate coating obtained by the process of claim 7.
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