CN115011198B - Preparation method of hybrid fluorocarbon latex coating with synergistic performance - Google Patents
Preparation method of hybrid fluorocarbon latex coating with synergistic performance Download PDFInfo
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- 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
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Abstract
The invention relates to a preparation method of a hybrid fluorocarbon latex coating with synergistic performance. The method takes polyacrylate latex as a seed and Polysilsesquioxane (PSQ) precursor as a unique stabilizer to replace the traditional micromolecule emulsifier; CTFE and IBVE are taken as comonomers, and core-shell organic-inorganic hybrid composite latex particles are successfully prepared by a soap-free seed emulsion polymerization method (SSEP); self-assembling to form a film through the aggregation among latex particles and the mutual diffusion of macromolecular chains at a constant temperature of 60 ℃. The hybrid fluorocarbon latex coating with excellent synergistic performance, which is obtained by the invention, solves the problems of poor film-forming property, weak adhesion to base materials and the like of the polychlorotrifluoroethylene, and also improves the ultraviolet resistance, organic solvent resistance and thermal stability of the coating.
Description
Technical Field
The invention belongs to the technical field of preparation of water-based coatings, and particularly relates to a preparation method of a hybrid fluorocarbon latex coating with excellent synergistic performance.
Background
Conventional solvent-based coatings generate large amounts of Volatile Organic Compounds (VOCs) that are released into the atmosphere during manufacture and use. In view of the harm of VOC to the environment and human health, the environmental-friendly water-based fluorocarbon coating has excellent weather resistance and can be widely applied to the protection of bridges, steel structures and other outdoor facilities, so that people are receiving more and more attention. However, it is still difficult to achieve solvent-based coating-like properties (such as weather resistance, adhesion, etc.). Therefore, there is still a need to develop high performance waterborne fluorocarbon coatings.
Polychlorotrifluoroethylene (PCTFE) has outstanding properties of weather resistance, chemical medium corrosion resistance and the like, but PCTFE has poor film forming property and weak adhesion to a substrate due to its often high crystallinity, is difficult to be used alone as an aqueous coating material, and has high production cost. Isobutyl vinyl ether (IBVE) can be reacted with CTFE to form alternating copolymers which show good film forming properties. However, their adhesion to various substrates is poor. In addition, in the preparation process of the CTFE copolymer latex, the use of the conventional small molecular emulsifier often causes the water resistance, stain resistance, etc. of the latex coating to be reduced.
Therefore, it is important to prepare a hybrid fluorocarbon latex coating with excellent overall properties, to design and optimize the functions and functions of its components, to maintain and improve the optimum performance of each component, and to eliminate (or reduce) the inherent drawbacks of each component to obtain the optimum synergistic effect between the components.
Disclosure of Invention
The invention aims to provide a preparation method of a hybrid fluorocarbon latex coating with excellent synergistic performance, and aims to solve the problem that the functions of all components are difficult to coordinate in the process of preparing a water-based CTFE-co-IBVE copolymer hybrid composite coating. The method takes polyacrylate latex as a seed and Polysilsesquioxane (PSQ) precursor as a unique stabilizer to replace the traditional micromolecule emulsifier; CTFE and IBVE are taken as comonomers, and core-shell organic-inorganic hybrid composite latex particles are successfully prepared by a soap-free seed emulsion polymerization method (SSEP); self-assembling to form the membrane through the aggregation among latex particles and the mutual diffusion of macromolecular chains at a constant temperature of 60 ℃. The hybrid fluorocarbon latex coating with excellent synergistic performance, which is obtained by the invention, solves the problems of poor film-forming property, weak adhesion to base materials and the like of the polychlorotrifluoroethylene, and also improves the ultraviolet resistance, organic solvent resistance and thermal stability of the coating.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a hybrid fluorocarbon latex coating with excellent synergistic performance, the method comprising the following steps:
firstly, deoxidizing the mixed solution of acrylic ester and deionized water for 5-30min, heating to 60-80 ℃, adding an aqueous solution containing potassium persulfate (KPS), reacting for 4-6h at 60-80 ℃, and performing rotary evaporation for 20-40min under reduced pressure to obtain polyacrylate latex seeds;
wherein the mass ratio of the acrylic ester to the deionized water is 1; the mass ratio of the KPS-containing water solution to the mixed solution of acrylic ester and deionized water is 1; the mass ratio of KPS to acrylic ester is 0.003-0.009;
secondly, adding the PSQ precursor and polyacrylate latex seeds into deionized water for mixing, and dispersing for 10-40min by adopting ultrasonic waves to obtain a dispersion liquid A;
wherein the mass ratio of the PSQ precursor, the polyacrylate latex seeds and the deionized water in the second step is 0.4-0.9: 1:60 to 100;
the PSQ precursor is a substance A and a substance B; wherein the mass ratio is as follows: a substance A: substance B =1 from 0.01 to 0.20; the substance A is methyl triethoxysilane-MTES or ethyl triethoxysilane-ETES, and the substance B is one or more of organosilane precursors with carbon-carbon double bonds;
a third step of subjecting the second stepAdding the dispersion liquid A into a high-pressure reaction kettle, and respectively adding NaHCO 3 KPS and IBVE, deoxidizing the mixture for 10-50min by using nitrogen with the pressure of 0.2-0.4MPa, and then decompressing and degassing; adding a CTFE monomer, and reacting the system for 6-9h at 40-70 ℃ under mechanical stirring to obtain polyacrylate/P (CTFE-co-IBVE)/PSQ composite latex particles;
wherein, the dispersion liquid A and NaHCO 3 The mass ratio of (A) to (B) is 1; KPS and NaHCO 3 The mass ratio of (A) to (B) is 0.1-0.5; IBVE and NaHCO 3 The mass ratio of (A) to (B) is 6-16; CTFE and NaHCO 3 The mass ratio of (A) to (B) is 25-45;
fourthly, performing ultrasonic dispersion treatment on the composite latex particles obtained in the third step for 20-50min to obtain emulsion, then coating the emulsion on a dried base material, and drying at the constant temperature of 40-70 ℃ for 24-48h to obtain a coating; the thickness of the coating is 40-60 mu m.
The acrylate in the first step is one of tert-butyl acrylate (tBA), isobutyl acrylate, n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ethyl acrylate, n-octyl acrylate, n-butyl methacrylate and hexyl methacrylate.
The precursor with carbon-carbon double bonds in the second step is one of Methacryloxypropyltrimethoxysilane (MPS), gamma-methacryloxypropyltrimethoxysilane (KH-570), vinyltrimethoxysilane (A171), vinyl-tris (2-, methoxyethoxy) silane (KH-172) and vinyltriethoxysilane (A151).
In the fourth step, the base material is one of a glass sheet, tinplate, leather, fabric and a steel plate.
The invention has the beneficial effects that:
the polychlorotrifluoroethylene homopolymer is independently used as a water-based coating, has poor film-forming property and weak adhesion with a base material, and has a few reports about the synthesis of the CTFE copolymer at present. Also, the prior art synthesized P (CTFE-co-IBVE) alternating copolymer, although good in film forming property, has poor adhesion to the substrate. The hybrid fluorocarbon latex coating with excellent synergistic performance is prepared, and has the characteristics of excellent adhesion (reaching 5B level), ultraviolet resistance (contact angle is hardly changed after ultraviolet irradiation for 600 hours), film forming property, organic solvent resistance, better transparency and the like, and the synergistic effect among the performances enables the coating to be used as a protective coating of various base materials.
Drawings
FIG. 1 is an SEM photograph of PtBA latex seeds;
FIG. 2 is a DMA curve for PtBA, P (CTFE-co-IBVE-2) and PtBA/P (CTFE-co-IBVE-2) particles;
FIG. 3 is a graph of adhesion test results for a P (CTFE-co-IBVE-2) copolymer coating on a glass substrate, wherein FIG. 3a is before 3M tape application and FIG. 3b is after 3M tape application;
FIG. 4 is a thermogravimetric plot of PtBA/P (CTFE-co-IBVE-2), ptBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles;
FIG. 5 is an optical microscope photograph of the surface of PtBA/P (CTFE-co-IBVE-2)/PSQ-0 composite latex coating on a glass plate;
FIG. 6 is an optical microscope photograph of the surface of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.05 composite latex coating on a glass plate;
FIG. 7 is an optical microscope photograph of the surface of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.1 composite latex coating on a glass plate;
FIG. 8 is an optical micrograph of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite latex coated surface on a glass slide;
FIG. 9 is a TEM photograph of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles;
FIG. 10 is an EDX-TEM image of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles;
FIG. 11 is a graph showing the adhesion test results of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite coating on a glass substrate, wherein FIG. 11a is before 3M tape application and FIG. 11b is after 3M tape application;
FIG. 12 shows the UV resistance of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite coating;
FIG. 13 is a graph of the resistance to organic solvents of a PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite coating, wherein FIG. 13a is before solvent wiping, FIG. 13b is a schematic diagram of the wiping action, and FIG. 13c is after solvent wiping;
FIG. 14 is an optical micrograph of the surface of a PtBA/P (CTFE-co-IBVE-3)/PSQ-0.15 composite coating;
FIG. 15 is an optical micrograph of the surface of PtBA/P (CTFE-co-IBVE-4)/PSQ-0.15 composite coating;
FIG. 16 is an optical micrograph of the surface of the PtBA/P (CTFE-co-IBVE-5)/PSQ-0.15 composite coating;
fig. 17 is a macro-topography of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15, ptBA/P (CTFE-co-IBVE-3)/PSQ-0.15, ptBA/P (CTFE-co-IBVE-4)/PSQ-0.15, and PtBA/P (CTFE-co-IBVE-5)/PSQ-0.15 glass-based latex coatings, where, when the mass ratio of MPS/MTES is 0.15, fig. 17a is an optical microscopic image of the surface microstructure of the PtBA/P (CTFE-co-IBVE)/PSQ composite particle coating prepared when the IBVE monomer addition amount is 2g, fig. 17b is an optical microscopic image of the surface microstructure of the PtBA/P (CTFE-co-IBVE)/PSQ composite particle coating prepared when the IBVE monomer addition amount is 3g, fig. 17c is an optical microscopic image of the PtBA/P (CTFE-co-IBVE)/PSQ composite particle coating prepared when the IBVE monomer addition amount is 4g, and fig. 17c is an optical microscopic image of the PtBA/P/PSQ composite particle coating prepared.
Detailed Description
Example 1:
the preparation method of the polyacrylate latex seed comprises the following specific steps:
20.00g of tBA and 200.0g of deionized water were added to a four-necked round bottom flask, and the mixture in the flask was deoxygenated by bubbling nitrogen at room temperature for 15min and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e.0.60% by weight of the added tBA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. Finally, the PtBA latex is subjected to rotary evaporation for 30min under reduced pressure to obtain PtBA latex seeds.
The surface topography of the PtBA latex seed was characterized using a scanning electron microscope model Nano 450 from FEI usa as shown in fig. 1. The PtBA latex seeds appeared uniformly spherical and smaller in size. The glass transition temperature (Tg) of PtBA latex seeds was tested using a dynamic thermo-mechanical analyzer, triton technology, inc, ltec 2000, uk, and the results are shown in fig. 2. The PtBA latex seed has a single glass transition peak at about 65 ℃.
Example 2:
the preparation method of the P (CTFE-co-IBVE-2) latex particles comprises the following specific steps:
80.0g of deionized water was added to a 250mL autoclave, followed by NaHCO 3 (0.33 g), KPS (0.06 g), SDS (0.15 g) and IBVE (2.00 g). It is subjected to pressure testing with 0.2MPa nitrogen, deoxygenated and then degassed under reduced pressure until vacuum (10) -2 mbar); CTFE (10.00 g) monomer was added by addition (i.e., the mass difference of the reaction system after and before the addition of CTFE gas was weighed) and the system was reacted for 8h with mechanical stirring at 60 ℃. After the reaction is finished, the high-pressure reaction kettle is cooled to room temperature and degassed to obtain the P (CTFE-co-IBVE-2) latex particles.
As shown in FIG. 2, the P (CTFE-co-IBVE-2) latex particles had a single glass transition peak at about 39 ℃.
P (CTFE-co-IBVE-2) latex particles are used for covering and coating a glass sheet, and the method comprises the following specific steps:
the obtained latex particles were further subjected to ultrasonic dispersion for 40min, and the glass sheet substrate was thoroughly washed with alcohol and an alkaline detergent, respectively, rinsed with deionized water, and dried. The ultrasonically treated latex particles are coated on a dry glass sheet by a dropping method and dried for 24 hours at a constant temperature of 60 ℃ to obtain a coating layer, and the thickness of the coating layer is 50 +/-2 mu m.
The cross-hatch method was used to observe the coating condition after stripping 100 cells of the P (CTFE-co-IBVE-2) latex coating on the glass sheet substrate, and the result is shown in FIG. 3 b. > 65% of the coating on the grid was peeled off, indicating poor adhesion at 0B.
Example 3:
the preparation method of the PtBA/P (CTFE-co-IBVE-2) composite particles comprises the following specific steps:
in the first step, 20.00g of tBA and 200.0g of deionized water were added to a four-necked round-bottomed flask, and the mixture in the flask was deoxygenated by bubbling nitrogen gas at room temperature for 15min and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e.0.60% by weight of the added tBA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. Finally, the PtBA latex is subjected to rotary evaporation for 30min under reduced pressure to obtain PtBA latex seeds.
In the second step, the latex containing 1.00g of PtBA particles was diluted with 80.00g of deionized water in a 250mL flask and mixed well while dispersing with ultrasonic waves for 30min to obtain dispersion A.
Thirdly, adding the dispersion liquid A into a 250mL high-pressure reaction kettle, and respectively adding NaHCO 3 (0.33 g), KPS (0.06 g) and IBVE (2.00 g). It is subjected to pressure testing with 0.2MPa nitrogen, deoxygenated and then degassed under reduced pressure until vacuum (10) -2 mbar); CTFE (10.00 g) monomer was added by addition (i.e., the mass difference of the reaction system after and before the addition of CTFE gas was weighed) and the system was reacted for 8h with mechanical stirring at 60 ℃. Thus obtaining the PtBA/P (CTFE-co-IBVE-2) composite particles.
As a result, as shown in fig. 2, the PtBA/P (CTFE-co-IBVE-2) composite exhibited two glass transition peaks, which were closer to those of the PtBA/P (CTFE-co-IBVE-2) composite than the individual glass transition peaks of the PtBA seed and the P (CTFE-co-IBVE-2) copolymer, indicating a certain degree of compatibility between the PtBA and P (CTFE-co-IBVE-2) polymers. Thermal stability of the PtBA/P (CTFE-co-IBVE-2) composite particles was tested using a thermogravimetric analyzer model SDT/Q-600 from TA, USA, and the results are shown in FIG. 4. The mass residue of the PtBA/P (CTFE-co-IBVE-2) composite particles at 800 ℃ was 0.44%.
Example 4:
the preparation method of the hybrid fluorocarbon latex coating comprises the following specific steps:
in the first step, 20.00g of tBA and 200.0g of deionized water were added to a four-necked round-bottomed flask, and the mixture in the flask was deoxygenated by bubbling nitrogen gas at room temperature for 15min and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e.0.60% by weight of the added tBA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. Finally, the PtBA latex is subjected to rotary evaporation for 30min under reduced pressure to obtain PtBA latex seeds.
In the second step, 0.66g of a PSQ precursor (MPS: MTES is 0.
Thirdly, adding the dispersion liquid A into a 250mL high-pressure reaction kettle, and respectively adding NaHCO 3 (0.33 g), KPS (0.06 g) and IBVE (2.00 g). It is subjected to pressure testing with 0.2MPa nitrogen, deoxygenated and then degassed under reduced pressure until vacuum (10) -2 mbar); CTFE (10.00 g) monomer was added by addition (i.e., the mass difference of the reaction system after and before the addition of CTFE gas was weighed) and the system was reacted for 8h with mechanical stirring at 60 ℃. Thus obtaining the PtBA/P (CTFE-co-IBVE-2)/PSQ-0 composite particles.
The PtBA/P (CTFE-co-IBVE-2)/PSQ-0 latex particles are used for covering the coating of the glass sheet, and the specific steps are as follows:
the obtained latex particles were further subjected to ultrasonic dispersion for 40min, and the glass sheet substrate was thoroughly washed with alcohol and an alkaline detergent, respectively, rinsed with deionized water, and dried. The latex particles after ultrasonic treatment are coated on a dry glass sheet by a dropping method and dried for 24 hours at a constant temperature of 60 ℃ to obtain a coating layer with the thickness of 50 +/-2 mu m.
The surface microstructure of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0 composite coating is tested by adopting an optical microscope with the model number of DMM-300C of Shanghai Chuikang optical instruments GmbH; as a result, as shown in FIG. 5, the PSQ phase was not uniformly dispersed and the size of the dispersed phase was large.
Example 5:
this example is substantially the same as example 4 except that, in the preparation of dispersion A, the total mass of the PSQ precursor was unchanged (0.66 g), the mass ratio of MPS/MTES was 0.05, and as can be seen from FIG. 6, the PSQ dispersed phase size of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.05 composite latex coating was reduced and the dispersion became uniform.
Example 6:
this example is substantially the same as example 4 except that, in preparing dispersion A, the total mass of the PSQ precursor was unchanged, the mass ratio of MPS/MTES was 0.1, and as can be seen from FIG. 7, the PSQ dispersed phase size of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.1 composite latex coating was significantly reduced and dispersed more uniformly.
Example 7:
this example is substantially the same as example 4 except that the total mass of the PSQ precursor was unchanged and the mass ratio of MPS/MTES was 0.15 when preparing the dispersion a.
As can be seen from FIG. 8, the dispersed phase size of the PSQ of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite latex coating is very small and the dispersion is very uniform. This means that as the amount of MPS increases, the compatibility of the organic and inorganic phases increases, since MPS has an active C = C bond in its structure, which can participate in the free radical polymerization of the comonomer, creating a stable covalent bond between PSQ and the organic polymer. Therefore, as the amount of MPS added increases, the compatibility between PSQ and PtBA/P (CTFE-co-IBVE-2) polymers increases, the degree of phase separation decreases, the overall uniformity and dispersion of the dispersed phase is improved accordingly, and the transparency of the coating becomes better and better.
The internal morphological structure of PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles was studied by transmission electron microscopy of the American FEI company, model number Talos F200; as shown in FIG. 9, the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles showed uniform spherical shape, and the particle size of the PtBA latex seed in FIG. 1 was increased, the color of the core layer of the composite particle was darker, and the color of the shell layer was lighter, indicating the successful preparation of the core-shell type PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles. Detecting the surface element composition of the PtBA/P (CTFE-co-IBVE-2)/PSQ composite coating by adopting an X-ray photoelectron spectrometer with the model number of ESCALB 250Xi of American Saimer Feishell science and technology Limited company; the results are shown in FIG. 10, in which the distribution range of silicon atoms is larger than that of fluorine atoms, which indicates that the PSQ precursor is mainly distributed at the periphery of the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particle, and further indicates that MPS and MTES play dual roles as a stabilizer and a PSQ precursor. Observing the condition of the coating stripped from 100 small lattices on the glass sheet base material by adopting a grid cutting method; as a result, as shown in fig. 11B, the coating on the mesh was hardly peeled off, and the adhesion reached 5B level, which is much stronger than that shown in fig. 3, indicating that the latex coating has excellent adhesion. The ultraviolet resistance of the coating was evaluated by the change in contact angle after irradiation with an ultraviolet lamp, and as a result, as shown in fig. 12, the water contact angle was almost unchanged even after irradiation with ultraviolet light for 600 hours, and the coating had excellent ultraviolet resistance. Testing the organic solvent resistance of the composite coating by manually wiping, placing a forefinger with safety protection in the center of absorbent cotton soaked by dimethylbenzene, forming an angle of 45 degrees with the surface of the test coating, wiping the rectangular test area for 25 times with proper pressure, and visually observing whether the surface of the coating is corroded and damaged or not and whether the substrate is exposed or not; the results are shown in FIG. 13c, where the wiped coating was completely undamaged and the substrate was not exposed, indicating that the composite coating has good resistance to organic solvents. As shown in fig. 17a, the coating has good transparency. As a result, as shown in FIG. 4, the mass retention at 800 ℃ was 9.71%, which was significantly larger than that of PtBA/P (CTFE-co-IBVE) composite particles (0.44%). In general, the thermal decomposition temperature of silane-based materials is very high and does not decompose at high temperatures of 800 ℃. This also demonstrates that in PtBA/P (CTFE-co-IBVE)/PSQ composite particles, MTES and MPS have been converted to PSQ. In addition, the initial decomposition temperature of the PtBA/P (CTFE-co-IBVE)/PSQ hybrid composite particle is slightly higher than that of the PtBA/P (CTFE-co-IBVE) composite particle, which also indicates that the addition of the PSQ precursor improves the thermal stability of the coating to a certain extent.
Example 8:
the preparation method of the hybrid fluorocarbon latex coating with excellent synergistic performance comprises the following specific steps:
in the first step, 20.00g of tBA and 200.0g of deionized water were added to a four-necked round-bottomed flask, and the mixture in the flask was deoxygenated by bubbling nitrogen gas at room temperature for 15min and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e.0.60% by weight of the added tBA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. Finally, the PtBA latex is subjected to rotary evaporation for 30min under reduced pressure to obtain PtBA latex seeds.
In the second step, 0.57g of MTES, 0.09g of MPS (MPS/MTES mass ratio is 0.15) and a latex containing 1.00g of PtBA particles were diluted with 80.00g of deionized water in a 250mL flask and mixed uniformly while dispersing for 30min by ultrasonic waves to obtain dispersion A.
Thirdly, adding the dispersion liquid A into a 250mL high-pressure reaction kettle, and respectively adding NaHCO 3 (0.33 g), KPS (0.06 g) and IBVE (3.00 g). It is subjected to pressure testing with 0.2MPa nitrogen, deoxygenated and then degassed under reduced pressure until vacuum (10) -2 mbar); CTFE (10.00 g) monomer was added by addition (i.e., the mass difference of the reaction system after and before the addition of CTFE gas was weighed) and the system was reacted for 8h with mechanical stirring at 60 ℃. Thus obtaining the PtBA/P (CTFE-co-IBVE-2)/PSQ-0.15 composite particles.
The PtBA/P (CTFE-co-IBVE-3)/PSQ-0.15 composite latex particles are used for the glass sheet covering coating, and the specific steps are as follows:
further ultrasonically dispersing the obtained composite latex for 40min, respectively and thoroughly cleaning a glass sheet substrate by using alcohol and an alkaline detergent, washing with deionized water and drying. And (3) coating the ultrasonically treated composite latex on a dry glass sheet by a dropping coating method, and drying at a constant temperature of 60 ℃ for 24 hours to obtain a coating, wherein the thickness of the coating is 50 +/-2 microns.
As a result, as shown in FIG. 12, the PtBA/P (CTFE-co-IBVE-3)/PSQ-0.15 composite coating had almost no change in water contact angle even after being irradiated with ultraviolet rays for 600 hours, and had excellent ultraviolet resistance. As shown in fig. 14, the PSQ phase exhibited good overall uniformity and dispersion. As shown in fig. 17b, the coating had good transparency.
Example 9:
this example is substantially the same as example 6 except that, in the case of PtBA/P (CTFE-co-IBVE)/PSQ composite particles, the amount of IBVE added was 4g.
As can be seen from FIG. 12, the PtBA/P (CTFE-co-IBVE-4)/PSQ-0.15 composite coating has almost no change in water contact angle even after being irradiated under ultraviolet rays for 600 hours, and has excellent ultraviolet resistance. As shown in fig. 15, the PSQ phase exhibited better overall uniformity and dispersion. As shown in fig. 17c, the coating had good transparency.
Example 10:
this example is substantially the same as example 6 except that, in the case of PtBA/P (CTFE-co-IBVE)/PSQ composite particles, the amount of IBVE added was 5g.
As shown in fig. 16, the uniformity and dispersibility of the PSQ phase become very poor. As shown in fig. 17d, the coating was opaque and white. This is because P (CTFE-co-IBVE) is a soft segment whose glass transition temperature is lower than PtBA, and the increasing content of the soft segment leads to the improvement of the molecular chain mobility and side chain conformation adjustment ability, thereby increasing the probability of PSQ aggregation and the degree of phase separation.
Example 11:
the preparation method of the hybrid fluorocarbon latex coating with excellent synergistic performance comprises the following specific steps:
in the first step, 20.00g MA and 200.0g deionized water were added to a four-necked round bottom flask, and the mixture in the flask was deoxygenated by nitrogen bubbling at room temperature for 15min, and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e., 0.60wt% of MA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. And finally, performing rotary evaporation on the PMA latex under reduced pressure for 30min to obtain PMA latex seeds.
In the second step, 0.60g of MTES, 0.06g of MPS (MPS/MTES mass ratio: 0.1) and a latex containing 1.00g of PMA particles were diluted with 80.00g of deionized water in a 250mL flask and mixed uniformly while dispersing for 30min by ultrasonic waves to obtain dispersion A.
Thirdly, adding the dispersion liquid A into a 250mL high-pressure reaction kettle, and respectively adding NaHCO 3 (0.33 g), KPS (0.06 g) and IBVE (4.00 g). It is pressure-tested with 0.2MPa nitrogen, deoxygenated, then degassed under reduced pressure until vacuum (10 MPa) -2 mbar); CTFE (10.00 g) monomer was added by an addition method (i.e. the difference in mass between after and before the addition of CTFE gas by weighing the reaction system). The system is reacted for 8 hours under mechanical stirring at 60 ℃. Thus obtaining PMA/P (CTFE-co-IBVE-4)/PSQ-0.1 composite particles.
The PMA/P (CTFE-co-IBVE-4)/PSQ-0.1 composite latex particles are used for leather covering coating, and the method comprises the following specific steps:
and further carrying out ultrasonic dispersion on the obtained composite latex for 40min, respectively using alcohol and alkaline detergent to thoroughly clean the leather substrate, washing with deionized water and drying. And (3) coating the ultrasonically treated composite latex on the dried leather by a dropping coating method, and drying at a constant temperature of 60 ℃ for 24 hours to obtain a coating, wherein the thickness of the coating is 50 +/-2 microns.
The prepared hybrid fluorocarbon coating has excellent film forming property, transparency and organic solvent resistance, the adhesive force reaches 5B level, and the ultraviolet radiation resistance lasts for 600 hours.
Example 12:
the preparation method of the hybrid fluorocarbon latex coating with excellent synergistic performance comprises the following specific steps:
in the first step, 20.00g MA and 200.0g deionized water were added to a four-necked round bottom flask, and the mixture in the flask was deoxygenated by nitrogen bubbling at room temperature for 15min, and then warmed to 70 ℃. 5.00g of an aqueous solution containing 0.12g of KPS (i.e., 0.60wt% of MA monomer) was added to the system, and the stirring rate was adjusted to 250rpm, and the reaction was carried out at 70 ℃ for 5 hours. And finally, carrying out rotary evaporation on the PMA latex under reduced pressure for 30min to obtain PMA latex seeds.
In the second step, 0.60g of MTES, 0.06g of KH-570 (KH-570/MTES mass ratio: 0.1), and a latex containing 1.00g of PMA particles were diluted with 80.00g of deionized water in a 250mL flask and mixed well, and simultaneously dispersed for 30min by ultrasonic waves to obtain a dispersion A.
Thirdly, adding the dispersion liquid A into a 250mL high-pressure reaction kettle, and respectively adding NaHCO 3 (0.33 g), KPS (0.06 g) and IBVE (4.00 g). It is subjected to pressure testing with 0.2MPa nitrogen, deoxygenated and then degassed under reduced pressure until it approaches vacuum (10) -2 mbar); CTFE (10.00 g) monomer was added by an addition method (i.e. the difference in mass between after and before the addition of CTFE gas by weighing the reaction system). The system reacts for 8 hours under mechanical stirring at 60 ℃. Thus obtaining PMA/P (CTFE-co-IBVE-4)/PSQ-0.1 composite particles.
The PMA/P (CTFE-co-IBVE-4)/PSQ-0.1 composite latex particles are used for a tinplate covering coating, and the specific steps are as follows:
further ultrasonically dispersing the obtained composite latex for 40min, respectively and thoroughly cleaning the tinplate base material by using alcohol and an alkaline detergent, washing with deionized water and drying. And (3) coating the ultrasonically treated composite latex on dry tinplate by a dropping coating method, and drying at a constant temperature of 60 ℃ for 24 hours to obtain a coating, wherein the thickness of the coating is 50 +/-2 microns.
The prepared hybrid fluorocarbon coating has excellent film forming property, transparency and organic solvent resistance, the adhesive force reaches 5B level, and the ultraviolet irradiation resistance lasts for 600 hours.
It can be seen from the above examples that the thermal stability of the composite coating can be effectively improved by introducing PSQ as the only stabilizer. And, as the amount of MPS silane precursor increases, more C = C bonds can participate in the free radical polymerization of the comonomer, creating stable covalent bonds between PSQ and the organic polymer making the coating transparent better; the best effect is achieved when the mass ratio of MPS to MTES is 0.15 at the maximum. Then, the mass ratio of the silane precursor is fixed, the amount of IBVE is changed, and the IBVE can be subjected to free radical copolymerization with CTFE to generate a satisfactory alternating copolymer with excellent performance. Here, the amount of CTFE added during the copolymerization is in excess to ensure that the IBVE monomer is fully reacted. Therefore, the content of the P (CTFE-co-IBVE) copolymer in the hybrid composite particles can be adjusted by varying the amount of IBVE added. With the increase of the amount of the IBVE flexible chain segment, the movement capability of a molecular chain and the side chain conformation adjustment capability are improved, so that the PSQ aggregation probability and the phase separation degree are improved, the coating has obvious phase separation, and the transparency is gradually deteriorated. Moreover, the adhesive force is obviously improved due to the addition of the polyacrylate. PSQ and CTFE impart excellent properties (hydrophobicity, thermal stability, uv resistance, and organic solvent resistance) to the hybrid composite coating itself without affecting other properties (transparency, adhesion properties, etc.), thus solving the major challenges faced by hybrid composite particles.
The invention is not the best known technology.
Claims (4)
1. A method for preparing a hybrid fluorocarbon latex coating with synergistic properties, characterized in that it comprises the following steps:
firstly, mixing acrylate with deionized water, deoxidizing the obtained mixed solution for 5-30min, heating to 60-80 ℃, adding an aqueous solution containing potassium persulfate KPS, reacting for 4-6h at 60-80 ℃, and performing rotary evaporation for 20-40min under reduced pressure to obtain polyacrylate latex seeds;
wherein the mass ratio of the acrylic ester to the deionized water is 1; the mass ratio of the KPS-containing aqueous solution to the mixed solution of acrylic ester and deionized water is 1; the mass ratio of KPS to acrylate is 0.003 to 0.009;
secondly, adding the PSQ precursor and polyacrylate latex seeds into deionized water for mixing, and simultaneously dispersing for 10-40min by adopting ultrasonic waves to obtain a dispersion liquid A;
wherein the mass ratio of the PSQ precursor, the polyacrylate latex seed and the deionized water in the second step is 0.4 to 0.9:1:60 to 100;
the PSQ precursor is a substance A and a substance B; wherein the mass ratio is: substance A: substance B =1, 0.01 to 0.20; the substance A is methyl triethoxysilane or ethyl triethoxysilane, and the substance B is an organosilane precursor with carbon-carbon double bonds;
thirdly, adding the dispersion liquid A obtained in the second step into a high-pressure reaction kettle, and respectively adding NaHCO 3 KPS and IBVE, deoxidizing the crude oil for 10-50min by using nitrogen with the pressure of 0.2-0.4MPa, and then decompressing and degassing; then adding CTFE monomer, reacting the system for 6-9h at 40-70 ℃ under mechanical stirring to obtain polyacrylate/P (CTFE-co-IBVE)/PSQ composite latex particles;
wherein, the dispersion liquid A and NaHCO 3 The mass ratio of (1) to (0.001) - (0.010); KPS and NaHCO 3 The mass ratio of (A) to (B) is 0.1 to 0.5; the mass ratio of IBVE to CTFE is 2-4: 10;
fourthly, performing ultrasonic dispersion treatment on the composite latex particles obtained in the third step for 20-50min to obtain emulsion, then coating the emulsion on a dried base material, and drying at the constant temperature of 40-70 ℃ for 24-48h to obtain a coating; the thickness of the coating is 40 to 60 mu m.
2. The method of claim 1, wherein the acrylate in the first step is t-butyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ethyl acrylate, n-octyl acrylate, n-butyl methacrylate or hexyl methacrylate.
3. The method of claim 1, wherein the organosilane precursor having carbon-carbon double bond is one of methacryloxy trimethoxysilane, gamma-methacryloxy propyl trimethoxysilane, vinyl-tris (2-methoxyethoxy) silane, or vinyl triethoxysilane.
4. The method for preparing hybrid fluorocarbon latex coating with synergistic effect as claimed in claim 1, wherein the substrate in the fourth step is glass sheet, tinplate, leather, fabric or steel plate.
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