CN111925525A - Preparation method and application of amino fluorosilicone resin and composition thereof - Google Patents
Preparation method and application of amino fluorosilicone resin and composition thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of amino fluorosilicone resin and a composition thereof, wherein the novel amino fluorosilicone resin with high refractive index and high transparency is prepared by carrying out hydrolytic polymerization and purification on the combination of organic silicon monomers such as trifluoropropyl methyl cyclotrisiloxane (D3F),1H,1H,2H, 2H-perfluoroalkyl (C7-C12) trimethoxy (or ethoxy) silane, dimethyl diethoxy silane, diphenyl dimethoxy silane, KH-550 (gamma-aminopropyl trimethoxy silane), KH-602 (N-aminoethyl-gamma-aminopropyl methyl dimethoxy silane), ethyl orthosilicate and the like. The product formed by the resin, epoxy resin, nano silicon dioxide, nano insulating carbon black and other compositions has excellent characteristics of super hydrophobicity, high transparency, scratch resistance and the like, and can be applied to the fields of circuit board protective coatings, LED display screen coating coatings, mobile phone glass panel coatings, high-temperature resistant transparent coatings, flame retardant coatings and the like.
Description
Technical Field
The invention relates to the field of new organic silicon materials, in particular to amino fluorosilicone resin and a preparation method and application of a composition thereof.
Background
The characteristic of the liquid drop that is difficult to stay on the super-hydrophobic surface is called the "lotus effect". The super-hydrophobic coating has the functions of water resistance, ice resistance, fog resistance, self-cleaning and the like, and has wide application prospects in the aspects of aerospace, transportation, communication equipment, electronics and electrics, daily life and the like. The wettability of the surface of an object is determined by the composition of surface chemical components and a micro-geometric structure, and the current scientific community has unified knowledge that the low-surface-energy material can obtain super-hydrophobic performance by combining with a surface micro-nano structure. The super-hydrophobic coating is mainly achieved by chemically synthesizing a fluorine-containing substance with low surface energy and forming a micro-rough structure on the required surface through process design at present, and common preparation methods comprise a hydrothermal method, a sol-gel method, an etching method and the like. (details are shown in the research progress of the super-hydrophobic anticorrosion coating [ J ], material engineering, 2020,48(6):73-81, Wangyonghong, Navy and Liu, etc. ] the research progress of the non-metal super-hydrophobic nano coating technology [ J ], material guide [ 2020,34(z1):66-71, 20319and Wei, Dangsheng, bionic super-hydrophobic surface development and application research progress [ J ], inorganic material science report, 2019,34(11):1133 and 1144, Wuli, Liuyong, Zhanghong, etc. ] the research progress of the durable super-hydrophobic material [ J ]. adhesion, 2018,39(5): 59-62.);
the application of the super-hydrophobic coating to the photoelectronic product needs to solve the following technical problems: 1. the coating and the substrate need to be firmly adhered; 2. the light transmittance of the coating is high, and is generally required to be more than 85%; 3. the scratch and abrasion resistance of the material is improved, and the service life of the performance is maintained. The organosilicon fluorine silicon material has very low surface energy, excellent performances such as heat resistance, cold resistance, high voltage resistance, weather aging resistance and the like, and performances such as solvent resistance, water resistance, oil resistance, acid and alkali resistance and the like. But the application range of the organic silicon material is greatly limited due to the defects of poor bonding force and mechanical strength, large water permeability and air permeability and the like of the organic silicon material. (Guo hope, Guo Jianhua, great happiness, research on fluorosilicone rubber [ J ]. elastomer, 2017,27(1): 60-66; Wang Liwei, Lihui, Liebing, preparation of fluorosilicone resin and performance research thereof [ J ].2019,49(3): 38-41; Subrocade, Wuchuan, Dianthus superbus and the like ] preparation and performance research of fluorine-containing organosilicon material [ J ].2019,25(1):7-11.) epoxy resin has excellent binding force, mechanical strength and electrical insulation performance, is widely applied to the fields of paint, adhesive, electronic packaging material and the like, but due to the characteristics of a cross-linked network structure, the cured epoxy resin has poor brittleness, impact resistance and stress cracking resistance, poor high-temperature yellow edge resistance and poor weather resistance, and increases risks in many material application aspects. (see patent documents CN201910880714.9, CN201911374079.3, CN201910795156.6, CN 201710782936.8; Chengjing. development of epoxy resin for electronic packaging [ J ].2017, (1): 179-180; Chengjun. application and development of epoxy resin in semiconductor devices [ J ]. development of chemical engineering [ 2001,20(5):28-31 ]), it can be seen that the organic fluorine silicon material and the epoxy resin have strong complementary advantages in performance, and the organic fluorine silicon chain segment is introduced into the epoxy resin, so that the surface energy of the material can be fully reduced, the toughness, heat resistance, water resistance, humidity resistance and the like of the material can be enhanced, and the high adhesion, high structural strength and air tightness of the epoxy resin can be fully utilized, so that the preparation of the super-hydrophobic, high-transparent and scratch-resistant coating becomes possible. However, the compatibility of the organic fluorosilicone material and the epoxy resin is poor, most of the organic fluorosilicone polymers and the epoxy resin are completely incompatible, and the requirements of optoelectronic products on the super-hydrophobic material cannot be met by simple blending and copolymerization. The preparation and the performance of the fluorine-containing organic silicon modified epoxy resin composite material [ J ]. the Chinese adhesive, 2017,26(12) 34-37, Tudongbo, Chua Zhongzi, equation and the like [ J ]. 120 and 125 ] therefore, the compatibility problem and the surface micro-structure of the organic fluorine-containing silicon material and the epoxy resin are solved, and the method is a key technology for preparing the high-performance super-hydrophobic coating.
Chinese patent No. CN201510753841.4 discloses a method for preparing aminosiloxane by platinum-catalyzed hydrosilylation reaction of cyclic or linear hydrogenpolysiloxane and unsaturated amine compound, and does not illustrate the specific application field of synthesizing the aminosiloxane. Chinese patent No. CN201710302107.5 discloses a method for preparing a kind of amino silicone resin composition by organotin or organotitanium catalyzed condensation reaction of silicone resin containing hydroxyl group or siloxane group and amine compound containing hydroxyl group, the composition can be baked and cured with epoxy resin at room temperature or low temperature as epoxy curing agent to obtain coating or composite material with excellent heat resistance, weather resistance and hot hardness, and the document does not mention the compatibility and transparency problem of the prepared compound with epoxy resin. Chinese patent document No. CN201611199746.5 discloses a super-hydrophobic and anti-icing transparent coating and a preparation method thereof, wherein the super-hydrophobic and anti-icing transparent coating is prepared by mixing super-hydrophobic inorganic nano particles, fluorosilane, fluorocarbon varnish, a curing agent and an organic diluent; chinese patent document No. CN201710592317.2 discloses a water-based transparent super-hydrophobic coating and a preparation method thereof, which is prepared from SiO2Micron composite powder, tetraethyl orthosilicate, alkyl siloxane and water-based organic silicon or silicon modified resin; chinese patent document No. CN201611192769.3 discloses a large-scale preparation method of a transparent super-hydrophobic/super-amphiphobic coating, which is a transparent suspension of fluorine-free or fluorine-containing organosilane polymer-nanoparticle composite; and so on. None of these documents is concerned with non-organicFluorosilicone and epoxy systems, nor the adhesion and durability problems of superhydrophobic coatings.
In recent years, with the rapid development of the optoelectronic industry in China, the requirements for new optoelectronic materials are higher and higher, wherein the super-hydrophobic coating has a very large demand in the fields of high-performance circuit board protective coatings, LED display screen coating coatings, mobile phone glass panel coatings and the like, and the preparation of the high-transparency super-hydrophobic material with lasting and stable performance has important theoretical research and practical application significance. In view of the fact that the conventional organic fluorosilicone material and epoxy resin material can not meet the performance requirements of the application fields, the invention solves the problem that the organic fluorosilicone resin can be compatible with most of epoxy resin by carrying out material structure design and synthesis from monomers, and the method for forming the super-hydrophobic composition has essential difference from the method described in the above document, thereby being a brand-new original work.
Disclosure of Invention
The present invention aims to overcome the above-mentioned shortcomings and provide a technical solution to solve the above-mentioned problems.
Under the protection of nitrogen, trifluoropropylmethylcyclotrisiloxane (D3F),1H,1H,2H, 2H-perfluoroalkyl (C7-C12) trimethoxy (or ethoxy) silane, phenyltrimethoxy (or ethoxy) silane, dimethyldiethoxy (or methoxy) silane, diphenyldimethoxy (or ethoxy) silane, KH-550 (gamma-aminopropyltrimethoxysilane), KH-602 (N-aminoethyl-gamma-aminopropylmethyldimethoxysilane), organosilicon monomer combinations such as ethyl orthosilicate and the like and an ethanol solution of distilled water are respectively added into a reactor, stirred and reacted for 6 hours at the temperature of 60-80 ℃ under the catalysis of a small amount of potassium hydroxide and strong base, and then the system is slowly heated to 120 ℃ to evaporate alcohol and excessive moisture generated by the reaction, a clear viscous oil was obtained; adding a certain amount of cyclohexane or toluene into the oily matter for dilution, removing a strong base catalyst in a reaction system by adopting 732 cation exchange resin, distilling the liquid obtained after filtration to 140 ℃ to remove the solvent, and then thoroughly removing low-boiling-point matters in vacuum to obtain high-transparency high-purity amino fluorine-silicon resin; the organic fluorine-silicon resin and the compositions of epoxy resin, nano silicon dioxide, nano insulating carbon black and the like form a high-transparency super-hydrophobic coating.
Preferably, the synthesized amino fluorosilicone resin has the structural formula described as follows:
each monomer chain link unit is abbreviated as:
(CnH4F2n-3SiO1.5)a(CF3CH2CH2RSiO)b(RN2SiO)c(RSiO1.5)d(N1SiO1.5)e(SiO2)f(R2SiO)g
the structural formula satisfies: if it is set
Then 0.4 > (a + d +2f) > 0.01; a + b is less than or equal to 0.6; the content of phenyl accounts for 10-30% of the total mass.
Preferably, the sum of alkoxy groups (including methoxy and ethoxy) contained in all siloxane monomers added is calculated, and the ratio of the molar amount of the reactive distilled water added in the polymerization reaction to the molar amount of the alkoxy groups is controlled to be 1.0-1.5: 2.0. The polymerization temperature is 60-80 ℃, and the heat preservation reaction time is more than 3 hours; and (3) separating and purifying the product, and removing the residual solvent and the low molecular weight polymer at the temperature of 130-140 ℃ and the final vacuum degree of less than-0.09 Mpa.
Preferably, the adopted strong base catalyst is potassium hydroxide, and the addition amount is one ten thousandth to one hundredth of the total mass of the monomers; in the process of resin separation and purification, toluene or cyclohexane is used as a viscosity diluent, 732 cation exchange resin is used for removing a strong base catalyst in a reaction system, and the total exchange capacity of the cation exchange resin is 3-10 times of the molar weight of the added potassium hydroxide.
Preferably, the refractive index of the prepared amino fluorosilicone resin is between 1.45 and 1.49, the mass content of fluorine element is between 5 and 25 percent, the content of phenyl is between 10 and 35 percent, the active hydrogen value on amino is between 0.1 and 1.0(mol/100g), and the viscosity is between 1500 and 50000 cps; the epoxy resin used in the composition comprises liquid or solid epoxy resin such as bisphenol A epoxy resin, aliphatic epoxy resin, epoxy silicone oil and the like, and the used nano silicon dioxide, nano insulating carbon black and the like are surface microstructure adjusting components.
Preferably, a product formed by the composition has excellent characteristics of super-hydrophobicity, high transparency, high bonding force, high toughness, low hardness, low water absorption, cold and heat shock resistance, high temperature aging resistance, flame retardance and the like, and can be applied to the fields of circuit board protective coatings, LED display screen coating coatings, mobile phone glass panel coatings, high temperature transparent coatings, flame retardant coatings and the like.
Compared with the prior art, the invention has the beneficial effects that: the invention has invented a amino fluoro silicone resin and its preparation method and application of composition, the invention carries on material structure design and synthesis from monomer, have provided a brand-new preparation method of amino fluoro silicone resin, through introducing phenyl organosilicon monomer chain link on the polymer structure, have solved the compatibility problem of organosilicon resin and most epoxy resin fundamentally, viscosity, refractive index and active hydrogen value can be adjusted flexibly at the same time; the composition formed by the amino fluorosilicone resin, the epoxy resin, the nano silicon dioxide and the like simultaneously solves a plurality of problems of mutual limitation such as super hydrophobicity, high transparency, high adhesive force, high hardness, scratch resistance and the like, is original work, and provides a brand-new and reliable solution for the fields of circuit board protective coatings, LED display screen coating coatings, mobile phone glass panel coatings, high-temperature-resistant transparent coatings, flame-retardant coatings and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples of the present invention, example 1:
s1, under the protection of nitrogen, respectively adding 3F 1200G of D3, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane 117G, 300G of dimethyldiethoxysilane, 704G of diphenyl dimethoxysilane, 20G of phenyltrimethoxysilane, KH-602357G and 42G of ethyl orthosilicate into a reactor, then dissolving 0.3G of potassium hydroxide into 440G of ethanol-water (the mass ratio of ethanol to water is 1: 1) solution, stirring and adding into the reactor, heating to 60-80 ℃ for reacting for 6 hours, slowly heating the system to 130 ℃ to evaporate alcohol and excessive water generated by the reaction, and obtaining a transparent viscous oily substance. Cooling the system to below 60 ℃, adding 2000-4000 g of toluene into the oily matter for dilution, then adding 20g of 732 cation exchange resin (the mass exchange capacity is 0.45mmol/g) for uniformly stirring, adding the filtered liquid into a reactor, heating to 135-140 ℃ under the protection of nitrogen, and then thoroughly removing the solvent and low-boiling-point substances in vacuum to obtain 2586g of transparent yellowish amino fluorine-silicon resin. The fluorosilicone resin has viscosity of 4800cps, refractive index of 1.465, and active hydrogen value on amino group of 0.19(mol/100g) at 25 deg.C;
s2 composition and its Properties: taking 370g of the prepared amino fluorosilicone resin, E5180g bisphenol A epoxy resin, 40g of south Asia solid epoxy resin 901(E value of 0.2) and 40g of hexahydrophthalic acid diglycidyl ester, uniformly dissolving the amino fluorosilicone resin, spraying or blade-coating the solution on the surface of glass, heating the solution at 80-150 ℃ for 4 hours to cure the solution after the solution is completely volatilized to obtain a transparent coating, wherein the hardness of the transparent coating is 3B (test standard GB/T6739-; if 25g of nano-silica is added into the composition to be uniformly dispersed, the water contact angle of the coating obtained by the same process is 154 degrees.
Example 2:
s1, under the protection of nitrogen, respectively adding 3F 1350G of D3, 1H,1H,2H, 2H-perfluorodecyltriethoxysilane 122G, 60G of dimethyldiethoxysilane, 140G of diphenyldimethoxysilane, 890G of phenyltrimethoxysilane, KH-602412G and KH-550100G into a reactor, then dissolving 0.5G of potassium hydroxide into 500G of ethanol-water (the mass ratio of ethanol to water is 1: 1) solution, stirring and adding into the reactor, heating to 60-80 ℃ for reaction for 6 hours, slowly heating the system to 130 ℃ to evaporate alcohol and excessive water generated by the reaction, and obtaining a transparent viscous oily substance. Cooling the system to below 60 ℃, adding 2000-4000 g of toluene into the oily matter for dilution, then adding 732 g of cation exchange resin (the mass exchange capacity is 0.45mmol/g) for uniformly stirring, adding the filtered liquid into a reactor, heating to 135-140 ℃ under the protection of nitrogen, and then thoroughly removing the solvent and low-boiling-point substances in vacuum to obtain 2593g of transparent amino fluorosilicone resin. The detection shows that the silicone resin is a non-flowing solid resin at 25 ℃, the refractive index is 1.458, and the active hydrogen value on amino is 0.30(mol/100 g);
s2 composition and its Properties: taking 300g of the prepared amino fluorosilicone resin, bisphenol A epoxy resin E5160g, phenyl epoxy silicone oil (E value is 0.35), 60g and 60g of hexahydrophthalic acid diglycidyl ester, uniformly dissolving the amino fluorosilicone resin, spraying or blade-coating the amino fluorosilicone resin and the diglycidyl ester to the surface of glass, heating the mixture at 80-150 ℃ for 4 hours to cure the mixture after the solvent is completely volatilized to obtain a transparent coating, wherein the hardness of the transparent coating is 2H (test standard GB/T6739-; if 25g of nano silicon dioxide is added into the composition to be uniformly dispersed, the water contact angle of the coating obtained by the same process is 168 degrees; if 25g of nano silicon dioxide and 5g of nano insulating carbon black are added into the composition and uniformly dispersed, the water contact angle of the coating obtained by the same process is 165 degrees, and the color is elegant and black.
Example 3:
s1, under the protection of nitrogen, respectively adding 3F 1350G of D3, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane 58G, 360G of dimethyldiethoxysilane, 1100G of diphenyldimethoxysilane, 100G of phenyltrimethoxysilane, KH-602742G and KH-550100G into a reactor, then dissolving 0.5G of potassium hydroxide into 550G of ethanol-water (the mass ratio of ethanol to water is 1: 1) solution, stirring and adding into the reactor, heating to 60-80 ℃ for reaction for 6 hours, slowly heating the system to 130 ℃ to evaporate alcohol and excessive water generated by the reaction, and obtaining a transparent viscous oily substance. Cooling the system to below 60 ℃, adding 2000-4000 g of toluene into the oily matter for dilution, then adding 732 g of cation exchange resin (the mass exchange capacity is 0.45mmol/g) for uniformly stirring, adding the filtered liquid into a reactor, heating to 135-140 ℃ under the protection of nitrogen, and then thoroughly removing the solvent and low-boiling-point substances in vacuum to obtain 2595g of transparent amino fluorosilicone resin. Through detection, the viscosity of the silicone resin is 13000cps at 25 ℃, the refractive index is 1.485, and the active hydrogen value on amino is 0.44(mol/100 g);
s2 composition and its Properties: taking 200g of the prepared amino fluorosilicone resin, bisphenol A epoxy resin E5180g, phenyl epoxy silicone oil (E value is 0.35), 60g and xylonite aliphatic epoxy resin 2021P (3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formic ether) 40g, uniformly dissolving by using an organic solvent, spraying or blade-coating to the surface of glass, heating at 80-150 ℃ for 4 hours to cure after the solvent is completely volatilized to obtain a transparent coating, wherein the test coating hardness is 2-3H (test standard GB/T6739-; if 20g of nano silicon dioxide is added into the composition and uniformly dispersed, the water contact angle of the coating obtained by the same process is 148 degrees; if 20g of nano silica and 5g of nano insulating carbon black are added into the composition and uniformly dispersed, the water contact angle of the coating obtained by the same process is 145 degrees, and the color is elegant and black.
Example 5:
s1, under the protection of nitrogen, respectively adding D3F 582G, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane 58G, dimethyldiethoxysilane 150G, diphenyl dimethoxysilane 915G, KH-602830G and KH-55088G into a reactor, then dissolving 0.4G of potassium hydroxide into 420G of ethanol-water (the mass ratio of ethanol to water is 1: 1) solution, stirring and adding into the reactor, heating to 60-80 ℃ for reaction for 6 hours, slowly heating the system to 130 ℃ to evaporate alcohol and excessive water generated by the reaction, and obtaining a transparent viscous oily substance. Cooling the system to below 60 ℃, adding 2000-4000 g of toluene into the oily matter for dilution, then adding 732 g of cation exchange resin (the mass exchange capacity is 0.45mmol/g) for uniformly stirring, adding the filtered liquid into a reactor, heating to 135-140 ℃ under the protection of nitrogen, and then thoroughly removing the solvent and low-boiling-point substances in vacuum to obtain 2583g of transparent amino fluorosilicone resin. The detection shows that the viscosity of the silicone resin is about 2500cps at 25 ℃, the refractive index is 1.474, and the active hydrogen value on amino is 0.79(mol/100 g);
s2 composition and its Properties: taking 120G of the prepared amino fluorosilicone resin, bisphenol A epoxy resin E5180G, 40G of south Asia solid epoxy resin 901(E value of 0.2), 40G of hexahydrophthalic acid diglycidyl ester and 60G of phenyl epoxy silicone oil (E value of 0.35), uniformly dissolving the materials by using an organic solvent, spraying or blade-coating the materials on the surface of glass, heating the materials at 80-150 ℃ for 4 hours to cure after the solvent is completely volatilized, and obtaining a transparent coating, wherein the hardness of the test coating is 4H (test standard GB/T6739-; if 25g of nano-silica is added into the composition to be uniformly dispersed, the water contact angle of the coating obtained by the same process is 138 degrees.
Example 6:
s1, under the protection of nitrogen, respectively adding D3F 440G, 1H,1H,2H, 2H-perfluorooctyltriethoxysilane 58G, dimethyldiethoxysilane 240G, diphenyl dimethoxysilane 850G, KH-6021783G and ethyl orthosilicate 63G into a reactor, then dissolving 0.3G of potassium hydroxide into 600G of ethanol-water (the mass ratio of ethanol to water is 1: 1) solution, stirring and adding into the reactor, heating to 60-80 ℃ for reaction for 6 hours, slowly heating the system to 130 ℃ to evaporate alcohol and excessive water generated by the reaction, and obtaining a transparent viscous oily substance. Cooling the system to below 60 ℃, adding 2000-4000 g of toluene into the oily matter for dilution, then adding 20g of 732 cation exchange resin (the mass exchange capacity is 0.45mmol/g) for uniformly stirring, adding the filtered liquid into a reactor, heating to 135-140 ℃ under the protection of nitrogen, and then thoroughly removing the solvent and low-boiling-point substances in vacuum to obtain 2578g of transparent amino fluorosilicone resin. The detection shows that the viscosity of the silicone resin is about 1800cps at 25 ℃, the refractive index is 1.462, and the active hydrogen value on amino is 1.02(mol/100 g);
s2 composition and its Properties: taking 95G of the prepared amino fluorosilicone resin, bisphenol A epoxy resin E5180G, 40G of south Asia solid epoxy resin 901(E value of 0.2), 40G of hexahydrophthalic acid diglycidyl ester and 60G of phenyl epoxy silicone oil (E value of 0.35), uniformly dissolving the materials by using an organic solvent, spraying or blade-coating the materials on the surface of glass, heating the materials at 80-150 ℃ for 4 hours to cure after the solvent is completely volatilized, and obtaining a transparent coating, wherein the hardness of the test coating is 4H (test standard GB/T6739-; if 25g of nano-silica is added into the composition to be uniformly dispersed, the water contact angle of the coating obtained by the same process is 122 degrees.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. An amino fluorosilicone resin and a preparation method and application of a composition thereof are characterized in that under the protection of nitrogen, trifluoropropylmethyl cyclotrisiloxane (D3F),1H,1H,2H, 2H-perfluoroalkyl (C7-C12) trimethoxy (or ethoxy) silane, phenyltrimethoxy (or ethoxy) silane, dimethyldiethoxy (or methoxy) silane, diphenyldimethoxy (or ethoxy) silane, KH-550 (gamma-aminopropyl trimethoxy silane), KH-602 (N-aminoethyl-gamma-aminopropyl methyl dimethoxysilane), organosilicon monomer combinations such as ethyl orthosilicate and the like and ethanol solution of distilled water are respectively added into a reactor, stirred and reacted for 6 hours at the temperature of 60-80 ℃ under the catalysis of a small amount of potassium hydroxide strong base, and then the system is slowly heated to 120 ℃ to generate alcohol and excessive water, a clear viscous oil was obtained; adding a certain amount of cyclohexane or toluene into the oily matter for dilution, removing a strong base catalyst in a reaction system by adopting 732 cation exchange resin, distilling the liquid obtained after filtration to 140 ℃ to remove the solvent, and then thoroughly removing low-boiling-point matters in vacuum to obtain high-transparency high-purity amino fluorine-silicon resin; the organic fluorine-silicon resin and the compositions of epoxy resin, nano silicon dioxide, nano insulating carbon black and the like form a high-transparency super-hydrophobic coating.
2. The preparation method and application of the amino fluorosilicone resin and the composition thereof according to claim 1, wherein the structural formula of the synthesized amino fluorosilicone resin is described as follows:
in the general formula, n is 7-12; r ═ methyl Me-or phenyl Ph-
Each monomer chain link unit is abbreviated as:
(CnH4F2n-3SiO1.5)a(CF3CH2CH2RSiO)b(RN2SiO)c(RSiO1.5)d(N1SiO1.5)e(SiO2)f(R2SiO)g
the structural formula satisfies: if it is set
Then 0.4 > (a + d +2f) > 0.01; a + b is less than or equal to 0.6; the content of phenyl accounts for 10-30% of the total mass.
3. The preparation method and application of amino fluorosilicone resin and composition thereof according to claim 1, wherein the total of alkoxy groups (including methoxy and ethoxy groups) contained in all added siloxane monomers is calculated, and the ratio of the molar weight of reactive distilled water added in the polymerization reaction to the molar weight of the alkoxy groups is controlled to be 1.0-1.5: 2.0. The polymerization temperature is 60-80 ℃, and the heat preservation reaction time is more than 3 hours; and (3) separating and purifying the product, and removing the residual solvent and the low molecular weight polymer at the temperature of 130-140 ℃ and the final vacuum degree of less than-0.09 Mpa.
4. The preparation method and application of the amino fluorosilicone resin and the composition thereof according to claim 1, wherein the adopted strong base catalyst is potassium hydroxide, and the addition amount is one ten thousandth to one hundredth of the total mass of the monomers; in the process of resin separation and purification, toluene or cyclohexane is used as a viscosity diluent, 732 cation exchange resin is used for removing a strong base catalyst in a reaction system, and the total exchange capacity of the cation exchange resin is 3-10 times of the molar weight of the added potassium hydroxide.
5. The preparation method and application of amino fluorosilicone resin and composition thereof as claimed in claim 1, wherein the refractive index of the prepared amino fluorosilicone resin is between 1.45-1.49, the mass content of fluorine element is between 5-25%, the content of phenyl group is between 10-35%, the value of active hydrogen on amino group is between 0.1-1.0 (mol/100g), and the viscosity is between 1500-50000 cps; the epoxy resin used in the composition comprises liquid or solid epoxy resin such as bisphenol A epoxy resin, aliphatic epoxy resin, epoxy silicone oil and the like, and the used nano silicon dioxide, nano insulating carbon black and the like are surface microstructure adjusting components.
6. The preparation method and application of the amino fluorosilicone resin and the composition thereof according to claim 1 are characterized in that a product formed by the composition has excellent characteristics of super hydrophobicity, high transparency, high adhesive force, high toughness and hardness, low water absorption, thermal shock resistance, high temperature aging resistance, flame retardance and the like, and can be applied to the fields of circuit board protective coatings, LED display screen coating coatings, mobile phone glass panel coatings, high temperature transparent coatings, flame retardant coatings and the like.
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| CN113292906A (en) * | 2021-06-08 | 2021-08-24 | 东莞市溢美材料科技有限公司 | Preparation and application of high-hardness wear-resistant coating |
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