CN113845684B - Production process of wear-resistant PC glass plate - Google Patents
Production process of wear-resistant PC glass plate Download PDFInfo
- Publication number
- CN113845684B CN113845684B CN202111081535.2A CN202111081535A CN113845684B CN 113845684 B CN113845684 B CN 113845684B CN 202111081535 A CN202111081535 A CN 202111081535A CN 113845684 B CN113845684 B CN 113845684B
- Authority
- CN
- China
- Prior art keywords
- wear
- substrate
- resistant
- coating
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The invention discloses a production process of a wear-resistant PC glass plate, and belongs to the field of preparation of polycarbonate glass plates. And the production process of the PC glass plate comprises the following steps: step one, preparing a PC substrate; step two, heat treatment of the PC substrate: and step three, spraying the wear-resistant coating. In addition, vinyl poly-half-time siloxane is added in the production process of the PC substrate, so that the flame retardant property of the PC substrate is improved, and meanwhile, the adhesive property of the PC substrate and the coating is improved; secondly, the modified silicon resin is selected as the coating of the wear-resistant layer, the excellent viscoelasticity of the modified borosiloxane chain segment is utilized, the adhesive force of the silicon resin coating is further improved, the elasticity of the coating is further improved, and meanwhile, the modified polyborosiloxane is introduced, so that the modified silicon resin contains fluorine-containing branched chains, and the water resistance and the solvent resistance of the modified silicon resin coating are further improved.
Description
Technical Field
The invention belongs to the field of polycarbonate glass plate preparation, and particularly relates to a production process of a wear-resistant PC glass plate.
Background
Polycarbonate (PC) is an amorphous polymer in a nearly colorless glassy state, has good optical properties, high toughness, high impact resistance and good heat resistance, and is widely used in the fields of glass assembly industry, automobile industry, electronics industry, electrical appliance industry and the like. However, compared with most plastic materials, the wear resistance of the polycarbonate is relatively poor, and the polycarbonate is at a medium level, so that the popularization of the polycarbonate in places with easy-wear application is limited. Therefore, the research on the abrasion-resistant PC glass plate is always one focus of the research on the modification of the PC glass plate.
For example, chinese patent CN212097876U discloses an abrasion-resistant PC board, which comprises a PC board, wherein a phenolic resin layer is fixedly connected to the upper surface of the PC board, a tungsten carbide layer is fixedly connected to the upper surface of the phenolic resin layer, and an abrasion-resistant nylon layer is fixedly connected to the upper surface of the tungsten carbide layer. The utility model discloses a through set up phenolic resin layer, tungsten carbide layer and wear-resisting nylon layer on the PC base plate, and improve the wear resistance of PC board. However, the multilayer structure of the utility model is complicated in the production process of the PC board, and tungsten carbide is a hard alloy material, and the adhesion between the tungsten carbide and the polymer (phenolic resin, nylon) is not strong, and the tungsten carbide is liable to peel off.
In the prior art, siloxane resin coatings are usually selected for wear-resistant layers of PC boards, and the wear-resistant layers are simple in preparation method and have excellent wear resistance, high temperature resistance and weather resistance. However, new problems are introduced at the same time, such as poor adhesion of the coating film to the substrate material, poor solvent resistance, and brittleness of the coating film.
Therefore, the invention provides a production process of the wear-resistant PC glass plate.
Disclosure of Invention
The invention aims to provide a production process of a wear-resistant PC glass plate, and provides the wear-resistant PC glass plate which comprises a PC substrate and a wear-resistant coating on the PC substrate.
The technical problems to be solved by the invention are as follows: the problem of insufficient wear resistance of the existing PC glass plate.
The purpose of the invention can be realized by the following technical scheme:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: uniformly mixing PC, vinyl polysilsesquioxane, an antioxidant and a lubricant, and extruding and granulating through an extruder to obtain granules; preheating the mold for 3min, and then injecting the granules into the mold to form a PC substrate by injection molding;
step two, heat treatment of the PC substrate: placing the PC substrate in an oven, keeping the temperature at 100 ℃ for 15min, then heating to 118 ℃, keeping the temperature for 35min, then cooling to 60 ℃ along with the oven, and taking air as a heat treatment medium to obtain a treated PC substrate;
step three, spraying the wear-resistant coating: and ultrasonically cleaning the PC substrate by adopting ethanol or isopropanol, naturally airing or air-drying or baking, coating the wear-resistant coating on the outer surface of the treated PC substrate, and curing the PC substrate coated with the wear-resistant coating at 80-110 ℃ for 3-5min to obtain the wear-resistant PC glass plate.
Further, in the first step, the mass ratio of the PC to the vinyl polysilsesquioxane to the antioxidant to the lubricant is 75-90:6-15:0.5-2.5:0.5-3.5.
Further, in the first step, the preheating temperature of the die is 95-100 ℃, the injection molding temperature is 180-250 ℃, and the injection molding pressure is 100MPa.
Furthermore, the coating mode in the third step is one of dip coating and curtain coating.
Further, the antioxidant is an antioxidant 168, and the antioxidant 1010 is mixed according to a mass ratio of 2-3:1, mixing the components.
Further, the lubricant is one of silicone oil, white mineral oil and paraffin.
Further, the wear-resistant coating is prepared by the following steps:
s1, adding phenylboronic acid into a reaction container, vacuumizing the system, introducing nitrogen, then adding anhydrous ether and triethylamine, dropwise adding an ether solution of dimethylvinylchlorosilane under a stirring state, reacting at room temperature for 4-6h at a dropwise adding speed of 1 drop/second, washing for 2-3 times by using deionized water, drying with anhydrous sodium sulfate, removing ether by rotary evaporation, and carrying out reduced pressure distillation to obtain a boron-containing siloxane monomer, wherein the dosage ratio of the phenylboronic acid to the anhydrous ether to the triethylamine to the dimethylvinylchlorosilane is 0.041-0.042mol:80-150mL:0.02mol:0.02mol;
the molecular structural formula of the boron-containing siloxane monomer is shown as follows:
s2, uniformly mixing gamma-methacryloxypropyltrimethoxysilane, a boron-containing siloxane monomer, dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a potassium persulfate isopropanol aqueous solution at the dropping speed of 2 drops/second, continuing to react for 3 hours after the dropwise adding is completed, cooling and washing for 2-3 times, and performing rotary evaporation on an organic layer to remove a solvent to obtain the modified polyborosiloxane, wherein the mass ratio of the gamma-methacryloxypropyltrimethoxysilane to the boron-containing siloxane monomer to the dodecafluoroheptyl acrylate is 12-21:44-58:20-35, the addition amount of potassium persulfate isopropanol is 8-10% of the total mass of gamma-methacryloxypropyltrimethoxysilane, the boracic siloxane monomer and the dodecafluoroheptyl acrylate, and the volume ratio of isopropanol to water in the potassium persulfate isopropanol water solution is 3:1;
the molecular structural formula of the modified polyborosiloxane is shown as follows:
in the reaction, an olefin monomer polymerization reaction is utilized, and a trimethylsilane chain and a fluorine-containing chain are connected into a molecular chain of the polyborosiloxane, so that on one hand, the connection of the trimethylsilane chain lays a foundation for the subsequent steps, and on the other hand, the fluorine-containing chain is introduced to improve the property of easy hydrolysis of the borosiloxane bond;
s3, uniformly mixing ethyl orthosilicate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon, deionized water and isopropanol, adding acetic acid to control the pH value of a reaction system to be 5.5-6.5, controlling the temperature to be 35 ℃, stirring for reaction for 40-70min, then dropwise adding an isopropanol aqueous solution of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reaction for 4h, and performing rotary evaporation to obtain the modified silicon resin, wherein the mass ratio of the ethyl orthosilicate to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon to the modified polyborosiloxane is 35-45:14-26:25-47;
in the reaction, tetraethoxysilane and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon are used as silane monomers to generate silicon resin under hydrolysis reaction, modified polyborosiloxane is added in the hydrolysis reaction process, and the trimethylsiloxane chain contained in the modified polyborosiloxane can be continuously hydrolyzed, so that the molecular chain of the polyborosiloxane and the molecular chain of the generated silicon resin are crosslinked to obtain a modified silicon resin solution;
s4, adding the modified silicone resin into a composite solvent, stirring for 30min at 400-500r/min, then adding a curing agent and an adhesion promoter, namely poly (1, 4-butylene glycol adipate) at 400-500r/min, and uniformly stirring to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol butyl ether in a volume ratio of 3:1.5-2.5, wherein the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to the mass ratio of 1:1.5, the addition mass of the curing agent is 0.2-0.3% of the mass of the silicon resin, and the addition mass of the adhesion promoter is 1% of the mass of the silicon resin.
The invention has the beneficial effects that:
the production process provided by the invention comprises the following steps: the injection molding of the PC substrate, the heat treatment of the PC substrate and the preparation of the coating are simple to operate and easy for large-scale production; in addition, the vinyl poly-half-time siloxane is added in the production process of the PC substrate, so that the flame retardant property of the PC substrate is improved, and the adhesive property of the PC substrate and the coating is improved, because the vinyl on the surface of the PC substrate can be crosslinked with functional groups (free double bonds in the modified polyborosiloxane) in the coating material; secondly, the modified silicone resin is selected as the coating of the wear-resistant layer, the excellent viscoelasticity of the borosilicate chain segment is utilized, the adhesive force of the silicone resin coating is further improved, the elasticity of the coating is further improved, and meanwhile, the modified polyborosiloxane is introduced, so that the modified silicone resin contains the fluorine-containing branched chain, when the modified silicone resin is formed into a film, the fluorine-containing branched chain is easy to migrate to the surface of the coating to form a fluorine-containing chain layer, and the water resistance and the solvent resistance of the modified silicone resin coating are further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1:
the vinyl polysilsesquioxane is prepared by the following steps:
adding 0.1mol of vinyl trichlorosilane and 200mL of acetone into a 500mL three-neck flask provided with a thermometer, a reflux condenser and nitrogen protection, slowly dropwise adding 70mL of distilled water, stirring and reacting at 40 ℃ for 5d after dropwise adding, centrifuging after the reaction is finished, washing with acetone, centrifuging again, dissolving the centrifuged solid with tetrahydrofuran, and recrystallizing at room temperature to obtain the vinyl polysilsesquioxane.
Example 2:
the wear-resistant coating is prepared by the following steps:
s1, adding 0.041mol of phenylboronic acid into a reaction container, vacuumizing the system, introducing nitrogen, then adding 80mL of anhydrous ether and 0.02mol of triethylamine, dropwise adding 0.02mol of ether solution of dimethylvinylchlorosilane under a stirring state at a dropping speed of 1 drop/second, reacting for 4 hours at room temperature, washing for 2 times with deionized water, drying with anhydrous sodium sulfate, performing rotary evaporation to remove ether, and performing reduced pressure distillation to obtain a boron-containing siloxane monomer;
s2, uniformly mixing 12g of gamma-methacryloxypropyltrimethoxysilane, 58g of a boracic siloxane monomer, 20g of dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a propanol aqueous solution containing 8g of potassium persulfate isopropyl (the volume ratio of isopropanol to water is 3;
s3, uniformly mixing 35g of ethyl orthosilicate, 14g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon, 70mL of deionized water and 30mL of isopropanol, adding acetic acid to control the pH value of a reaction system to be 5.5, controlling the temperature to be 35 ℃, stirring for reacting for 40min, then dropwise adding an isopropanol aqueous solution containing 47g of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reacting for 4h, and carrying out rotary evaporation to obtain modified silicon resin;
s4, adding 100g of a composite solvent into 14g of modified silicon resin, stirring for 30min at 400r/min, then adding 0.28g of a curing agent and 0.14g of an adhesion promoter, namely 1, 4-butanediol adipate, and uniformly stirring at 400r/min to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol monobutyl ether according to a volume ratio of 3:1.5, and the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to the mass ratio of 1:1.5 mixing.
Example 3:
the wear-resistant coating is prepared by the following steps:
s1, adding 0.042mol of phenylboronic acid into a reaction container, vacuumizing the system, introducing nitrogen, then adding 150mL of anhydrous ether and 0.02mol of triethylamine, dropwise adding 0.02mol of ether solution of dimethylvinylchlorosilane under a stirring state at a dropping speed of 1 drop/second, reacting at room temperature for 5 hours, washing for 2 times with deionized water, drying with anhydrous sodium sulfate, removing ether by rotary evaporation, and distilling under reduced pressure to obtain a boron-containing siloxane monomer;
s2, uniformly mixing 17g of gamma-methacryloxypropyl trimethoxysilane, 51g of a borosiloxane monomer, 27g of dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a propanol water solution containing 8g of potassium persulfate isopropyl (the volume ratio of isopropanol to water is 3;
s3, uniformly mixing 39g of ethyl orthosilicate, 17g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 70mL of deionized water and 30mL of isopropanol, adding acetic acid to control the pH value of a reaction system to be 6, controlling the temperature to be 35 ℃, stirring for reaction for 50min, then dropwise adding an aqueous solution of isopropanol containing 30g of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reaction for 4h, and carrying out rotary evaporation to obtain modified silicon resin;
s4, adding 100g of composite solvent into 16g of modified silicon resin, stirring for 30min at the speed of 450r/min, then adding 0.32g of curing agent and 0.16g of adhesion promoter poly (1, 4-butylene glycol adipate) at the speed of 400r/min, and uniformly stirring to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol monobutyl ether according to the volume ratio of 3:2, and the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to a mass ratio of 1:1.5 mixing.
Example 4:
the wear-resistant coating is prepared by the following steps:
s1, adding 0.041mol of phenylboronic acid into a reaction container, vacuumizing the system, introducing nitrogen, then adding 100mL of anhydrous ether and 0.02mol of triethylamine, dropwise adding 0.02mol of ether solution of dimethylvinylchlorosilane under a stirring state at a dropping speed of 1 drop/second, reacting for 6 hours at room temperature, washing for 3 times with deionized water, drying with anhydrous sodium sulfate, performing rotary evaporation to remove ether, and performing reduced pressure distillation to obtain a boron-containing siloxane monomer;
s2, uniformly mixing 21g of gamma-methacryloxypropyltrimethoxysilane, 44g of a borosiloxane monomer, 35g of dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a propanol water solution containing 13g of potassium persulfate isopropyl (the volume ratio of isopropanol to water is 3;
s3, uniformly mixing 45g of ethyl orthosilicate, 26g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon, 70mL of deionized water and 30mL of isopropanol, adding acetic acid to control the pH value of a reaction system to be 5.5-6.5, controlling the temperature to be 35 ℃, stirring for reaction for 70min, then dropwise adding an isopropanol aqueous solution containing 47g of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reaction for 4h, and performing rotary evaporation to obtain modified silicon resin;
s4, adding 100g of composite solvent into 18g of modified silicon resin, stirring for 30min at 500r/min, then adding 0.54g of curing agent and 0.18g of adhesion promoter poly (1, 4-butylene glycol adipate) and uniformly stirring at 500r/min to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol monobutyl ether according to a volume ratio of 3:2.5, the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to the mass ratio of 1:1.5 mixing.
Example 5:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: 75g of PC, 6g of the vinyl polysilsesquioxane prepared in example 1, 0.5g of antioxidant and 0.5g of lubricant are uniformly mixed, and then extruded and granulated through an extruder to obtain granules; preheating a mould for 3min at 95 ℃, then injecting the granules into the mould to form a PC substrate by injection molding, wherein the injection molding temperature is 180 ℃, the injection molding pressure is 100MPa, and the antioxidant is antioxidant 168 and antioxidant 1010, and the mass ratio is 2:1, mixing the components, wherein the lubricant is silicone oil;
step two, heat treatment of the PC substrate: placing the PC substrate in an oven, keeping the temperature at 100 ℃ for 15min, then heating to 118 ℃, keeping the temperature for 35min, then cooling to 60 ℃ along with the oven, and taking air as a heat treatment medium to obtain a treated PC substrate;
step three, spraying the wear-resistant coating: and ultrasonically cleaning the PC substrate by adopting ethanol, naturally airing, coating the wear-resistant coating prepared in the embodiment 2 on the outer surface of the treated PC substrate, and curing the PC substrate coated with the wear-resistant coating at 80 ℃ for 5min to obtain the wear-resistant PC glass plate.
Example 6:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: 75g of PC, 6g of the vinyl polysilsesquioxane prepared in example 1, 0.5g of antioxidant and 0.5g of lubricant are uniformly mixed, and then extruded and granulated by an extruder to obtain granules; preheating a mold for 3min at 95 ℃, then injecting the granules into the mold, and performing injection molding to obtain a PC substrate, wherein the injection molding temperature is 180 ℃, the injection molding pressure is 100MPa, and the antioxidant is antioxidant 168, and the antioxidant 1010 is prepared from the following components in a mass ratio of 2:1, mixing the components, wherein the lubricant is silicone oil;
step two, heat treatment of the PC substrate: placing the PC substrate in an oven, keeping the temperature at 100 ℃ for 15min, then heating to 118 ℃, keeping the temperature for 35min, then cooling to 60 ℃ along with the oven, and taking air as a heat treatment medium to obtain a treated PC substrate;
step three, spraying the wear-resistant coating: and ultrasonically cleaning the PC substrate by using ethanol or isopropanol, naturally drying, coating the wear-resistant coating prepared in the embodiment 3 on the outer surface of the treated PC substrate, and curing the PC substrate coated with the wear-resistant coating at 80 ℃ for 5min to obtain the wear-resistant PC glass plate.
Example 7:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: uniformly mixing 80g of PC, 12g of the vinyl polysilsesquioxane prepared in example 1, 2g of an antioxidant and 2g of a lubricant, and extruding and granulating the mixture by using an extruder to obtain granules; preheating a mold at 97 ℃ for 3min, then injecting the granules into the mold, and performing injection molding on the PC substrate, wherein the injection molding temperature is 200 ℃, the injection molding pressure is 100MPa, and the antioxidant is antioxidant 168 and antioxidant 1010, and the mass ratio of the antioxidant to the antioxidant is 3:1, mixing the components, wherein the lubricant is white mineral oil;
step two, heat treatment of the PC substrate: placing the PC substrate in an oven, keeping the temperature at 100 ℃ for 15min, then heating to 118 ℃, keeping the temperature for 35min, then cooling to 60 ℃ along with the oven, and taking air as a heat treatment medium to obtain a treated PC substrate;
step three, spraying the wear-resistant coating: and ultrasonically cleaning the PC substrate by adopting ethanol or isopropanol, drying at 30 ℃, coating the wear-resistant coating prepared in the embodiment 4 on the outer surface of the treated PC substrate, and curing the PC substrate coated with the wear-resistant coating at 100 ℃ for 4min to obtain the wear-resistant PC glass plate.
Comparative example 1:
the wear-resistant coating is prepared by the following steps:
s1, adding 0.041mol of phenylboronic acid into a reaction container, vacuumizing the system, introducing nitrogen, then adding 80mL of anhydrous ether and 0.02mol of triethylamine, dropwise adding 0.02mol of ether solution of dimethylvinylchlorosilane under a stirring state at a dropping speed of 1 drop/second, reacting for 4 hours at room temperature, washing for 2 times with deionized water, drying with anhydrous sodium sulfate, performing rotary evaporation to remove ether, and performing reduced pressure distillation to obtain a boron-containing siloxane monomer;
s2, uniformly mixing 12g of gamma-methacryloxypropyltrimethoxysilane, 58g of a borosiloxane monomer and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a propanol aqueous solution containing 5g of potassium persulfate isopropyl (the volume ratio of isopropanol to water is 3: 1) at a speed of 2 drops/second, continuously reacting for 3 hours after the dropwise adding is completed, cooling and washing for 2 times, and removing the solvent by rotary evaporation of an organic layer to obtain modified polyborosiloxane;
s3, uniformly mixing 35g of ethyl orthosilicate, 14g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon, 70mL of deionized water and 30mL of isopropanol, adding acetic acid to control the pH value of a reaction system to be 5.5, controlling the temperature to be 35 ℃, stirring for reacting for 40min, then dropwise adding an isopropanol aqueous solution containing 47g of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reacting for 4h, and carrying out rotary evaporation to obtain modified silicon resin;
s4, adding 100g of composite solvent into 14g of modified silicon resin, stirring for 30min at 400r/min, then adding 0.28g of curing agent and 0.14g of adhesion promoter poly (1, 4-butylene glycol adipate) and uniformly stirring at 400r/min to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol monobutyl ether according to a volume ratio of 3:1.5, and the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to the mass ratio of 1:1.5 mixing.
Comparative example 2:
the wear-resistant coating is prepared by the following steps:
s1, uniformly stirring 0.1mol of hydroxyl polydimethylsiloxane, 0.2mol of acrylic acid and 100mL of glacial acetic acid, adding 2.3g of p-toluenesulfonic acid, controlling the reaction temperature to be 75 ℃, stirring for reaction for 4h, cooling to room temperature, washing for 2 times, performing rotary evaporation on an organic layer at 30 ℃, and performing vacuum drying to obtain double-bond end-capped polydimethylsiloxane;
s2, uniformly mixing 17g of gamma-methacryloxypropyl trimethoxysilane, 51g of double-bond end-capped polydimethylsiloxane, 27g of dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, then dropwise adding a propanol aqueous solution containing 8g of potassium persulfate isopropyl (the volume ratio of isopropanol to water is 3;
s3, uniformly mixing 39g of ethyl orthosilicate, 17g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon, 70mL of deionized water and 30mL of isopropanol, adding acetic acid to control the pH value of a reaction system to be 6, controlling the temperature to be 35 ℃, stirring for reaction for 50min, then dropwise adding an isopropanol aqueous solution containing 30g of modified polyborosiloxane, slowly heating to 82 ℃, stirring for reaction for 4h, and carrying out rotary evaporation to obtain modified silicon resin;
s4, adding 100g of composite solvent into 16g of modified silicon resin, stirring for 30min at the speed of 450r/min, then adding 0.32g of curing agent and 0.16g of adhesion promoter poly (1, 4-butylene glycol adipate) at the speed of 400r/min, and uniformly stirring to obtain the wear-resistant coating, wherein the composite solvent is isopropanol and ethylene glycol monobutyl ether according to the volume ratio of 3:2, and the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to a mass ratio of 1:1.5 mixing.
Comparative example 3:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: the difference from step one in example 5 is that no vinyl polysilsesquioxane was added;
step two, heat treatment of the PC substrate: the same as the second step in example 5;
step three, spraying the wear-resistant coating: the same procedure as in step three of example 5.
Comparative example 4:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: the same as the first step in example 6;
step two, heat treatment of the PC substrate: the same as the second step in example 6;
step three, spraying the wear-resistant coating: compared to step three in example 6, except that the abrasion resistant coating used was prepared as in comparative example 1.
Comparative example 5:
a production process of a wear-resistant PC glass plate comprises the following steps:
step one, preparing a PC substrate: the same as step one in example 7;
step two, heat treatment of the PC substrate: the same as step two in example 7;
step three, spraying the wear-resistant coating: compared to step three in example 7, except that the abrasion resistant coating used was prepared as in comparative example 2.
Example 8:
the PC glass sheets obtained in examples 5 to 7 and comparative examples 3 to 5 were subjected to the following property tests:
coating adhesion force: the adhesion test adopts GB/T9286-1998 as a determination standard, and the degree of damage among the fine scratches of the coating film is observed according to a circling method to judge the grade of the adhesion;
coating hardness: the hardness is tested by a pencil method according to GB/T6739-2006;
coating flexibility: using the disc that curvature radius is different as the template, bending the sample along the circumference, observing the fracture action of coating, judging coating pliability, defining: on a disc with a certain curvature radius, half of a central angle corresponding to the arc length of 6cm is a bending angle borne by the coating, and according to the definition, when the bending angle of the coating is an instrument, the curvature radius of a corresponding circumference can be calculated according to a formula r = 540/(alpha pi);
coating light transmittance: testing by a UV-2550 ultraviolet-visible spectrophotometer of Shimadzu corporation according to GB/T2410-2008;
wear resistance of the coating: placing the sample under 0000 steel wool with 500g load, rubbing the surface of the sample back and forth for 40 times, and judging the wear resistance of the coating according to the number of scratches, wherein 0-5 scratches are excellent; 5-10 scratches are good; more than 10 scratches are poor;
and (3) coating water resistance: placing the sample plate in deionized water at the temperature of 80 ℃, soaking for 1h, taking out, airing, observing the change of the sample plate coating, and judging the boiling resistance of the coating;
the test results are shown in the following table.
It can be seen from the above data that the coating properties of examples 5-7 are superior to those of comparative examples 3-5.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (6)
1. A production process of a wear-resistant PC glass plate is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a PC substrate: uniformly mixing PC, vinyl polysilsesquioxane, an antioxidant and a lubricant, and performing extrusion granulation and injection molding to obtain a PC substrate;
step two, heat treatment of the PC substrate: carrying out heat treatment on the PC substrate to obtain a treated PC substrate;
step three, spraying the wear-resistant coating: pretreating a PC substrate, coating the outer surface of the treated PC substrate with a wear-resistant coating, and curing at 80-110 ℃ for 3-5min to obtain a wear-resistant PC glass plate;
the wear-resistant coating is prepared by the following method:
adding the modified silicone resin into the composite solvent, stirring for 30min, then adding the curing agent and the poly (1, 4-butylene adipate) and uniformly stirring to obtain the wear-resistant coating;
the modified silicone resin is prepared by the following steps:
uniformly mixing ethyl orthosilicate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, deionized water and isopropanol, adding acetic acid to control the pH value of a reaction system to be 5.5-6.5, controlling the temperature to be 35 ℃, stirring and reacting for 40-70min, then dropwise adding an isopropanol aqueous solution of modified polyborosiloxane, heating to 82 ℃, stirring and reacting for 4h, and carrying out rotary evaporation to obtain modified silicon resin;
the modified polyborosiloxane is prepared by the following method:
uniformly mixing gamma-methacryloxypropyltrimethoxysilane, a boracic siloxane monomer, dodecafluoroheptyl acrylate and toluene, heating to 93 ℃ under the protection of nitrogen, dropwise adding an aqueous solution of potassium persulfate isopropanol, continuously reacting for 3 hours after complete dropwise addition, cooling, washing, and rotationally steaming an organic layer to obtain the modified polyborosiloxane.
2. The process of claim 1 for producing a wear resistant PC glass sheet, wherein: in the first step, the mass ratio of the PC to the vinyl polysilsesquioxane to the antioxidant to the lubricant is 75-90:6-15:0.5-2.5:0.5-3.5.
3. The process of claim 1 for producing a wear resistant PC glass sheet, wherein: the composite solvent is prepared from isopropyl alcohol and ethylene glycol monobutyl ether according to a volume ratio of 3: 1.5-2.5.
4. The process of claim 1 for producing a wear resistant PC glass sheet, wherein: the curing agent is aluminum acetylacetonate and methyl hexahydrophthalic anhydride according to the mass ratio of 1:1.5 mixing.
5. The process of claim 1 for producing a wear resistant PC glass sheet, wherein: the mass ratio of the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silicon to the modified polyborosiloxane is 35-45:14-26:25-47.
6. The process of claim 1 for producing a wear resistant PC glass sheet, wherein: the mass ratio of the gamma-methacryloxypropyl trimethoxy silane to the boron-containing siloxane monomer to the dodecafluoroheptyl acrylate is 12-21:44-58:20-35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111081535.2A CN113845684B (en) | 2021-09-15 | 2021-09-15 | Production process of wear-resistant PC glass plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111081535.2A CN113845684B (en) | 2021-09-15 | 2021-09-15 | Production process of wear-resistant PC glass plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113845684A CN113845684A (en) | 2021-12-28 |
| CN113845684B true CN113845684B (en) | 2022-11-29 |
Family
ID=78974116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111081535.2A Active CN113845684B (en) | 2021-09-15 | 2021-09-15 | Production process of wear-resistant PC glass plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113845684B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093689A (en) * | 2022-06-27 | 2022-09-23 | 安徽赤诚塑胶科技有限公司 | Low-creep and stable-size PC film production process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2496708A (en) * | 2011-11-17 | 2013-05-22 | Dow Corning | Solvent-borne scratch resistant coating compositions containing polymetallosiloxanes |
| CN105670258A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | High-transparent halogen-free flame-retarding scratch-resistant polycarbonate composite material and preparation method thereof |
| CN109054634A (en) * | 2018-08-09 | 2018-12-21 | 望江县天长光学仪器有限公司 | A kind of polycarbonate lens coating |
-
2021
- 2021-09-15 CN CN202111081535.2A patent/CN113845684B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2496708A (en) * | 2011-11-17 | 2013-05-22 | Dow Corning | Solvent-borne scratch resistant coating compositions containing polymetallosiloxanes |
| CN105670258A (en) * | 2014-11-21 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | High-transparent halogen-free flame-retarding scratch-resistant polycarbonate composite material and preparation method thereof |
| CN109054634A (en) * | 2018-08-09 | 2018-12-21 | 望江县天长光学仪器有限公司 | A kind of polycarbonate lens coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113845684A (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20070078247A1 (en) | Fast curing primary optical fiber coatings | |
| CN107936746B (en) | Organic silicon modified cationic light-cured alicyclic epoxy resin coating and application thereof | |
| CN103819681A (en) | Ultraviolet light polymerization adhesive and preparation method thereof | |
| WO1994014878A1 (en) | Molding with hard-coating layer and process for producing the same | |
| CN1754915A (en) | Silicone resin composition and molded product thereof | |
| CN113845684B (en) | Production process of wear-resistant PC glass plate | |
| CN109735144B (en) | Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof | |
| EP3591017A1 (en) | Resin composition for hard coating, and hard-coating film comprising cured form of same as coating layer | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| CN114479665A (en) | High-transparency flexible scratch-resistant coating, functional coating and preparation method thereof | |
| CN107501829A (en) | A kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys | |
| TW201245167A (en) | Oxetane-cyclic epoxy compound, method of preparing the same, and composite sheet for display substrate including the same | |
| CN110408034B (en) | Synthetic method of phenyl block silicone resin | |
| Hu et al. | UV-cured organic–inorganic hybrid nanocomposite initiated by trimethoxysilane-modified fragmental photoinitiator | |
| CN115286834B (en) | Wear-resistant oil-proof protective film and preparation method thereof | |
| CN110997842B (en) | Coating resin composition and coating film comprising cured product of the coating resin composition as coating layer | |
| TWI656028B (en) | Surface-reinforced transparent substrate and method of manufacturing same | |
| CN110678525B (en) | Resin composition for coating and coating film containing cured product thereof as coating layer | |
| CN113185888B (en) | Preparation method of fluorosilicone coating with scratch resistance, fingerprint resistance and high light transmittance | |
| CN111777941B (en) | Curable organic silicon composition and preparation method and application thereof | |
| CN117106402B (en) | Organic silicon composite ultraviolet curing adhesive and preparation method thereof | |
| CN1583875A (en) | Epithio-epoxy composite resin and preparing process thereof | |
| KR20040104155A (en) | Organic-inorganic hybrid ultraviolet curable hard coating composition and method for preparing same, and hard coat film manufactured by using same | |
| CN113683988A (en) | Glass adhesive and preparation method thereof | |
| CN110922599B (en) | Bisphenol S hybrid silicon resin and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |