CN112341657A - High-temperature-resistant low-precipitation three-layer co-extrusion BOPET film coated on line - Google Patents
High-temperature-resistant low-precipitation three-layer co-extrusion BOPET film coated on line Download PDFInfo
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Abstract
The invention discloses an online coated high-temperature-resistant low-precipitation three-layer co-extrusion BOPET film, which comprises a PET base layer and high-temperature-resistant layers coated on the two side surfaces of the PET base layer on line, wherein the high-temperature-resistant layers are made of high-temperature-resistant coating, the high-temperature-resistant coating takes organic silicon resin molecules and bisphenol A type epoxy resin as raw materials, the organic silicon resin and the epoxy resin both have good heat resistance, wear-resistant filler and migration-resistant plasticizer are prepared, the wear-resistant filler is coated on the surface of graphene by nano silicon dioxide, so that the wear resistance of the BOPET film is improved, the migration-resistant plasticizer takes isobutyraldehyde as a raw material, aldol condensation reaction is firstly carried out, then quaternary precursor reaction is carried out to prepare 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and isooctanoic acid are subjected to esterification reaction to, thereby prolonging the service life of the BOPET film.
Description
Technical Field
The invention belongs to the technical field of polyester film preparation, and particularly relates to an online coated high-temperature-resistant low-precipitation three-layer co-extrusion BOPET film.
Background
The biaxially oriented polyester film (BOPET) has excellent comprehensive performance, high mechanical strength, good optical performance, wide use temperature, excellent barrier property, oil resistance, corrosion resistance and the like, so the biaxially oriented polyester film has wide application fields. The BOPET film is most commonly applied in the aspects of printing, compounding, vacuum aluminizing and the like; PET resin is a polar polymer material; generally, the surface properties of common biaxially oriented polyester films (BOPET), such as printing, compounding, vacuum aluminum plating, and the like, can meet the process requirements.
The high temperature resistant effect of current BOPET film is relatively poor, and in the use, equipment generates heat for a long time for BOPET film's performance reduces, influences the use, and self wearability is general, can take place wearing and tearing after long-time the use, makes life reduce.
Disclosure of Invention
The invention aims to provide a high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film coated on line.
The technical problems to be solved by the invention are as follows:
the high temperature resistant effect of current BOPET film is relatively poor, and in the use, equipment generates heat for a long time for BOPET film's performance reduces, influences the use, and self wearability is general, can take place wearing and tearing after long-time the use, makes life reduce.
The purpose of the invention can be realized by the following technical scheme:
an online coated high-temperature-resistant low-precipitation three-layer co-extruded BOPET film comprises a PET base layer and high-temperature-resistant layers coated on the surfaces of two sides of the PET base layer on line; the high temperature resistant layer is made of high temperature resistant paint which is prepared by the following steps:
step A1: adding dimethyl diethoxy silane, phenyl triethoxy silane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-;
step A2: adding the organic silicon resin prepared in the step A1, the bisphenol A epoxy resin, the xylene and the ethyl acetate into a reaction kettle, stirring the mixture under the condition that the rotating speed is 300-500r/min until the organic silicon resin and the bisphenol A epoxy resin are completely dissolved, adding a hydrochloric acid aqueous solution, and performing reflux reaction for 2 to 3 hours under the condition that the temperature is 140-150 ℃ to prepare modified resin;
step A3: and D, adding the modified resin prepared in the step A2, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the defoaming agent into a stirring kettle, and stirring uniformly under the condition of 800-1000r/min to prepare the high-temperature-resistant coating.
Further, the mass ratio of the dimethyldiethoxysilane to the phenyltriethoxysilane in the step A1 is 1:1, the mass of the hydrochloric acid aqueous solution is 1-2 times of the sum of the mass of the tridecafluorooctyltriethoxysilane, the dimethyldiethoxysilane and the phenyltriethoxysilane, and the mass fraction of the hydrochloric acid aqueous solution is 15-20%.
Furthermore, the dosage mass ratio of the organic silicon resin and the bisphenol A type epoxy resin in the step A2 is 1:4, the dosage of the hydrochloric acid aqueous solution is 0.02-0.04% of the mass of the organic silicon resin, and the concentration of the hydrochloric acid aqueous solution is the same as that of the hydrochloric acid aqueous solution in the step A1.
Further, the amount mass ratio of the modified resin, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the defoaming agent in the step A3 is 90-100:4-6:1-3:20-30, and the defoaming agent is one or two of fatty acid methyl ester and tributyl phosphate which are mixed in any proportion.
Further, the thickness of the PET base layer is 12-75 μm, and the thickness of the high temperature resistant coating material layer is 0.5-10% of the thickness of the PET base film layer.
Further, the wear-resistant filler is prepared by the following steps:
step B1: adding ethyl orthosilicate, ethanol and hydrochloric acid aqueous solution into a reaction kettle, and reacting for 5-8h at the rotation speed of 200-300r/min and the temperature of 55-60 ℃ to obtain sol;
step B2: adding concentrated sulfuric acid into a reaction kettle, stirring and adding ammonium persulfate under the condition that the rotating speed is 120-150r/min, adding graphite after the ammonium persulfate is completely dissolved, reacting for 4-6h under the condition that the temperature is 75-85 ℃, cooling to room temperature, adding deionized water, standing for 8-10h, filtering to remove filtrate, and drying a filter cake to obtain pre-oxidized graphite;
step B3: adding concentrated sulfuric acid into a reaction kettle, stirring and adding the pre-oxidized graphite prepared in the step B2 under the condition that the rotation speed is 120-150r/min, adding potassium permanganate after the pre-oxidized graphite is dissolved, stirring for 3-5h at the temperature of 30-40 ℃, adding aqueous hydrogen peroxide, continuing stirring for 5-8h, standing for 8-10h, filtering to remove filtrate, cleaning a filter cake with aqueous hydrochloric acid, and cleaning with deionized water to be neutral to prepare graphite oxide;
step B4: dispersing the graphite oxide prepared in the step B3 in dimethylformamide, adding toluene diisocyanate and introducing nitrogen for protection, reacting at the rotation speed of 200-300r/min and the temperature of 75-85 ℃ for 20-25h, adjusting the reaction pH value to 9-10, heating to the temperature of 90-95 ℃, adding hydrazine hydrate, reacting for 1.5-3h, filtering to remove filtrate, and drying a filter cake to obtain modified graphene;
step B5: and (3) adding the modified graphene prepared in the step B4 into the sol prepared in the step B1, stirring for 5-10min at the rotation speed of 150-200r/min, adding potassium carbonate, reacting for 3-5h at the temperature of 80-85 ℃ and the frequency of 3-5MHz, heating to the temperature of 110-120 ℃, and distilling to remove the distillate to prepare the wear-resistant filler.
Further, the dosage ratio of the ethyl orthosilicate, the ethanol and the hydrochloric acid aqueous solution in the step B1 is 9g:18mL of: 2mL, the concentration of the hydrochloric acid aqueous solution is 0.1mol/L, and the dosage ratio of the concentrated sulfuric acid, the ammonium persulfate, the graphite and the deionized water in the step B2 is 15mL:2.5g:3g:50mL, wherein the dosage ratio of the concentrated sulfuric acid, the pre-oxidized graphite, the potassium permanganate and the aqueous hydrogen peroxide solution in the step B3 is 25mL:1g:3g:40mL, the mass fraction of the aqueous hydrogen peroxide solution is 10-15%, the mass fractions of the concentrated sulfuric acids in the step B2 and the step B3 are both 75%, the mass ratio of the graphite oxide, the toluene diisocyanate and the hydrazine hydrate in the step B4 is 1:10:1, the mass ratio of the modified graphene and the sol in the step B5 is 1:5, and the mass ratio of the potassium carbonate is 10-15% of the mass of the modified graphene.
Further, the migration-resistant plasticizer is prepared by the following steps:
step C1: adding isobutyraldehyde into a reaction kettle, stirring and slowly adding a dilute sodium hydroxide aqueous solution under the conditions that the rotation speed is 500-800r/min and the temperature is 25-30 ℃, stirring for 2-3h, adding a concentrated sodium hydroxide aqueous solution, heating to 70 ℃, reacting for 1-2h, adding deionized water, standing until layering, distilling a lower layer solution at the temperature of 140-150 ℃ to remove a distillate, and distilling a substrate at the vacuum degree of 1.1kPa and the temperature of 105 ℃ to prepare 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
step C2: and D, adding the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid prepared in the step C1 into a reaction kettle, stirring until the mixture is uniformly mixed, adding concentrated sulfuric acid and introducing nitrogen for protection, reacting for 3-5h at the temperature of 80-100 ℃, and distilling at the vacuum degree of 1.1kPa and the temperature of 110-120 ℃ to prepare the migration-resistant plasticizer.
Further, the using amount ratio of the isobutyraldehyde, the dilute aqueous sodium hydroxide solution and the concentrated aqueous sodium hydroxide solution in the step C1 is 25g:2.5mL:1mL, the mass fraction of the dilute aqueous sodium hydroxide solution is 15%, the mass fraction of the concentrated aqueous sodium hydroxide solution is 50%, the using amount molar ratio of the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid in the step C2 is 1:1, the using amount of the concentrated sulfuric acid is 2-3% of the sum of the mass of the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid, and the mass fraction of the concentrated sulfuric acid is 70%.
The invention has the beneficial effects that: the invention prepares a high-temperature resistant coating in the process of preparing a double-sided online coated high-temperature resistant low-precipitation three-layer co-extruded BOPET film, wherein the high-temperature resistant coating takes dimethyl diethoxysilane and phenyl triethoxysilane as raw materials to prepare organic silicon resin, the side chain of the organic silicon resin contains a large number of benzene rings which are good heat-resistant groups, the resin is further subjected to dehydration condensation with bisphenol A type epoxy resin to connect organic silicon resin molecules with bisphenol A type epoxy resin molecules to prepare modified resin, the organic silicon resin and the epoxy resin both have good heat resistance to ensure that the BOPET film has good temperature resistance, wear-resistant filler and migration-resistant plasticizer are prepared, the wear-resistant filler takes tetraethoxysilane as the raw materials to react to prepare sol, and graphite is pre-oxidized and then oxidized to prepare graphite oxide, and then reacting graphite oxide with toluene diisocyanate to graft isocyanate groups on the surface of the graphite oxide to obtain modified graphene, adding the modified graphene into the sol to react isocyanate on the surface of the modified graphene with hydroxyl on the surface of nano-silica in the sol to coat the nano-silica on the surface of the graphene to obtain the wear-resistant filler, so that the wear resistance of the BOPET film is improved, carrying out aldol condensation reaction on a migration-resistant plasticizer by taking isobutyraldehyde as a raw material, then carrying out a quaternary precursor reaction to obtain 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, carrying out esterification reaction on the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and isooctanoic acid to obtain the migration-resistant plasticizer, and further prolonging the service life of the BOPET film.
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.
Example 1
An online coated high-temperature-resistant low-precipitation three-layer co-extruded BOPET film comprises a PET base layer and high-temperature-resistant layers coated on the surfaces of two sides of the PET base layer on line; the high temperature resistant layer is made of high temperature resistant paint which is prepared by the following steps:
step A1: adding dimethyldiethoxysilane, phenyltriethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 60 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5h, after dropwise adding, heating to the temperature of 75 ℃, continuously stirring for 3h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 140 ℃ to remove distillate to obtain the organic silicon resin;
step A2: adding the organic silicon resin prepared in the step A1, bisphenol A epoxy resin, xylene and ethyl acetate into a reaction kettle, stirring at the rotating speed of 300r/min until the organic silicon resin and the bisphenol A epoxy resin are completely dissolved, adding a hydrochloric acid aqueous solution, and performing reflux reaction 2 at the temperature of 140 ℃ to prepare modified resin;
step A3: and D, adding the modified resin prepared in the step A2, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the fatty acid methyl ester into a stirring kettle, and stirring uniformly under the condition of 800r/min to prepare the high-temperature-resistant coating.
The wear-resistant filler is prepared by the following steps:
step B1: adding ethyl orthosilicate, ethanol and hydrochloric acid aqueous solution into a reaction kettle, and reacting for 5 hours at the rotating speed of 200r/min and the temperature of 55 ℃ to obtain sol;
step B2: adding concentrated sulfuric acid into a reaction kettle, stirring and adding ammonium persulfate under the condition that the rotating speed is 120r/min, adding graphite after the ammonium persulfate is completely dissolved, reacting for 4 hours at the temperature of 75 ℃, cooling to room temperature, adding deionized water, standing for 8 hours, filtering to remove filtrate, and drying a filter cake to obtain pre-oxidized graphite;
step B3: adding concentrated sulfuric acid into a reaction kettle, stirring and adding the pre-oxidized graphite prepared in the step B2 under the condition that the rotating speed is 120r/min, adding potassium permanganate after the pre-oxidized graphite is dissolved, stirring for 3 hours at the temperature of 30 ℃, adding aqueous hydrogen peroxide, continuously stirring for 5 hours, standing for 8 hours, filtering to remove filtrate, cleaning a filter cake with aqueous hydrochloric acid, and cleaning with deionized water to be neutral to prepare graphite oxide;
step B4: dispersing the graphite oxide prepared in the step B3 in dimethylformamide, adding toluene diisocyanate, introducing nitrogen for protection, reacting for 20 hours at the rotation speed of 200r/min and the temperature of 75 ℃, adjusting the pH value of the reaction to 9, heating to the temperature of 90 ℃, adding hydrazine hydrate, reacting for 1.5 hours, filtering to remove filtrate, and drying a filter cake to obtain modified graphene;
step B5: and B4, adding the modified graphene prepared in the step B1 into the sol prepared in the step B1, stirring for 5min at the rotation speed of 150r/min, adding potassium carbonate, reacting for 3h at the temperature of 80 ℃ and the frequency of 3MHz, heating to 110 ℃, and distilling to remove distillate to prepare the wear-resistant filler.
The migration-resistant plasticizer is prepared by the following steps:
step C1: adding isobutyraldehyde into a reaction kettle, stirring and slowly adding a dilute sodium hydroxide aqueous solution under the conditions that the rotation speed is 500r/min and the temperature is 25 ℃, stirring for 2 hours, adding a concentrated sodium hydroxide aqueous solution, heating to 70 ℃, reacting for 1 hour, adding deionized water, standing until layering, distilling a lower-layer solution at the temperature of 140 ℃ to remove a distillate, and distilling a substrate at the temperature of 105 ℃ under the vacuum degree of 1.1kPa to prepare 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
step C2: and D, adding the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid prepared in the step C1 into a reaction kettle, stirring until the mixture is uniformly mixed, adding concentrated sulfuric acid and introducing nitrogen for protection, reacting for 3 hours at the temperature of 80 ℃, and distilling at the vacuum degree of 1.1kPa and the temperature of 110 ℃ to prepare the migration-resistant plasticizer.
Example 2
An online coated high-temperature-resistant low-precipitation three-layer co-extruded BOPET film comprises a PET base layer and high-temperature-resistant layers coated on the surfaces of two sides of the PET base layer on line; the high temperature resistant layer is made of high temperature resistant paint which is prepared by the following steps:
step A1: adding dimethyldiethoxysilane, phenyltriethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid aqueous solution for 1h, heating to the temperature of 75 ℃ after dropwise adding, continuously stirring for 5h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 140 ℃ to remove distillate to obtain the organic silicon resin;
step A2: adding the organic silicon resin prepared in the step A1, bisphenol A epoxy resin, xylene and ethyl acetate into a reaction kettle, stirring at the rotation speed of 500r/min until the organic silicon resin and the bisphenol A epoxy resin are completely dissolved, adding a hydrochloric acid aqueous solution, and carrying out reflux reaction at the temperature of 140 ℃ for 3 hours to prepare modified resin;
step A3: and D, adding the modified resin prepared in the step A2, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the fatty acid methyl ester into a stirring kettle, and stirring uniformly under the condition of 800r/min to prepare the high-temperature-resistant coating.
The wear-resistant filler is prepared by the following steps:
step B1: adding ethyl orthosilicate, ethanol and hydrochloric acid aqueous solution into a reaction kettle, and reacting for 8 hours at the rotating speed of 300r/min and the temperature of 55 ℃ to obtain sol;
step B2: adding concentrated sulfuric acid into a reaction kettle, stirring and adding ammonium persulfate under the condition that the rotating speed is 120r/min, adding graphite after the ammonium persulfate is completely dissolved, reacting for 4 hours at the temperature of 85 ℃, cooling to room temperature, adding deionized water, standing for 10 hours, filtering to remove filtrate, and drying a filter cake to obtain pre-oxidized graphite;
step B3: adding concentrated sulfuric acid into a reaction kettle, stirring and adding the pre-oxidized graphite prepared in the step B2 under the condition that the rotating speed is 120r/min, adding potassium permanganate after the pre-oxidized graphite is dissolved, stirring for 3 hours at the temperature of 40 ℃, adding aqueous hydrogen peroxide, continuously stirring for 8 hours, standing for 8 hours, filtering to remove filtrate, cleaning a filter cake with aqueous hydrochloric acid, and cleaning with deionized water to be neutral to prepare graphite oxide;
step B4: dispersing the graphite oxide prepared in the step B3 in dimethylformamide, adding toluene diisocyanate, introducing nitrogen for protection, reacting for 25 hours at the rotation speed of 300r/min and the temperature of 75 ℃, adjusting the pH value of the reaction to 9, heating to the temperature of 95 ℃, adding hydrazine hydrate, reacting for 1.5 hours, filtering to remove filtrate, and drying a filter cake to obtain modified graphene;
step B5: and B4, adding the modified graphene prepared in the step B1 into the sol prepared in the step B1, stirring for 5min at the rotation speed of 200r/min, adding potassium carbonate, reacting for 5h at the temperature of 85 ℃ and the frequency of 3MHz, heating to 110 ℃, and distilling to remove distillate to prepare the wear-resistant filler.
The migration-resistant plasticizer is prepared by the following steps:
step C1: adding isobutyraldehyde into a reaction kettle, stirring and slowly adding a dilute sodium hydroxide aqueous solution under the conditions that the rotation speed is 800r/min and the temperature is 25 ℃, stirring for 3 hours, adding a concentrated sodium hydroxide aqueous solution, heating to 70 ℃, reacting for 1 hour, adding deionized water, standing until layering, distilling a lower-layer solution at the temperature of 150 ℃ to remove a distillate, and distilling a substrate at the temperature of 105 ℃ under the vacuum degree of 1.1kPa to obtain 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
step C2: and D, adding the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid prepared in the step C1 into a reaction kettle, stirring until the mixture is uniformly mixed, adding concentrated sulfuric acid and introducing nitrogen for protection, reacting for 5 hours at the temperature of 80 ℃, and distilling at the vacuum degree of 1.1kPa and the temperature of 110 ℃ to prepare the migration-resistant plasticizer.
Example 3
An online coated high-temperature-resistant low-precipitation three-layer co-extruded BOPET film comprises a PET base layer and high-temperature-resistant layers coated on the surfaces of two sides of the PET base layer on line; the high temperature resistant layer is made of high temperature resistant paint which is prepared by the following steps:
step A1: adding dimethyldiethoxysilane, phenyltriethoxysilane and xylene into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid aqueous solution for 1h, heating to the temperature of 80 ℃ after dropwise adding, continuously stirring for 5h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 150 ℃ to remove distillate to obtain the organic silicon resin;
step A2: adding the organic silicon resin prepared in the step A1, bisphenol A epoxy resin, xylene and ethyl acetate into a reaction kettle, stirring at the rotation speed of 500r/min until the organic silicon resin and the bisphenol A epoxy resin are completely dissolved, adding a hydrochloric acid aqueous solution, and carrying out reflux reaction at the temperature of 150 ℃ for 3 hours to prepare modified resin;
step A3: and D, adding the modified resin prepared in the step A2, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the fatty acid methyl ester into a stirring kettle, and stirring uniformly under the condition of 1000r/min to prepare the high-temperature-resistant coating.
The wear-resistant filler is prepared by the following steps:
step B1: adding ethyl orthosilicate, ethanol and hydrochloric acid aqueous solution into a reaction kettle, and reacting for 8 hours at the rotating speed of 300r/min and the temperature of 60 ℃ to obtain sol;
step B2: adding concentrated sulfuric acid into a reaction kettle, stirring and adding ammonium persulfate under the condition that the rotating speed is 150r/min, adding graphite after the ammonium persulfate is completely dissolved, reacting for 6 hours at the temperature of 85 ℃, cooling to room temperature, adding deionized water, standing for 10 hours, filtering to remove filtrate, and drying a filter cake to obtain pre-oxidized graphite;
step B3: adding concentrated sulfuric acid into a reaction kettle, stirring and adding the pre-oxidized graphite prepared in the step B2 under the condition that the rotating speed is 150r/min, adding potassium permanganate after the pre-oxidized graphite is dissolved, stirring for 5 hours at the temperature of 40 ℃, adding aqueous hydrogen peroxide, continuously stirring for 8 hours, standing for 10 hours, filtering to remove filtrate, cleaning a filter cake with aqueous hydrochloric acid, and cleaning with deionized water to be neutral to prepare graphite oxide;
step B4: dispersing the graphite oxide prepared in the step B3 in dimethylformamide, adding toluene diisocyanate, introducing nitrogen for protection, reacting at 85 ℃ at a rotation speed of 300r/min for 25h, adjusting the pH value of the reaction to 10, heating to 95 ℃, adding hydrazine hydrate, reacting for 3h, filtering to remove filtrate, and drying a filter cake to obtain modified graphene;
step B5: and B4, adding the modified graphene prepared in the step B1 into the sol prepared in the step B1, stirring for 10min at the rotation speed of 200r/min, adding potassium carbonate, reacting for 5h at the temperature of 85 ℃ and the frequency of 5MHz, heating to 120 ℃, and distilling to remove distillate to prepare the wear-resistant filler.
The migration-resistant plasticizer is prepared by the following steps:
step C1: adding isobutyraldehyde into a reaction kettle, stirring and slowly adding a dilute sodium hydroxide aqueous solution under the conditions that the rotation speed is 800r/min and the temperature is 30 ℃, stirring for 3 hours, adding a concentrated sodium hydroxide aqueous solution, heating to 70 ℃, reacting for 2 hours, adding deionized water, standing until layering, distilling a lower-layer solution at the temperature of 150 ℃ to remove a distillate, and distilling a substrate under the conditions that the vacuum degree is 1.1kPa and the temperature is 105 ℃ to prepare 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
step C2: and D, adding the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid prepared in the step C1 into a reaction kettle, stirring until the mixture is uniformly mixed, adding concentrated sulfuric acid and introducing nitrogen for protection, reacting for 5 hours at the temperature of 100 ℃, and distilling at the vacuum degree of 1.1kPa and the temperature of 120 ℃ to prepare the migration-resistant plasticizer.
Comparative example
The comparative example is a common three-layer co-extruded BOPET film in the market.
The three-layer co-extruded BOPET films prepared in examples 1-3 and comparative example were subjected to performance tests, and the test results are shown in Table 1 below;
high temperature resistance: the three-layer co-extruded BOPET films prepared in examples 1-3 and comparative example were placed at 130 ℃ for 72 hours, 96 hours and 120 hours, and the tensile strength and elongation at break were measured.
TABLE 1
From the above table 1, it can be seen that the tensile strength of the BOPET films prepared in examples 1-3 is 282-285MPa, the elongation at break is 109-112%, the tensile strength of the BOPET film prepared in comparative example is 212MPa, the elongation at break is 92%, the BOPET films prepared in examples 1-3 are placed at 130 ℃ for 72, 96 and 120 hours, respectively, the tensile strength and the elongation at break of the BOPET films prepared in examples 1-3 are not reduced, the tensile strength and the elongation at break of the BOPET films prepared in comparative example are reduced, the pencil hardness of the BOPET films prepared in examples 1-3 is 2H, and the pencil hardness of the BOPET films prepared in comparative example is HB, which indicates that the present invention has high temperature resistance and wear resistance.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (9)
1. The utility model provides a three-layer is crowded BOPET film altogether to high temperature resistant low precipitation of online coating, includes PET basic unit and the high temperature resistant layer of online coating on PET basic unit both sides surface, its characterized in that: the high temperature resistant layer is made of high temperature resistant paint which is prepared by the following steps:
step A1: adding dimethyl diethoxy silane, phenyl triethoxy silane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-;
step A2: adding the organic silicon resin prepared in the step A1, the bisphenol A epoxy resin, the xylene and the ethyl acetate into a reaction kettle, stirring the mixture under the condition that the rotating speed is 300-500r/min until the organic silicon resin and the bisphenol A epoxy resin are completely dissolved, adding a hydrochloric acid aqueous solution, and performing reflux reaction for 2 to 3 hours under the condition that the temperature is 140-150 ℃ to prepare modified resin;
step A3: and D, adding the modified resin prepared in the step A2, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the defoaming agent into a stirring kettle, and stirring uniformly under the condition of 800-1000r/min to prepare the high-temperature-resistant coating.
2. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the mass ratio of the dimethyl diethoxy silane to the phenyl triethoxy silane in the step A1 is 1:1, the mass of the hydrochloric acid aqueous solution is 1-2 times of the sum of the mass of the tridecafluorooctyl triethoxy silane, the dimethyl diethoxy silane and the phenyl triethoxy silane, and the mass fraction of the hydrochloric acid aqueous solution is 15-20%.
3. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the mass ratio of the dosage of the organic silicon resin and the bisphenol A type epoxy resin in the step A2 is 1:4, the dosage of the hydrochloric acid aqueous solution is 0.02-0.04% of the mass of the organic silicon resin, and the concentration of the hydrochloric acid aqueous solution is the same as that of the hydrochloric acid aqueous solution in the step A1.
4. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the mass ratio of the modified resin, the wear-resistant filler, the migration-resistant plasticizer, the deionized water and the defoaming agent in the step A3 is 90-100:4-6:1-3:20-30, and the defoaming agent is one or two of fatty acid methyl ester and tributyl phosphate which are mixed in any proportion.
5. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the thickness of the PET base layer is 12-75 μm, and the thickness of the high temperature resistant coating material layer is 0.5-10% of the thickness of the PET base film layer.
6. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the wear-resistant filler is prepared by the following steps:
step B1: adding ethyl orthosilicate, ethanol and hydrochloric acid aqueous solution into a reaction kettle, and reacting for 5-8h at the rotation speed of 200-300r/min and the temperature of 55-60 ℃ to obtain sol;
step B2: adding concentrated sulfuric acid into a reaction kettle, stirring and adding ammonium persulfate under the condition that the rotating speed is 120-150r/min, adding graphite after the ammonium persulfate is completely dissolved, reacting for 4-6h under the condition that the temperature is 75-85 ℃, cooling to room temperature, adding deionized water, standing for 8-10h, filtering to remove filtrate, and drying a filter cake to obtain pre-oxidized graphite;
step B3: adding concentrated sulfuric acid into a reaction kettle, stirring and adding the pre-oxidized graphite prepared in the step B2 under the condition that the rotation speed is 120-150r/min, adding potassium permanganate after the pre-oxidized graphite is dissolved, stirring for 3-5h at the temperature of 30-40 ℃, adding aqueous hydrogen peroxide, continuing stirring for 5-8h, standing for 8-10h, filtering to remove filtrate, cleaning a filter cake with aqueous hydrochloric acid, and cleaning with deionized water to be neutral to prepare graphite oxide;
step B4: dispersing the graphite oxide prepared in the step B3 in dimethylformamide, adding toluene diisocyanate and introducing nitrogen for protection, reacting at the rotation speed of 200-300r/min and the temperature of 75-85 ℃ for 20-25h, adjusting the reaction pH value to 9-10, heating to the temperature of 90-95 ℃, adding hydrazine hydrate, reacting for 1.5-3h, filtering to remove filtrate, and drying a filter cake to obtain modified graphene;
step B5: and (3) adding the modified graphene prepared in the step B4 into the sol prepared in the step B1, stirring for 5-10min at the rotation speed of 150-200r/min, adding potassium carbonate, reacting for 3-5h at the temperature of 80-85 ℃ and the frequency of 3-5MHz, heating to the temperature of 110-120 ℃, and distilling to remove the distillate to prepare the wear-resistant filler.
7. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 6, wherein: the dosage ratio of the ethyl orthosilicate, the ethanol and the hydrochloric acid aqueous solution in the step B1 is 9g:18mL of: 2mL, the concentration of the hydrochloric acid aqueous solution is 0.1mol/L, and the dosage ratio of the concentrated sulfuric acid, the ammonium persulfate, the graphite and the deionized water in the step B2 is 15mL:2.5g:3g:50mL, wherein the dosage ratio of the concentrated sulfuric acid, the pre-oxidized graphite, the potassium permanganate and the aqueous hydrogen peroxide solution in the step B3 is 25mL:1g:3g:40mL, the mass fraction of the aqueous hydrogen peroxide solution is 10-15%, the mass fractions of the concentrated sulfuric acids in the step B2 and the step B3 are both 75%, the mass ratio of the graphite oxide, the toluene diisocyanate and the hydrazine hydrate in the step B4 is 1:10:1, the mass ratio of the modified graphene and the sol in the step B5 is 1:5, and the mass ratio of the potassium carbonate is 10-15% of the mass of the modified graphene.
8. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the migration-resistant plasticizer is prepared by the following steps:
step C1: adding isobutyraldehyde into a reaction kettle, stirring and slowly adding a dilute sodium hydroxide aqueous solution under the conditions that the rotation speed is 500-800r/min and the temperature is 25-30 ℃, stirring for 2-3h, adding a concentrated sodium hydroxide aqueous solution, heating to 70 ℃, reacting for 1-2h, adding deionized water, standing until layering, distilling a lower layer solution at the temperature of 140-150 ℃ to remove a distillate, and distilling a substrate at the vacuum degree of 1.1kPa and the temperature of 105 ℃ to prepare 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
step C2: and D, adding the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid prepared in the step C1 into a reaction kettle, stirring until the mixture is uniformly mixed, adding concentrated sulfuric acid and introducing nitrogen for protection, reacting for 3-5h at the temperature of 80-100 ℃, and distilling at the vacuum degree of 1.1kPa and the temperature of 110-120 ℃ to prepare the migration-resistant plasticizer.
9. The on-line coated high-temperature-resistance low-precipitation three-layer co-extrusion BOPET film as claimed in claim 1, which is characterized in that: the using amount ratio of the isobutyraldehyde, the dilute sodium hydroxide aqueous solution and the concentrated sodium hydroxide aqueous solution in the step C1 is 25g:2.5mL:1mL, the mass fraction of the dilute sodium hydroxide aqueous solution is 15%, the mass fraction of the concentrated sodium hydroxide aqueous solution is 50%, the using amount molar ratio of the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid in the step C2 is 1:1, the using amount of the concentrated sulfuric acid is 2-3% of the mass sum of the 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and the isooctanoic acid, and the mass fraction of the concentrated sulfuric acid is 70%.
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| CN113117417A (en) * | 2021-04-20 | 2021-07-16 | 安徽省太和县众友筛网滤布制造有限公司 | Preparation method of high-strength corrosion-resistant industrial filter cloth |
| CN114369325A (en) * | 2021-12-28 | 2022-04-19 | 周菊青 | High-pressure-resistant pipeline plastic and preparation method thereof |
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