CN113583225A - Synthesis method of polyester chip for high-aging-resistance backboard film - Google Patents
Synthesis method of polyester chip for high-aging-resistance backboard film Download PDFInfo
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- CN113583225A CN113583225A CN202110897150.7A CN202110897150A CN113583225A CN 113583225 A CN113583225 A CN 113583225A CN 202110897150 A CN202110897150 A CN 202110897150A CN 113583225 A CN113583225 A CN 113583225A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Polymers & Plastics (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of polyester chip preparation, and provides a synthetic method of a polyester chip for a high-aging-resistance back plate film, which comprises the following steps: esterification reaction: adding isophthalic acid and ethylene glycol into an esterification reaction device, adding a titanium-cobalt compound catalyst, pulping, and performing esterification reaction to obtain an esterification intermediate; first polycondensation reaction: pumping the esterification intermediate into a polycondensation device to obtain a pre-polycondensation product; and (3) second polycondensation reaction: adding a dispersant, a UV monomer and an additive into the pre-polycondensation body and the ethylene glycol nitroisophthalate, and polymerizing to reach specified viscosity to obtain a final compact; molding: and discharging, pelletizing and drying the final compact to obtain the polyester chip. The film prepared from the polyester chip has the excellent characteristics of aging resistance, water vapor permeation resistance, weather resistance and the like, and the polyester chip synthesized by the invention has good application prospect in the field of high-aging-resistance backboard films.
Description
Technical Field
The invention relates to the technical field of polyester chip preparation, in particular to a synthetic method of a polyester chip for a high-aging-resistance back plate film.
Background
Optical films made of polyester chips have been widely used in recent years, for example, solar cell back sheet films, electronic device films, glass laminates, and backlight module optical films. The optical film is inexpensive, has excellent high light transmittance, low haze, high definition, good surface adhesion, and good mechanical properties, but is inferior in moisture and heat resistance, water vapor permeability, aging resistance, and the like. The optical film is easily aged and broken under the influence of a high-temperature and high-humidity environment with the lapse of time. The preparation method commonly used in the prior art comprises the following steps: one is that the polyester slices prepared by polymerizing one isomer or a plurality of dicarboxylic acids and at least one diol improve the crystallization property and the crystal configuration of the polyester, but the preparation method has high cost, and the polyester film prepared by blending is not uniformly dispersed due to the increase of the types of the prepared polyester slices; the other is that a chain extender such as acid anhydride is added to improve the optical property and the mechanical property of the polyester, but the method also has the problem that the physical and chemical properties of the further prepared polyester film are reduced because the types of the synthesized polyester slices are increased.
Disclosure of Invention
In order to solve at least one problem, the invention provides a synthesis method of a polyester chip for a high-aging-resistance backboard film, the synthesis method is simple in synthesis process, the types of the synthesized polyester chips are few, and the manufactured backboard film is good in aging resistance and stable in mechanical property.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a synthetic method of polyester chips for high-aging-resistance backboard films comprises the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.2-2.0: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, beating, and carrying out esterification reaction at the temperature of 250 ℃ under the nitrogen pressure of 0.15-0.4Mpa for 140-200min to obtain an esterification intermediate;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40-50min at the temperature of 255-270 ℃ and the pressure of 2-9kpa to obtain a pre-polycondensation product;
s30, second polycondensation: adding a dispersant, a UV monomer and an additive into the pre-condensation polymer and the ethylene glycol nitroisophthalate, and polymerizing the mixture to a specified viscosity at a temperature of 270-280 ℃ under a pressure of 40-100 pa to obtain a final condensation body;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
In some preferred embodiments, the method between S10 and S20 further comprises step S11, adding concentrated sulfuric acid and concentrated nitric acid to the esterification intermediate to react to obtain nitroethylene isophthalate and its derivatives, and purifying the nitroethylene isophthalate as a raw material of the nitroethylene isophthalate in step S30.
In some preferred embodiments, the mole ratio of the S30 bishydroxyethyl isophthalate to the nitroethylene isophthalate is 10-15: 1.
In some preferred embodiments, the water produced during the S10 reaction is continuously removed and reacted to an esterification rate of at least 92%.
In some preferred embodiments, the built catalyst comprises 0.01-0.1% of the mass of the alkyd mixture.
In some preferred embodiments, the titanium-based catalyst is at least one of tetrabutyl titanate, tetraisopropyl titanate or titanium glycol, the cobalt-based catalyst is cobalt acetate, and the mass ratio of the titanium-based catalyst to the cobalt-based catalyst is 1-2: 1.
In some preferred embodiments, the dispersant is a nonylphenol polyethylene glycol ether dispersant.
In some preferred embodiments, the UV monomer is an acrylic resin.
In some preferred embodiments, the additive comprises at least one of a flame retardant, an antioxidant.
In some preferred embodiments, the viscosity specified in step S30 is not less than 0.75 dL/g.
Compared with the prior art, the invention has the beneficial effects and advantages that:
1. in the preparation process of the polyester chip, the nitroisophthalic acid glycol ester participates in the polycondensation reaction, so that the esterification efficiency is improved, and the chemical and mechanical properties of the polyester chip are improved. The titanium-cobalt complex catalyst is adopted, particularly the titanium catalyst is an ester titanium catalyst, so that the degradation degree of the product is slowed down, the melting point is improved, the b value is small, the quality of the prepared film is improved, the film prepared from the polyester chip has the excellent characteristics of aging resistance, water vapor permeation resistance, weather resistance and the like, and the polyester chip synthesized by the method has a good application prospect in the field of high-aging-resistance backboard films.
2. The invention has the advantages of few raw material types, simple synthesis process, low cost, few types of prepared polyester chips, good product uniformity and stable physical and chemical properties.
Detailed Description
The present invention will be described in further detail by way of examples, but the present invention is not limited thereto, in order to make the objects, technical solutions and advantages of the present invention more apparent.
A synthetic method of polyester chips for high-aging-resistance backboard films comprises the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.2-2.0: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, beating, carrying out an esterification reaction at the temperature of 230-250 ℃ under the nitrogen pressure of 0.15-0.4Mpa, wherein the esterification time is 140-200min, so as to obtain an esterification intermediate, continuously removing generated water in the S10 reaction process until the esterification rate is at least 92%, continuously removing water in the reaction process, so as to improve the esterification efficiency and yield, and in addition, obtaining ethylene glycol isophthalate with lower water content, so as to improve the preparation efficiency of S11; the compound catalyst accounts for 0.01-0.1% of the mass of the alkyd mixture, the titanium catalyst is at least one of tetrabutyl titanate, tetraisopropyl titanate or titanium glycol, the cobalt catalyst is cobalt acetate, and the mass ratio of the titanium catalyst to the cobalt catalyst is 1-2: 1;
s11, adding concentrated sulfuric acid and concentrated nitric acid into the esterification intermediate to react to obtain nitroisophthalic acid glycol ester and derivatives thereof, and purifying the nitroisophthalic acid glycol ester to be used as a raw material of nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40-50min at the temperature of 255-270 ℃ and the pressure of 2-9kpa to obtain a pre-polycondensation product;
s30, second polycondensation: adding a dispersant, a UV monomer and an additive into a pre-condensation polymer and ethylene glycol nitroisophthalate with the molar ratio of dihydroxyethyl isophthalate to ethylene glycol nitroisophthalate being 10-15:1, polymerizing at a temperature of 270-280 ℃ under a pressure of 40-100 pa until the viscosity is not less than 0.75dL/g to obtain a final condensation body, wherein the nitro group is a polar group and has an adsorption effect on water, and the final condensation body can adsorb moisture at a back plate and block oxygen after being made into a film at a later stage; the dispersing agent is nonylphenol polyethylene glycol ether dispersing agent, and has a dispersing effect, so that the reaction is promoted to be carried out stably and quickly; the UV monomer is acrylic resin; the additive comprises at least one of a flame retardant and an antioxidant, and the flame retardant and the antioxidant ensure that the polyester has good flame retardance and oxidation resistance;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
The present invention will be described in further detail with reference to the following specific examples, which are not intended to limit the scope of the present invention in any way, and reagents and starting materials used in the present invention are commercially available except for those prepared by themselves.
Embodiment 1, a method for synthesizing a polyester chip for a high-aging-resistant back sheet film, comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.2: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, pulping, performing esterification reaction at 230-250 ℃ under the nitrogen pressure of 0.3Mpa for 140min to obtain an esterification intermediate, continuously removing generated water in the reaction process of S10 until the esterification rate reaches 92%, wherein the compound catalyst accounts for 0.01% of the mass of the alkyd mixture, the titanium catalyst is tetrabutyl titanate, the cobalt catalyst is cobalt acetate, and the mass ratio of tetrabutyl titanate to cobalt acetate is 1: 1;
s11, adding concentrated sulfuric acid into the esterification intermediate, slowly dropwise adding concentrated nitric acid, heating to 80 ℃, reacting at constant temperature for 13 hours, and obtaining the nitroisophthalic acid glycol ester and the derivative thereof, wherein the mass of the concentrated nitric acid is 5% of that of the esterification intermediate, the yield of the nitroisophthalic acid glycol ester is 63.9%, and the nitroisophthalic acid glycol ester is purified and used as a raw material of the nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 50min at the temperature of 255 ℃ and the pressure of 2kpa to obtain a pre-polycondensation polymer;
s30, second polycondensation: adding a pre-condensation polymer and ethylene glycol nitroisophthalate, wherein the molar ratio of the dihydroxy ethyl isophthalate to the ethylene glycol nitroisophthalate is 10:1, adding a dispersing agent, a UV monomer and an additive which account for 0.1%, 0.1% and 0.05% of the total mixture respectively, polymerizing at the temperature of 280 ℃ under the pressure of 40pa until the viscosity is 0.82dL/g, and obtaining a final condensation body, wherein the dispersing agent is a nonylphenol polyethylene glycol ether dispersing agent; the UV monomer is acrylic resin; the additive comprises diethyl aluminum phosphinate flame retardant and antioxidant 1010, and the mass ratio of the flame retardant to the antioxidant is 1: 1;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
Embodiment 2, a method for synthesizing a polyester chip for a high aging resistant back sheet film, comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.4: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, pulping, performing esterification reaction at 230-250 ℃ under the nitrogen pressure of 0.3Mpa for 150min to obtain an esterification intermediate, continuously removing generated water in the reaction process of S10 until the esterification rate reaches 92%, wherein the compound catalyst accounts for 0.02% of the mass of the alkyd mixture, the titanium catalyst is tetrabutyl titanate and tetraisopropyl titanate, and the cobalt catalyst is cobalt acetate, tetrabutyl titanate, tetraisopropyl titanate and cobalt acetate in a mass ratio of 0.5:0.5: 1;
s11, adding concentrated sulfuric acid into the esterification intermediate, slowly dropwise adding concentrated nitric acid, heating to 80 ℃, reacting at constant temperature for 13 hours, and obtaining the nitroisophthalic acid glycol ester and the derivative thereof, wherein the mass of the concentrated nitric acid is 5% of that of the esterification intermediate, the yield of the nitroisophthalic acid glycol ester is 63.9%, and the nitroisophthalic acid glycol ester is purified and used as a raw material of the nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 50min at the temperature of 260 ℃ and the pressure of 7kpa to obtain a pre-polycondensation polymer;
s30, second polycondensation: adding a pre-condensation polymer and ethylene glycol nitroisophthalate, wherein the molar ratio of hydroxyethyl isophthalate to ethylene glycol nitroisophthalate is 12:1, adding a dispersing agent and a UV monomer which account for 0.1% and 0.1% of the total mixture respectively, and polymerizing at the temperature of 270 ℃ under the pressure of 40pa until the viscosity is 0.93dL/g to obtain a final compact, wherein the dispersing agent is a nonylphenol polyethylene glycol ether dispersing agent; the UV monomer is acrylic resin;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
Embodiment 3, a method for synthesizing a polyester chip for a high aging resistant back sheet film, comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.6: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, pulping, performing esterification reaction at the temperature of 230 ℃ and 250 ℃ under the nitrogen pressure of 0.3Mpa for 200min to obtain an esterification intermediate, continuously removing generated water in the reaction process of S10 until the esterification rate reaches 93 percent, wherein the compound catalyst accounts for 0.5 percent of the mass of the alkyd mixture, the titanium catalyst is tetrabutyl titanate and ethylene glycol titanium, and the cobalt catalyst is cobalt acetate, and the mass ratio of tetrabutyl titanate to ethylene glycol titanium to cobalt acetate is 0.5:1.5: 1;
s11, adding concentrated sulfuric acid into the esterification intermediate, slowly dropwise adding concentrated nitric acid, heating to 80 ℃, reacting at constant temperature for 13 hours, and obtaining the nitroisophthalic acid glycol ester and the derivative thereof, wherein the mass of the concentrated nitric acid is 5% of that of the esterification intermediate, the yield of the nitroisophthalic acid glycol ester is 63.9%, and the nitroisophthalic acid glycol ester is purified and used as a raw material of the nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40min at the temperature of 270 ℃ and the pressure of 9kpa to obtain a pre-polycondensation polymer;
s30, second polycondensation: adding a pre-condensation polymer and ethylene glycol nitroisophthalate, wherein the molar ratio of dihydroxyethyl isophthalate to ethylene glycol nitroisophthalate is 13:1, adding a dispersing agent, a UV monomer and an additive which account for 0.1%, 0.1% and 0.05% of the total mixture by mass respectively, polymerizing at the temperature of 270 ℃ under the pressure of 100pa until the viscosity is 0.9dL/g, and obtaining a final condensation body, wherein the additive comprises an aluminum diethylphosphinate flame retardant and an antioxidant 1010, and the mass ratio of the flame retardant to the aluminum diethylphosphinate flame retardant to the antioxidant 1010 is 1: 1;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
Embodiment 4, a method for synthesizing a polyester chip for a high aging resistant back sheet film, comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.8: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, pulping, performing esterification reaction at the temperature of 230 ℃ and 250 ℃ under the nitrogen pressure of 0.3Mpa for 180min to obtain an esterification intermediate, continuously removing generated water in the reaction process of S10 until the esterification rate reaches 93 percent, wherein the compound catalyst accounts for 0.8 percent of the mass of the alkyd mixture, the titanium catalyst is tetrabutyl titanate, tetraisopropyl titanate and titanium glycol, and the cobalt catalyst is cobalt acetate, tetrabutyl titanate, tetraisopropyl titanate, titanium glycol and cobalt acetate in the mass ratio of 0.8:0.8:0.6: 1;
s11, adding concentrated sulfuric acid into the esterification intermediate, slowly dropwise adding concentrated nitric acid, heating to 80 ℃, reacting at constant temperature for 13 hours, and obtaining the nitroisophthalic acid glycol ester and the derivative thereof, wherein the mass of the concentrated nitric acid is 5% of that of the esterification intermediate, the yield of the nitroisophthalic acid glycol ester is 63.9%, and the nitroisophthalic acid glycol ester is purified and used as a raw material of the nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40min at the temperature of 270 ℃ and the pressure of 9kpa to obtain a pre-polycondensation polymer;
s30, second polycondensation: adding a pre-condensation polymer and ethylene glycol nitroisophthalate, wherein the molar ratio of dihydroxyethyl isophthalate to ethylene glycol nitroisophthalate is 14:1, adding a dispersing agent, a UV monomer and an additive which account for 0.1%, 0.1% and 0.05% of the total mixture by mass respectively, polymerizing at the temperature of 270 ℃ under the pressure of 100pa until the viscosity is 0.85dL/g, and obtaining a final condensation body, wherein the additive comprises an antioxidant 1010;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
Embodiment 5, a method for synthesizing polyester chip for high aging resistant back sheet film, comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 2.0: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, pulping, performing esterification reaction at the temperature of 230 ℃ and 250 ℃ under the nitrogen pressure of 0.3Mpa for 200min to obtain an esterification intermediate, continuously removing generated water in the reaction process of S10 until the esterification rate reaches 92%, wherein the compound catalyst accounts for 0.1% of the mass of the alkyd mixture, the titanium catalyst is ethylene glycol titanium, the cobalt catalyst is cobalt acetate, and the mass ratio of the ethylene glycol titanium to the cobalt acetate is 2: 1;
s11, adding concentrated sulfuric acid into the esterification intermediate, slowly dropwise adding concentrated nitric acid, heating to 80 ℃, reacting at constant temperature for 13 hours, and obtaining the nitroisophthalic acid glycol ester and the derivative thereof, wherein the mass of the concentrated nitric acid is 5% of that of the esterification intermediate, the yield of the nitroisophthalic acid glycol ester is 63.9%, and the nitroisophthalic acid glycol ester is purified and used as a raw material of the nitroisophthalic acid glycol ester in the next step;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40min at the temperature of 270 ℃ and the pressure of 9kpa to obtain a pre-polycondensation polymer;
s30, second polycondensation: adding a pre-condensation polymer and ethylene glycol nitroisophthalate, wherein the molar ratio of dihydroxyethyl isophthalate to ethylene glycol nitroisophthalate is 15:1, adding a dispersing agent, a UV monomer and an additive which account for 0.1%, 0.1% and 0.05% of the total mixture by mass respectively, polymerizing at 280 ℃ under the pressure of 100pa until the viscosity is not less than 0.9dL/g to obtain a final condensation body, wherein the additive comprises an aluminum diethylphosphinate flame retardant and an antioxidant 1010, and the mass ratio of the flame retardant to the antioxidant is 1: 1;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
Comparative example 1: the difference from example 2 is that step S11 is omitted, and ethylene nitroisophthalate is not added in the second polycondensation of S30, and the rest of the preparation method, the raw material component ratio and the reaction parameters are the same as those of example 2.
Comparative example 2: the difference from example 2 is that no UV monomer is added, and the other preparation methods, raw material component ratios and reaction parameters are the same as example 2.
The polyester chips of examples 1 to 5 and comparative examples 1 to 2 were melt-extruded in a twin-screw extruder at 285 ℃ and then cast into cast sheets through an extrusion die, followed by longitudinal stretching (stretching ratio of 3.0) and transverse stretching (stretching ratio of 4.5) in this order at 220 ℃ under an irradiation dose of 100kGy and setting, and finally drawn and wound to obtain a film having a thickness of 0.03mm, and the results of the performance tests on the film are shown in Table 1.
TABLE 1 Performance test Table for film made of polyester chip
In the examples 1 to 5, the raw material ratio, the catalyst addition amount and the process parameters of each reaction stage in the polyester chip preparation process are respectively blended, and in the polyester chip preparation process, the nitroisophthalic acid glycol ester participates in the polycondensation reaction, so that the esterification efficiency is improved, and the chemical and mechanical properties of the polyester chip are improved. The titanium-cobalt complex catalyst is adopted, particularly the titanium catalyst is an ester titanium catalyst, so that the degradation degree of the product is slowed down, the melting point is improved, the b value is small, the quality of the prepared film is improved, the film prepared from the polyester chip has the excellent characteristics of aging resistance, water vapor permeation resistance, weather resistance and the like, and the polyester chip synthesized by the method has a good application prospect in the field of high-aging-resistance backboard films.
Testing and comparison of the properties of the polyester chips prepared in the examples of Table 1 As can be seen from the UV94 flame retardant rating values in example 2 and comparative example 1, the addition of ethylene nitroisophthalate in the second polycondensation improves the flame retardancy of the films prepared from the polyester chips.
As can be seen from the film melting point in the embodiment 2 and the comparative example 2, the addition of the UV monomer and the irradiation excitation during film making enable the prepared film to form UV groups or functional chain ends, thereby improving the stability of the prepared film and further improving the aging resistance of the film.
Finally, it should be understood that the above description is only exemplary of the present invention, and is not intended to limit the present invention, and that any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A synthetic method of polyester chips for a high-aging-resistance backboard film is characterized by comprising the following steps:
s10, esterification: adding isophthalic acid and ethylene glycol into an esterification reaction device, wherein the molar ratio of the alkyd is 1.2-2.0: 1, adding a compound catalyst of a titanium catalyst and a cobalt catalyst, beating, and carrying out esterification reaction at the temperature of 250 ℃ under the nitrogen pressure of 0.15-0.4Mpa for 140-200min to obtain an esterification intermediate;
s20, first polycondensation: pumping the esterification intermediate into a polycondensation device, and reacting for 40-50min at the temperature of 255-270 ℃ and the pressure of 2-9kpa to obtain a pre-polycondensation product;
s30, second polycondensation: adding a dispersant, a UV monomer and an additive into the pre-condensation polymer and the ethylene glycol nitroisophthalate, and polymerizing the mixture to a specified viscosity at a temperature of 270-280 ℃ under a pressure of 40-100 pa to obtain a final condensation body;
s40, forming: and discharging, pelletizing and drying the final compact to obtain the polyester chip.
2. The method for synthesizing the polyester chip for the high aging resistant backboard film according to claim 1, wherein the step between S10 and S20 is S11, the esterification intermediate is taken and concentrated sulfuric acid and concentrated nitric acid are added to react to obtain the ethylene nitroisophthalate and the derivatives thereof, and the ethylene nitroisophthalate is purified to be used as the raw material of the ethylene nitroisophthalate in the step S30.
3. The method for synthesizing the polyester chip for the high aging resistant backboard film according to claim 1, wherein the molar ratio of the dihydroxy ethyl isophthalate and the ethylene nitroisophthalate of S30 is 10-15: 1.
4. The method for synthesizing polyester chip for back sheet film with high aging resistance as claimed in claim 1, wherein during the S10 reaction, the water produced is continuously removed and reacted until the esterification rate is at least 92%.
5. The method for synthesizing the polyester chip for the high-aging-resistance backboard film according to claim 1, wherein the compound catalyst accounts for 0.01-0.1% of the mass of the alkyd mixture.
6. The method for synthesizing the polyester chip for the high-aging-resistance back plate film according to claim 1, wherein the titanium catalyst is at least one of tetrabutyl titanate, tetraisopropyl titanate or titanium glycol, the cobalt catalyst is cobalt acetate, and the mass ratio of the titanium catalyst to the cobalt catalyst is 1-2: 1.
7. The method for synthesizing the polyester chip for the high aging resistant backboard film according to claim 1, wherein the dispersant is nonylphenol polyethylene glycol ether dispersant.
8. The method for synthesizing the polyester chip for the high aging resistant backboard film as claimed in claim 1, wherein the UV monomer is acrylic resin.
9. The method for synthesizing the polyester chip for the high aging resistant back plate film as claimed in claim 1, wherein the additive comprises at least one of a flame retardant and an antioxidant.
10. The method for synthesizing the polyester chip for the back sheet film with high aging resistance as claimed in claim 1, wherein the viscosity specified in the step of S30 is not less than 0.75 dL/g.
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| CN116948156A (en) * | 2023-08-17 | 2023-10-27 | 常州勤邦新材料科技有限公司 | Preparation method of polyester chip for ageing-resistant backboard film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116948156A (en) * | 2023-08-17 | 2023-10-27 | 常州勤邦新材料科技有限公司 | Preparation method of polyester chip for ageing-resistant backboard film |
| CN116948156B (en) * | 2023-08-17 | 2024-04-02 | 常州勤邦新材料科技有限公司 | Preparation method of polyester chip for ageing-resistant backboard film |
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