CN114075325A - Polyester and polyester film resistant to damp-heat aging and preparation method thereof - Google Patents

Polyester and polyester film resistant to damp-heat aging and preparation method thereof Download PDF

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Publication number
CN114075325A
CN114075325A CN202010836761.6A CN202010836761A CN114075325A CN 114075325 A CN114075325 A CN 114075325A CN 202010836761 A CN202010836761 A CN 202010836761A CN 114075325 A CN114075325 A CN 114075325A
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polyester
heat
aging
wet
resistant
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Inventor
王树霞
司虎
戴钧明
周刚
祁连进
王坤
王玉合
李映
胡兆麟
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China Petroleum and Chemical Corp
Sinopec Yizheng Chemical Fibre Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yizheng Chemical Fibre Co Ltd
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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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a wet heat aging resistant polyester, a polyester film and a preparation method thereof, wherein the wet heat aging resistant polyester comprises the following raw material components: the intrinsic viscosity of the base polyester is 0.45dL/g to 0.65dL/g, and the terminal carboxyl of the base polyester is 10mol/t to 18 mol/t; the intrinsic viscosity of the wet heat and aging resistant polyester is 0.65dL/g to 1.00dL/g, and the carboxyl end group of the wet heat and aging resistant polyester is 5mol/t to 10.0mol/t. The invention adopts the introduction of inorganic additives and a two-step method to prepare the moisture-heat aging resistant reinforced polyester, and provides a polyester film and a preparation method thereof. The moisture-heat aging resistant polyester film sample strip prepared by the invention has the breaking elongation retention rate of more than 75% for 72h, the moisture-heat aging resistant performance of more than 5 times that of the conventional moisture-heat aging resistant polyester, and the moisture-heat aging resistant polyester film sample strip has the characteristic of obvious moisture-heat aging resistant performance.

Description

Polyester and polyester film resistant to damp-heat aging and preparation method thereof
Technical Field
The invention relates to polyester, a polyester film and a preparation method thereof, in particular to polyester, a polyester film and a preparation method thereof.
Background
With the rise and development of photovoltaic cells, 3C industries and the like, the market share of special functional polyester films in the aspects of new energy and the like is higher and higher, for example, BOPET applied to photovoltaic solar cell back plates supports and protects cell components in outdoor environment for a long time, and the special functional polyester films are required to have good moisture-heat aging resistance and insulation property and maintain certain mechanical properties in the long-term use process; for drive motors for hybrid and pure electric vehicles, they are often used in ATF oils containing water and high temperatures, which requires that PET films are more resistant to hydrolysis than before.
In order to prepare polyester with excellent wet and heat aging resistance and subsequent products, relevant scholars improve the polyester by introducing wet and heat aging resistance additives through polyester modification and melt blending, adding additives through in-situ polymerization, optimizing subsequent coating and the like. In the patent CN 201511018433.0 and CN 201811126561.0, neopentyl glycol is introduced as a modified monomer, and two huge methyl groups of the neopentyl glycol provide shield-shaped protection for ester bonds, so that the polyester fiber has excellent hydrolytic stability and wet-heat aging resistance, the method increases the raw material cost of the polyester, and the improvement on the wet-heat aging resistance is not obvious. The patents CN 201110398870.5 and CN 201610287330.2 both adopt a melt blending mode to prepare the wet and heat aging resistant polyester master batch, and an auxiliary agent such as a light stabilizer, an ultraviolet light absorber and the like is introduced into the melt blending mode. The patent CN 201711296733.4 adopts diatomite and nano titanium dioxide as raw materials to prepare the polyester with resistance to heat and humidity aging, and the source and quality of the diatomite are difficult to stably control, so that the diatomite is difficult to popularize on a large scale. Patent CN 201910524514.X discloses an aqueous coating liquid for high humidity and heat aging resistant humidity and heat resistant polyester film and a preparation method thereof, the adopted thermoplastic acrylic resin has good humidity and heat aging resistant property, light and color retention property, water resistance and acid and alkali resistance, but the improvement of the coating mode is limited, and the coating liquid is not suitable for non-coated films and products.
In summary, with the wider application of polyester products, the requirements on the wet and heat aging resistance of polyester are higher, but the wet and heat aging resistance polyester prepared by the existing methods of polyester modification, melt blending, introduction of wet and heat aging resistance additives, in-situ polymerization and addition of additives, subsequent coating optimization and the like generally has the problems of poor wet and heat aging resistance effect, uneven blending effect, difficulty in large-scale popularization and application and the like.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a polyester which can resist wet heat and aging, the second purpose of the invention is to provide a preparation method of the polyester, the third purpose of the invention is to provide a polyester film which can resist wet heat and aging, and the fourth purpose of the invention is to provide a preparation method of the polyester film which can resist wet heat and aging.
The technical scheme is as follows: the polyester comprises the following raw material components: the intrinsic viscosity of the base polyester is 0.45dL/g to 0.65dL/g, and the terminal carboxyl of the base polyester is 10mol/t to 18 mol/t; the intrinsic viscosity of the wet heat and aging resistant polyester is 0.65dL/g to 1.00dL/g, and the carboxyl end group of the wet heat and aging resistant polyester is 5mol/t to 10.0mol/t.
The intrinsic viscosity or terminal carboxyl of the basic polyester chip is too low, the tackifying rate is slow, and stable production is difficult; the intrinsic viscosity or terminal carboxyl of the basic polyester chip is too high, and the prepared polyester film has poor heat and humidity resistance and aging resistance.
The raw materials also comprise 0.05-0.5% of inorganic additives in percentage by mass of the basic polyester. The inorganic additive is one of silicon dioxide, titanium dioxide or barium sulfate.
The median particle size of the inorganic additive is 0.3-3.0 μm. When the particle size is too small, the prepared polyester chips are difficult to uniformly disperse, and the mechanical property of the subsequent film is influenced; the excessively large particle size does not improve the crystallinity and does not significantly improve the resistance to wet heat and aging of the polyester.
The raw materials also comprise a chain extender accounting for 0-0.18 percent of the mass percentage of the basic polyester. The chain extender is one or more of bisoxazoline, pyromellitic dianhydride, a diepoxide ethane compound, a bicyclic imine ether compound, diisocyanate or bicyclic carboxylic anhydride.
The preparation method of the polyester resisting wet heat aging comprises the following steps:
(1) introducing an inorganic additive in the process of preparing polyester by in-situ polymerization, and preparing a basic polyester chip by pre-polycondensation reaction and final polycondensation reaction, wherein a chain extender is introduced in the final polycondensation reaction stage;
(2) and (3) pre-crystallizing and drying the basic polyester chip, and then carrying out solid-phase tackifying to prepare the polyester with the resistance to heat and aging.
The PTA method is adopted for in-situ polymerization.
The invention relates to a heat and humidity resistant aging film prepared by utilizing heat and humidity resistant aging polyester.
The preparation method of the film resisting wet heat and aging comprises the following steps: and (3) carrying out melt extrusion on the polyester chips with the resistance to heat and aging to prepare a polyester thick sheet, and carrying out biaxial stretching on the polyester thick sheet to prepare the polyester film with the resistance to heat and aging.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: compared with the existing moisture-heat aging resistant polyester with the same performance index, the moisture-heat aging resistant polyester prepared by the two-step method is prepared by the two-step method of in-situ polymerization and solid phase polycondensation, and the inorganic additive with proper particle size is adopted to improve the crystallinity of the polyester and reduce the gaps among the molecular chains of the polyester, so that water vapor molecules are difficult to permeate into the interior of a high molecular chain segment; by controlling a proper basic slice intrinsic viscosity index, the solid-phase tackifying can ensure tackifying rate and improve hydrolysis resistance of polyester; compared with the existing film sample strip of the heat and humidity resistant aging polyester, the heat and humidity resistant aging polyester film sample strip prepared by the invention has the breaking elongation retention rate of more than 70% for 72h, the heat and humidity resistant aging performance of more than 5 times that of the conventional heat and humidity resistant aging polyester, and has the obvious heat and humidity resistant aging characteristic.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
After mixing, pre-dispersing and ball-milling barium sulfate powder and ethylene glycol, preparing barium sulfate/ethylene glycol suspension with the concentration of 18%, wherein the median of the particle size of barium sulfate is 500 nm. 60kg of PTA, EG32kg, 19.95g of ethylene glycol antimony catalyst and 386g of the barium sulfate/ethylene glycol suspension are added into a 150L general polymerization reaction kettle, and the conventional esterification reaction is carried out under the conditions that the gauge pressure is 0.2-0.3 Mpa and the temperature is 230-255 ℃. After the esterification reaction is finished, carrying out pre-polycondensation reaction for 45min at 260-275 ℃, finally controlling the polycondensation reaction temperature to carry out final polycondensation reaction at 275-285 ℃, controlling the absolute pressure to be below 100pa, extruding, granulating and drying by a melt pump after the reaction is finished to obtain the moisture-heat-aging-resistant polyester base slice, and adding 69.4g of chain extender bisoxazoline 5min before the discharging is finished, wherein the content of the chain extender in the base slice is 0.10%. The content of barium sulfate in the basic slice is 0.1 percent, the intrinsic viscosity is 0.504dL/g, and the content of carboxyl end groups is 14.9 mol/t. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 13h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.675dL/g, and the content of carboxyl end groups is 6.7mol/t.
The damp-heat aging resistant reinforced polyester is dried and extruded to prepare a damp-heat aging resistant polyester thick sheet, and the thickness of the thick sheet is 1000 mu m. After the slab was left to stand for one day, the slab was stretched in a biaxial stretcher under the conditions of a preheating temperature of 105 ℃ for 50 seconds at a stretching ratio of 3.5 × 3.5 to prepare a wet-heat aging-resistant film having a thickness of 90 μm. The film is cut into sample strips of 200mm x 20mm, and the sample strips are placed in a stress acceleration test aging box for evaluation of the wet and heat performance, wherein the test conditions are that the temperature is 121 ℃, the humidity is 100 percent and the time is 72 hours.
The elongation of the film before and after wet heat aging was measured, and the elongation at break retention W of the film was calculated to be 81.2%, where W ═ L1/L0100% of L, wherein1Elongation at break, L, of the film after humid heat ageing0Is the original elongation at break of the film before aging.
Example 2
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. The difference is that the inorganic additive adopted in the process of preparing the basic slice by in-situ polymerization is titanium dioxide with the median diameter of 300nm, the added titanium dioxide/ethylene glycol suspension is 1928g, the intrinsic viscosity of the obtained polyester basic slice resistant to heat and humidity aging is 0.608dL/g, the content of the carboxyl end group is 15.1mol/t, the chain extender is a mixture of pyromellitic anhydride and a diepoxyethane compound (the mass ratio is 1:1), and the content of the chain extender in the basic slice is 0.10%. Wherein the content of titanium dioxide in the base slice is 0.5%. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 6.5h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.755dL/g, and the content of carboxyl end groups is 7.1mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 79.8%.
Example 3
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. Except that the inorganic additive adopted in the process of preparing the base slice by in-situ polymerization is silicon dioxide with the median particle diameter of 3000nm, the added silicon dioxide/ethylene glycol suspension is 193g, the intrinsic viscosity of the obtained polyester base slice resistant to heat and humidity aging is 0.650dL/g, the content of terminal carboxyl groups is 12.5mol/t, 125g of the mixture (the mass ratio is 1:1) of the dicyclic imine ether compound and the dicyclic carboxylic anhydride is added as the chain extender, and the content of the chain extender in the base slice is 0.18 percent, wherein the content of the silicon dioxide in the polyester is 0.05 percent. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 14h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 1.00dL/g, and the content of carboxyl end groups is 6.4mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 76.5%.
Example 4
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. Except that the inorganic additive adopted in the process of preparing the basic slice by in-situ polymerization is silicon dioxide with the median particle diameter of 1000nm, the added silicon dioxide/ethylene glycol suspension is 1157g, the intrinsic viscosity of the obtained polyester basic slice resistant to heat and humidity aging is 0.545dL/g, the content of terminal carboxyl groups is 10.0mol/t, and no chain extender is added, wherein the content of the silicon dioxide in the polyester is 0.30 percent. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 9 hours, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.675dL/g, and the content of carboxyl end groups is 5.0mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 75.3%.
Example 5
The method is characterized in that a basic slice is produced continuously and industrially, wherein the median of the particle size of titanium dioxide is 300nm, the content of the titanium dioxide is 0.3%, the intrinsic viscosity is 0.45dL/g, the content of carboxyl end groups is 18.0mol/t, 34.7g of diisocyanate is added as a chain extender, and the content of the chain extender in the basic slice is 0.05%. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 17 hours, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.650dL/g, and the content of carboxyl end groups is 10.0mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 76.8%.
Comparative example 1
The polyester resistant to wet heat aging was prepared in the same manner as in example 2. Except that the intrinsic viscosity of the polyester base chip resistant to wet heat aging was 0.679dL/g, and the carboxyl end group content was 8.7 mol/t. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 10h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.725dL/g, and the content of carboxyl end groups is 4.6mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 10.7%.
Comparative example 2
The conventional polyester with the same formula as that of example 2 and equivalent intrinsic viscosity is prepared in an in-situ polymerization mode, the intrinsic viscosity of the conventional polyester is 0.755dL/g, the content of carboxyl end groups is 9.5mol/t, the conventional polyester is subjected to melt extrusion casting and biaxial stretching to prepare a conventional film, the conventional film is fragile after being aged by damp and heat, and the elongation at break retention rate W is 3.2%.
Comparative example 3
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. Except that the intrinsic viscosity of the polyester base chip resistant to wet heat aging was 0.428dL/g and the carboxyl end group content was 24.8 mol/t. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 24 hours, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.541dL/g, and the content of carboxyl end groups is 11.7mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 35.1%.
Comparative example 4
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. Except that the inorganic additive adopted in the process of preparing the basic slice by in-situ polymerization is titanium dioxide with the median particle size of 100nm, the added titanium dioxide/ethylene glycol suspension is 3860g, the intrinsic viscosity of the obtained polyester basic slice resistant to wet-heat aging is 0.602dL/g, the content of carboxyl end groups is 14.9mol/t, and the content of the titanium dioxide in the polyester is 1.00 percent. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 6.5h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.764dL/g, and the content of carboxyl end groups is 7.2mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 24.5%.
Comparative example 5
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. Except that the inorganic additive adopted in the process of preparing the basic slice by in-situ polymerization is silicon dioxide with the median particle diameter of 3000nm, the added silicon dioxide/ethylene glycol suspension is 1930g, the intrinsic viscosity of the obtained polyester basic slice resistant to wet-heat aging is 0.598dL/g, the content of carboxyl end groups is 17.6mol/t, and the content of the silicon dioxide in the polyester is 0.5 percent. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 6.5h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.745dL/g, and the content of carboxyl end groups is 9.7mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 59.8%.
Comparative example 6
A polyester resistant to wet heat aging was prepared in the same manner as in example 1. The difference is that no inorganic additive is added in the process of preparing the basic slice by in-situ polymerization, the intrinsic viscosity of the obtained polyester basic slice resistant to heat and aging is 0.510dL/g, the content of carboxyl end groups is 15.2mol/t, 208.2g of bisoxazoline serving as a chain extender is added, and the content of the chain extender in the basic slice is 0.30 percent. The wet-heat-aging-resistant polyester is prepared by adopting a rotary drum to carry out a solid-phase tackifying test, wherein the tackifying temperature is 215 ℃, the tackifying time is 13h, the intrinsic viscosity of the prepared wet-heat-aging-resistant polyester is 0.679dL/g, and the content of carboxyl end groups is 7.1mol/t.
After the film resistant to wet heat aging is subjected to wet heat aging, the elongation at break retention rate W is 61.8%.
Table 1 Main experimental parameters of examples and comparative examples and test results of resistance to wet heat aging of corresponding films
Figure BDA0002639993840000051
Figure BDA0002639993840000061
Relevant performance parameters of the embodiment and the comparative example of the invention are listed in table 1, wherein the comparative example 1 and the comparative example 2 are conventional weather-resistant polyester films prepared by two methods, the comparative example 1 is a sample tackified by a two-step method and has the elongation at break retention rate of 10.7%, the comparative example 2 is a polyester sample with higher intrinsic viscosity and not directly prepared by the two-step method and has the elongation at break retention rate of only 3.2%, and the sample strips are brittle. Compared with the samples prepared by the comparative examples 1 and 2, the samples prepared by the examples 1 to 5 have the advantages that the resistance to heat and humidity of the polyester film prepared by the invention is remarkably improved, the breaking elongation retention rate of the sample is over 75 percent, and the resistance to heat and humidity is improved by over 5 times.
Comparative example 1 shows that the intrinsic viscosity of the base chip is too high and the resistance to wet heat aging of the polyester prepared is poor. Comparative example 2 shows that the reinforced polyester with higher intrinsic viscosity directly prepared without adopting the two-step method has poor heat and humidity resistance and aging resistance, and the preparation method of the two-step method has obvious effect on improving the heat and humidity resistance and aging resistance of the polyester. Comparative example 3 shows that the intrinsic viscosity of the base slice is too low, which results in slow subsequent tackifying rate and difficulty in stable production. Comparative example 4 is the moisture and heat aging resistant polyester prepared by using the nano powder, the breaking elongation retention rate is not high, the micro morphology is observed that the nano powder is easy to agglomerate, the addition amount of the additive is too much, the strength weakness is formed in a sample strip, and the film is easy to break, which shows that the weakness exists in the film due to the too small particle size of the inorganic additive. Comparative example 5 shows that the excessive particle size of the additive does not improve the crystallinity, and the aging resistance of the film is different from the effect of the present invention. Comparative example 6 shows that, without the addition of the inorganic additive, the aging resistance is significantly reduced, and the viscosity increasing reaction rate is reduced due to the addition of the chain extender in an excessively high content.
In conclusion, compared with the conventional reinforced polyester film, the reinforced polyester with remarkably improved moisture-heat aging resistance is prepared by adopting three ways of introducing a proper inorganic additive, adopting an in-situ polymerization-solid-phase tackifying two-step production mode and controlling the intrinsic viscosity and the terminal carboxyl performance indexes of a basic slice.

Claims (10)

1. The polyester capable of resisting heat and humidity aging is characterized by comprising the following raw material components: a base polyester, the intrinsic viscosity of the base polyester being 0.45dL/g to 0.65dL/g, the terminal carboxyl groups of the base polyester being 10mol/t to 18 mol/t; the intrinsic viscosity of the wet-heat-aging-resistant polyester is 0.65dL/g to 1.00dL/g, and the carboxyl end group of the wet-heat-aging-resistant polyester is 5mol/t to 10.0mol/t.
2. The polyester according to claim 1, wherein: the raw materials also comprise 0.05-0.5% of inorganic additives in percentage by mass of the basic polyester.
3. The polyester according to claim 2, wherein: the inorganic additive is one of silicon dioxide, titanium dioxide or barium sulfate.
4. The polyester according to claim 2, wherein: the median particle size of the inorganic additive is 0.3-3.0 μm.
5. The polyester according to claim 1, wherein: the raw materials also comprise a chain extender accounting for 0-0.18% of the mass percentage of the basic polyester.
6. The polyester according to claim 5, wherein: the chain extender is one or more of bisoxazoline, pyromellitic dianhydride, a diepoxide ethane compound, a bicyclic imine ether compound, diisocyanate or bicyclic carboxylic anhydride.
7. The preparation method of the polyester resistant to wet heat aging is characterized by comprising the following steps:
(1) introducing an inorganic additive in the process of preparing polyester by in-situ polymerization, and preparing a basic polyester chip by pre-polycondensation reaction and final polycondensation reaction, wherein a chain extender is introduced in the final polycondensation reaction stage;
(2) and pre-crystallizing and drying the basic polyester chip, and performing solid-phase tackifying to prepare the polyester with resistance to heat and humidity.
8. The process for preparing polyester resistant to wet heat aging according to claim 7, wherein: the in-situ polymerization adopts a PTA method.
9. A heat and humidity resistant polyester film obtained by using the heat and humidity resistant polyester of claim 1.
10. A method for preparing the polyester film with resistance to wet heat aging of claim 9, which comprises the following steps: the polyester chip with resistance to wet and heat aging of claim 1 is melt-extruded to prepare a thick polyester sheet, and the thick polyester sheet is biaxially stretched to prepare the polyester film with resistance to wet and heat aging.
CN202010836761.6A 2020-08-19 2020-08-19 Polyester and polyester film resistant to damp-heat aging and preparation method thereof Pending CN114075325A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013187244A (en) * 2012-03-06 2013-09-19 Teijin Dupont Films Japan Ltd Biaxially stretched polyester film for solar battery backside protection
CN103627150A (en) * 2013-11-21 2014-03-12 浙江南洋科技股份有限公司 Preparation method of polyether material, polyether film and preparation method thereof
CN105542138A (en) * 2015-12-17 2016-05-04 常州乐凯高性能材料有限公司 Preparation method of polyester chip for solar battery back film
CN109867771A (en) * 2019-03-27 2019-06-11 佛山杜邦鸿基薄膜有限公司 It is a kind of it is low extraction, high-temperature insulation polyester film preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013187244A (en) * 2012-03-06 2013-09-19 Teijin Dupont Films Japan Ltd Biaxially stretched polyester film for solar battery backside protection
CN103627150A (en) * 2013-11-21 2014-03-12 浙江南洋科技股份有限公司 Preparation method of polyether material, polyether film and preparation method thereof
CN105542138A (en) * 2015-12-17 2016-05-04 常州乐凯高性能材料有限公司 Preparation method of polyester chip for solar battery back film
CN109867771A (en) * 2019-03-27 2019-06-11 佛山杜邦鸿基薄膜有限公司 It is a kind of it is low extraction, high-temperature insulation polyester film preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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Application publication date: 20220222