CN112142962A - Preparation method and application of high molecular weight transparent polyester - Google Patents

Preparation method and application of high molecular weight transparent polyester Download PDF

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Publication number
CN112142962A
CN112142962A CN201910561022.8A CN201910561022A CN112142962A CN 112142962 A CN112142962 A CN 112142962A CN 201910561022 A CN201910561022 A CN 201910561022A CN 112142962 A CN112142962 A CN 112142962A
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polyester
film
molecular weight
acid
transparent
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程正载
熊景
周佳丽
申露萍
周淑雯
李贝贝
李光要
马里奥
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Wuhan University of Science and Engineering WUSE
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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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Abstract

The invention discloses a preparation method and application of novel high molecular weight transparent polyester, belonging to the field of polyester synthesis. Terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and dihydric alcohol or other dihydroxy compounds are taken as raw materials, and a series of novel polyesters with high molecular weight are synthesized by a melt polymerization method. The method has the advantages of small catalyst consumption, high reaction efficiency and high transparency of the obtained polyester, and the synthesized polyester has the characteristics of high molecular weight, wide molecular weight distribution, good thermal property, excellent mechanical property and the like, and is easy for the next thermal processing treatment. The transparent high molecular weight polyester prepared by the invention can be used as a main component for processing bottle-grade polyester materials and can also be used as a base material of transparent conductive polyester film materials.

Description

Preparation method and application of high molecular weight transparent polyester
Technical Field
The invention belongs to the field of chemistry, and relates to preparation and application of novel polyester. The transparent polyester with high molecular weight is prepared by taking terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and a dihydroxy compound as raw materials and performing two-step reaction of catalytic esterification exchange reaction and catalytic polycondensation, can be used as a main component material of a transparent polyester bottle in the food and beverage industry, can also be used as a main raw material of a transparent conductive film, and belongs to the field of polymer synthesis and application.
Background
The polyester is a general name of polymers obtained by polycondensing polyalcohol and polybasic acid, is a high molecular material with excellent performance and wide application, and can be made into polyester fibers, polyester films, polyester bottles and the like. The major polyester products on the market include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyarylate (PAR), and the like. The polyester material has the advantages of excellent performance, high cost performance, easy preparation and the like which are enough to be comparable with the traditional materials such as metal, wood and the like, is widely applied to the fields of traffic, construction, agriculture, daily necessities, medicine and the like, and greatly enriches the living standard of people.
In recent years, much attention has been paid to the research of polyesters that are degradable under natural environmental conditions (microorganisms such as water, soil, air, bacteria, etc.). The main chain of the polyester polymer capable of being naturally degraded is mostly formed by connecting aliphatic structural units through ester bonds which are easy to hydrolyze, and the main chain is soft and smooth, so that the polyester polymer is easy to degrade in compost or natural soil environment. However, as research progresses, disadvantages of the aliphatic polyester itself are gradually revealed, such as: low melting point, poor mechanical property and poor processability, and is difficult to meet the requirements of practical application on various aspects of material properties.
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and the like are discarded after use, and become a part of the source of white contamination. In order to avoid the influence of environmental problems caused by waste polyester, researchers have been actively developing degradable polyester materials in recent years. Among them, polyesters synthesized from bio-based materials have excellent degradation characteristics, which has become a research hotspot. Meanwhile, the polyester synthesized by adopting the bio-based polyester as the raw material can reduce the dependence of polyester production on fossil resources, and has a wide prospect, but the bio-based polyester does not contain a rigid group, so that the strength of the material is weak.
2, 5-furandicarboxylic acid (FDCA) is an important furan derivative, has wide source, can be obtained from biomass resources such as straw, pericarp, fructose and galactose, and is a renewable resource. In structure and performance, 2, 5-furandicarboxylic acid (FDCA) is similar to terephthalic acid (PTA) derived from fossil resources, and is expected to be a PTA substitute. Ginger allergy and the like are prepared by taking isophthalic acid (PTA), 2, 5-furandicarboxylic acid (FDCA) and Ethylene Glycol (EG) as raw materials and tetrabutyl titanate as a catalyst, and synthesizing poly (isophthalic acid) -2, 5-furandicarboxylic acid ethylene glycol random copolyester (PEFT) by adopting a direct esterification method, wherein the PEFT has certain thermal stability and mechanical property, and research results show that the synthesis of polyester by partially substituting isophthalic acid with 2, 5-furandicarboxylic acid is feasible. However, the polyester synthesized by esterification polycondensation and the method by using tetrabutyl titanate as a catalyst has poor transparency and deep color, cannot meet the requirement of food-grade bottle-grade polyester on chromaticity, has low molecular weight and poor tensile property, cannot be processed into a film with ultra-thin thickness, and cannot be applied to the field of conductive transparent film components.
Disclosure of Invention
The existing bio-based polyester has low molecular weight, low melting point, poor mechanical property and processability, and the catalyst dosage of a catalytic polymerization system is large, the catalytic polymerization efficiency is low, so that the color of a polymerization product is deep, the light transmittance is poor, the obtained polyester can not be used as a raw material of bottle-grade polyester in the food and beverage industry, and the obtained polyester can not be processed into an ultrathin polyester film meeting the strength requirement of the film due to poor tensile property or film forming property, so that the polyester film can not be used for preparing a conductive transparent polyester film component. In view of the above problems, the main object of the present invention is to provide a method for preparing a high molecular weight transparent polyester and the application thereof, specifically comprising: terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and a dihydroxy compound are taken as raw materials, and a high molecular weight transparent copolyester is prepared through two-step reactions of catalytic esterification and catalytic polycondensation. Compared with the polyester reported in the prior literature, the polyester with high molecular weight has the advantages of high melting point, good thermal stability, strong mechanical property, high viscosity and good tensile film-forming property.
The invention adopts the following technical scheme:
in order to better realize the technical scheme of the invention, the invention discloses a preparation method of high molecular weight transparent copolyester, which comprises the following steps:
1) terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and dihydric alcohol or other dihydroxy compounds are taken as raw materials. Stirring and reacting the three raw materials at 150-175 ℃ for 3.0-4.0 h under the action of a catalyst under the protection of nitrogen, then raising the temperature to 220-240 ℃, and reacting for 2.0-3.0 h under the pressure environment of 5-15 KPa to obtain a crude polymer product.
2) And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding low-carbon alcohol such as methanol/ethanol or isopropanol into the filtrate until the generated precipitate is not increased any more. Washing the filter residue obtained after filtration with methanol or pure water, and then drying in vacuum at 60-70 ℃ for 2.0-3.0 h to obtain the required high molecular weight transparent copolyester.
More preferably, in the step 1), the diol is one of the following aliphatic diols: 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, neopentyl glycol, 2-methyl-1, 3-propanediol; or one of the following aliphatic cyclic diols: 1, 3-cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, tricyclo [5.2.10 (2, 6) ] decanedimethanol (i.e. tricyclodecanedimethanol), 2,4,8, 10-tetraoxaspiro [5, 5] undecane-3, 9-diethanol (i.e. Spiropentanediol (SPG));
3) more preferably, in the step 1), the other dihydroxy compound is one of the following: hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, catechol dihydroxyethyl ether, bis (2-hydroxyethyl) isophthalate, bis (2-hydroxyethyl) terephthalate, bis (2-hydroxyethyl) phthalate.
4) More preferably, in the step 1), the molar ratio of the p-or isophthalic acid to the 2, 5-furandicarboxylic acid is 0.9: 0.1 to 0.1: 0.9, and the copolyester is synthesized by a melt polymerization method, wherein the molar ratio of the total amount of the acid to the total amount of the alcohol is 1.0: 1.0 to 1.2.
5) More preferably, in the step 1), the catalyst is one of sulfonic acid catalysts such as trifluoromethanesulfonic acid, sulfamic acid, p-fluorobenzenesulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, o-trifluoromethylbenzenesulfonic acid, m-trifluoromethylbenzenesulfonic acid, and p-trifluoromethylbenzenesulfonic acid, one of group IVB metal catalysts such as fluorotitanic acid, ammonium fluorotitanate, and tetraisopropyl titanate, or one of group IVB metal catalysts such as lanthanum trifluoromethanesulfonate, zinc oxalate, butylstannoic acid, stannous octoate, dibutyltin oxide, dibutyltin oxyhydroxide, and dibutyltin chlorooxide. The amount of the catalyst is 0.1-0.5% of the total amount of the acid.
6) A transparent polyester of high molecular weight based on a mixed diacid of furandicarboxylic acid and terephthalic acid or isophthalic acid as monomers, prepared according to claim 1, for use as a main component in the processing of bottle-grade polyester materials, and also for the manufacture of tanks, protective sleeves and the like, hollow containers or sleeves, which may use polyester as a main component, characterized in that: the polyester is fully mixed according to the mass ratio, after the high molecular weight transparent polyester taking the mixed diacid of the furandicarboxylic acid and the isophthalic acid as monomers, the plasticizer and the stabilizer are mixed according to the mass ratio of 100 to (5-6) to (1-2), the subsequent forming processes such as extrusion, stretching, blow molding and the like can be carried out. The plasticizer is one of triethyl citrate, acetyl tri-n-butyl citrate, tri-n-hexyl citrate, acetyl tri-n-hexyl citrate, epoxidized soybean oil, dioctyl phthalate, diisohexyl sebacate and the like; the stabilizer is one of barium stearate, barium cinnamoate, barium ricinoleate, calcium stearate, calcium ricinoleate, magnesium stearate, zinc stearate and 2-ethyl lead acetate.
7) A transparent polyester film material of high molecular weight based on a mixed diacid of furandicarboxylic acid and terephthalic acid or isophthalic acid as a monomer, prepared according to claim 1, which is used as a raw material for a substrate of the transparent conductive polyester film material, and the method for preparing the transparent conductive polyester film material by using the transparent polyester of high molecular weight as a main raw material is characterized in that: preparing a transparent polyester film with a photon transmittance of more than 98% and a film thickness of 5-20 mu m by adopting the high-molecular-weight transparent polyester prepared according to the claim 1 through a blown film method or a cast film method, uniformly coating the transparent polyester film with a film thickness of 5-20 mu m on a transparent polyester film with a film thickness of 5-20 mu m by taking the film as a base material and adopting nano silver paste with a silver concentration of 4-8% as a coating liquid, so that the content of the nano silver distributed on the film reaches 20-150 mg/m2. And drying the obtained film by a vacuum dust-free oven at 60-150 ℃ to obtain the nano-silver transparent conductive film material with the photon transmittance of more than 95%, and the nano-silver transparent conductive film material can be used for assembling various transparent conductive film components.
8) The nano silver paste of claim 7, which is prepared from nano silver, a dispersant and a surfactant, wherein the nano silver has the following specification: the silver wire nanometer material is 10-20 mu m in length and 15-20 nm in diameter, the mass content of the silver wire nanometer material in silver paste is 4-8%, and the dispersing agent is hydroxypropyl methyl cellulose (HPMC) and the mass content of the dispersing agent is 5%; the rest component of the silver paste is polyoxyethylene octyl phenol ether-10 (OP-10).
Advantageous effects
1. Polyester is a generic name for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids, and the market is Predominantly Ethylene Terephthalate (PET). However, PET is mainly prepared by using xylene separated from aromatic hydrocarbons in oil refineries as a main starting material, Preparing Terephthalic Acid (PTA) through oxidation, and performing polycondensation reaction with ethylene glycol obtained in petrochemical industry or coal chemical industry. However, xylene will be limited by insufficient supply of petroleum resources in the future, and therefore, it is of strategic importance to develop a polyester synthesis route capable of replacing or partially replacing xylene. Renewable biological resources are used as raw materials, a bio-based monomer is obtained through biological technical conversion, and then further polymerization is the main method for preparing the bio-based polyester. 2, 5-furandicarboxylic acid (FDCA) can be prepared from renewable biomass resources, has a structure and performance similar to those of terephthalic acid, has a cyclic conjugated system and two carboxyl groups, and becomes an ideal substitute raw material of PTA.
2. The synthesized polyester has excellent mechanical property and thermal property: the introduction of 2, 5-furandicarboxylic acid with a conjugated system rigid aromatic ring structure greatly improves the mechanical properties of polyester, including tensile strength, tensile modulus, bending strength, bending modulus, impact strength and the like, improves the thermal properties of the polyester in use, such as a melting point far higher than that of commercial polyester PET, and greatly improves the thermal decomposition temperature.
3. Compared with the prior commercial polyester PET, the polyester P synthesized by the invention1～P19Weight average molecular weight M ofwWeight average molecular weight M of PET than commercial polyesterwHigher by 5.6X 104~6.69×104Da; polyester P1～P19Temperature T required for thermal decomposition of 10%10%Temperature T10% higher than that required for thermal decomposition of commercial polyester PET10%The height is 9-33 ℃; polyester P1～P19The melting point or softening point of the polyester is 80.2-98.9 ℃ higher than that of commercial polyester PET; polyester P1～P19The tensile strength of the polyester is 112.5-152.6 MPa higher than that of commercial polyester PET; polyester P1～P19The elongation at break of the polyester is 50.2-71.3% higher than that of the commercial polyester PET; polyester P1～P19The bending strength ratio ofThe bending strength of the polyester PET is 33.2-38.5 MPa; polyester P1～P19The impact strength of the polyester PET is 20.2-23.5 MPa higher than that of the commercial polyester PET. Based on the data, the molecular weight, the thermal property, the mechanical property and the like of the polyester prepared by the invention are obviously improved.
4. The polyester prepared by the invention adopts high-efficiency sulfonic acid catalysts or high-efficiency catalysts such as IVB group metal catalysts and the like, and the polyester with good service performance is prepared by two-step reaction of catalytic ester exchange and catalytic polycondensation. The same catalyst is used in the two-step reaction, the catalyst does not need to be separated in the reaction process, the catalyst consumption is small, the catalysis cost is low, the transparent polyester with the weight-average molecular weight of 140,000-250,000 Da and the high molecular weight is obtained, and the metal content in the polyester is extremely low or does not contain metal, so that the requirements of the packaging material and the medicine material field of high-grade beverage and food industries on the color quality of the raw materials are met.
5. The high molecular weight transparent polyester prepared according to claim 1 is subjected to a blown film method or a cast film method to prepare a transparent polyester film with the film thickness of 5-20 mu m, and the photon transmittance exceeds 98%. The film is used as a base material, nano silver paste with the silver concentration of 4-8% is used as a coating liquid, the coating liquid is uniformly coated, and then the nano silver transparent conductive film material with the photon light transmittance of more than 95% can be obtained after vacuum dust-free drying at 60-150 ℃, so that the film can be used for assembling various transparent conductive film components such as medium-size and large-size capacitive touch screens or touch screens, intelligent dimming film components and intelligent video display screens.
Drawings
FIG. 1 shows the preparation of polyester P in example 1 of the invention1Is/are as follows1H NMR chart.
FIG. 2 shows a high molecular weight polyester P according to example 1 of the present invention1GPC chart (A) of (B).
FIG. 3 shows a high molecular weight polyester P according to example 1 of the present invention1TG pattern of (a).
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples. The raw materials in the invention are all conventional and commercially available.
To determine the structure, molecular weight and thermal properties of the polyester prepared in this example, the polyester P prepared in examples 1-19 was subjected to a Bruker Avance DMX600 nuclear magnetic resonance spectrometer manufactured by Bruker Spectroscopy, VERTEX70 Fourier transform infrared spectrometer manufactured by Bruker Spectroscopy, United states Water gel chromatograph, and Netzsch STA 449F 3 Jupite thermogravimetric analyzer manufactured by Delhi1~P19Relevant characterization and testing was performed.
Mechanical testing in the examples: the tensile property test is carried out according to the GB/T1040.2-2006 standard; the bending performance is implemented according to the GB/T9341-2008 standard; impact performance is performed according to GB/T1843-2008 standard;
results were averaged over 5 test specimens each.
Yield =100% x actual amount of target product/theoretical amount of target product produced.
Example 1: in a 50 mL single neck flask were added 2.989g (18.2 mmol) of terephthalic acid, 0.316 g (2.1 mmol) of 2, 5-furandicarboxylic acid and 2.629g (18.2 mmol) of 1, 8-octanediol and 0.015 g (0.1 mmol) of trifluoromethanesulfonic acid in that order and the reaction mixture was reacted at 175 ℃ for 4.0h under nitrogen. Then raising the temperature to 220 ℃ and reacting for 3.0h under the pressure environment of 15KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. Washing the filter residue with methanol, and vacuum drying at 70 deg.C for 3.0h to obtain polyester P with high molecular weight of 3.295g1The weight average molecular weight was 140,000 Da, the molecular weight distribution was 1.9, and the yield was 89.98%.
To determine the polyester P prepared in this example1The polyester P prepared in example 1 was subjected to a Bruker Avance DMX600 nuclear magnetic resonance spectrometer, a Waters-Breeze gel chromatograph and a Netzsch STA 449F 3 Jupiter thermogravimetric analyzer1Performing related characterization andand (6) testing. P1The structure of (A) is shown in formula I below:
Figure RE-DEST_PATH_IMAGE002
formula I
In formula 11H NMR (500 MHz, CDCl3): ppm 1.38 (m, 16H, OCH2CH2 2 4(CH)CH2CH2O), 1.76 (m, 8H, OCH2 2CH(CH2)4 2CHCH2O), 4.32 (m, 8H, O 2CH(CH2)6 2CHO), 7.18 (s, 4H, ArH), 8.09 (s, 2H, C=CHCH=C)，IR (KBr) ν (cm-1): 2925, 2850, 1717, 1265, 1125, 730。
FIG. 1 shows the preparation of polyester P in example 1 of the invention1Is/are as follows1H NMR chart.
FIG. 2 shows the polyester P prepared in example 1 of the present invention1GPC chart of (1), MwUp to 14.12X 104Da。
FIG. 3 shows a polyester P prepared in example 1 of the present invention1From the TG diagram, it can be found that the temperature at which 12% mass loss occurs is 390 ℃ and that, therefore, the polyester P prepared in example 1 of the present invention can be obtained1Has good thermal stability.
For other test data, please refer to table 1 for the same reason, which is not repeated.
Polyester P1The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials by the following method: polyester P1Mixing triethyl citrate and barium stearate according to the mass ratio of 100: 5: 1, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P1Preparing a transparent polyester film with the film thickness of 5 mu m by a blown film method, uniformly coating the film serving as a base material and nano silver paste with the silver concentration of 4% serving as a coating liquid on the transparent polyester film with the film thickness of 5 mu m, and drying the obtained film in a vacuum dust-free oven at 60 ℃ to obtain the film with the photon transmittance of 95%The nano-silver transparent conductive film material can be used for assembling various transparent conductive film components.
Example 2: in a 50 mL single-neck flask were added 2.989 (18.2 mmol) of isophthalic acid, 0.316 g (2.1 mmol) of 2, 5-furandicarboxylic acid and 2.629g (18.2 mmol) of 1, 8-octanediol and 0.010g (0.1 mmol) of sulfamic acid in that order, and the reaction mixture was reacted at 165 ℃ for 3.0h under nitrogen. Then raising the temperature to 225 ℃ and reacting for 3.0h under the pressure environment of 15KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 70 ℃ for 3.0h to give 3.452g of polyester P2The weight average molecular weight was 140, 328Da, the molecular weight distribution was 2.3, and the yield was 90.05%.
Polyester P2The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P2Mixing triethyl citrate and calcium stearate according to the mass ratio of 100: 6: 1, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P2The transparent polyester film with the film thickness of 12 micrometers is prepared through a blown film method, the film is used as a base material, nanometer silver paste with the silver concentration of 6% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 12 micrometers, and the obtained film is dried through a vacuum dust-free oven at 80 ℃, so that the nanometer silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nanometer silver transparent conductive film material can be used for assembling various transparent conductive film assemblies.
Example 3: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.292 g (2.1 mmol) of 1, 8-octanediol and 0.018 g (0.1 mmol) of p-fluorobenzenesulfonic acid in that order, and the reaction mixture was reacted at 170 ℃ for 4.0h under nitrogen protection. Then, the temperature is increased to 230 ℃ and the reaction is carried out for 3.0h under the pressure environment of 15 KPa. Cooling the crude polymer product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any moreUntil now. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 70 ℃ for 3.0h to give 3.232g of polyester P3The weight average molecular weight was 150,000 Da, the molecular weight distribution was 3.0, and the yield was 89.95%.
Polyester P3The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P3Mixing triethyl citrate and magnesium stearate according to the mass ratio of 100: 5: 1, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P3The method comprises the steps of preparing a transparent polyester film with the film thickness of 10 micrometers by a blown film method, uniformly coating the film serving as a base material on the transparent polyester film with the film thickness of 10 micrometers by using nano silver paste with the silver concentration of 6% as a coating liquid, and drying the obtained film in a vacuum dust-free oven at 75 ℃ to obtain a nano silver transparent conductive film material with the photon light transmittance of 95%, wherein the nano silver transparent conductive film material can be used for assembling a transparent conductive film component.
Example 4: in a 50 mL single-neck flask were charged 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.288 g (2.1 mmol) of 1, 4-cyclohexanedimethanol, followed by 0.019g (0.1 mmol) of p-chlorobenzenesulfonic acid, and the reaction mixture was reacted at 170 ℃ for 4.0h under nitrogen. Then raising the temperature to 235 ℃, and reacting for 3.0h under the pressure environment of 10KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 70 ℃ for 4.0h to give 4.235g of polyester P4The weight average molecular weight was 190,000 Da, the molecular weight distribution was 3.2, and the yield was 91.25%.
Polyester P4The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P4Mixing acetyl tri-n-hexyl citrate and zinc stearate in the mass ratio of 100: 6: 1, and injection molding to prepare the transparent polyester bottle.
Polyester P4Preparing transparent polymer with film thickness of 10 mu m by using blown film methodAnd (3) taking the film as a base material, adopting nano silver paste with the silver concentration of 7% as a coating liquid, uniformly coating the coating liquid on a transparent polyester film with the film thickness of 10 mu m, and drying the obtained film through a vacuum dust-free oven at 85 ℃ to obtain the nano silver transparent conductive film material with the photon transmittance of 95%, wherein the nano silver transparent conductive film material can be used for assembling a transparent conductive film component.
Example 5: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.288 g (2.1 mmol) of 1, 4-cyclohexanedimethanol, followed by 0.020g (0.1 mmol) of p-nitrobenzenesulfonic acid in that order, and the reaction mixture was reacted at 175 ℃ for 4.0h under nitrogen. Then, the temperature is increased to 230 ℃ and the reaction is carried out for 3.0h under the pressure environment of 15 KPa. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then vacuum-dried at 70 ℃ for 3.0h to give 3.532g of polyester P5The weight average molecular weight was 200,000 Da, the molecular weight distribution was 2.8, and the yield was 90.25%.
Polyester P5The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P4Mixing triethyl citrate and calcium ricinoleate according to the mass ratio of 100: 6: 2, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P5The transparent polyester film with the film thickness of 15 mu m is prepared by a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 15 mu m, and the obtained film is dried by a vacuum dust-free oven at 95 ℃ to obtain the nano silver transparent conductive film material with the photon transmittance of 95%, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film component.
Example 6: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis hydroxyethyl ether and 0.019g (0.1 mmol) of o-trifluoromethylbenzenesulfonic acid in that order and the reaction mixture was reacted 4 under nitrogen protection at 165 ℃0 h. Then raising the temperature to 235 ℃, and reacting for 3.0h under the pressure environment of 5KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 72 ℃ for 3.0h to give 3.624g of polyester P6The weight average molecular weight was 170,000 Da, the molecular weight distribution was 3.6, and the yield was 90.60%.
Polyester P6The molecular weight is 170,000, and the method can be used as a main component for processing bottle-grade polyester materials and comprises the following steps: polyester P6Mixing tri-n-butyl citrate and barium cinnamate according to the mass ratio of 100: 6: 1, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P6The transparent polyester film with the film thickness of 15 mu m is prepared by a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 15 mu m, and the obtained film is dried by a vacuum dust-free oven at 90 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling various transparent conductive film components.
Example 7: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.396g (2.1 mmol) of resorcinol bis-hydroxyethyl ether followed by 0.034 g (0.1 mmol) of m-trifluoromethylbenzenesulfonic acid in that order and the reaction mixture was reacted for 4.0h at 165 ℃ under nitrogen. Then raising the temperature to 235 ℃, and reacting for 3.0h under the pressure environment of 12KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 70 ℃ for 3.0h to give 3.754g of polyester P7The weight average molecular weight was 180,000 Da, the molecular weight distribution was 3.4, and the yield was 90.92%.
Polyester P7Has high molecular weight of 180,000, and can be used as bottle grade polyester materialThe main components of the method are as follows: polyester P7Mixing acetyl triethyl citrate and magnesium stearate according to the mass ratio of 100: 6: 2, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P7The transparent polyester film with the film thickness of 16 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 16 micrometers, and the obtained film is dried through a vacuum dust-free oven at 100 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling various transparent conductive film assemblies.
Example 8: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.396g (2.1 mmol) of resorcinol bis-hydroxyethyl ether followed by 0.029g (0.1 mmol) of p-trifluoromethylbenzenesulfonic acid in that order and the reaction mixture was reacted for 4.0h at 165 ℃ under nitrogen. Then raising the temperature to 240 ℃ and reacting for 3.0h under the pressure environment of 8KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 110 ℃ for 3.0h to give 4.252g of polyester P8The weight average molecular weight was 160,000 Da, the molecular weight distribution was 2.8, and the yield was 93.23%.
Polyester P8The molecular weight reaches 160,000, the molecular weight distribution is 2.8, and the method can be used as a main component for processing bottle-grade polyester materials and comprises the following steps: polyester P8Mixing diisohexyl sebacate and barium stearate in the mass ratio of 100 to 6 to 1, and injection molding to prepare the transparent polyester bottle.
Polyester P8Preparing a transparent polyester film with the film thickness of 17 mu m by a blown film method, uniformly coating the film serving as a base material and a nano silver paste with the silver concentration of 8% serving as a coating liquid on the transparent polyester film with the film thickness of 17 mu m, and drying the obtained film in a vacuum dust-free oven at 100 ℃ to obtain the nano silver transparent conductive film material with the photon transmittance of 96%The method can be used for assembling various transparent conductive film components.
Example 9: in a 50 mL single-neck flask were placed 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis-hydroxyethyl ether in that order and 0.016 g (0.1 mmol) of fluorotitanic acid, and the reaction mixture was reacted at 165 ℃ for 4.0h under nitrogen. Then raising the temperature to 240 ℃ and reacting for 3.0h under the pressure environment of 13KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 95 ℃ for 3.0h to give 3.624g of polyester P9The weight average molecular weight was 220,000 Da, the molecular weight distribution was 3.7, and the yield was 90.22%.
Polyester P9The molecular weight is up to 220,000, the molecular weight distribution is up to 3.7, and the method can be used as a main component for processing bottle-grade polyester materials and comprises the following steps: polyester P8Mixing acetyl tributyl citrate and calcium ricinoleate according to the mass ratio of 100: 5: 1, and then carrying out injection molding processing to prepare the transparent polyester bottle.
Polyester P9The transparent polyester film with the film thickness of 18 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 18 micrometers, and the obtained film is dried through a vacuum dust-free oven at 110 ℃, so that the nano silver transparent conductive film material with the photon light transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling various transparent conductive film assemblies.
Example 10: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis-hydroxyethyl ether in that order and 0.020g (0.1 mmol) of ammonium fluorotitanate, and the reaction mixture was reacted at 165 ℃ for 4.0h under nitrogen. Then raising the temperature to 240 ℃ and reacting for 3.0h under the pressure environment of 7KPa to obtain a crude polymer product. Cooling the crude polymer, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and filteringMethanol was added to the solution until the precipitate produced did not increase. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 70 ℃ for 3.0h to give 4.124g of polyester P10The weight average molecular weight was 240,000 Da, the molecular weight distribution was 3.4, and the yield was 93.11%.
Polyester P10The molecular weight is up to 240,000, the molecular weight distribution is up to 3.4, and the method can be used as a main component for processing bottle-grade polyester materials and comprises the following steps: polyester P10The transparent polyester bottle is prepared by banburying sebacic acid diisohexyl ester and barium ricinoleate according to the mass ratio of 100: 5: 1 and then performing injection molding.
Polyester P10The transparent polyester film with the film thickness of 19 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 19 micrometers, and the obtained film is dried through a vacuum dust-free oven at 120 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling various transparent conductive film assemblies.
Example 11: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis hydroxyethyl ether and 0.028g (0.1 mmol) of tetraisopropyl titanate in that order and the reaction mixture was reacted for 4.0h under nitrogen at 165 ℃. Then raising the temperature to 230 ℃ and reacting for 3.0h under the pressure environment of 15KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 125 ℃ for 3.0h to give 4.248g of polyester P11The weight average molecular weight was 250,000 Da, the molecular weight distribution was 3.8, and the yield was 93.20%.
Polyester P11The molecular weight is up to 250,000, the molecular weight distribution is up to 3.8, and the method can be used as a main component for processing bottle-grade polyester materials and comprises the following steps: polyester P11Mixing diisohexyl sebacate and calcium ricinoleate in the mass ratio of 100: 5: 1, and injection moldingMaking into transparent polyester bottle.
Polyester P11The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 130 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling various transparent conductive film assemblies.
Example 12: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of terephthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis-hydroxyethyl ether in that order and 0.059 g (0.1 mmol) of lanthanum triflate and the reaction mixture was reacted for 3.0h under nitrogen at 165 ℃. Then raising the temperature to 235 ℃, and reacting for 3.0h under the pressure environment of 11KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 60 ℃ for 3.0h to give 4.301g of polyester P12The weight average molecular weight was 210,000 Da, the molecular weight distribution was 3.5, and the yield was 93.29%.
Polyester P12The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P12Mixing dioctyl phthalate and calcium stearate according to the mass ratio of 100: 6: 2, and then carrying out injection molding processing to prepare the transparent polyester bottle.
Polyester P12The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 125 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 95% is obtained and can be used for assembling a transparent conductive film assembly.
Example 13: a50 mL single-neck flask was charged with 0.332g (2.1 mmol) of isophthalic acid,2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bishydroxyethyl ether and 0.059 g (0.1 mmol) of lanthanum triflate, the reaction mixture is reacted at 155 ℃ for 4.0h under nitrogen. Then raising the temperature to 235 ℃, and reacting for 3.0h under the pressure environment of 13KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 145 ℃ for 3.0h to give 5.021g of polyester P13The weight average molecular weight was 180,000 Da, the molecular weight distribution was 3.3, and the yield was 95.39%.
Polyester P13The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P13Mixing dioctyl phthalate and calcium stearate according to the mass ratio of 100: 6: 2, and then carrying out injection molding processing to prepare the transparent polyester bottle.
Polyester P13The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a 135 ℃ vacuum dust-free oven, so that the nano silver transparent conductive film material with the photon transmittance of 95% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
Example 14: in a 50 mL single-neck flask were charged 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid, 0.420g (2.1 mmol) of hydroquinone bis-hydroxyethyl ether and 0.019g (0.1 mmol) of zinc oxalate in that order, and the reaction mixture was reacted for 3.0h under nitrogen protection at 150 ℃. Then raising the temperature to 225 ℃ and reacting for 3.0h under the pressure environment of 14KPa to obtain a crude polymer product. And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding ethanol into the filtrate until the generated precipitate is not increased any more. The filter residue obtained after filtration was washed with pure water and then vacuum-dried at 65 ℃ for 3.0 hours to obtain 4.422g of polyester P14Having a weight average molecular weight of150,000 Da, molecular weight distribution 3.6, yield 94.21%.
Polyester P14The polyester has higher molecular weight and is transparent, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P14Mixing dioctyl phthalate and barium stearate according to the mass ratio of 100: 6: 2, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P14The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a 135 ℃ vacuum dust-free oven, so that the nano silver transparent conductive film material with the photon transmittance of 95% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
Example 15: in a 50 mL single neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.420g (2.1 mmol) of hydroquinone bis hydroxyethyl ether and 0.021 g (0.1 mmol) of butyl stannoic acid in that order and the reaction mixture was reacted for 4.0h under nitrogen protection at 155 ℃. Then raising the temperature to 230 ℃ and reacting for 3.0h under the pressure environment of 9KPa to obtain a crude polymer product. Cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding methanol into the filtrate until the generated precipitate does not increase any more. The filter residue obtained after filtration was washed with methanol and then dried under vacuum at 75 ℃ for 3.0h to give 4.378g of polyester P15The weight average molecular weight was 186,000 Da, the molecular weight distribution was 2.4, and the yield was 93.91%.
Polyester P15The polyester has higher molecular weight and is transparent, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P15Mixing epoxidized soybean oil and barium cinnamate in the mass ratio of 100 to 6 to 2, and injection molding to obtain transparent polyester bottle.
Polyester P15Preparing a transparent polyester film with the film thickness of 20 mu m by a blown film method, taking the film as a base material, adopting nano silver paste with the silver concentration of 8% as a coating liquid, and uniformly coating the coating liquid on the transparent polyester film with the film thickness of 20 mu mAnd (3) drying the obtained film on the film by a vacuum dust-free oven at 140 ℃ to obtain the nano-silver transparent conductive film material with the photon transmittance of 95%, which can be used for assembling transparent conductive film components.
Example 16: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.292 g (2.1 mmol) of 1, 8-octanediol and 0.041 g (0.1 mmol) of stannous octoate in that order and the reaction mixture was reacted for 4.0h at 165 ℃ under nitrogen. Then raising the temperature to 220 ℃ and reacting for 3.0h under the pressure environment of 6KPa to obtain a crude polymer product. And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding ethanol into the filtrate until the generated precipitate is not increased any more. The filter residue obtained after filtration was washed with pure water and then vacuum-dried at 65 ℃ for 3.0 hours to obtain 3.232g of polyester P16The weight average molecular weight was 253,000 Da, the molecular weight distribution was 2.6, and the yield was 87.95%.
Polyester P16The polyester has higher molecular weight and is transparent, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P16Mixing tri-n-butyl citrate and barium cinnamate according to the mass ratio of 100: 5: 1, and then carrying out injection molding to prepare the transparent polyester bottle.
Polyester P16The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 150 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
Example 17: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.292 g (2.1 mmol) of 1, 8-octanediol and 0.025g (0.1 mmol) of dibutyltin oxide in that order, and the reaction mixture was reacted at 165 ℃ for 4.00 hours under a nitrogen atmosphere. Then raising the temperature to 225 ℃, and reacting for 3.0h under the pressure environment of 7KPa to obtain a crude polymer product. Cooling the polymer crude productThen, a certain amount of chloroform was added, shaking was performed to promote dissolution, and after filtration, isopropanol was added to the filtrate until the generated precipitate did not increase any more. The residue obtained after filtration was washed with pure water and then vacuum-dried at 70 ℃ for 3.0 hours to give 3.421g of polyester P17The weight average molecular weight was 190,000 Da, the molecular weight distribution was 2.9, and the yield was 89.95%.
Polyester P17The polyester has higher molecular weight and is transparent, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P17Mixing epoxidized soybean oil and barium cinnamate in the mass ratio of 100 to 5 to 1, and injection molding to obtain transparent polyester bottle.
Polyester P17The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 150 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
Example 18: in a 50 mL single-neck flask were charged 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid, and 0.292 g (2.1 mmol) of 1, 8-octanediol and 0.030g (0.1 mmol) of dibutyltin oxyhydroxide in this order, and the reaction mixture was reacted at 165 ℃ for 4.0 hours under a nitrogen atmosphere. Then raising the temperature to 220 ℃, and reacting for 3.0h under the pressure environment of 8KPa to obtain a crude polymer product. And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding ethanol into the filtrate until the generated precipitate is not increased any more. The filter residue obtained after filtration was washed with pure water and then vacuum-dried at 85 ℃ for 3.0 hours to obtain 3.611g of polyester P18The weight average molecular weight was 240,000 Da, the molecular weight distribution was 2.3, and the yield was 90.01%.
Polyester P18The polyester has higher molecular weight and is transparent, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P18Mixing epoxidized soybean oil and 2-ethyl lead acetate according to the mass ratio of 100: 5: 1, and then carrying out injection molding processing to prepare the epoxy soybean oil-lead acetate rubberA transparent polyester bottle.
Polyester P18The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 150 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
Example 19: in a 50 mL single-neck flask were added 0.332g (2.1 mmol) of isophthalic acid, 2.54g (18.2 mmol) of 2, 5-furandicarboxylic acid and 0.292 g (2.1 mmol) of 1, 8-octanediol and 0.060 g (0.1 mmol) of dibutyltin oxychloride in this order, and the reaction mixture was reacted at 165 ℃ for 4.0 hours under a nitrogen atmosphere. Then raising the temperature to 240 ℃ and reacting for 3.0h under the pressure environment of 9KPa to obtain a crude polymer product. And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding isopropanol into the filtrate until the generated precipitate is not increased any more. The residue obtained after filtration was washed with pure water and then vacuum-dried at 70 ℃ for 3.0 hours to give 3.402g of polyester P19The weight average molecular weight was 199,000 Da, the molecular weight distribution was 2.7, and the yield was 88.70%.
Polyester P19The polyester material has high molecular weight and transparency, and can be used as a main component for processing bottle-grade polyester materials, and the method comprises the following steps: polyester P19The transparent polyester bottle is prepared by banburying acetyl tri-n-hexyl citrate and barium ricinoleate according to the mass ratio of 100: 5: 1 and then performing injection molding.
Polyester P19The transparent polyester film with the film thickness of 20 micrometers is prepared through a blown film method, the film is used as a base material, nano silver paste with the silver concentration of 8% is used as a coating liquid, the coating liquid is uniformly coated on the transparent polyester film with the film thickness of 20 micrometers, and the obtained film is dried through a vacuum dust-free oven at 150 ℃, so that the nano silver transparent conductive film material with the photon transmittance of 96% is obtained, and the nano silver transparent conductive film material can be used for assembling a transparent conductive film assembly.
TABLE 1 mechanical Properties of samples of polyesters P1-P19 vs. polyethylene isophthalate PET in examples 1-19Ratio of
Sample (I) Tensile strength/MPa Elongation at break/% Flexural Strength/MPa Impact Strength/(kJ. m)-2 )
P1 3788 323.2 60.3 26.9
P2 3225 365.5 58.1 25.1
P3 3286 339.2 51.2 24.5
P4 3557 354.2 53.6 25.4
P5 3823 356.2 52.6 25.3
P6 3798 365.2 63.2 25.6
P7 3408 325.4 59.6 26.3
P8 3958 332.1 56.3 27.5
P9 3327 336.5 54.2 24.1
P10 3659 349.6 60.5 26.3
P11 3253 347.1 63.1 28.9
P12 3115 324.6 68.1 29.1
P13 3956 312.9 59.1 27.6
P14 3653 389.6 56.9 27.1
P15 3524 376.5 57.3 26.3
P16 3785 398.6 57.1 25.1
P17 3968 310.5 53.2 25.3
P18 3654 398.4 54.1 28.1
P19 3987 396.3 61.3 29.4
PET[1] 1115 291.1 21.7 9.8
[1] Synthesis and characterization of polyethylene glycol polyisoisophthalate-2, 5-furandicarboxylate random copolyester [ J ] polymer science, 2013, 46(8): 1092-.
As can be seen from the comparison of the data in Table 1, the tensile strength of the ethylene isophthalate PET is 1115MPa, whereas the polyester P of the present invention, which is synthesized from isophthalic acid, 2, 5-furandicarboxylic acid and a diol as raw materials1～P19The tensile strength of the polyester is 2000-2872 MPa higher than that of the ethylene isophthalate PET; the elongation at break of the isophthalic acid glycol ester PET is 291.1 percent, and the invention takes the isophthalic acid, the 2, 5-furandicarboxylic acid and the dihydric alcohol as the raw materials to synthesize the polyester P1～P19The elongation at break of the polyester is 19.4-107.5% higher than that of the ethylene isophthalate PET; the bending strength of the isophthalic acid glycol ester PET is 21.7Mpa, and the invention takes the isophthalic acid, the 2, 5-furandicarboxylic acid and the dihydric alcohol as the raw materials to synthesize the polyester P1～P19The bending strength of the material is 29.5-46.4 MPa higher than that of the ethylene isophthalate PET; the impact strength of the isophthalic acid glycol ester PET is 9.8Mpa, and the invention takes the isophthalic acid, the 2, 5-furandicarboxylic acid and the dihydric alcohol as the raw materials to synthesize the polyester P1～P19The impact strength of the alloy is 14.3-19.6 MPa higher than that of the ethylene isophthalate PET.
As can be seen from the above data, the present invention uses terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and diol as raw materials,the synthesized polyester P1～P19Compared with the ethylene isophthalate PET, the molecular weight, the thermal property, the mechanical property and the like of the PET are obviously improved, the mechanical properties (including tensile strength, tensile modulus, bending strength, bending modulus and impact strength) of the polyester are greatly improved, the thermal property of the PET in use is improved, and if the melting point is far higher than that of the commercial polyester PET, the thermal decomposition temperature is also greatly improved.
In summary, the synthesis of bio-based polyester materials reported in the prior literature requires relatively more catalysts, the catalytic efficiency is low, the obtained polyester has a darker color, and the molecular weight of the polyester product is low, so that the polyester has weak strength, poor mechanical properties and processability, and is difficult to meet the requirements of practical application on various material properties. In view of the above problems in the prior art, the main object of the present invention is to provide a method for preparing a high molecular weight transparent copolyester based on mixed diacid as a monomer and a use thereof, specifically, a series of polyesters are synthesized by taking terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and dihydric alcohol or other dihydroxy compounds as raw materials and sulfonic acid catalysts or group IV B transition metals as catalysts through efficient melt polymerization. The series of high molecular weight transparent copolyesters based on mixed diacid as monomers are prepared through two-step reactions of catalytic esterification exchange reaction and catalytic polycondensation. The transparent polyester with high molecular weight has the weight average molecular weight of 140,000-250,000 Da, and the polyester has extremely low metal content or no metal, and compared with the existing bio-based polyester, the transparent polyester has the advantages of high melting point, good thermal stability, strong mechanical property and good service performance. Therefore, the invention patent of 'a preparation method and application of high molecular weight transparent copolyester based on mixed diacid as a monomer' meets the requirements of the fields of packaging materials and medical materials of high-grade beverage and food industries on the color quality of raw materials on one hand; on the other hand, the prepared high-molecular-weight transparent polyester can be prepared into a transparent polyester film with the film thickness of 5-20 mu m by a blown film method or a cast film method, and the photon light transmittance exceeds 98%. The film is used as a base material, nano silver paste with the silver concentration of 4-8% is used as a coating liquid, the coating liquid is uniformly coated, and then the nano silver transparent conductive film material with the photon light transmittance of more than 95% can be obtained after vacuum dust-free drying at 60-150 ℃, so that the film can be used for assembling various transparent conductive film components such as medium-size and large-size capacitive touch screens or touch screens, intelligent dimming film components and intelligent video display screens.
As mentioned above, the high molecular weight transparent polyester prepared by the invention has good market prospect.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (8)

1.1) taking terephthalic acid or isophthalic acid, 2, 5-furandicarboxylic acid and dihydric alcohol or other dihydroxy compounds as raw materials, and synthesizing the series of polyesters by a melt polymerization method. Stirring and reacting the three raw materials at 150-175 ℃ for 3.0-4.0 h under the action of a catalyst under the protection of nitrogen, then raising the temperature to 220-240 ℃, and reacting for 2.0-3.0 h under the pressure environment of 5-15 KPa to obtain a crude polymer product.
2) And cooling the polymer crude product, adding a certain amount of chloroform, shaking to promote dissolution, filtering, and adding low-carbon alcohol such as methanol/ethanol or isopropanol into the filtrate until the generated precipitate is not increased any more. Washing the filter residue obtained after filtration with methanol or pure water, and then drying in vacuum at 60-70 ℃ for 2.0-3.0 h to obtain the required high molecular weight polyester.
2. The method for preparing a transparent polyester with high molecular weight according to claim 1, wherein in the step 1), the diol is one of the following aliphatic diols: 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, neopentyl glycol, 2-methyl-1, 3-propanediol; or one of the following aliphatic cyclic diols: 1, 3-cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, tricyclo [5.2.10 (2, 6) ] decanedimethanol (i.e. tricyclodecanedimethanol), 2,4,8, 10-tetraoxaspiro [5, 5] undecane-3, 9-diethanol (i.e. Spiropentanediol (SPG)).
3. The method for preparing a transparent polyester having a high molecular weight according to claim 1, wherein in the step 1), the other dihydroxy compound is one of the following compounds: hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, catechol dihydroxyethyl ether, bis (2-hydroxyethyl) isophthalate, bis (2-hydroxyethyl) terephthalate, bis (2-hydroxyethyl) phthalate.
4. The method of claim 1, wherein the molar ratio of terephthalic acid or isophthalic acid to 2, 5-furandicarboxylic acid in step 1) is 0.9: 0.1 to 0.1: 0.9, and the molar ratio of the mixed diacid to the diol or other dihydroxy compound is 1.0: 1.0 to 1.2.
5. The method according to claim 1, wherein the catalyst in step 1) is one of sulfonic acid catalysts such as trifluoromethanesulfonic acid, sulfamic acid, p-fluorobenzenesulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, o-trifluoromethylbenzenesulfonic acid, m-trifluoromethylbenzenesulfonic acid, and p-trifluoromethylbenzenesulfonic acid, or one of group IVB metal catalysts such as fluorotitanic acid, ammonium fluorotitanate, and tetraisopropyl titanate, or one of other group metal catalysts such as lanthanum trifluoromethanesulfonate, zinc oxalate, butylstannic acid, stannous octoate, dibutyltin oxide, dibutyltin oxyhydroxide, and dibutyltin chlorooxide. The amount of the catalyst is 0.1-0.5% of the amount of the acid substance.
6. A high molecular weight transparent polyester prepared according to claim 1, which is used as a main component for processing bottle-grade polyester materials, and can be used for manufacturing hollow containers or sleeves for storage tanks, protective sleeves and the like, which can use polyester as a main component, characterized in that: the polyester is fully mixed according to the mass ratio, after the high molecular weight transparent polyester taking the mixed diacid of the furandicarboxylic acid and the isophthalic acid as monomers, the plasticizer and the stabilizer are mixed according to the mass ratio of 100 to (5-6) to (1-2), the subsequent forming processes such as extrusion, stretching, blow molding and the like can be carried out. The plasticizer is one of triethyl citrate, acetyl tri-n-butyl citrate, tri-n-hexyl citrate, acetyl tri-n-hexyl citrate, epoxidized soybean oil, dioctyl phthalate, diisohexyl sebacate and the like; the stabilizer is one of barium stearate, barium cinnamoate, barium ricinoleate, calcium stearate, calcium ricinoleate, magnesium stearate, zinc stearate and 2-ethyl lead acetate.
7. A transparent polyester having a high molecular weight prepared according to claim 1, which is used as a raw material for a substrate of a transparent conductive polyester film material, and a method for producing a transparent conductive polyester film material using the transparent polyester having a high molecular weight as a main raw material, characterized by comprising: preparing a transparent polyester film with a photon transmittance of more than 98% and a film thickness of 5-20 mu m by adopting the high-molecular-weight transparent polyester prepared according to the claim 1 through a blown film method or a cast film method, uniformly coating the transparent polyester film with a film thickness of 5-20 mu m on a transparent polyester film with a film thickness of 5-20 mu m by taking the film as a base material and adopting nano silver paste with a silver concentration of 4-8% as a coating liquid, so that the content of the nano silver distributed on the film reaches 20-150 mg/m2. And drying the obtained film by a vacuum dust-free oven at 60-150 ℃ to obtain the nano-silver transparent conductive film material with the photon transmittance of more than 95%, and the nano-silver transparent conductive film material can be used for assembling various transparent conductive film components.
8. The nano silver paste of claim 7, which is prepared from nano silver, a dispersant and a surfactant, wherein the nano silver has the following specification: the silver wire nanometer material is 10-20 mu m in length and 15-20 nm in diameter, the mass content of the silver wire nanometer material in silver paste is 4-8%, and the dispersing agent is hydroxypropyl methyl cellulose (HPMC) and the mass content of the dispersing agent is 5%; the rest component of the silver paste is polyoxyethylene octyl phenol ether-10 (OP-10).
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