CN108503809B - Furan bio-polyether ester copolymer and preparation method thereof - Google Patents

Furan bio-polyether ester copolymer and preparation method thereof Download PDF

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CN108503809B
CN108503809B CN201810442837.XA CN201810442837A CN108503809B CN 108503809 B CN108503809 B CN 108503809B CN 201810442837 A CN201810442837 A CN 201810442837A CN 108503809 B CN108503809 B CN 108503809B
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polyether ester
ppegf
glycol
ester copolymer
ethylene glycol
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CN108503809A (en
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周光远
王瑞
姜敏
王国强
张强
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Wuhu Wanlong New Material 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
    • C08G63/66—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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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Abstract

The invention providesA polyether ester copolymer having a structure represented by formula (I); wherein n is 10-200; m is 0 to 200; p is selected from one or more of 1, 2, 3 and 4. The furan bio-polyether ester copolymer product provided by the invention has a high-content glycol chain segment in the structure, and has good thermodynamic property and good color. In addition, the invention can directly carry out polycondensation reaction by FDCA and bio-based ethylene glycol under the catalysis of a metal complex catalyst by adopting a simple synthesis means, and efficiently prepare the furan all-bio-based polyether ester copolymer with high viscosity and a novel structure at a lower temperature in a shorter time, wherein the molecule of the copolymer contains an oligoethylene glycol chain segment with controllable content, and the preparation method has the advantages of stable reaction process, easy control and mild conditions, is economic and environment-friendly, and is suitable for large-scale industrial production.

Description

Furan bio-polyether ester copolymer and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of furan-based polyether ester, relates to a furan-based polyether ester copolymer and a preparation method thereof, and particularly relates to a furan bio-based polyether ester copolymer with a novel structure and a preparation method thereof.
Background
2, 5-Furanedicarboxylic acid (FDCA) of formula C6H4O5Structural formula is
Figure BDA0001656316120000011
As an important derivative of furan, the bio-based polymer aromatic ring monomer with a 'rigid' planar structure can be polymerized with monomers such as glycol, diamine and the like to prepare a novel bio-based polymer synthetic material with excellent performance, and is an important chemical raw material and an organic chemical intermediate.
At present, with the wide application of polyester products, the high-speed development of polyester raw material industry is driven. Among them, the development of bio-based polyester monomers for substituting petroleum-based raw materials has become one of the hot spots of research in the field of current polyesters. Aromatic polyesters, polyethylene terephthalate (PET), are important thermoplastic polyesters, have excellent heat resistance, chemical resistance, and high recovery rate, and are widely used in the field of packaging. At present, the ethylene glycol as raw material for producing PET can be prepared by using biomass raw material, for example, the prior art has successfully prepared a completely recyclable bio-based PET beverage bottle by using bio-based ethylene glycol as raw material. However, another feedstock, terephthalic acid (PTA), for PET production, is produced from the catalytic oxidation of p-xylene (PX), a petroleum-based industrial feedstock, such that the resulting PET plastic product contains only 30% plant-based components. Although succinic acid, a raw material monomer of bio-based polyester, which has been studied vigorously in recent years, has a potential to partially replace petroleum-based diacid, it has greatly limited the properties of the corresponding polyester product because it cannot provide a rigid aromatic benzene ring structure like terephthalic acid. Therefore, how to obtain the polyester raw material dibasic acid with the rigid ring structure from the biomass is an important development direction in the field of polyester raw material development.
Research in recent years has found that 2, 5-furandicarboxylic acid (FDCA), which is an important raw material for developing all-biobased polyesters as an ideal polyester raw material for replacing PTA, not only has a similar rigid aromatic ring structure, but also contains carbon number, is less aromatic than benzene rings, and is more easily degraded, and more importantly, 2, 5-furandicarboxylic acid is a biobased monomer that can be prepared from biomass. Thus, the polyester material corresponding to 2, 5-furandicarboxylic acid, poly (ethylene 2, 5-furandicarboxylate) (PEF), is receiving increasing attention from researchers and research and development departments of enterprises. For example, CN102453242A, CN104072954A, WO2015137804 and the like all report the preparation method of PEF homopolyester and the thermodynamic properties of corresponding high molecular products. At present, besides preparation of PEF homopolyester, copolymerization of other monomers, FDCA and ethylene glycol is also an important method for developing and expanding the variety of furan bio-based polyester, and mainly copolymerization of other monomers, FDCA and ethylene glycol is introduced, for example, CN102432847 reports the copolyester of FDCA, ethylene glycol and terephthalic acid monomer.
However, these newly introduced comonomers often have high cost, or are non-bio-based monomers such as terephthalic acid, so that the all-bio-based polyester product loses the properties of 100% bio-based materials, and the environmental protection significance is greatly reduced.
Therefore, how to obtain a novel full-bio-based furan bio-based polyether ester polymer material, which not only has the properties of a 100% bio-based material, but also can avoid the problems of operation, additional cost and the like caused by adding a monomer, has become one of the focuses of great attention of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a furan bio-based polyether ester copolymer and a preparation method thereof, and in particular, to a furan all-bio-based polyether ester copolymer with a novel structure, wherein the product structure of the furan bio-based polyether ester copolymer provided by the present invention has a high content of glycol segments, and has good thermodynamic properties and good color and luster; meanwhile, the reaction process in the preparation process is stable and easy to control, and the preparation method is economic, environment-friendly and suitable for large-scale industrial production.
The invention provides a polyether ester copolymer which has a structure shown in a formula (I);
Figure BDA0001656316120000021
wherein n is 10-200; m is 0 to 200;
p is selected from one or more of 1, 2, 3 and 4.
Preferably, in the polyether ester copolymer, n/(n + m) is 1 or less;
in the polyether ester copolymer, n/(n + m) is 0.3-0.7;
in the polyether ester copolymer, n/(n + m) is 0.1-0.4.
Preferably, the polyether ester copolymer is obtained by polymerizing 2, 5-furandicarboxylic acid and an alcohol monomer;
the alcohol monomer comprises glycol, or a mixture of glycol and ethylene glycol; the glycol comprises one or more of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol;
the number average molecular weight of the polyether ester copolymer is 20000-70000.
The invention provides a preparation method of a polyether ester copolymer, which comprises the following steps:
1) under the conditions of protective atmosphere and metal complex catalyst, 2, 5-furandicarboxylic acid and ethylene glycol are subjected to esterification reaction, pre-polycondensation reaction and polycondensation reaction to obtain polyether ester copolymer;
in the polyether ester copolymer, the content of the mole number of the glycol chain segment in the polyether ester copolymer is 30-70%.
The invention provides a preparation method of a polyether ester copolymer, which comprises the following steps:
1') under the conditions of protective atmosphere and esterification catalyst, 2, 5-furandicarboxylic acid and ethylene glycol are subjected to esterification reaction, then to pre-polycondensation reaction, and then to polycondensation reaction, and after a metal complex catalyst is added in the polycondensation reaction process, a polyether ester copolymer is obtained;
in the polyether ester copolymer, the content of the mole number of the glycol chain segment in the polyether ester copolymer is 10-40%.
Preferably, the metal complex has the formula LnX3；
The ligand of the metal complex comprises one or more of trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropane sulfonic acid group, nonafluorobutanesulfonic acid group and trifluoromethanesulfonylimide group;
the metal elements of the metal complex comprise one or more of rare earth elements, tin, bismuth, zinc, copper, alkali metals and alkaline earth metals;
the molar ratio of the 2, 5-furandicarboxylic acid to the ethylene glycol is 1 (2-8);
the ratio of the mole number of the metal complex catalyst to the mole number of the 2, 5-furandicarboxylic acid is 0.5-4 per mill.
The invention also provides a preparation method of the polyether ester copolymer, which comprises the following steps:
1') under the conditions of protective atmosphere and esterification catalyst, 2, 5-furandicarboxylic acid and alcohol monomer are subjected to esterification reaction, and then to pre-polycondensation reaction and polycondensation reaction to obtain the polyether ester copolymer.
Preferably, the molar ratio of the 2, 5-furandicarboxylic acid to the alcohol monomer is 1 (2-8);
the alcohol monomer comprises glycol, or a mixture of glycol and ethylene glycol;
the glycol comprises one or more of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
Preferably, the esterification catalyst comprises one or more of stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate and stannous hydroxide;
the ratio of the mole number of the esterification catalyst to the mole number of the 2, 5-furandicarboxylic acid is 0.5-4 per mill;
the pressure in the pre-polycondensation reaction process is reduced from the pressure of the esterification reaction to the pressure of the polycondensation reaction.
Preferably, the temperature of the esterification reaction is 170-210 ℃; the esterification reaction time is 1-4 h; the pressure of the esterification reaction is 1-3 atm;
the pre-polycondensation reaction is a decompression reaction; the time of the pre-polycondensation reaction is 10-60 min; the temperature of the pre-polycondensation reaction is 170-210 ℃;
the pressure of the polycondensation reaction is 20-50 Pa; the temperature of the polycondensation reaction is 180-250 ℃; the time of the polycondensation reaction is 2-12 h.
The invention provides a polyether ester copolymer which has a structure shown in a formula (I); wherein n is 10-200; m is 0 to 200; p is selected from one or more of 1, 2, 3 and 4. Compared with the prior art, the invention aims at the defects that other monomers are required to be introduced to copolymerize with FDCA and ethylene glycol for the existing poly (ethylene 2, 5-furandicarboxylate), especially copolyester, and the newly introduced comonomers often have higher cost or non-bio-based monomers, so that the fully bio-based polyester product loses the property of 100 percent bio-based materials, and the environmental protection significance is greatly reduced.
The invention creatively provides a furan full-bio-polyether ester copolymer with a novel structure, and the product structure of the furan full-bio-polyether ester copolymer has a high-content glycol chain segment, good thermodynamic property and good color. The furan-based polyether ester copolymer provided by the invention can be copolymerized by common oligo-glycol, FDCA and ethylene glycol, and the product prepared by copolymerizing the oligo-glycol with the FDCA and the ethylene glycol loses the attribute of 100% biobased material by considering that the oligo-glycol (diethylene glycol, triethylene glycol and the like) is a non-biobased monomer. The invention creatively utilizes the characteristic that a metal catalyst containing a strong electron-withdrawing ligand can catalyze etherification reaction at higher temperature under the catalytic action of the metal complex catalyst, adopts a simple synthesis method, utilizes direct polycondensation reaction of FDCA and bio-based glycol, and efficiently prepares the furan all-bio-based polyether ester copolymer with high viscosity and a novel structure at lower temperature in a shorter time, wherein the molecule of the furan all-bio-based polyether ester copolymer contains a content-controllable oligoethylene glycol chain segment, and the preparation method has the advantages of stable reaction process, easy control and mild conditions, is economic and environment-friendly, and is suitable for large-scale industrial production.
The furan all-bio-polyether ester copolymer with a novel structure and the preparation method thereof provided by the invention can obtain a novel all-bio-polymer material and can solve the problems of operation, additional cost and the like caused by adding oligoethylene glycol in the preparation process. The furan bio-based polyether ester product with the novel structure promotes and realizes the development and utilization of furan renewable resources and the preparation of environment-friendly novel bio-based polyester, gradually gets rid of the dependence on petroleum resources, solves the problems of resource shortage, environmental pollution and the like in the polymer industry in China, and has important promotion and application value for realizing the sustainable development of the polymer material industry in China.
Experimental results show that the glass transition temperature of the novel bio-polyether ester prepared by the invention can be controlled at 30-85 ℃, the 5% thermal degradation temperature is 280-400, the tensile strength is 10-85 MPa, and the elongation at break is 4-400%.
Drawings
FIG. 1 shows the NMR spectrum of the furan-based polyether ester copolyester prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs analytical purity or purity conventional in the art of furan-based polyether ester synthesis.
All the noun expressions and acronyms of the invention belong to the noun expressions and acronyms which are conventional in the art, and each noun expression and acronym is clearly and uniquely understood by those skilled in the art according to the noun expressions and acronyms.
The invention provides a polyether ester copolymer which has a structure shown in a formula (I);
Figure BDA0001656316120000051
wherein n is 10-200; m is 0 to 200;
p is selected from one or more of 1, 2, 3 and 4.
The present invention is not limited to the polyetherester copolymer having the structure shown in formula (I), and those skilled in the art will understand that the polyetherester copolymer may have the structure or may contain a segment of the structure, and the present invention is not limited to the structure. The core of the structure of the polyether ester copolymer with the structure shown in the formula (I) is a copolymer containing polyethylene glycol 2, 5-furandicarboxylate and polyethylene glycol furandicarboxylate copolymerized with polyol ester, wherein a chain segment of the copolymer contains a 2, 5-furandicarboxylate segment and also contains a 2, 5-furandicarboxylate polyol segment; its abbreviation can be written as: PPEGF, named poly (ethylene 2, 5-furandicarboxylate-co-2, 5-furandicarboxylate)
In the structure shown in formula (I), the part corresponding to n is a 2, 5-furandicarboxylic acid polyglycol ester fragment, so the selection range of n is not particularly limited, and can be selected and adjusted according to the actual application situation, quality control and product requirements by the skilled in the art, and n in the structure shown in formula (I) is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the structure shown in formula (I), the part corresponding to m is a 2, 5-furandicarboxylic acid diol ester fragment, so the selection range of m is not particularly limited, and can be selected and adjusted according to the practical application situation, quality control and product requirements by the skilled in the art, and m in the structure shown in formula (I) is preferably 0-200, more preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the present invention, both m and n are preferably the number of moles.
In the structure of formula (I) of the present invention, the portion corresponding to p is a specific number of the polyglycols, and can be selected and adjusted by those skilled in the art according to practical application, quality control and product requirements, and the polyglycols of the present invention can include one or more of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol, i.e. p is preferably one or more of 1, 2, 3 and 4, more preferably 1, 2, 3 or 4, more preferably 1, 1 and 2 and 3 and 4, or 1 and 2, 3 and 4 and 5.
The specific ratio of n to m is not particularly limited in the present invention, and may be a conventional molar ratio well known to those skilled in the art, and those skilled in the art can select and adjust the specific ratio according to the practical application, quality control and product requirements, and in the polyether ester copolymer of the present invention, n/(n + m) is preferably not more than 1, and may be not more than 1, i.e., m is 0, and may also be not more than 0.8, and may also be not more than 0.6, and may also be not more than 0.4, or not more than 0.2. In the polyether ester copolymer, n/(n + m) can be 0.3-0.7, 0.35-0.65, 0.4-0.6, or 0.45-0.55 according to different preparation methods. In the polyether ester copolymer, n/(n + m) can be 0.1-0.4, 0.15-0.35 or 0.2-0.3 according to different preparation methods.
The invention has no special limitation on other parameters of the polyether ester copolymer, and the conventional parameters of the polyether ester copolymer known by the skilled person in the art can be used, and the skilled person in the art can select and adjust the parameters according to the actual application situation, quality control and product requirements, and the number average molecular weight of the polyether ester copolymer in the invention is preferably 20000-70000, more preferably 30000-60000, and more preferably 40000-50000.
The method for preparing the polyether ester copolymer is not particularly limited, and the conventional method for preparing the copolymer, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the polyether ester copolymer is preferably obtained by polymerizing 2, 5-furandicarboxylic acid and alcohol monomers.
The alcohol monomers of the present invention include, in particular, glycols, or mixtures of glycols and ethylene glycol.
The specific choice of the glycol is not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual application, quality control and product requirements, and the glycol of the present invention preferably includes one or more of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol, and more preferably diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol.
The present invention is not particularly limited in terms of the specific manner and procedure of the polymerization, and may be carried out in conventional manners well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control, and product requirements.
The invention provides three independent preparation methods of the furan-based polyether ester copolymer, in order to further improve the controllability of the polyether ester copolymer product, develop the furan all-bio-based polyether ester copolymer, perfect and refine the preparation process and improve a more complete technical scheme for industrial application.
The invention provides a preparation method of a polyether ester copolymer, which comprises the following steps:
1) under the conditions of protective atmosphere and metal complex catalyst, 2, 5-furandicarboxylic acid and ethylene glycol are subjected to esterification reaction, pre-polycondensation reaction and polycondensation reaction to obtain polyether ester copolymer;
in the polyether ester copolymer, the content of the mole number of the glycol chain segment in the polyether ester copolymer is 30-70%.
In the preparation method of the polyether ester copolymer, the selection, combination and preferable range of the polyether ester copolymer can correspond to the selection, combination and preferable range of the polyether ester copolymer, and thus, the detailed description is omitted.
The structure of the polyether ester copolymer is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the content of the mole number of the glycol segment in the polyether ester copolymer of the present invention is preferably 30% to 70%, more preferably 35% to 65%, more preferably 40% to 60%, and more preferably 45% to 55% of the mole number of the polyether ester copolymer. The 2, 5-furandicarboxylic acid of the present invention preferably comprises a biobased 2, 5-furandicarboxylic acid.
The protective atmosphere is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and preferably comprises nitrogen and/or an inert gas, more preferably nitrogen or argon.
The specific choice of the metal complex catalyst is not particularly limited in the present invention, and may be a conventional metal complex catalyst well known to those skilled in the art, and those skilled in the art may select and adjust the catalyst according to actual production conditions, quality control and product requirements, and the metal complex of the present invention may have a general formula of LnX3. The ligand of the metal complex catalyst preferably comprises one or more of trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropanesulfonic acid group, nonafluorobutanesulfonic acid group and trifluoromethanesulfonylimide group, and more preferably comprises trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropanesulfonic acid group, nonafluorobutanesulfonic acid group or trifluoromethanesulfonylimide group. The metal element of the metal complex of the present invention preferably includes one or more of rare earth element, tin, bismuth, zinc, copper, alkali metal and alkaline earth metal, and more preferably rare earth element, tin, bismuth, zinc, copper, alkali metal or alkaline earth metal.
The specific selection of the rare earth elements is not particularly limited, and the rare earth elements are commonly used rare earth elements well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the rare earth elements in the invention are preferably non-radiative rare earth elements, and specifically can be one or more of lanthanum La, cerium Ce, praseodymium Pr, europium Eu, neodymium Nd, samarium Sm, gadolinium Ga, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, yttrium Y and scandium Sc.
The amount of the metal complex catalyst used in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the ratio of the mole number of the metal complex catalyst in the present invention to the mole number of the 2, 5-furandicarboxylic acid is preferably 0.5 to 4%, more preferably 1 to 3.5%, still more preferably 1.5 to 3%, still more preferably 2 to 2.5%.
The amount of the ethylene glycol is not particularly limited in the present invention, and may be conventional amount for such reaction, which is well known to those skilled in the art, and those skilled in the art can select and adjust the amount according to the actual production situation, quality control and product requirements, and the molar ratio of the 2, 5-furandicarboxylic acid to the ethylene glycol in the present invention is preferably 1 (2-8), more preferably 1 (3-7), and more preferably 1 (4-6).
The esterification reaction conditions are not particularly limited, and can be selected and adjusted by the ordinary esterification reaction conditions well known by the technicians in the field according to the actual production conditions, quality control and product requirements, and the esterification reaction temperature is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The esterification reaction time is preferably 1-4 h, more preferably 1.5-3.5 h, and more preferably 2-3 h. The pressure of the esterification reaction in the invention may be normal pressure or micro-positive pressure, and is preferably 1 to 3atm (atmospheric pressure, which may be 0.1MPa), more preferably 1.2 to 2.8atm, and even more preferably 1.5 to 2.5 atm.
After the esterification reaction, the esterification product is directly subjected to the pre-polycondensation reaction without separation. The conditions and steps of the pre-polycondensation reaction are not particularly limited, and can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the temperature of the pre-polycondensation reaction is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The time of the pre-polycondensation reaction is preferably 10-60 min, more preferably 20-50 min, and more preferably 30-40 min.
The pre-polycondensation reaction is preferably a reduced pressure reaction, and the specific reaction mode can be a reduced pressure distillation reaction and can remove excessive dihydric alcohol in the system. The pressure of the pre-polycondensation reaction of the present invention is preferably a variable value, and the range of the pressure may be specifically reduced from the pressure of the esterification reaction to the pressure of the polycondensation reaction.
After the pre-polycondensation reaction, the invention finally carries out the polycondensation reaction under the low vacuum condition. The conditions and steps of the polycondensation reaction are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the pressure of the polycondensation reaction in the present invention is preferably 20 to 50Pa, more preferably 25 to 45Pa, and more preferably 30 to 40 Pa. The temperature of the polycondensation reaction is preferably 180-250 ℃, more preferably 190-240 ℃, more preferably 200-230 ℃, and more preferably 210-220 ℃. The time of the polycondensation reaction is preferably 2-12 h, more preferably 4-10 h, and more preferably 6-8 h.
In order to further ensure the performance, integrity and refinement of the preparation process of the final product, the preparation method specifically comprises the following steps:
a melt polycondensation method is adopted to directly prepare the novel furan all-biobased polyether ester copolymer with controllable esterification and etherification structure proportion of 30-70 percent through three steps of esterification, prepolymerization and polymerization of 2, 5-furandicarboxylic acid and dihydric alcohol (ethylene glycol). Under the action of a metal complex catalyst, directly esterifying 2, 5-furandicarboxylic acid and bio-based diol to generate 2, 5-furandicarboxylic acid diol ester; then, the esterification product is not required to be separated, the reduced pressure distillation is continuously utilized for pre-polymerization, and excessive dihydric alcohol in the reaction system is removed; finally, the polycondensation reaction is carried out under the condition of low vacuum to prepare the high molecular weight polyether ester product.
The above preparation process of the present invention can be specifically represented by the reaction formula (1):
Figure BDA0001656316120000091
the steps of the invention provide a preparation method of a novel furan all-bio-polyether ester copolymer, and the structural chain segment of the novel all-bio-polyether ester prepared by the method mainly comprises a part of polyethylene glycol furandicarboxylate (PEF) and a part of glycol chain segment, wherein the glycol chain segment comprises diethylene glycol and triethylene glycol, and also comprises a part of tetraethylene glycol and/or pentaethylene glycol. The glycol chain segment in the prepared polyether ester structure accounts for 30-70% of the total mole percentage of the polymer, namely n/(n + m) is 0.3-0.7, n is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the invention, m is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the present invention, both m and n are preferably the number of moles.
The invention adopts the metal complex catalyst to catalyze the direct esterification polymerization of glycol and furandicarboxylic acid, and efficiently prepares the novel 100 percent bio-based furan polyether ester with high viscosity at lower temperature in shorter time, the reaction process is stable and easy to control, the color and luster of the product are better, and the prepared product has high content of glycol chain segments in the structure. The invention can also effectively regulate and control the proportion of the glycol chain segment in the polyether ester product by adjusting the feeding proportion of the dihydric alcohol and the furan dicarboxylic acid, and the conditions of esterification time, temperature, polycondensation time, temperature and the like in the reaction process. Furthermore, the invention particularly preferably selects the rare earth metal complex catalyst which is low in content or non-toxic, so that the prepared novel polymer material is more in line with the concept of green environmental protection and is suitable for the preparation method of large-scale industrial production.
The invention also provides another preparation method of the polyether ester copolymer, which comprises the following steps:
1') under the conditions of protective atmosphere and esterification catalyst, 2, 5-furandicarboxylic acid and ethylene glycol are subjected to esterification reaction, then to pre-polycondensation reaction, and then to polycondensation reaction, and after a metal complex catalyst is added in the polycondensation reaction process, a polyether ester copolymer is obtained;
in the polyether ester copolymer, the content of the mole number of the glycol chain segment in the polyether ester copolymer is 10-40%.
In the preparation method of the polyether ester copolymer, the selection, combination and preferable range of the polyether ester copolymer can correspond to the selection, combination and preferable range of the polyether ester copolymer, and thus, the detailed description is omitted.
The structure of the polyether ester copolymer is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the content of the mole number of the glycol segment in the polyether ester copolymer of the present invention is preferably 10% to 40%, more preferably 15% to 35%, and still more preferably 20% to 30% based on the mole number of the polyether ester copolymer. The 2, 5-furandicarboxylic acid of the present invention preferably comprises a biobased 2, 5-furandicarboxylic acid.
The protective atmosphere is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and preferably comprises nitrogen and/or an inert gas, more preferably nitrogen or argon.
The esterification catalyst is not particularly limited in the present invention, and may be a conventional esterification catalyst for such compounds, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the esterification catalyst of the present invention preferably includes one or more of stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate and stannous hydroxide, and more preferably stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or stannous hydroxide. The amount of the esterification catalyst used in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the ratio of the mole number of the esterification catalyst in the present invention to the mole number of the 2, 5-furandicarboxylic acid is preferably 0.5 to 4%, more preferably 1 to 3.5%, more preferably 1.5 to 3%, and still more preferably 2 to 2%.
The amount of the ethylene glycol is not particularly limited in the present invention, and may be conventional amount for such reaction, which is well known to those skilled in the art, and those skilled in the art can select and adjust the amount according to the actual production situation, quality control and product requirements, and the molar ratio of the 2, 5-furandicarboxylic acid to the ethylene glycol in the present invention is preferably 1 (2-8), more preferably 1 (3-7), and more preferably 1 (4-6).
The esterification reaction conditions are not particularly limited, and can be selected and adjusted by the ordinary esterification reaction conditions well known by the technicians in the field according to the actual production conditions, quality control and product requirements, and the esterification reaction temperature is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The esterification reaction time is preferably 1-4 h, more preferably 1.5-3.5 h, and more preferably 2-3 h. The pressure of the esterification reaction in the invention may be normal pressure or micro-positive pressure, and is preferably 1 to 3atm (atmospheric pressure, which may be 0.1MPa), more preferably 1.2 to 2.8atm, and even more preferably 1.5 to 2.5 atm.
After the esterification reaction, the esterification product is directly subjected to the pre-polycondensation reaction without separation. The conditions and steps of the pre-polycondensation reaction are not particularly limited, and can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the temperature of the pre-polycondensation reaction is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The time of the pre-polycondensation reaction is preferably 10-60 min, more preferably 20-50 min, and more preferably 30-40 min.
The pre-polycondensation reaction is preferably a reduced pressure reaction, and the specific reaction mode can be a reduced pressure distillation reaction and can remove excessive dihydric alcohol in the system. The pressure of the pre-polycondensation reaction of the present invention is preferably a variable value, and the range of the pressure may be specifically reduced from the pressure of the esterification reaction to the pressure of the polycondensation reaction.
After the pre-polycondensation reaction, the invention finally carries out the polycondensation reaction under the low vacuum condition. The conditions and steps of the polycondensation reaction are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the pressure of the polycondensation reaction in the present invention is preferably 20 to 50Pa, more preferably 25 to 45Pa, and more preferably 30 to 40 Pa. The temperature of the polycondensation reaction is preferably 180-250 ℃, more preferably 190-240 ℃, more preferably 200-230 ℃, and more preferably 210-220 ℃. The time of the polycondensation reaction is preferably 2-12 h, more preferably 4-10 h, and more preferably 6-8 h.
The metal complex catalyst is added in the polycondensation reaction, wherein the polycondensation reaction can be started or in the process of the polycondensation reaction. The specific time for adding the metal complex catalyst is not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual production conditions, quality control and product requirements, and the adding time of the metal complex catalyst is preferably 0-3 hours from the beginning of the polycondensation reaction, namely 0-3 hours, also can be 0.5-2.5 hours, and also can be 1-2 hours.
The specific choice of the metal complex catalyst is not particularly limited in the present invention, and may be a conventional metal complex catalyst well known to those skilled in the art, and those skilled in the art may select and adjust the catalyst according to actual production conditions, quality control and product requirements, and the metal complex of the present invention may have a general formula of LnX3. The ligand of the metal complex catalyst preferably comprises one or more of trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropanesulfonic acid group, nonafluorobutanesulfonic acid group and trifluoromethanesulfonylimide group, and more preferably comprises trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropanesulfonic acid group, nonafluorobutanesulfonic acid group or trifluoromethanesulfonylimide group. The metal element of the metal complex of the present invention preferably includes one or more of rare earth element, tin, bismuth, zinc, copper, alkali metal and alkaline earth metal, and more preferably rare earth element, tin, bismuth, zinc, copper, alkali metal or alkaline earth metal.
The specific selection of the rare earth elements is not particularly limited, and the rare earth elements are commonly used rare earth elements well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the rare earth elements in the invention are preferably non-radiative rare earth elements, and specifically can be one or more of lanthanum La, cerium Ce, praseodymium Pr, europium Eu, neodymium Nd, samarium Sm, gadolinium Ga, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, yttrium Y and scandium Sc.
The amount of the metal complex catalyst used in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the ratio of the mole number of the metal complex catalyst in the present invention to the mole number of the 2, 5-furandicarboxylic acid is preferably 0.5 to 4%, more preferably 1 to 3.5%, still more preferably 1.5 to 3%, still more preferably 2 to 2%.
In order to further ensure the performance, integrity and refinement of the preparation process of the final product, the preparation method specifically comprises the following steps:
a melt polycondensation method is adopted to directly prepare a controllable novel furan all-biobased polyether ester copolymer with the esterification and etherification structure ratio of 10-40 percent through three steps of esterification, prepolymerization and polymerization of 2, 5-furandicarboxylic acid and dihydric alcohol (ethylene glycol). Under the action of a conventional esterification catalyst (PEF esterification catalyst), 2, 5-furandicarboxylic acid is directly esterified with bio-based diol to generate 2, 5-furandicarboxylic acid diol ester; then, the esterification product is not required to be separated, the reduced pressure distillation is continuously utilized for pre-polymerization, and excessive dihydric alcohol in the reaction system is removed; then, the catalyst LnX can be added in different time periods3And carrying out polycondensation reaction under the condition of low vacuum to prepare a high molecular weight polyether ester product.
The above preparation process of the present invention can be specifically represented by the reaction formula (2):
Figure BDA0001656316120000121
the steps of the invention provide a preparation method of a novel furan all-bio-polyether ester copolymer, and the structural chain segment of the novel all-bio-polyether ester prepared by the method mainly comprises a part of polyethylene glycol furandicarboxylate (PEF) and a part of glycol chain segment, wherein the glycol chain segment comprises diethylene glycol and triethylene glycol, and also comprises a part of tetraethylene glycol and/or pentaethylene glycol. The glycol chain segment in the prepared polyether ester structure accounts for 10-40% of the total mole percentage of the polymer, namely n/(n + m) is 0.1-0.4, n is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the invention, m is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the present invention, both m and n are preferably the number of moles.
The invention adopts the metal complex catalyst to catalyze the direct esterification polymerization of glycol and furandicarboxylic acid, and efficiently prepares the novel 100 percent bio-based furan polyether ester with high viscosity at lower temperature in shorter time, the reaction process is stable and easy to control, the color and luster of the product are better, and the prepared product has higher glycol chain segment with controllable content in the structure. The invention can also effectively regulate and control the proportion of the glycol chain segment in the polyether ester product by adjusting the feeding proportion of the dihydric alcohol and the furan dicarboxylic acid, and the conditions of esterification time, temperature, polycondensation time, temperature and the like in the reaction process. Furthermore, the invention particularly preferably selects the rare earth metal complex catalyst which is low in content or non-toxic, so that the prepared novel polymer material is more in line with the concept of green environmental protection and is suitable for the preparation method of large-scale industrial production.
The invention also provides a preparation method of the general polyether ester copolymer, which comprises the following steps:
1') under the conditions of protective atmosphere and esterification catalyst, 2, 5-furandicarboxylic acid and alcohol monomer are subjected to esterification reaction, and then to pre-polycondensation reaction and polycondensation reaction to obtain the polyether ester copolymer.
In the preparation method of the polyether ester copolymer, the selection, combination and preferable range of the polyether ester copolymer can correspond to the selection, combination and preferable range of the polyether ester copolymer, and thus, the detailed description is omitted.
The structure of the polyether ester copolymer is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the content of the mole number of the glycol segment in the polyether ester copolymer of the present invention in terms of the mole number of the polyether ester copolymer is preferably 0 to 100%, more preferably 10 to 90%, more preferably 20 to 80%, more preferably 30 to 70%, and more preferably 40 to 60%. The 2, 5-furandicarboxylic acid of the present invention preferably comprises a biobased 2, 5-furandicarboxylic acid.
The protective atmosphere is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and preferably comprises nitrogen and/or an inert gas, more preferably nitrogen or argon.
The esterification catalyst is not particularly limited in the present invention, and may be a conventional esterification catalyst for such compounds, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the esterification catalyst of the present invention preferably includes one or more of stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate and stannous hydroxide, and more preferably stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or stannous hydroxide. The amount of the esterification catalyst used in the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the ratio of the mole number of the esterification catalyst in the present invention to the mole number of the 2, 5-furandicarboxylic acid is preferably 0.5 to 4%, more preferably 1 to 3.5%, more preferably 1.5 to 3%, and still more preferably 2 to 2%.
The selection of the alcohol monomer is not particularly limited in the present invention, and may be a conventional alcohol monomer well known to those skilled in the art, and those skilled in the art can select and adjust the alcohol monomer according to actual production conditions, quality control and product requirements, and the alcohol monomer preferably includes glycol or a mixture of glycol and ethylene glycol. The glycol of the present invention preferably comprises one or more of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol, more preferably diethylene glycol or triethylene glycol.
In the present invention, when the alcohol monomer is glycol, n is 1 in the structure of formula (I) of the polyetherester copolymer; when the alcohol monomer is a mixture of glycol and ethylene glycol, n/(n + m) in the structure of the formula (I) of the polyether ester copolymer is less than 1. In the present invention, when the above-described preparation method is employed, the end product can be considered to be a non-all-bio polyether ester copolymer before the glycol cannot be bio-based (completely prepared from biological raw materials) due to the use of glycol.
The amount of the alcohol monomer is not particularly limited in the present invention, and may be any amount conventionally used for such reactions, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the molar ratio of the 2, 5-furandicarboxylic acid to the alcohol monomer in the present invention is preferably 1 (2-8), more preferably 1 (3-7), and more preferably 1 (4-6).
The esterification reaction conditions are not particularly limited, and can be selected and adjusted by the ordinary esterification reaction conditions well known by the technicians in the field according to the actual production conditions, quality control and product requirements, and the esterification reaction temperature is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The esterification reaction time is preferably 1-4 h, more preferably 1.5-3.5 h, and more preferably 2-3 h. The pressure of the esterification reaction in the invention may be normal pressure or micro-positive pressure, and is preferably 1 to 3atm (atmospheric pressure, which may be 0.1MPa), more preferably 1.2 to 2.8atm, and even more preferably 1.5 to 2.5 atm.
After the esterification reaction, the esterification product is directly subjected to the pre-polycondensation reaction without separation. The conditions and steps of the pre-polycondensation reaction are not particularly limited, and can be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the temperature of the pre-polycondensation reaction is preferably 170-210 ℃, more preferably 175-205 ℃, more preferably 180-200 ℃, and more preferably 185-195 ℃. The time of the pre-polycondensation reaction is preferably 10-60 min, more preferably 20-50 min, and more preferably 30-40 min.
The pre-polycondensation reaction is preferably a reduced pressure reaction, and the specific reaction mode can be a reduced pressure distillation reaction and can remove excessive dihydric alcohol in the system. The pressure of the pre-polycondensation reaction of the present invention is preferably a variable value, and the range of the pressure may be specifically reduced from the pressure of the esterification reaction to the pressure of the polycondensation reaction.
After the pre-polycondensation reaction, the invention finally carries out the polycondensation reaction under the low vacuum condition. The conditions and steps of the polycondensation reaction are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, quality control and product requirements, and the pressure of the polycondensation reaction in the present invention is preferably 20 to 50Pa, more preferably 25 to 45Pa, and more preferably 30 to 40 Pa. The temperature of the polycondensation reaction is preferably 180-250 ℃, more preferably 190-240 ℃, more preferably 200-230 ℃, and more preferably 210-220 ℃. The time of the polycondensation reaction is preferably 2-12 h, more preferably 4-10 h, and more preferably 6-8 h.
In order to further ensure the performance, integrity and refinement of the preparation process of the final product, the preparation method specifically comprises the following steps:
a melt polycondensation method is adopted to directly prepare the controllable novel furan polyether ester copolymer with the ratio of esterification and etherification structures of 0.1-100 percent through three steps of esterification, prepolymerization and polymerization of 2, 5-furan dicarboxylic acid and alcohol monomer. Under the action of a conventional esterification catalyst (PEF esterification catalyst), directly esterifying 2, 5-furandicarboxylic acid and an alcohol monomer to generate 2, 5-furandicarboxylic acid diol ester and 2, 5-furandicarboxylic acid diethylene glycol ester; then, the esterification product is not required to be separated, the reduced pressure distillation is continuously utilized for pre-polymerization, and excessive alcohol monomers in the reaction system are removed; then, the polycondensation reaction is carried out under the condition of low vacuum to prepare the high molecular weight polyether ester product.
The steps of the invention provide a preparation method of a novel furan polyether ester copolymer, and the structural chain segment of the novel all-biobased polyether ester prepared by the method mainly comprises a part of polyethylene glycol furan dicarboxylate (PEF) units and a part or all of glycol ester chain segments, wherein the glycol chain segments comprise diethylene glycol and triethylene glycol, and also comprise a part of tetraethylene glycol and/or pentaethylene glycol. The glycol chain segment in the prepared polyether ester structure accounts for 0.1-100% of the total mole percentage of the polymer, namely n/(n + m) can be less than or equal to 1, and n is preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the invention, m is preferably 0-200, more preferably 10-200, more preferably 30-180, more preferably 50-150, and more preferably 80-120. In the present invention, both m and n are preferably the number of moles.
The invention adopts the esterification catalyst to catalyze the direct esterification polymerization of the alcohol monomer and the furan dicarboxylic acid, and efficiently prepares the novel furan polyether ester copolymer with high viscosity at lower temperature and in shorter time, the reaction process is stable, the control is easy, the color and luster of the product are better, and the prepared product has higher glycol chain segment with controllable content in the structure. The invention can also effectively regulate and control the proportion of the glycol chain segment in the polyether ester product by adjusting the feeding proportion of the alcohol monomer and the furan dicarboxylic acid, and the conditions of esterification time, temperature, polycondensation time, temperature and the like in the reaction process.
The polyether ester copolymer is a furan full-bio-polyether ester copolymer with a novel structure, and the furan bio-polyether ester copolymer product provided by the invention has a high-content glycol chain segment, has good thermodynamic performance and has good color. The furan-based polyether ester copolymer provided by the invention can be copolymerized by common oligo-glycol, FDCA and ethylene glycol, and the product prepared by copolymerizing the oligo-glycol with the FDCA and the ethylene glycol loses the attribute of 100% biobased material by considering that the oligo-glycol (diethylene glycol, triethylene glycol and the like) is a non-biobased monomer. The invention utilizes the characteristic that the metal catalyst containing the strong electron-withdrawing ligand can catalyze etherification reaction at higher temperature, particularly under the catalytic action of the rare earth metal complex catalyst, adopts a simple synthesis method, utilizes FDCA and bio-based ethylene glycol to directly carry out polycondensation reaction, and efficiently prepares the furan full bio-based polyether ester copolymer with high viscosity and a novel structure at lower temperature in a shorter time, wherein the molecule of the furan full bio-based polyether ester copolymer contains a content-controllable oligoethylene glycol chain segment, and the reaction process is stable, easy to control and mild in condition, thereby being an economic and environment-friendly preparation method which is suitable for large-scale industrial production.
The furan all-bio-polyether ester copolymer with a novel structure and the preparation method thereof provided by the invention can obtain a novel all-bio-polymer material and can solve the problems of operation, additional cost and the like caused by adding oligoethylene glycol in the preparation process. The furan bio-based polyether ester product with the novel structure promotes and realizes the development and utilization of furan renewable resources and the preparation of environment-friendly novel bio-based polyester, gradually gets rid of the dependence on petroleum resources, solves the problems of resource shortage, environmental pollution and the like in the polymer industry in China, and has important promotion and application value for realizing the sustainable development of the polymer material industry in China.
Experimental results show that the glass transition temperature of the novel bio-polyether ester prepared by the invention can be controlled at 30-85 ℃, the 5% thermal degradation temperature is 280-400, the tensile strength is 10-85 MPa, and the elongation at break is 4-400%.
For further understanding of the present invention, the present invention provides a furan-based polyetherester copolymer and a method for preparing the same, which is illustrated below with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 87 mg (accounting for 0.15 percent of the total amount of dicarboxylic acid monomers) of samarium trifluoromethanesulfonate into the reactor, and esterifying the mixture for 105 minutes at 180 ℃ in a nitrogen atmosphere to obtain an esterified product; after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain yellow poly (ethylene glycol 2, 5-furandicarboxylate-co-2, 5-furandicarboxylate triethylene glycol), which is marked as PPEGF.
The furan-based polyether ester copolymer prepared in the embodiment 1 of the invention is characterized, and the PPEGF copolyester is subjected to nuclear magnetic resonance analysis by taking deuterated trifluoroacetic acid as a solvent.
Referring to fig. 1, fig. 1 is a nuclear magnetic resonance hydrogen spectrum of the furan-based polyether ester copolyester prepared in example 1 of the present invention. As can be seen from fig. 1, the PPEGF copolyester has a structure shown in formula (II), wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
Figure BDA0001656316120000171
The PPEGF copolyester prepared in the above way is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.91 dL/g.
The furan-based polyether ester copolymer prepared in the embodiment of the invention is subjected to performance detection.
Referring to table 1, table 1 shows the properties of furan-based polyetheresters of typical structure prepared in the examples of the present invention.
TABLE 1
Figure BDA0001656316120000172
Example 2
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 1.01 dL/g.
Example 3
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 85 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of neodymium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterified product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.83 dL/g.
Example 4
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 85 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of lanthanum trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterified product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.96 dL/g.
Example 5
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 85 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of cerium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterified product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.69 dL/g.
Example 6
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 85 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of thulium trifluoromethanesulfonate into the reactor, and esterifying the mixture for 105 minutes at 180 ℃ in a nitrogen atmosphere to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.94 dL/g.
Example 7
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium pentafluoroethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the dark brown PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 1.00 dL/g.
Example 8
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of heptafluoro-isopropyl scandium into the reactor, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the dark brown PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.95 dL/g.
Example 9
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of trifluoromethanesulfonylimino scandium, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the dark brown PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 1.01 dL/g.
Example 10
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 92 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of bismuth trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterified product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the dark brown PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 1.05 dL/g.
Example 11
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 58 mg (accounting for 0.12 percent of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 1: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.96 dL/g.
Example 12
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 12.0 g (0.2mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 2 hours at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 65: the glycol segment in the structure includes diethylene glycol and triethylene glycol 35.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.92 dL/g.
Example 13
Respectively adding 15.6 g (1mol) of 2, 5-furandicarboxylic acid and 15.0 g (0.25mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under a nitrogen atmosphere to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 60: the glycol segment in the structure includes diethylene glycol and triethylene glycol 40.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.82 dL/g.
Example 14
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 24.0 g (0.4mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 45: the glycol segment in the structure comprises diethylene glycol and triethylene glycol 55.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.98 dL/g.
Example 15
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 30.0 g (0.5mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 43: the glycol segments in the structure include diethylene glycol and triethylene glycol 57.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.71 dL/g.
Example 16
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 170 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 60: the glycol segment in the structure includes diethylene glycol and triethylene glycol 40.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.90 dL/g.
Example 17
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 190 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 44: and 56, the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.98 dL/g.
Example 18
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 200 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 37: and 63, the glycol segment in the structure comprises diethylene glycol, triethylene glycol and tetraethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.81 dL/g.
Example 19
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 210 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 30: the glycol segment in the structure comprises diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.65 dL/g.
Example 20
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 60 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 68: 32, the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.81 dL/g.
Example 21
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 90 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 55: the glycol segment in the structure comprises diethylene glycol and triethylene glycol 45.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.86 dL/g.
Example 22
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 150 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 45: the glycol segment in the structure comprises diethylene glycol and triethylene glycol 55.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.75 dL/g.
Example 23
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 210 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 4 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the PPEGF copolyester structure is 42: the glycol segments in the structure include diethylene glycol and triethylene glycol 58.
The intrinsic viscosity of the PPEGF copolyester is measured by dissolving the PPEGF copolyester in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃, and the intrinsic viscosity is 0.57 dL/g.
Example 24
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 180 ℃, and carrying out melt polycondensation reaction for 4 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the PPEGF copolyester structure is 42: the glycol segments in the structure include diethylene glycol and triethylene glycol 58.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.45 dL/g.
Example 25
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 190 ℃, and carrying out melt polycondensation reaction for 4 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 44: and 56, the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.50 dL/g.
Example 26
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 200 ℃, and carrying out melt polycondensation reaction for 4 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 47: the glycol segment in the structure comprises diethylene glycol and triethylene glycol 53.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.85 dL/g.
Example 27
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 220 ℃, and carrying out melt polycondensation reaction for 4 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 56: the glycol segments in the structure include diethylene glycol and triethylene glycol 44.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 1.08 dL/g.
Example 28
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, and carrying out melt polycondensation reaction for 1 hour when the pressure is reduced to 20-50 Pa within 25 minutes to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 46: the glycol segments in the structure include diethylene glycol and triethylene glycol 54.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.65 dL/g.
Example 29
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, and carrying out melt polycondensation reaction for 2 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 46: the glycol segments in the structure include diethylene glycol and triethylene glycol 54.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.70 dL/g.
Example 30
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, increasing the pressure to 20-50 Pa within 25 minutes, and carrying out melt polycondensation for 2.5 hours to obtain the yellow PPEGF copolymer.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 49: the glycol segment in the structure includes diethylene glycol and triethylene glycol 51.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane with the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.80 dL/g.
Example 31
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid and 18.0 g (0.3mol) of ethylene glycol into a reactor, adding 72 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of scandium trifluoromethanesulfonate, and esterifying for 105 minutes at 180 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, heating to 210 ℃, and carrying out melt polycondensation reaction for 3 hours to obtain the yellow PPEGF copolymer, wherein the pressure is increased to 20-50 Pa within 25 minutes.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 50: and 50, the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
The PPEGF copolyester is dissolved in a mixed solvent of phenol and tetrachloroethane at the mass ratio of 1:1 at 25 ℃ to measure the intrinsic viscosity, and the intrinsic viscosity is 0.87 dL/g.
Example 32
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid, 18.0 g (0.3mol) of ethylene glycol and 24 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of stannous oxalate into a reactor, and esterifying for 105 minutes at 210 ℃ in a nitrogen atmosphere to obtain an esterified product; and after the esterification reaction is finished, the pressure is increased to 20-50 Pa within 25 minutes at 210 ℃, the melt polycondensation reaction is carried out for 0.5 hour, 72 mg of scandium trifluoromethanesulfonate is added, and the polycondensation is continued for 3.5 hours, so that the yellow PPEGF copolymer is prepared.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the structure of the PPEGF copolyester is 78: the glycol segment in the structure comprises diethylene glycol and triethylene glycol 22.
Dissolving the PPEGF copolyester into a mixture of 1: the intrinsic viscosity of the mixture of phenol and tetrachloroethane of 1 was measured, and it was 0.70 dL/g.
Example 33
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid, 18.0 g (0.3mol) of ethylene glycol and 24 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of stannous oxalate into a reactor, and esterifying for 105 minutes at 210 ℃ in a nitrogen atmosphere to obtain an esterified product; and after the esterification reaction is finished, the pressure is increased to 20-50 Pa within 25 minutes at 210 ℃, the melt polycondensation reaction is carried out for 3 hours, 72 mg of scandium trifluoromethanesulfonate is added, and the polycondensation is continued for 1 hour, so that the yellow PPEGF copolymer is prepared.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of the ethylene glycol chain segment to the ethylene glycol chain segment in the PPEGF copolyester structure is 90: the glycol segment in the structure comprises diethylene glycol and triethylene glycol.
Dissolving the PPEGF copolyester into a mixture of 1: the intrinsic viscosity of the mixture of phenol and tetrachloroethane of 1 was measured, and it was 0.78 dL/g.
Example 34
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid, 6.0 g (0.1mol) of ethylene glycol and 10.6 g (0.1mol) of diethylene glycol into a reactor, adding 24 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of stannous oxalate, and esterifying for 105 minutes at 210 ℃ under the atmosphere of nitrogen to obtain an esterified product; and after the esterification reaction is finished, the pressure is reduced to 20-50 Pa within 25 minutes at 230 ℃, and the melt polycondensation reaction is carried out for 4 hours. Yellow PPEGF copolymer with structure containing diethylene glycol and ethylene glycol chain segments is prepared.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of ethylene glycol chain segments to diethylene glycol chain segments in the structure of the PPEGF copolyester is 1: 1.4.
dissolving the PPEGF copolyester into a mixture of 1:1 in the mixed solvent of phenol and tetrachloroethane, the intrinsic viscosity was measured and found to be 0.63 dL/g.
Example 35
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid, 6.0 g (0.1mol) of ethylene glycol and 15 g (0.1mol) of triethylene glycol into a reactor, adding 24 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of stannous oxalate, and esterifying for 105 minutes at 210 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, the pressure is reduced to 20-50 Pa within 25 minutes at 230 ℃, and the melt polycondensation reaction is carried out for 4 hours. Yellow PPEGF copolymer with structure containing triethylene glycol and ethylene glycol chain segments is prepared.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of ethylene glycol chain segments to triethylene glycol chain segments in the structure of the PPEGF copolyester is 1: 3.
dissolving the PPEGF copolyester into a mixture of 1: the intrinsic viscosity of the mixture of phenol and tetrachloroethane of 1 was measured, and it was 0.65 dL/g.
Example 36
Respectively adding 15.6 g (0.1mol) of 2, 5-furandicarboxylic acid, 10.6 g (0.1mol) of diethylene glycol and 15 g (0.1mol) of triethylene glycol into a reactor, adding 24 mg (accounting for 0.15% of the total amount of dicarboxylic acid monomers) of stannous oxalate, and esterifying for 105 minutes at 210 ℃ under the atmosphere of nitrogen to obtain an esterification product; and after the esterification reaction is finished, the pressure is reduced to 20-50 Pa within 25 minutes at 230 ℃, and the melt polycondensation reaction is carried out for 4 hours. Yellow PPEGF copolymer having a structure comprising triethylene glycol and diethylene glycol segments was prepared.
Performing nuclear magnetic resonance analysis on the PPEGF copolyester by using deuterated trifluoroacetic acid as a solvent, wherein the ratio of ethylene glycol chain segments to triethylene glycol chain segments in the structure of the PPEGF copolyester is 1: 2.
dissolving the PPEGF copolyester into a mixture of 1: the intrinsic viscosity of the mixture of phenol and tetrachloroethane of 1 was measured, and it was 0.60 dL/g.
While the present invention has been described in detail with respect to a furan bio-based polyether ester copolymer having a novel structure and a method for preparing the same, and while the principles and embodiments of the present invention have been illustrated herein using specific examples, the above description is only for the purpose of facilitating an understanding of the method and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (4)

1. A preparation method of a polyether ester copolymer is characterized by comprising the following steps:
1) under the conditions of protective atmosphere and organic metal salt catalyst, 2, 5-furandicarboxylic acid and ethylene glycol are subjected to esterification reaction, pre-polycondensation reaction and polycondensation reaction to obtain polyether ester copolymer;
in the polyether ester copolymer, the content of the mole number of the glycol chain segment in the polyether ester copolymer is 30-70%;
the organic group of the organic metal salt comprises one or more of trifluoromethanesulfonic acid group, pentafluoroethanesulfonic acid group, heptafluoroisopropane sulfonic acid group, nonafluorobutanesulfonic acid group and trifluoromethanesulfonylimide group;
the metal element of the organic metal salt comprises a rare earth element;
the molar ratio of the 2, 5-furandicarboxylic acid to the ethylene glycol is 1 (2-8);
the ratio of the mole number of the organic metal salt catalyst to the mole number of the 2, 5-furandicarboxylic acid is 0.5-4 per mill;
the temperature of the esterification reaction is 170-210 ℃; the esterification reaction time is 1-4 h;
the temperature of the polycondensation reaction is 180-250 ℃; the time of the polycondensation reaction is 2-12 h.
2. The method according to claim 1, wherein the pressure of the esterification reaction is 1 to 3 atm;
the pre-polycondensation reaction is a decompression reaction; the time of the pre-polycondensation reaction is 10-60 min; the temperature of the pre-polycondensation reaction is 170-210 ℃;
the pressure of the polycondensation reaction is 20-50 Pa.
3. A polyether ester copolymer prepared by the preparation method according to any one of claims 1 or 2, having a structure represented by formula (I);
Figure 981991DEST_PATH_IMAGE002
（I）；
wherein n is 10-200; m is 0 to 200;
p is selected from a plurality of 1, 2, 3 and 4;
in the polyether ester copolymer, n/(n + m) is 0.3-0.7.
4. The polyether ester copolymer according to claim 3, wherein the number average molecular weight of the polyether ester copolymer is 20000 to 70000.
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