CN115260505A - Tough furan dicarboxylic acid polyester and preparation method thereof - Google Patents
Tough furan dicarboxylic acid polyester and preparation method thereof Download PDFInfo
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
The invention discloses a tough furan dicarboxylic acid polyester and a preparation method thereof, relating to the technical field of polyester copolymerization modification, wherein the invention firstly utilizes flexible polyester with the average molecular mass of 1000-30000 g/mol to copolymerize with 2, 5-furan dicarboxylic acid glycol ester, the synthesized structure is shown as formula 1, and the preparation process comprises the following steps: mixing 2, 5-furan dicarboxylic acid glycol ester and flexible polyester, raising the temperature to 230-280 ℃, reducing the reaction pressure to 60-100Pa, and carrying out polycondensation reaction for 3-10 h to obtain the flexible furan dicarboxylic acid polyester. The prepared PEF modified material has unusual performances of tensile strength, young modulus and elongation at break, the tensile strength can be adjusted and controlled to be 38-75 MPa, the Young modulus can be adjusted and controlled to be 2680-3380 MPa, and the elongation at break can be adjusted and controlled to be 193-885%. The brittle-tough transition can be realized under the condition of low content of the flexible polyester, and the elongation at break is obviously improved.
Description
Technical Field
The invention relates to the technical field of polyester copolymerization modification, in particular to a tough furan dicarboxylic acid polyester and a preparation method thereof.
Background
Furan dicarboxylic acid based polyester represented by poly-2, 5-furan dicarboxylic acid ethylene (PEF) has higher tensile strength and Young modulus, and furan rings in a molecular structure endow the furan dicarboxylic acid based polyester with outstanding barrier property, so that the furan dicarboxylic acid based polyester has wide application prospect in the field of packaging materials, but the furan dicarboxylic acid based polyester has the defects of poor toughness, low tensile elongation at break, deep product color and the like, so that the industrial application of the furan dicarboxylic acid based polyester is restricted, and various attempts are made in the prior art for modifying the furan dicarboxylic acid based polyester for the development of the PEF.
At present, PEF is modified mainly in two categories, namely macromolecular blending modification and micromolecular copolymerization modification.
For the blending modification, some researchers have prepared PBAT/PEF blends of poly (butylene terephthalate-adipate) (PBAT) modified PEF by melt blending method, but the improvement of mechanical properties is not obvious (New Journal of Chemistry,2020,44 (7): 3112-3121.), and in patent application documents with patent publication numbers CN107964221B and CN104072954B, the utilization of auxiliaries is proposed to form PEF compounds with certain improved mechanical properties, but the improvement effect is still not ideal.
For copolymerization modification, it is currently widely believed that macromolecules are difficult to use for copolymerization modification of PEF due to reaction sites and the like, and small molecules are generally used for copolymerization modification, but one property is often sacrificed to improve another property. For example, sebacic acid is copolymerized with furandicarboxylic acid (FDCA) and Ethylene Glycol (EG), and although the elongation at break of the resulting copolymer can be increased from 3% of PEF to 1500% of the maximum value, the Young's modulus of the copolymer is decreased from 2080MPa of PEF to 30MPa of the minimum value (RSC adv.,2017, 23): 13798-13807.). Copolymerization of FDCA and EG with 2,2,4,4-tetramethyl-1, 3-cyclobutanediol improved the Young's modulus of the copolymer from 2800MPa for PEF to 3300MPa, but the elongation at break (4%) of the copolymer was not improved as compared to the elongation at break (5%) of PEF (Polymers, 2017,9 (9): 305-320.). By copolymerizing epsilon-caprolactone with FDCA and EG, the elongation at break is increased from 40% to 981% when the content of epsilon-caprolactone is increased from 30% to 40%, and the tensile strength is decreased from 82MPa to 51MPa (European Polymer Journal,2018, 109. The authors disclose in patent CN 108467479B that 2, 5-furandicarboxylic acid, dihydric alcohol and cyclic lactone are used as raw materials to prepare PEF-based copolyester with adjustable tensile strength and elongation at break, the molar ratio of FDCA to epsilon-caprolactone is 2. Chinese patent CN108659209A discloses a copolyester of 2, 5-furandicarboxylic acid or its diester, ethylene glycol or propylene glycol and C4-30 α, ω -glycol ester, the tensile elongation at break of the copolyester is significantly increased, but the tensile strength is reduced to different degrees (the reduction is 1-14%). Patents CN104072954B and CN107964221B disclose a compounding method for preparing a composite material by blending PEF and a polymer, and patents CN 108659209B, CN 114057998B, CN 111454439B, CN 111286012B, CN 109810248B, CN 109721716B, CN 110407991B, CN 109810248A, CN 109721716B, CN 104341585B and CN 108264634B disclose a preparation method and a molding processing technology for preparing a PEF polyester by copolymerizing PEF and a small molecular monomer.
It is obvious that the prior patents or published techniques, although proposing the method of modifying PEF, all adopt the modification method of blending modification, flexible monomer, rigid monomer and furandicarboxylic acid, glycol copolymerization. The blending modification method is simple and convenient, but the mechanical property is not obviously improved; the single flexible monomer modified PEF can improve the elongation at break of the polyester, but the Young modulus and the glass transition temperature of the material are obviously reduced; the single rigid monomer modified PEF can improve the tensile strength and Young modulus of the polymer, but the elongation at break is not obviously improved. Although the copolyester with excellent mechanical properties can be prepared by copolymerizing epsilon-caprolactone with FDCA and EG, the barrier property of the copolyester is reduced due to the high content of the required modifier, and the application requirement of a packaging material is still difficult to meet.
Disclosure of Invention
Aiming at the problems that the blending modification method in the prior art is simple and convenient, but the mechanical property of the blending material is not obviously improved, and the tensile strength, young modulus, elongation at break and glass transition temperature of the PEF-based polyester copolymerized and modified by the small molecular monomer still cannot meet the application requirements of a packaging material, and the like, the invention provides the tough furan dicarboxylic acid polyester and the preparation method thereof.
The technical scheme adopted by the invention is as follows:
a tough furandicarboxylic acid polyester comprising ethylene 2, 5-furandicarboxylic acid polyester segments and flexible polyester segments, having the formula 1:
wherein R is a flexible polyester chain segment, and m ranges from 2.5 to 680.
Preferably, the flexible polyester forming the flexible polyester chain segment R is one or more of poly (1, 4-cyclohexanedimethanol terephthalate), polybutylene terephthalate adipate and polycaprolactone.
Further, the preparation method of the flexible polyester chain segment R comprises the following steps: adding a monomer and a catalyst required for preparing R into a reactor, reacting for 2 hours under normal pressure at 160-180 ℃ under the protection of inert gas, raising the temperature to 220-250 ℃, reducing the pressure to 60-100Pa, and reacting for 0.5-4 hours to prepare R with different molecular weights.
More preferably, the raw material ratios required for preparing R are respectively as follows: (1) preparation of polybutylene terephthalate adipate: the method is characterized in that adipic acid, terephthalic acid and 1, 4-butanediol are taken as monomers, the molar ratio of the adipic acid to the terephthalic acid to the 1, 4-butanediol is 0.5: (2) Preparation of 1, 4-Cyclohexanedimethanol terephthalate: terephthalic acid and 1, 4-cyclohexanedimethanol are used as monomers, the molar ratio is 1; (3) preparation of polycaprolactone: the epsilon-caprolactone is taken as a monomer, and the dosage of the tetrabutyl titanate is 0.1wt% of the caprolactone.
Preferably, the content of the R in the flexible furan dicarboxylic acid polyester is 10-50 wt%.
Further, the content of the R in the flexible furan dicarboxylic acid polyester is 20-40 wt%.
Preferably, the average molecular mass of R is 1000 to 30000g/mol, and the average molecular mass of R is 3000 to 20000 g/mol.
The preparation method of the tough furan dicarboxylic acid polyester comprises the following steps: adding 2, 5-furandicarboxylic acid, ethylene glycol and dibutyltin oxide into a reactor, carrying out esterification reaction for 2-3 h at 160-230 ℃ under normal pressure under the protection of inert gas, then adding the prepared flexible polyester R with certain molecular mass, gradually raising the temperature to 230-280 ℃, gradually reducing the pressure to 60-100Pa, and carrying out polycondensation reaction for 2-8 h to prepare the tough furandicarboxylic acid block copolyester.
Preferably, the polycondensation reaction time is 3 to 6 hours
Preferably, in the preparation process of the 2, 5-furandicarboxylic acid glycol ester, the molar ratio of the ethylene glycol to the 2, 5-furandicarboxylic acid is 1.2 to 2, and the dibutyl tin oxide is 0.1 to 0.5wt% of the 2, 5-furandicarboxylic acid.
In summary, compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention firstly utilizes the flexible polyester with the average molecular mass of 1000-30000 g/mol to copolymerize with 2, 5-furandicarboxylic acid glycol ester to prepare the PEF modified material: the tensile strength, young modulus and elongation at break of the tough furan dicarboxylic acid polyester are all shown in a bad way, the tensile strength can be adjusted to 38-75 MPa, the Young modulus can be adjusted to 2680-3380 MPa, and the elongation at break can be adjusted to 193-885%;
2. according to the invention, by regulating the molecular structure and molecular weight of the flexible polyester and changing the proportion of the flexible polyester segment R to FDCA and EG, the block copolyester with different molecular chain structures and mechanical properties can be prepared, and the preparation method is convenient to adapt to different working scenes;
3. according to the invention, under the condition of low content of flexible polyester, the brittle-tough transition can be realized, the elongation at break is obviously improved, and the influence of oxygen barrier property caused by excessive use amount of aliphatic modifier is reduced;
4. according to the invention, the flexible polyester with different structures and different molecular masses is prepared, and then the flexible polyester is copolymerized with FDCA and EG, so that the structure of the PEF modified material is convenient to control;
5. the PEF modified material prepared by the invention has good heat resistance, and meets the requirements of various application fields on the material performance;
6. the method has the advantages of mature process, simple and convenient operation, stable product performance and low production cost, can meet the requirements of different application fields, is convenient for industrial production, and fills the blank of the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to various embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad invention, that is, the embodiments described are merely illustrative of some rather than all embodiments of the invention, and that modifications and variations can be made by persons skilled in the art in light of the above teachings without departing from the scope of the invention.
In the concrete examples of the invention, the raw materials are all obtained from the market, and in order to ensure the experimental precision, the temperature control error about the reaction temperature of each example and each comparative example is not more than 2 ℃, and the reaction pressure is not more than 10Pa when the reaction pressure fluctuates up and down.
Example 1
Preparation of flexible polyester polybutylene terephthalate with a certain molecular weight. The molar ratio of adipic acid to terephthalic acid to 1, 4-butanediol is 0.5. The effect of the polycondensation time on the average molecular weight of polybutylene terephthalate adipate is shown in Table 1.
TABLE 1 Effect of polycondensation time on the average molecular weight of polybutylene terephthalate adipate
Example 2
Preparation of a Flexible polyester Poly (1, 4-cyclohexanedimethylene terephthalate) having an average molecular weight of 9900 g/mol. The molar ratio of terephthalic acid to 1, 4-cyclohexanedimethanol is 1.
Example 3
Preparation of a Flexible polyester polycaprolactone having an average molecular weight of 1100 g/mol. The monomer is epsilon-caprolactone, the dosage of the catalyst tetrabutyl titanate is 0.1wt% of the caprolactone, ring opening reaction is carried out for 4h at 200 ℃, the polycondensation temperature is 260 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 2h.
Example 4
The copolyester was prepared using polybutylene terephthalate adipate with an average molecular weight of 6800 g/mol. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide serving as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate-adipate is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The resulting product had a glass transition temperature of 59.4 deg.C, a tensile strength of 75.28MPa, a Young's modulus of 3351MPa, and an elongation at break of 193%.
Example 5
The copolyester was prepared using polybutylene terephthalate adipate with an average molecular weight of 9950 g/mol. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate adipate is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 58.3 ℃, the tensile strength is 73.33MPa, the Young modulus is 3286MPa, and the elongation at break is 224%.
Example 6
The copolyester was prepared using polybutylene terephthalate adipate with an average molecular weight of 24700 g/mol. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide serving as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate-adipate is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 56.1 ℃, the tensile strength is 72.07MPa, the Young modulus is 3212MPa, and the elongation at break is 287%.
Example 7
Preparation of a copolyester containing 30% of polybutylene terephthalate adipate (average molecular weight 24700 g/mol). The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate adipate is 30 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 49.5 ℃, the tensile strength is 62.57MPa, the Young modulus is 3200MPa, and the elongation at break is 470%.
Example 8
Preparation of a copolyester containing 40% of polybutylene terephthalate adipate (average molecular weight 24700 g/mol). The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide serving as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate-adipate is 40 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 37.7 ℃, the tensile strength is 38.92MPa, the Young modulus is 2953MPa, and the elongation at break is 608%.
Example 9
The copolyester was prepared by polycondensation of polybutylene terephthalate adipate with an average molecular weight of 24700g/mol for 6h. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polybutylene terephthalate adipate is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 6 hours. The resulting product had a glass transition temperature of 47.8 deg.C, a tensile strength of 59.75MPa, a Young's modulus of 2964MPa, and an elongation at break of 415%.
Example 10
The copolyester was prepared using poly (1, 4-cyclohexanedimethanol terephthalate) having an average molecular weight of 9900 g/mol. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of poly (1, 4-cyclohexanedimethanol) ester is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 250 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 6 hours. The glass transition temperature of the obtained product is 64.8 ℃, the tensile strength is 76.42MPa, the Young modulus is 3383MPa, and the elongation at break is 218 percent.
Example 11
The copolyesters were prepared with polycaprolactone having an average molecular weight of 1100 g/mol. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide serving as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of polycaprolactone is 25 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 4 hours. The glass transition temperature of the obtained product is 52.8 ℃, the tensile strength is 58.42MPa, the Young modulus is 2683MPa, and the elongation at break is 317%.
Example 12
Meanwhile, poly terephthalic acid-1, 4-cyclohexyl dimethyl ester with the average molecular weight of 9900g/mol and polycaprolactone with the average molecular weight of 1100g/mol are adopted to prepare the copolyester. The molar ratio of 2, 5-furandicarboxylic acid to ethylene glycol is 1.8, the mass fraction of dibutyltin oxide serving as a catalyst is 0.25 percent of that of 2, 5-furandicarboxylic acid, the mass fraction of poly (1, 4-cyclohexanedimethylene terephthalate) is 20 percent, the mass fraction of polycaprolactone is 20 percent, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 250 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 48 ℃, the tensile strength is 49.38MPa, the Young modulus is 2960MPa, and the elongation at break is 885%.
Comparative example 1
The molar ratio of the 2, 5-furandicarboxylic acid to the ethylene glycol is 1.8, the mass fraction of the dibutyltin oxide serving as a catalyst is 0.25 percent of that of the 2, 5-furandicarboxylic acid, the esterification temperature is 200 ℃, the esterification time is 4 hours, the polycondensation temperature is 230 ℃, the polycondensation pressure is 100Pa, and the polycondensation time is 8 hours. The glass transition temperature of the obtained product is 87.4 ℃, the tensile strength is 40.34MPa, the Young modulus is 3937MPa, and the elongation at break is 10%.
From the results of the above examples 1-12 and comparative example 1, it can be seen that the flexible furan dicarboxylic acid polyester and the preparation method thereof provided by the present invention can prepare the block copolyester with different molecular chain structures and mechanical properties by adjusting the molecular weight and molecular structure of the flexible polyester, changing the ratio of the flexible polyester to FDCA and EG, and controlling the copolymerization process. The brittle-tough transition can be realized under the condition of low content of the flexible polyester, and the elongation at break is obviously improved.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which all belong to the protection scope of the present application.
Claims (10)
1. The tough furan dicarboxylic acid polyester is characterized by comprising a 2, 5-furan dicarboxylic acid ethylene glycol polyester segment and a flexible polyester segment, and the structural formula of the tough furan dicarboxylic acid polyester segment is as shown in a formula 1:
wherein R is a flexible polyester segment.
2. A tough furan dicarboxylic acid polyester according to claim 1, wherein: the flexible polyester forming the flexible polyester chain segment R is one or more of poly (1, 4-cyclohexanedimethanol terephthalate), polybutylene terephthalate adipate and polycaprolactone.
3. A tough furan dicarboxylic acid polyester according to claim 2, wherein the flexible polyester segment R is prepared by: adding a monomer and a catalyst required for preparing R into a reactor, reacting for 2h under the normal pressure at 160-180 ℃ under the protection of inert gas, raising the temperature to 220-250 ℃, reducing the pressure to 60-100Pa, and reacting for 0.5-4h to prepare R with different molecular weights.
4. The tough furan dicarboxylic acid polyester of claim 3, wherein the raw materials for preparing R are in the following proportions: (1) preparation of polybutylene terephthalate adipate: the method is characterized in that adipic acid, terephthalic acid and 1, 4-butanediol are taken as monomers, the molar ratio of the adipic acid to the terephthalic acid to the 1, 4-butanediol is 0.5: (2) Preparation of 1, 4-Cyclohexanedimethanol terephthalate: terephthalic acid and 1, 4-cyclohexanedimethanol are used as monomers, the molar ratio is 1; (3) preparation of polycaprolactone: the epsilon-caprolactone is taken as a monomer, and the dosage of the tetrabutyl titanate is 0.1wt% of the caprolactone.
5. A tough furan dicarboxylic acid polyester according to claim 1, wherein: the content of the R in the tough furan dicarboxylic acid polyester is 10-50 wt%.
6. The flexible furan dicarboxylic acid polyester of claim 5, wherein: the content of the R in the tough furan dicarboxylic acid polyester is 20-40 wt%.
7. The flexible furan dicarboxylic acid polyester of claim 1, wherein: the average molecular mass of R is 1000-30000 g/mol.
8. A process for the preparation of a tough furan dicarboxylic acid polyester according to any of claims 1 to 7, which comprises: adding 2, 5-furandicarboxylic acid, ethylene glycol and dibutyltin oxide into a reactor, carrying out esterification reaction for 2-3 h at 160-230 ℃ under normal pressure under the protection of inert gas, then adding the prepared flexible polyester R with certain molecular mass, gradually raising the temperature to 230-280 ℃, gradually reducing the pressure to 60-100Pa, and carrying out polycondensation reaction for 2-8 h to prepare the tough furandicarboxylic acid block copolyester.
9. The process for preparing a flexible furan dicarboxylic acid polyester of claim 8, wherein: the polycondensation reaction time is 3-6 h.
10. The process for preparing a flexible furan dicarboxylic acid polyester of claim 8, wherein: in the preparation process of the 2, 5-furandicarboxylic acid glycol ester, the molar ratio of the ethylene glycol to the 2, 5-furandicarboxylic acid is 1.2-2, and the dibutyl tin oxide accounts for 0.1-0.5 wt% of the 2, 5-furandicarboxylic acid.
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| CN115819744A (en) * | 2022-11-23 | 2023-03-21 | 河南省生物基材料产业研究院有限公司 | Synthetic method of toughness-increasing bio-based polyethylene glycol furanoate |
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