CN111454439A - Preparation method of 2, 5-furandicarboxylic acid based block copolyester - Google Patents
Preparation method of 2, 5-furandicarboxylic acid based block copolyester Download PDFInfo
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- CN111454439A CN111454439A CN202010181967.XA CN202010181967A CN111454439A CN 111454439 A CN111454439 A CN 111454439A CN 202010181967 A CN202010181967 A CN 202010181967A CN 111454439 A CN111454439 A CN 111454439A
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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 preparation method of 2, 5-furandicarboxylic acid-based block copolyester, which relates to the technical field of polyester preparation and comprises the following preparation steps: 1) mixing 2, 5-furandicarboxylic acid and/or ester thereof, dihydric alcohol, a catalyst and a heat stabilizer for esterification reaction to obtain an esterified substance A; 2) mixing 2, 5-furandicarboxylic acid and dihalogenated sulfoxide for reaction to obtain a furandicarboxylic acid halide; 3) performing esterification reaction on a furan dicarboxylic acid halide, a bio-based rigid cyclic diol, a catalyst and a heat stabilizer to obtain an esterified substance B; 4) carrying out pre-polycondensation reaction on the esterified substance B to obtain a prepolymer; 5) mixing and polycondensing the prepolymer and the esterified substance A prepared in the step 1) to obtain the 2, 5-furan diformyl block copolyester. The method is simple and feasible, is suitable for industrial production, has good product toughness, good hue and excellent thermodynamic property, and can be widely applied to the fields of packaging, fibers and the like.
Description
Technical Field
The invention relates to the technical field of polyester preparation, in particular to a preparation method of 2, 5-furan diformyl block copolyester.
Background
The bio-based polymer materials mainly focus on polylactic acid (P L A), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), butylene adipate, butylene terephthalate (PBAT) and polybutylene succinate (PBS), and the bio-based polymer materials are mainly characterized in that the structure of the bio-based polymer materials is lack of a rigid aromatic ring structure, and the mechanical properties (such as strength, modulus and the like) and heat resistance (such as heat distortion temperature) of the bio-based polymer materials are obviously lower than those of petroleum-based polymer materials containing benzene rings, such as polyethylene terephthalate (PET), Polycarbonate (PC), aromatic nylon (PA) and the like, so that the application range of the bio-based polymer materials is severely limited.
The emergence of 2, 5-furandicarboxylic acid as a bio-based provides a new idea for solving the limitation, and 2, 5-furandicarboxylic acid (FDCA) has a rigid cyclic structure similar to that of terephthalic acid and is a bio-based monomer which is expected to be used as a substitute for petroleum-based terephthalic acid in the future. The bio-based aromatic polyester-polyethylene furan dicarboxylate (PEF) can be obtained by polycondensation of bio-based 2, 5-furan dicarboxylate as a monomer and dihydric alcohol such as glycol. Because the structural rigidity of furan rings is stronger than that of benzene rings, the rigidity of PEF molecular chain structures is stronger than that of PET, and the symmetry of PEF molecular chains is lower than that of PET, the crystallinity of PEF is poorer than that of PET, so that the PEF material has better mechanical properties than that of PET and has better transparency. Due to the aromaticity and electron conjugation effect of the furan ring structure, the glass transition temperature and the heat distortion temperature of PEF are higher than those of conventional PET, and thus the heat resistance is also more excellent. Compared with a benzene ring in PET, furan rings in the PEF molecular chains are in a coplanar structure, so that the PEF molecular chains are stacked more tightly and regularly, and according to the theory of free volume of macromolecules, gas small molecules are more difficult to pass through the PEF material, so that the PEF material has excellent gas barrier property. The PEF material has excellent heat resistance, good mechanical property and excellent gas barrier property, and can be widely applied to beverage packaging materials.
However, the elongation at break of the PEF obtained by the current synthesis process is only about 3%, and the PEF belongs to a typical brittle material. These factors severely limit the use of PEF in the plastic packaging industry. Therefore, the PEF must be toughened and modified to have certain use value. At present, the toughening modification of the PEF mainly focuses on introducing dibasic acid or diol monomers containing flexible chain segments or symmetrical rigid structures for copolymerization modification, for example, a biodegradable polyester and a preparation method thereof disclosed in the patent with the publication number of CN 103570925A. Copolymerization with dibasic acids, however, results in a significant reduction in furan ring content, resulting in a significant reduction in gas barrier properties, and thus copolymerization with dibasic acids is not a good option. In addition, the introduction of the soft segment can obviously reduce the tensile modulus and strength of the PEF while improving the toughness of the PEF, and the crystallization property and the gas barrier property of the formed random copolymer are greatly changed. Therefore, the current modification method still has certain defects, and the original thermodynamic properties of the PEF material can not be maintained while toughening is achieved.
Disclosure of Invention
The invention provides a preparation method of 2, 5-furan diformyl block copolyester with excellent performances, aiming at overcoming the problems that the PEF obtained by the existing synthesis process is brittle, and the original performances of the PEF copolyester obtained by introducing dibasic acid or diol monomer containing a flexible chain segment or a symmetrical rigid structure for copolymerization modification are reduced to different degrees.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of 2, 5-furandicarboxylic acid based block copolyester comprises the following preparation steps:
1) mixing 2, 5-furandicarboxylic acid and/or ester thereof, dihydric alcohol, a catalyst and a heat stabilizer for esterification reaction to prepare an esterified substance A;
2) mixing 2, 5-furandicarboxylic acid and dihalogenated sulfoxide for reaction to prepare a furandicarboxylic acid halide;
3) placing a furan dicarboxylic acid halide, a bio-based rigid cyclic diol, a catalyst and a heat stabilizer in a reaction kettle, uniformly stirring, and then carrying out an esterification reaction in a protective gas atmosphere to prepare an esterified substance B;
4) carrying out pre-polycondensation reaction on the esterified substance B to prepare a prepolymer;
5) mixing and polycondensing the prepolymer and the esterified substance A prepared in the step 1) to prepare the 2, 5-furan diformyl block copolyester.
According to the invention, firstly furan dicarboxylic acid and/or ester thereof and a dihydric alcohol monomer are prepared into an esterified substance A, then a halogenated furan dicarboxylic acid and a bio-based rigid cyclic dihydric alcohol are esterified and polycondensed to obtain an oligomer, because the reactivity of the bio-based rigid cyclic dihydric alcohol is poor, the halogenated furan dicarboxylic acid and the bio-based rigid cyclic dihydric alcohol are selected to carry out esterification and polycondensation reaction to obtain the oligomer, when the esterified substance A and the oligomer are mixed and polycondensed, the transesterification reactivity of the esterified substance A is higher than that of the oligomer B, so that the polycondensation reaction is mainly carried out between the esterified substances A to obtain another oligomer in the polycondensation stage, then the oligomer obtained by the polycondensation of the esterified substance A and the oligomer obtained in the step 4) carry out the transesterification reaction, and finally the 2, 5-furan dicarboxylic acid group block copolyester is synthesized. Different from random copolymerization, the preparation method of the invention not only can toughen the PEF polyester, but also can not cause too large changes to the chemical structure and chain segment conformation of the polyester, thus having no adverse effect on the thermodynamic property, the crystallization property and the gas barrier property of the PEF polyester.
Preferably, the esterification reaction temperature in the step 1) is 190-200 ℃.
Preferably, the sulfoxide dihalide in the step 2) comprises one or two of thionyl chloride and dibromosulfoxide; the molar ratio of the 2, 5-furandicarboxylic acid to the dihalogenated sulfoxide is 1: 1-1.2.
In the invention, when preparing the furan dicarboxylic acid halide, the proportion between the 2, 5-furan dicarboxylic acid and the dihalogenated sulfoxide needs to be strictly limited, and when the proportion is lower than the limited range, the side products are increased to influence the color phase of the polymer; when the ratio is higher than the limited range, the reaction is incomplete, the block ratio is reduced, and the toughening effect is poor.
Preferably, the reaction conditions in step 2) are 60-80 ℃ and 1-2h of heat preservation.
Preferably, the bio-based rigid cyclic diol in step 3) comprises one or both of 2, 5-furandimethanol, tetrahydrofuran dimethanol; the molar ratio of the furandicarboxylic acid halide to the bio-based rigid cyclic diol is 1: 1.2-1.6.
When the ratio of the furandicarboxylic acid halide to the bio-based rigid cyclic diol is lower than a limited range, incomplete esterification is easily caused, the block ratio is reduced during polycondensation, and the toughening effect is poor; when the ratio is higher than the above range, the amount of by-products increases, which affects the hue of the polymer.
Preferably, the catalyst in step 1) and step 3) comprises one or more of n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silica/titanium dioxide complex, a silica/titanium dioxide/nitrogen-containing compound complex and a silica/phosphorus-containing compound complex; the heat stabilizer comprises one or more of 1010, 1076, 425, 330, 1178, 618, 626, 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl diphosphite, pentaerythritol ditridecyl phosphite, pentaerythritol tetrapentaphenyl tridecyl tetraphosphite, phosphoric acid, phosphorous acid, polyphosphoric acid, and triethyl phosphonoacetate.
Preferably, the components in step 3) are mixed and then stirred for 1-2h at normal temperature, and then the temperature is raised to 160 ℃ within 1-1.5h for esterification reaction.
Preferably, the precondensation in step 4) is carried out at 200 ℃ and 210 ℃ for 0.5-1h at 1-200 Pa.
According to the invention, because the furan dicarboxylic acid halide is used as the monomer, the oligomer can be prepared under mild reaction conditions in the steps 3) and 4), and the problems that the monomer is decomposed under severe conditions, so that dark impurities are generated and the hue of the polyester is influenced are successfully solved.
Preferably, the molar ratio of the prepolymer to the ester in the step 5) is 1: 1.6-2.5.
Since the reactivity of the prepolymer is lower than that of the ester A, it is necessary to ensure that the oligomer is in excess and to promote the incorporation of the oligomer blocks into the polyester backbone. If the oligomer charge is too high, the unreacted oligomer is encapsulated by the polyester and is difficult to remove, and if the residual amount of the oligomer is too high, the thermodynamic properties of the polyester are affected.
Preferably, the polycondensation of step 5) is first reacted at 220-230 ℃ and-0.05-0.1 MPa for 0.5-1.5h, and then the temperature is raised to 240-250 ℃ and reacted at-100-200 Pa for 2-4 h.
The polycondensation is firstly carried out at 220-230 ℃ and-0.05-0.1 MPa for 0.5-1.5h, so that the ester A is firstly formed into an oligomer under the low vacuum condition, and the unreacted ester monomer can be removed under the low temperature and low vacuum condition. Then the low polymer obtained by pre-polycondensation of the esterified substance A under the conditions of high temperature of 240-250 ℃ and-100 to-200 Pa and high vacuum is subjected to ester exchange reaction with the low polymer obtained in the step 4) for polycondensation, and finally the 2, 5-furan diformyl block copolyester is obtained.
Therefore, the invention has the following beneficial effects: the preparation method is simple and feasible, is suitable for industrial production, and the prepared 2, 5-furandicarboxylic acid based block copolyester has good toughness, good hue, excellent thermodynamic property, high crystallinity and gas barrier property, and can be widely applied to the fields of packaging, fibers and the like.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: a preparation method of 2, 5-furandicarboxylic acid based block copolyester comprises the following preparation steps:
1) mixing 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of catalyst and 0.1g of stabilizer, and carrying out esterification reaction at 195 ℃ to prepare an esterified substance A;
2) mixing 160g of 2, 5-furandicarboxylic acid and 146g of thionyl chloride, and reacting for 2 hours at the temperature of 60 ℃ to prepare a furandicarboxylic acid halide;
3) placing 195g of furan dicarboxylic acid halide, 161g of tetrahydrofuran dimethanol, 0.1g of isopropyl titanate and 0.1g of heat stabilizer 425 in a reaction kettle, stirring for 1 hour at normal temperature, uniformly stirring, then heating to 140 ℃ within 1 hour, and carrying out esterification reaction under the atmosphere of protective gas to prepare an esterified substance B;
4) preserving the temperature of the esterified substance B at 200 ℃ for 1pa for 1h to carry out pre-polycondensation reaction to prepare a prepolymer;
5) mixing the prepolymer with the esterified substance A prepared in the step 1) in a molar ratio of 1:1.6, reacting for 1.5h at 220 ℃ and-0.05 MPa, then raising the temperature to 240 ℃ and reacting for 4h at-100 Pa to prepare the 2, 5-furandicarboxylic acid group block copolyester.
Example 2: a preparation method of 2, 5-furandicarboxylic acid based block copolyester comprises the following preparation steps:
1) mixing 118g of dimethyl 2, 5-furandicarboxylate, 64g of ethylene glycol, 0.1g of catalyst and 0.1g of stabilizer, and carrying out esterification reaction at 190 ℃ to prepare an esterified substance A;
2) mixing 2, 5-furandicarboxylic acid 200g and dibromosulfoxide 320g, and reacting at 80 ℃ for 1h to prepare a furandicarboxylic acid halide;
3) placing 430g of furandicarboxylic acid halide, 275g of tetrahydrofuran dimethanol, 0.1g of stannous octoate and 0.1g of triethyl phosphite in a reaction kettle, stirring for 2 hours at normal temperature, uniformly stirring, then heating to 160 ℃ within 1.5 hours, and carrying out esterification reaction in a protective gas atmosphere to prepare an esterified substance B;
4) keeping the temperature of the esterified substance B at 210 ℃ and 200pa for 0.5h for pre-polycondensation reaction to prepare a prepolymer;
5) mixing the prepolymer with the esterified substance A prepared in the step 1) in a molar ratio of 1:2, reacting for 0.5h at 230 ℃ and-0.1 MPa, then raising the temperature to 250 ℃ and reacting for 2h at-200 Pa to prepare the 2, 5-furandicarboxylic acid group block copolyester.
Example 3: a preparation method of 2, 5-furandicarboxylic acid based block copolyester comprises the following preparation steps:
1) mixing 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of catalyst and 0.1g of stabilizer, and carrying out esterification reaction at 200 ℃ to prepare an esterified substance A;
2) mixing 2, 5-furandicarboxylic acid 250g and thionyl chloride 229g, and reacting at 70 ℃ for 1.5h under heat preservation to prepare a furandicarboxylic acid halide;
3) placing 306g of furan dicarboxylic acid halide, 337g of 2, 5-furandimethanol, 0.1g of magnesium acetate and 0.1g of bis-phenyl tridecyl phosphite in a reaction kettle, stirring for 1.5h at normal temperature, uniformly stirring, subsequently heating to 150 ℃ within 1.3h, and carrying out esterification reaction in a protective gas atmosphere to prepare an esterified substance B;
4) keeping the temperature of the esterified substance B at 205 ℃ for 0.7h at 100pa for pre-polycondensation reaction to prepare a prepolymer;
5) mixing the prepolymer with the esterified substance A prepared in the step 1) in a molar ratio of 1:2.5, reacting for 1h at 225 ℃ and-0.07 MPa, then raising the temperature to 245 ℃, and reacting for 3h at-150 Pa to prepare the 2, 5-furandicarboxylic acid group block copolyester.
Comparative example 1: preparation of polyethylene furandicarboxylate:
1) mixing 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of catalyst and 0.1g of stabilizer, and carrying out esterification reaction at 195 ℃ to prepare an esterified substance A;
2) reacting the esterified substance prepared in the step 1) for 1h at 225 ℃ and-0.07 MPa, then raising the temperature to 245 ℃ and reacting for 3h at-150 Pa to prepare the polyethylene glycol furandicarboxylate.
Comparative example 2: the difference from example 1 is that 160g of 2, 5-furandicarboxylic acid and 157g of thionyl chloride were mixed and reacted in the step 2) to obtain a halogenated furandicarboxylic acid.
Comparative example 3: the difference from example 1 is that 160g of 2, 5-furandicarboxylic acid and 109g of thionyl chloride were mixed and reacted in the step 2) to obtain a halogenated furandicarboxylic acid.
Comparative example 4: the difference from example 1 is that 195g of furandicarboxylic acid halide and 190g of tetrahydrofuran dimethanol were used in the preparation of ester B.
Comparative example 5: the difference from example 1 is that 195g of furandicarboxylic acid halide and 360g of tetrahydrofuran dimethanol were used in the preparation of ester B.
The thermal properties of the polyesters prepared in the examples and comparative examples were characterized and the results are shown in the following table.
Wherein the glass transition temperature was measured using a TA DSC 2920 at a scanning rate of 20 ℃/min.
The heat distortion temperature test is that a sample strip of 10 × 15 × 120mm is prepared from polyester, the sample strip is placed on a heat distortion instrument and heated at the speed of 2 ℃/min under the load of 0.45MPa, and the temperature when the sample strip generates the deformation of 0.254mm is the heat distortion temperature.
As can be seen from the above data, the 2, 5-furandicarboxylic acid based block copolyesters prepared in examples 1-3 have excellent toughness, thermal properties, and hue, and compared with the pure polyethylene furandicarboxylic acid glycol ester of comparative example 1, the elongation at break in the examples is greatly increased, and further increased on the basis of the original thermal properties, and have better hue. Comparative example 2 excessive thionyl chloride was generated to prepare a furandicarboxylic acid halide in step 2), and by-products were increased, resulting in poor color compared to examples. Comparative example 3 in step 2) preparation of furandicarboxylic acid halide thionyl chloride is too little, reaction is incomplete, resulting in a reduction of block ratio, thus toughening effect is greatly reduced compared to the examples. Comparative example 4 in the preparation of the ester B, the amount of the furandicarboxylic acid halide was too large, resulting in deterioration of hue. Comparative example 5 furan dicarboxylic acid halide is too little when preparing the ester B, resulting in a reduced block ratio during final polycondensation and a greatly reduced toughening effect.
Claims (10)
1. The preparation method of the 2, 5-furandicarboxylic acid based block copolyester is characterized by comprising the following preparation steps:
1) mixing 2, 5-furandicarboxylic acid and/or ester thereof, dihydric alcohol, a catalyst and a heat stabilizer for esterification reaction to prepare an esterified substance A;
2) mixing 2, 5-furandicarboxylic acid and dihalogenated sulfoxide for reaction to prepare a furandicarboxylic acid halide;
3) placing a furan dicarboxylic acid halide, a bio-based rigid cyclic diol, a catalyst and a heat stabilizer in a reaction kettle, uniformly stirring, and then carrying out an esterification reaction in a protective gas atmosphere to prepare an esterified substance B;
4) carrying out pre-polycondensation reaction on the esterified substance B to prepare a prepolymer;
5) mixing and polycondensing the prepolymer and the esterified substance A prepared in the step 1) to prepare the 2, 5-furan diformyl block copolyester.
2. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to claim 1, wherein the esterification reaction temperature in step 1) is 190-200 ℃.
3. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to claim 1, wherein the sulfoxide dihalide in step 2) comprises one or two of thionyl chloride and dibromosulfoxide; the molar ratio of the 2, 5-furandicarboxylic acid to the dihalogenated sulfoxide is 1: 1-1.2.
4. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to claim 1, wherein the reaction condition in step 2) is a temperature of 60-80 ℃ for 1-2 h.
5. The method for preparing 2, 5-furandicarboxylic acid based block copolyester according to claim 1, wherein the bio-based rigid cyclic diol in step 3) comprises one or two of 2, 5-furandimethanol and tetrahydrofuran dimethanol; the molar ratio of the furandicarboxylic acid halide to the bio-based rigid cyclic diol is 1: 1.2-1.6.
6. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to any one of claims 1 to 5, wherein the catalyst in step 1) and step 3) comprises one or more of n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silica/titanium dioxide composite, a silica/titanium dioxide/nitrogen-containing compound composite, and a silica/phosphorus-containing compound composite; the heat stabilizer comprises one or more of 1010, 1076, 425, 330, 1178, 618, 626, 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl diphosphite, pentaerythritol ditridecyl phosphite, pentaerythritol tetrapentaphenyl tridecyl tetraphosphite, phosphoric acid, phosphorous acid, polyphosphoric acid, and triethyl phosphonoacetate.
7. The method for preparing 2, 5-furandicarboxylic acid based block copolyester according to any one of claims 1 to 5, wherein the components in step 3) are mixed and then stirred for 1-2h at normal temperature, and then the temperature is raised to 140-160 ℃ within 1-1.5h for esterification.
8. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to any one of claims 1 to 5, wherein the pre-polycondensation in step 4) is carried out at 200-210 ℃ for 0.5-1h at 1-200 pa.
9. The method for preparing 2, 5-furandicarboxylic acid-based block copolyester according to any one of claims 1 to 5, wherein the molar ratio of the prepolymer to the esterified substance in step 5) is 1: 1.6-2.5.
10. The method for preparing 2, 5-furandicarboxylic acid based block copolyester according to any of claims 1 to 5, wherein the polycondensation in step 5) is performed at 230 ℃, -0.05 to-0.1 MPa for 0.5 to 1.5h, and then the temperature is raised to 250 ℃ and the reaction is performed at-100 to-200 Pa for 2 to 4 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457475A (en) * | 2020-11-27 | 2021-03-09 | 天津理工大学 | Method for preparing modified PEF copolyester by using citric acid-based aromatic diester |
| CN114057998A (en) * | 2020-07-30 | 2022-02-18 | 中国科学院大连化学物理研究所 | 2, 5-furandicarboxylic acid copolyester and preparation method thereof |
| CN114058000A (en) * | 2020-09-04 | 2022-02-18 | 浙江糖能科技有限公司 | Bio-based polyester and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170145153A1 (en) * | 2014-05-09 | 2017-05-25 | Roquette Freres | Thermoplastic aromatic polyesters comprising tetrahydrofuran-dimethanol and furandicarboxylic acid motifs |
| CN106854274A (en) * | 2016-12-23 | 2017-06-16 | 清华大学 | A kind of preparation method of multi-block copolyesters and preparation method thereof and its compound |
-
2020
- 2020-03-16 CN CN202010181967.XA patent/CN111454439A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170145153A1 (en) * | 2014-05-09 | 2017-05-25 | Roquette Freres | Thermoplastic aromatic polyesters comprising tetrahydrofuran-dimethanol and furandicarboxylic acid motifs |
| CN106854274A (en) * | 2016-12-23 | 2017-06-16 | 清华大学 | A kind of preparation method of multi-block copolyesters and preparation method thereof and its compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057998A (en) * | 2020-07-30 | 2022-02-18 | 中国科学院大连化学物理研究所 | 2, 5-furandicarboxylic acid copolyester and preparation method thereof |
| CN114058000A (en) * | 2020-09-04 | 2022-02-18 | 浙江糖能科技有限公司 | Bio-based polyester and preparation method thereof |
| CN112457475A (en) * | 2020-11-27 | 2021-03-09 | 天津理工大学 | Method for preparing modified PEF copolyester by using citric acid-based aromatic diester |
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