CN114989445B - Catalytic modified difunctional auxiliary agent for synthesizing biodegradable polyester as well as preparation method and application thereof - Google Patents
Catalytic modified difunctional auxiliary agent for synthesizing biodegradable polyester as well as preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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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- 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 provides a catalytic modified difunctional biodegradable polyester synthesis auxiliary agent, a preparation method and application thereof, wherein the auxiliary agent comprises the following raw materials: cobalt acetate, aromatic carboxylic acid and N, N-dimethylformamide with the molar ratio of (0.9-1.1) to (3.6-4.4) to (120-130); the aromatic carboxylic acid is selected from one or more of terephthalic acid, 2, 5-dimethyl terephthalic acid and biphenyl phthalic acid. The auxiliary agent has double functions of catalysis and modification in the preparation of the biodegradable polyester material, so that potential side reactions of various auxiliary agents in the production process are avoided, the polyester production process is simplified, the production cost is saved, the production period is shortened, and the production efficiency is improved; and the polyester has excellent flexibility and thermal stability.
Description
Technical Field
The invention belongs to the technical field of degradable polymers, and particularly relates to a catalytic modified difunctional auxiliary agent for synthesizing biodegradable polyester, and a preparation method and application thereof.
Background
The problem of plastic pollution is solved unprecedentedly, and the biodegradable polyester material has great influence and change on daily life of people, and has attracted wide attention both internationally and domestically. The common biodegradable materials in the market comprise PLA, PCL, PBS, PBAT and the like, wherein the polyester comprises PBS, PBAT and the like, and can be directly or indirectly applied to various aspects of agricultural films, bag making, catering and the like. These polyester materials are usually prepared by the action of catalysts such as antimony-based, titanium-based and germanium-based catalysts and a series of modifying aids, so that the polyester has the advantages of improved molecular weight, color luster and excellent mechanical properties. The process steps are tedious and complicated, so that the production efficiency of the polyester is low. Therefore, the selection of a proper catalyst and a modification auxiliary agent or the development of a multifunctional auxiliary agent is of great significance to the industry of biodegradable polyester materials.
More polyester catalysts currently used in the industry comprise the following: (1) an antimony catalyst; the catalyst has moderate activity, generates fewer side reactions and is dominant in the polyester industry. However, it is notable that antimony-based compounds themselves are toxic and most coexist with other highly toxic substances, which is a significant drawback of antimony-based catalysts. (2) a germanium-based catalyst; typically, such catalysts are used for polyester synthesis, mainly germanium dioxide. Germanium dioxide has stable property, the catalytic polyester synthesis process is mild, the side reaction is less, the color of the synthesized polyester is white and clear, and the synthesized polyester is favored by most users. The germanium catalyst is rare in resource and high in price, is not widely used at present, and is more used for high-grade polyester synthesis. (3) a titanium-based catalyst; the most studied type of catalyst has the advantages of higher activity, less addition, shortened polymerization time and the like, and becomes the most favored type of catalyst in the market. However, the catalysts are easy to hydrolyze to produce side reactions, and the prepared polyester has yellow hue and high carboxyl end group content, so that the catalysts are limited in practical industrial application.
In addition, the modification mode of the biodegradable polyester material mainly comprises the following three means: the first chemical modification is to add one or more substances to the original polymer to perform chemical reaction so as to achieve the purpose of modification; the second step of physical modification is to complete modification of various polymers in proportion by a melt blending mode; (III) nanometer composite modification, which means that 1 nm-100 nm nanometer particles and organic polymer are constructed together, common nanometer particles comprise montmorillonite, talcum powder and SiO 2 、CaCO 3 Etc. The addition of certain nano particles in the polymer material has great effect on the functionalization of the material, so that the polymer material becomes a research hot spot in the polymer field.
In recent years, metal-organic frameworks (MOFs) have been increasingly developed, which are crystalline porous materials having a periodic network structure formed by coordination of inorganic metal centers (metal ions or metal clusters) and organic ligands. MOFs have the advantages of large specific surface area, designable structure, good thermal stability and the like, and have wide application prospects in the aspects of catalysis, gas storage, separation and the like.
Disclosure of Invention
In view of the above, the invention aims to provide a catalytic modified difunctional auxiliary agent for synthesizing biodegradable polyester, a preparation method and application thereof, wherein the auxiliary agent has both catalytic and modified functions in the preparation of biodegradable polyester materials.
The invention provides a catalytic modified difunctional biodegradable polyester synthesis auxiliary agent, which comprises the following raw materials:
cobalt acetate, aromatic carboxylic acid and N, N-dimethylformamide with the molar ratio of (0.9-1.1) to (3.6-4.4) to (120-130);
the aromatic carboxylic acid is selected from one or more of terephthalic acid, 2, 5-dimethyl terephthalic acid and biphenyl phthalic acid.
In the invention, the granularity of the catalytic modified difunctional biodegradable polyester synthesis auxiliary agent is 300-1000 nm.
In the invention, the catalytic modified difunctional biodegradable polyester synthesis auxiliary agent is a Co-MOF material, and can be used for preparing various biodegradable polyester materials; the preparation method has the advantages that the preparation process is simple and convenient, the addition amount is small, and the catalyst has double functions of catalysis and modification. The auxiliary agent not only avoids potential side reactions of various auxiliary agents in the production process, simplifies the polyester production process, saves the production cost, shortens the production period, improves the production efficiency, but also improves the flexibility and the thermal stability of the material.
The main mechanism of the catalytic method for the polycondensation of the biodegradable polyester is in chelate coordination, metal Co ions in the auxiliary still have unsaturated coordination points after being coordinated with ligands, can serve as active centers to provide empty orbits, and carbonyl in ester groups provides electron pairs to form coordination, so that the electropositivity of carbonyl carbon is increased, the hydroxyl oxygen at the other end is facilitated to attack, the reaction rate is accelerated, and on the other hand, the Co-MOF material is combined by virtue of coordination bonds, the bond energy is smaller, the release of the metal ions is more facilitated, the catalytic activity is further enhanced, and the polymerization time is shortened.
The invention provides a preparation method of the catalytic modified difunctional biodegradable polyester synthesis auxiliary agent, which comprises the following steps:
mixing a DMF solution of cobalt acetate and a DMF solution of aromatic carboxylic acid, reacting under stirring, and carrying out suction filtration to obtain the catalytic modified difunctional auxiliary agent for synthesizing the biodegradable polyester.
In the invention, the mole ratio of DMF in the cobalt acetate and the DMF solution of cobalt acetate to DMF in the DMF solution of aromatic carboxylic acid and aromatic carboxylic acid is (0.9-1.1): (60-65): (3.6-4.4): (60-65).
The method adopts equivalent N, N-Dimethylformamide (DMF) to dissolve cobalt acetate and aromatic carboxylic acid respectively, then rapidly pouring carboxylic acid/DMF solution into cobalt acetate/DMF solution, continuing stirring for reaction, and carrying out suction filtration after the reaction is finished, wherein the obtained powder is Co-MOF powder; the stirring reaction time is 55-65 min.
The invention provides a preparation method of biodegradable polyester, which comprises the following steps:
uniformly mixing an auxiliary agent and dibasic acid, mixing the mixture with dihydric alcohol, and carrying out esterification and polycondensation reaction to obtain biodegradable polyester;
the auxiliary agent is the auxiliary agent for synthesizing the catalytic modified difunctional biodegradable polyester prepared by the technical scheme or the auxiliary agent for synthesizing the catalytic modified difunctional biodegradable polyester prepared by the preparation method.
The auxiliary Co-MOF material adopted by the invention has excellent thermal stability, so that other materials still have good thermal stability after being compounded with the auxiliary Co-MOF material. The ligand of the Co-MOF material is carboxylic acid substance, has good compatibility with polyester, and can ensure that the nano particles are uniformly dispersed in the polyester. The auxiliary agent can improve the elongation at break of the polyester material and is beneficial to the downstream industrial application field of polyester.
The invention mixes the auxiliary agent with the corresponding dibasic acid of the synthetic polyester, and the mixture is stirred uniformly and taken out for standby; and secondly, adding the mixed dibasic acid (containing Co-MOF powder) and dihydric alcohol into a reaction kettle at the same time, and obtaining the corresponding polymer after esterification and polycondensation reaction.
In the invention, the addition amount of Co-MOF powder is 0.05 to 0.1 weight percent based on the biodegradable polyester. The auxiliary agent and the dibasic acid are mixed in a high-speed stirrer and stirred uniformly; in the invention, the auxiliary agent and the dibasic acid are preferably mixed uniformly at 1000-1500 rpm.
In the invention, the molar content ratio of the total molar content of the dibasic acid and the Co-MOF to the molar content of the dihydric alcohol is 50 (85-105).
In the present invention, the biodegradable polyester is selected from polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene succinate terephthalate (PBST), or polybutylene terephthalate adipate (PBAT).
The prior art has not found that the use of MOFs materials to catalyze the polycondensation of biodegradable polyesters has not found that MOFs materials can improve certain properties of the polymers. In the preparation process of the degradation polyester, the Co-MOF has small bond energy of coordination bonds, which is beneficial to the release of metal ions, and the metal ions can be used as active centers to catalyze the polycondensation of the polyester, so that the reaction is carried out in the forward direction, and meanwhile, the Co-MOF belongs to the nano-scale, has uniform dispersity in a polymer, can serve as a modification auxiliary agent, and improves the thermal stability and flexibility of the material.
The invention provides a catalytic modified difunctional biodegradable polyester synthesis auxiliary agent, which comprises the following raw materials: cobalt acetate, aromatic carboxylic acid and N, N-dimethylformamide with the molar ratio of (0.9-1.1) to (3.6-4.4) to (120-130); the aromatic carboxylic acid is selected from one or more of terephthalic acid, 2, 5-dimethyl terephthalic acid and biphenyl phthalic acid. The auxiliary agent has double functions of catalysis and modification in the preparation of the biodegradable polyester material, so that potential side reactions of various auxiliary agents in the production process are avoided, the polyester production process is simplified, the production cost is saved, the production period is shortened, and the production efficiency is improved; and the polyester has excellent flexibility and thermal stability.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe in detail the catalytic modified bifunctional biodegradable polyester synthesis aid, and the preparation method and application thereof, but they should not be construed as limiting the scope of the present invention.
1mol of cobalt acetate and 4mol of aromatic carboxylic acid (one of terephthalic acid, biphenyl dicarboxylic acid and 2, 5-dimethyl terephthalic acid) are weighed and respectively poured into two reaction kettles containing 60mol of DMF, the mixture is stirred and dissolved, carboxylic acid/DMF solution is discharged at room temperature, the mixture is poured into cobalt acetate/DMF solution, the mixture is discharged after reaction for 1 hour, and the corresponding Co-MOF powder is obtained after suction filtration, and the powder prepared by using terephthalic acid, biphenyl dicarboxylic acid and 2, 5-dimethyl terephthalic acid is respectively denoted as Co-MOF-I, co-MOF-II and Co-MOF-III.
The specific operation of the polymer modification process expressed in the following examples and comparative examples is that the polymer obtained through polycondensation and the corresponding auxiliary agent are mixed uniformly by a high-speed mixer and then added into a twin-screw extruder, the length-diameter ratio is 40/1, and the corresponding modified polyester is obtained by extruding air-cooled pellets at 140 ℃ and 150 rpm.
Example 1
Diacid (Co-MOF containing) preparation: 4.3g of Co-MOF-I powder (0.05%) and 5.9kg of succinic acid are weighed and added into a high-speed stirrer, and stirred and mixed uniformly to obtain a premix. PBS preparation: adding the succinic acid (containing Co-MOF) and 8.1kg of butanediol into a reaction kettle, stirring and heating to 230 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 245 ℃ for 1 hour to complete polycondensation, thus obtaining the PBS polymer.
Example 2
Diacid (Co-MOF containing) preparation: 8.6g of Co-MOF-I powder (0.1%) and 5.9kg of succinic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. PBS preparation: adding the succinic acid (containing Co-MOF) and 8.1kg of butanediol into a reaction kettle, stirring and heating to 230 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 245 ℃ for 1 hour to complete polycondensation, thus obtaining the PBS polymer.
Example 3
Diacid (Co-MOF containing) preparation: 7.5g of Co-MOF-II powder (0.08%), 2.95kg of succinic acid and 3.65kg of adipic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. Preparation of PBSA: adding the 6.6kg of the mixture of the dibasic acid (containing Co-MOF) and 7.65kg of butanediol into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 240 ℃ for 1 hour to complete polycondensation, thus obtaining the PBSA polymer.
Example 4
Diacid (Co-MOF containing) preparation: 7.5g of Co-MOF-II powder (0.08%), 2.95kg of succinic acid and 3.65kg of adipic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. Preparation of PBSA: adding the 6.6kg of the mixture of the dibasic acid (containing Co-MOF) and 7.65kg of butanediol into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 240 ℃ for 3 hours to complete polycondensation, thus obtaining the PBSA polymer.
Example 5
Diacid (Co-MOF containing) preparation: 12.0g of Co-MOF-III powder (0.07%), 2.71kg of succinic acid and 4.48kg of terephthalic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. PBST preparation: adding the mixture of about 7.2kg of the dibasic acid (containing Co-MOF) and 9.45kg of butanediol into a reaction kettle, stirring and heating to 220 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 235 ℃ for 1 hour to complete polycondensation, thus obtaining the PBST polymer.
Example 6
Diacid (Co-MOF containing) preparation: 12.0g of Co-MOF-II powder (0.07%), 2.71kg of succinic acid and 4.48kg of terephthalic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. PBST preparation: adding the mixture of about 7.2kg of the dibasic acid (containing Co-MOF) and 9.45kg of butanediol into a reaction kettle, stirring and heating to 220 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 235 ℃ for 1 hour to complete polycondensation, thus obtaining the PBST polymer.
Example 7
Diacid (Co-MOF containing) preparation: 9.5g of Co-MOF-III powder (0.09%), 3.5kg of adipic acid and 4.3kg of terephthalic acid are weighed and added into a high-speed stirrer, and the mixture is stirred and mixed uniformly to obtain a premix. Preparation of PBAT: adding 7.8kg of the mixture of the dibasic acid (containing Co-MOF) and 8.1kg of butanediol into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 255 ℃ for 1 hour to complete polycondensation, thus obtaining the PBAT polymer.
Example 8
Diacid (Co-MOF containing) preparation: 9.5g of Co-MOF-III powder (0.09%), 3.65kg of adipic acid and 4.15kg of terephthalic acid are weighed into a high-speed stirrer and stirred and mixed uniformly to obtain a premix. Preparation of PBAT: adding 7.8kg of the mixture of the dibasic acid (containing Co-MOF) and 8.1kg of butanediol into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, vacuumizing to 100Pa, and carrying out reaction at 255 ℃ for 1 hour to complete polycondensation, thus obtaining the PBAT polymer.
Comparative example 1
5.9kg of succinic acid, 8.1kg of butanediol and 8.6g of antimonous oxide (0.1%) are added into a reaction kettle, the temperature is raised to 230 ℃ with stirring, after esterification reaction for 2 hours, vacuum pumping is carried out to 100Pa, and reaction is carried out for 1 hour at 245 ℃ to complete polycondensation, thus obtaining the PBS polymer.
Comparative example 2
The same procedure as in comparative example 1 was followed except that the amount of antimony trioxide added was increased to 43g (0.5%).
Comparative example 3
2.95kg of succinic acid, 3.65kg of adipic acid, 7.65kg of butanediol and 9.3g of tetrabutyl titanate (0.1%) are added into a reaction kettle, the temperature is raised to 240 ℃ by stirring, the esterification reaction is carried out for 2 hours, then the vacuum is pumped to 100Pa, and the reaction is continued for 1 hour at 240 ℃ to complete the polycondensation, thus obtaining the PBSA polymer.
Comparative example 4
The procedure was the same as in comparative example 3 except that the reaction was continued for 3 hours at 240℃after the evacuation.
Comparative example 5
2.71kg of succinic acid, 4.48kg of terephthalic acid, 9.45kg of butanediol and 17.1g of tetrabutyl titanate (0.1%) are added into a reaction kettle, the mixture is stirred and heated to 220 ℃, after esterification reaction for 2 hours, vacuum is pumped to 100Pa, and the reaction is carried out for 1 hour at 235 ℃ to complete polycondensation, thus obtaining the PBST polymer.
Comparative example 6
The procedure was the same as in comparative example 5, except that after obtaining a PBST polymer, 3% montmorillonite was used for modification, and finally a PBST modified polymer was obtained.
Comparative example 7
3.5kg of adipic acid, 4.3kg of terephthalic acid, 8.1kg of butanediol and 10.5g of tetrabutyl titanate (0.1%) are added into a reaction kettle, the mixture is stirred and heated to 240 ℃ for esterification reaction for 2 hours, then vacuum pumping is carried out to 100Pa, and the reaction is carried out for 1 hour at 255 ℃ to complete polycondensation, thus obtaining the PBAT polymer.
Comparative example 8
The procedure was the same as in comparative example 7 except that tetrabutyl titanate was replaced with antimony trioxide.
The products prepared in the above examples and comparative examples were subjected to performance tests according to the following test standards, (1) molecular weight, gel permeation chromatograph, (2) elongation at break, GB/T1040.2-2006; (3) heat distortion temperature, GB/T1634.2-2019; the test results are shown in Table 1:
TABLE 1 relevant quality index for polyesters
| Numbering device | Synthetic polyesters class | Molecular weight (Wan) | Elongation at break (%) | Heat distortion temperature (DEG C) |
| Example 1 | PBS | 3.6 | 450 | 116 |
| Example 2 | PBS | 4.1 | 500 | 123 |
| Example 3 | PBSA | 3.5 | 508 | 70 |
| Example 4 | PBSA | 3.9 | 495 | 68 |
| Example 5 | PBST | 4.4 | 517 | 118 |
| Example 6 | PBST | 3.2 | 560 | 112 |
| Example 7 | PBAT | 5.2 | 610 | 65 |
| Example 8 | PBAT | 4.7 | 586 | 61 |
| Comparative example 1 | PBS | 1.2 | 315 | 94 |
| Comparative example 2 | PBS | 2.1 | 343 | 90 |
| Comparative example 3 | PBSA | 1.5 | 380 | 52 |
| Comparative example 4 | PBSA | 1.9 | 405 | 49 |
| Comparative example 5 | PBST | 1.9 | 424 | 98 |
| Comparative example 6 | PBST | 1.8 | 469 | 99 |
| Comparative example 7 | PBAT | 2.1 | 515 | 50 |
| Comparative example 8 | PBAT | 1.7 | 450 | 53 |
As can be seen from table 1: the same kind of polymer was synthesized using different auxiliaries, and the molecular weight of the polymer synthesized by Co-MOF (examples 1-8) was significantly higher than that synthesized by ordinary antimony-based, titanium-based catalysts (comparative examples 1-8), since Co-MOF was more catalytically active than ordinary type catalysts. The breaking elongation of the examples is larger than that of the comparative examples because the Co-MOF added in the examples is nano particles, the Co-MOF has a modification effect on the mechanical properties of the materials, and the Co-MOF has excellent thermal stability, and after being compounded with polyester, the overall heat resistance is enhanced, so that the heat deformation temperature of the materials is improved.
As can be seen from the data of examples 1 to 4 in the table, a polymer having a good flexibility can be synthesized in a short time with only a very small amount of Co-MOF, thereby demonstrating that the catalytic activity of Co-MOF is strong. The data of examples 5-8 show that the catalytic modification function of Co-MOF is not impaired or lost by the change of conditions (replacement of aromatic carboxylic acid of Co-MOF, replacement of polymer raw material ratio).
Comparative examples 1 to 2 in the table use antimony trioxide as a catalyst, and even after increasing the amount added, the molecular weight, elongation at break, heat distortion temperature of the synthetic polymer were still at a low level. In contrast, in comparative examples 3 to 8, the performance of the corresponding polymer in the examples was not excellent, except that the polycondensation time was increased on the basis of the above, or the montmorillonite was modified or replaced with a titanium catalyst.
Comprehensive results show that in the process of preparing biodegradable polyester, the Co-MOF of the nano particles has catalytic activity stronger than that of common antimony-based and titanium-based catalysts, and can be compounded with materials to further improve the flexibility and thermal stability of the materials.
From the above examples, it can be seen that the catalytic modified bifunctional biodegradable polyester synthesis aid comprises the following raw materials: cobalt acetate, aromatic carboxylic acid and N, N-dimethylformamide with the molar ratio of (0.9-1.1) to (3.6-4.4) to (120-130); the aromatic carboxylic acid is selected from one or more of terephthalic acid, 2, 5-dimethyl terephthalic acid and biphenyl phthalic acid. The auxiliary agent has double functions of catalysis and modification in the preparation of the biodegradable polyester material, so that potential side reactions of various auxiliary agents in the production process are avoided, the polyester production process is simplified, the production cost is saved, the production period is shortened, and the production efficiency is improved; and the polyester has excellent flexibility and thermal stability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. A preparation method of biodegradable polyester comprises the following steps:
uniformly mixing an auxiliary agent and dibasic acid, mixing the mixture with dihydric alcohol, and carrying out esterification and polycondensation reaction to obtain biodegradable polyester;
the auxiliary agent is a catalytic modified difunctional auxiliary agent for synthesizing biodegradable polyester;
the temperature of the esterification is 220-240 ℃;
the temperature of the polycondensation reaction is 235-255 ℃;
the biodegradable polyester is selected from polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate or polybutylene terephthalate adipate;
the catalytic modified difunctional auxiliary agent for synthesizing the biodegradable polyester comprises the following raw materials:
cobalt acetate, aromatic carboxylic acid and N, N-dimethylformamide with the molar ratio of (0.9-1.1) to (3.6-4.4) to (120-130);
the aromatic carboxylic acid is selected from one or more of terephthalic acid, 2, 5-dimethyl terephthalic acid and biphenyl phthalic acid.
2. The preparation method of the catalytic modified bifunctional biodegradable polyester synthesis auxiliary agent according to claim 1, comprising the following steps:
mixing a DMF solution of cobalt acetate and a DMF solution of aromatic carboxylic acid, reacting under stirring, and carrying out suction filtration to obtain the catalytic modified difunctional auxiliary agent for synthesizing the biodegradable polyester.
3. The method according to claim 2, wherein the molar ratio of DMF in the cobalt acetate, the DMF in the DMF solution of cobalt acetate, the aromatic carboxylic acid and the DMF in the DMF solution of aromatic carboxylic acid is (0.9-1.1): (60-65): (3.6-4.4): (60-65).
4. The preparation method according to claim 1, wherein the auxiliary agent and the dibasic acid are uniformly mixed at 1000-1500 rpm.
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| CN113976181A (en) * | 2021-09-29 | 2022-01-28 | 江苏大学 | Preparation of cobalt-based metal organic framework immobilized organic catalyst and application of catalyst in field of fuel oil desulfurization |
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| JP2005330476A (en) * | 2004-04-19 | 2005-12-02 | Toray Ind Inc | Polymerization catalyst for polyester |
| CN101525429A (en) * | 2009-03-30 | 2009-09-09 | 东华大学 | Binary composite catalyst for preparing biodegradable copolyester |
| CN107099038A (en) * | 2017-05-12 | 2017-08-29 | 宁夏大学 | A kind of synthesis metal-organic framework material Co MOF 71 method |
| CN107573233A (en) * | 2017-09-05 | 2018-01-12 | 桂林电子科技大学 | A kind of cobalt-based MOFs materials and its preparation method and application |
| CN113976181A (en) * | 2021-09-29 | 2022-01-28 | 江苏大学 | Preparation of cobalt-based metal organic framework immobilized organic catalyst and application of catalyst in field of fuel oil desulfurization |
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