Bio-based polyesteramide and preparation method thereof
By preparing bio-based polyester amide, the problem of single functionalization of polyester materials has been solved, the development of high-performance sustainable materials has been achieved, and they have excellent thermal and mechanical properties, thus expanding their application areas.
Patent Information
- Application Number
- CN202510820039.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-18
- Publication Date
- 2025-09-16
AI Technical Summary
Existing polyester materials have single functionality and are difficult to meet diverse practical application needs. In addition, the widespread use of petroleum-based plastics leads to environmental pollution and resource shortages.
By preparing bio-based polyester amides, amide-functionalized lactones are reacted with catalysts and initiators to prepare bio-based polyester amides with side chain furan rings, which have thermally reversible crosslinking and reprocessability.
Bio-based polyester amides have excellent thermal and mechanical properties, exhibit good structural design flexibility and versatility, and expand their application areas.
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Figure CN120647931A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of polymer synthetic chemistry, and in particular to a bio-based polyester amide and a preparation method thereof. Background Art
[0002] Polyesteramide is a type of functional polymer material that combines the characteristics of polyester and polyamide. It combines the biocompatibility and depolymerization of polyester, and also has the good thermal stability and mechanical properties of polyamide. It shows good application potential in the fields of biomedical materials, degradable plastics and engineering polymers, and is an important new type of functional polymer. At present, one of the most studied polyesteramides is polycaprolactone-polycaprolactam 6 copolymer (PCL-PA6), which is a typical thermoplastic copolymer. The PCL segment gives the material good flexibility and biodegradability, while the PA6 segment significantly improves its mechanical properties and thermal stability. By regulating the relative proportions of the two components, an effective balance of performance between degradability and structural stability can be achieved, thereby meeting the differentiated requirements of material performance in various application scenarios.
[0003] The widespread use of petroleum-based plastic products has led to a series of problems such as environmental pollution and resource shortages. To address this series of problems, the development and application of sustainable polymers is considered a key and effective strategy. Research on sustainable polymers mainly includes bio-based polymers synthesized from biomass as monomers, biodegradable polymers, and polymers that are degraded and recycled by chemical or physical methods. Among them, aliphatic polyesters are a type of polymer material containing ester bonds in the main chain, which has excellent biocompatibility and degradability. However, the functionalization of traditional polyester materials is single, which makes it difficult to meet the diverse practical application needs.
[0004] The bio-based polyester amide proposed in this patent not only retains the excellent biocompatibility and degradability of polyester, but also has the excellent thermal stability of polyamide, providing an important research basis and application prospects for the development of high-performance sustainable polymers. Summary of the Invention
[0005] Purpose of the invention: The technical problem to be solved by the present invention is to provide a bio-based polyester amide and a preparation method thereof in view of the shortcomings of the existing technology.
[0006] In order to solve the above technical problems, the present invention discloses the following technical solutions:
[0007] In a first aspect, the present invention discloses a bio-based polyester amide, the general formula of which is shown in Formula I:
[0008]
[0009] in,
[0010] The group of R is any one of the following:
[0011]
[0012] Y is selected from methoxy, ethoxy, isopropoxy, butoxy, tert-butoxy, benzyloxy, phenylethoxy, phenylpropoxy, diphenylmethoxy, 2,2-diphenylethoxy;
[0013] n is any integer selected from 5 to 1000;
[0014] The dispersion coefficient of the bio-based polyester amide is 1.00-1.25, such as 1.16, 1.20, and 1.23.
[0015] In some embodiments, the bio-based polyester amide is any one of Formula III;
[0016]
[0017] In a second aspect, the present invention discloses a method for preparing the above polymer.
[0018] The method comprises the following steps: reacting a catalyst, a solvent, an initiator and an amide functionalized lactone shown in formula IV; further, the method comprises the following steps: stirring the catalyst, the solvent and the initiator for 1-5 minutes, and then adding the amide functionalized lactone shown in formula IV to react; further, the method comprises the following steps: stirring the catalyst, the solvent and the initiator for 2-3 minutes, and then adding the amide functionalized lactone shown in formula IV to react.
[0019] In some embodiments, the method includes the following steps: stirring the catalyst, the first solvent and the initiator at 25-100°C for 1-5 minutes, then adding the solution of the amide functionalized lactone represented by formula IV and the second solvent and continuing to stir and react at 25-100°C for 1 minute to 48 hours; the first solvent and the second solvent are the same solvent; in some embodiments, the molar volume ratio of the amide functionalized lactone represented by formula IV to the first solvent and the second solvent is 1.0-2.5 mol / L, preferably 1.6 mol / L.
[0020] The structure of the amide functionalized lactone shown in Formula IV is as follows:
[0021]
[0022] In a third aspect, the present invention discloses a method for preparing the above-mentioned amide functionalized lactone.
[0023] The method comprises the following steps:
[0024] (1) 4-Hydroxy-L-proline was dissolved in dichloromethane, and 3 equivalents of triethylamine and an equivalent amount of the acyl chloride represented by Formula V were added. The mixture was stirred at room temperature overnight. After the reaction was completed, the reaction solution was washed with water and then saturated brine. The organic phase was collected and rotary evaporated. The crude product was purified by column chromatography (DCM:EA = 40:1 to 10:1) to obtain N-acylated 4-hydroxy-L-proline derivatives.
[0025] (2) N-acylated 4-hydroxy-L-proline derivatives were reacted with triphenylphosphine and diisopropyl azodicarboxylate to prepare proline-based amide functionalized lactones via Mitsunobu reaction.
[0026] Wherein, the acyl chloride shown in formula V is one of the following:
[0027]
[0028] Wherein, the catalyst includes 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazobispiro[5.4.0]undec-7-ene, 4-dimethylaminopyridine, tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,3-bis(2,4,6-trimethylphenyl)imidazole 2-ylidene, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2Λ5,4Λ5-bis(phosphorus nitrogen compound), tin(II) octanoate, tin chloride, aluminum triisopropoxide, tetraisopropoxytitanium, and tris[(trimethylsilyl)amino]yttrium.
[0029] Wherein, the reaction solvent is one of chloroform, toluene, tetrahydrofuran, dichloromethane and N,N-dimethylformamide.
[0030] Wherein, the initiator is an alcohol; preferably, the initiator is methanol, ethanol, isopropanol, butanol, tert-butanol, ethylene glycol, benzyl alcohol, phenylethyl alcohol, phenylpropanol, diphenylmethanol, 2,2-diphenylethanol.
[0031] Wherein, the molar ratio of the amide functionalized lactone represented by formula IV, the catalyst, and the initiator is (5-1000):(0.01-5):1, such as (5-10):0.01:1, such as (20-50):(0.04-0.1):1, such as 100:1:1, such as 500:3:1, such as 1000:5:1.
[0032] Wherein, the reaction temperature is 25-100° C.; and the reaction time is 5-2880 min.
[0033] In a fourth aspect, the present invention discloses the use of the bio-based polyester amide described in the first aspect or the bio-based polyester amide prepared by the method described in the second aspect in the preparation of chemically recyclable materials.
[0034] The bio-based polyester amide (side chain furan ring) prepared by the present invention can undergo Diels-Alder reaction under certain conditions, and is used to design a thermally reversible cross-linking network to impart reprocessability to the material.
[0035] The bio-based polyester amide prepared by the present invention has excellent thermal properties, and the 5% thermal decomposition temperature (T d,5％ ) is 310~350℃, the maximum thermal decomposition temperature (T d，max ) is 370~390℃, melting temperature (T m ) is 170~250℃, crystallization temperature (T c ) is 150~200℃.
[0036] Beneficial effects:
[0037] (1) The bio-based polyester amide synthesized in this invention uses proline as a raw material, which is renewable and resource-sustainable. Proline is widely available and low-cost, making the resulting polymer environmentally friendly and economical, providing a new path for the green synthesis of high-performance functional materials.
[0038] (2) The bio-based polyester amide synthesized in the present invention is a new type of polymer material. The presence of amide groups gives the material more interaction sites, such as hydrogen bonding, thereby improving the crystallization behavior and physical properties of the polymer, including excellent thermal and mechanical properties, and can give the material diverse functionalities and properties, expanding its application areas.
[0039] (3) The bio-based polyester amide with special side chains (furan rings on the side chains) prepared by the present invention can undergo thermally reversible dynamic crosslinking under certain conditions and has reprocessability.
[0040] (4) The bio-based polyester amide synthesized in the present invention exhibits good structural design flexibility, and can subsequently undergo various chemical transformations such as copolymerization, grafting, and cross-linking to further regulate its microstructure and macroscopic properties, thereby achieving multifunctionality and intelligent responsiveness.
[0041] (5) The synthesis method provided by the present invention is simple, highly controllable, and has a high product yield. BRIEF DESCRIPTION OF THE DRAWINGS
[0042] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more apparent.
[0043] Figure 1 The polymer of Example 11 H NMR spectrum.
[0044] Figure 2 The polymer of Example 1 13 C HMR diagram.
[0045] Figure 3 This is the matrix-assisted laser ionization desorption / ionization time-of-flight mass spectrum of the polymer in Example 1.
[0046] Figure 4 This is the GPC chart of the polymer in Example 1.
[0047] Figure 5 The polymer of Example 2 1 H NMR spectrum.
[0048] Figure 6 This is the matrix-assisted laser ionization desorption / ionization time-of-flight mass spectrum of the polymer in Example 2.
[0049] Figure 7 This is the TGA diagram of the polymer in Example 1.
[0050] Figure 8 This is the DSC graph of the polymer in Example 1. DETAILED DESCRIPTION
[0051] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.
[0052] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
[0053] In the following examples, a 400 MHz Bruker nuclear magnetic resonance instrument was used to measure the products: the deuterated reagent used tetramethylsilane (TMS) as the internal standard, the H NMR test concentration was about 8 mg / mL, the C NMR test concentration was about 20 mg / mL, and the deuterated reagent was deuterated chloroform.
[0054] The molecular weight and molecular weight distribution of the bio-based polyester amide described herein were determined using a Wyatt gel permeation chromatography (GPC) instrument. The polymer concentration in chromatography-grade DCM was approximately 6 mg / mL, using dichloromethane (DCM) as the mobile phase at a flow rate of 0.70 mL / min. Polystyrene (PS) was used as the standard. The molecular weight and molecular weight distribution of the polymer were determined using the relative method.
[0055] The topological structures of the polymers described herein were determined using a Microflex LRF mass spectrometer provided by Bruker Spectroscopy. The sample concentration was 10 mg / mL, using 2,5-dihydroxybenzoic acid (DHB) as the matrix at a concentration of 20 mg / mL in a solvent of 60% isopropanol and 40% chloroform. Sodium iodide was used as the cationic reagent at a concentration of 20 mg / mL in a methanol solvent. A mixture of sample / matrix / cationic reagent (1 / 10 / 1) was added dropwise to a test plate, dried, and then tested.
[0056] The thermal stability (T d，5％ , T d，max ) was measured by TGA-550 instrument. 4-8 mg of polymer product was weighed and placed on a platinum plate. -1 ), 20℃ min -1 The heating rate is increased to 800℃.
[0057] The melting temperature (T m ), crystallization temperature (T c ) was measured by DSC-250 instrument. The heating and cooling processes of the polymer were measured under nitrogen atmosphere with a gas flow rate of 50 mL min -1 , weigh 4-8 mg of sample into the sample pan, heat from 30℃ to 250℃ at a rate of 10℃ / min, hold for 3 minutes, then cool from 250℃ to 30℃ at a rate of 10℃ / min, and finally heat up to 250℃ again.
[0058] Example 1:
[0059] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 1 mmol of an amide-functionalized lactone (with a long carbon side chain, n=4) was weighed into ampoule #1 and dissolved in 300.4 μl of dried chloroform. 0.02 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed into ampoule #2, and 80 μl of chloroform was added to dissolve the catalyst. 0.033 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0060] After stirring at 25°C for 90 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol dissolved with benzoic acid to quench and precipitate. After centrifugation at 10,000 r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 96%, the polymer number average molecular weight was 6230 g / mol, and the dispersion coefficient was 1.23.
[0061] Example 2:
[0062] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 2 mmol of an amide-functionalized lactone (with a long carbon side chain, n=6) was weighed into ampoule #1 and dissolved in 545 μl of dry chloroform. 0.03 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed into ampoule #2, and 80 μl of chloroform was added to dissolve the catalyst. 0.02 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0063] After stirring at 25°C for 60 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol dissolved with benzoic acid to quench and precipitate. After centrifugation at 10,000 r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 60%, the polymer number average molecular weight was 14470 g / mol, and the dispersion coefficient was 1.21.
[0064] Example 3:
[0065] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 2 mmol of an amide-functionalized lactone (with a long carbon side chain, n=8) was weighed into ampoule #1 and dissolved in 915 μl of dry chloroform. 0.025 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed into ampoule #2, and 80 μl of chloroform was added to dissolve the catalyst. 0.005 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0066] After stirring at 25°C for 1440 minutes, 4-5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol dissolved with benzoic acid to quench and precipitate. After centrifugation at 10000r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 71%, the number average molecular weight of the polymer was 76040 g / mol, and the dispersion coefficient was 1.24.
[0067] Example 4:
[0068] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 2 mmol of an amide-functionalized lactone (with a long carbon side chain, n=10) was weighed and placed in ampoule #1. 1580 μl of redistilled toluene was added to dissolve it. 0.0125 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed and placed in ampoule #2. 80 μl of chloroform was added to dissolve the catalyst. 0.0025 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0069] After stirring at 50°C for 1800 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol dissolved with benzoic acid to quench and precipitate. After centrifugation at 10000r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 65%, the polymer number average molecular weight was 153730 g / mol, and the dispersion coefficient was 1.25.
[0070] Example 5:
[0071] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 2 mmol of an amide-functionalized lactone (with a long carbon side chain, n=4) was weighed and placed in ampoule #1. 527 μl of dry tetrahydrofuran was added to dissolve the amide. 0.04 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed and placed in ampoule #2. 100 μl of chloroform was added to dissolve the catalyst. 0.2 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0072] After stirring at 30°C for 30 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol dissolved with benzoic acid to quench and precipitate. After centrifugation at 10,000 r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 93%, the polymer number average molecular weight was 2430 g / mol, and the dispersion coefficient was 1.14.
[0073] Example 6:
[0074] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 1 mmol of an amide-functionalized lactone (with a long carbon side chain, n=4) was weighed and placed in ampoule #1. 820 μl of dry chloroform was added to dissolve the amide. 0.001 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed and placed in ampoule #2. 100 μl of chloroform was added to dissolve the catalyst. 0.1 mmol of benzyl alcohol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0075] After stirring at 25°C for 30 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol in which benzoic acid was dissolved to quench and precipitate. After centrifugation at 10,000 r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 92%, the polymer number average molecular weight was 2050 g / mol, and the dispersion coefficient was 1.16.
[0076] Example 7:
[0077] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, the mixture was filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 2 mmol of an amide-functionalized lactone (with a long carbon side chain, n=4) was weighed and placed in ampoule #1. 527 μl of dry chloroform was added to dissolve the amide. 0.05 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed and placed in ampoule #2. 100 μl of chloroform was added to dissolve the catalyst. 0.05 mmol of benzhydrol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0078] After stirring at 25°C for 180 minutes, 4 to 5 drops of the polymer solution were added to deuterated chloroform of benzoic acid to test the monomer conversion rate, and the remaining drops were added to ice methanol in which benzoic acid was dissolved to quench and precipitate. After centrifugation at 10,000 r / min for 3 minutes, the supernatant was poured out, and a small amount of dichloromethane (DCM) was used to completely dissolve the polymer and added dropwise to ice methanol for precipitation. This was repeated three times, and the polymer product was placed in a vacuum drying oven to dry for 12 hours. The conversion rate was measured by the reaction solution. 1 The polymer structure and molecular weight were calculated by H NMR. 1 The polymer was characterized by H NMR and its dispersion was determined by GPC. The conversion rate was 87%, the polymer number average molecular weight was 7290 g / mol, and the dispersion coefficient was 1.22.
[0079] Example 8:
[0080] Both ampoules were evacuated using a Schlenk apparatus and baked at high temperature using a Bunsen burner. After baking, they were filled with argon and repeated three times to completely remove any residual moisture. After cooling to room temperature, the treated ampoules were transferred to a glove box along with the desired reactants. In the glove box, 1 mmol of an amide-functionalized lactone (furan with side chain, n=0) was weighed into ampoule #1 and dissolved in 490 μl of dry chloroform. 0.08 mmol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was weighed into ampoule #2, and 80 μl of chloroform was added to dissolve the catalyst. 0.1 mmol of phenylpropanol was then added and stirred at 25°C for 2 minutes. Finally, the dissolved monomer was added to the ampoule containing the catalyst and initiator to initiate polymerization.
[0081] After stirring at 25°C for 30 minutes, add 4-5 drops of the polymer solution to a solution of benzoic acid in deuterated chloroform to test monomer conversion. The remaining droplets are then added to icy methanol dissolved with benzoic acid to quench and precipitate. Centrifuge at 10,000 rpm for 3 minutes, then discard the supernatant. Dissolve the polymer completely in a small amount of dichloromethane (DCM) and add the resulting solution dropwise to icy methanol for precipitation. Repeat this three times. The polymer product is then dried in a vacuum oven for 12 hours.
[0082] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.
Claims
1. A bio-based polyester amide, characterized in that The bio-based polyester amide is shown in Formula I; in, The group of R is any one of the following: Y is selected from methoxy, ethoxy, isopropoxy, butoxy, tert-butoxy, benzyloxy, phenylethoxy, phenylpropoxy, diphenylmethoxy, 2,2-diphenylethoxy; The number average molecular weight of the bio-based polyester amide is 1,000 to 300,000 g mol -1 .
2. The bio-based polyester amide according to claim 1, characterized in that The bio-based polyester amide is any one of formula III; 3. The method for preparing the bio-based polyester amide according to claim 1 or 2, characterized in that: The following steps are involved: reacting a catalyst, a solvent, an initiator, and an amide-functionalized lactone represented by formula IV; 4. The method for preparing the amide functionalized lactone according to claim 3, wherein The following steps are involved: (1) 4-Hydroxy-L-proline was dissolved in dichloromethane, and 3 equivalents of triethylamine and an equivalent amount of acyl chloride were added. The mixture was stirred at room temperature overnight. After the reaction was completed, the reaction solution was washed with water and saturated brine in sequence. The organic phase was collected and rotary evaporated. The crude product was purified by column chromatography (DCM:EA = 40:1 to 10:1) to obtain N-acylated 4-hydroxy-L-proline derivatives. (2) N-acylated 4-hydroxy-L-proline derivatives were reacted with triphenylphosphine and diisopropyl azodicarboxylate to prepare proline-based amide functionalized lactones via Mitsunobu reaction. The method for preparing an amide-functionalized lactone according to claim 4, wherein the acyl chloride is one of formula V:
5. The preparation method according to claim 3, characterized in that The catalyst includes 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazobispiro[5.4.0]undec-7-ene, 4-dimethylaminopyridine, tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,3-bis(2,4,6-trimethylphenyl)imidazole 2-ylidene, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2Λ5,4Λ5-bis(phosphorus nitrogen compound), tin(II) octanoate, tin chloride, aluminum triisopropoxide, tetraisopropoxytitanium, and tris[(trimethylsilyl)amino]yttrium.
6. The preparation method according to claim 3, characterized in that The solvent is any one of chloroform, toluene, tetrahydrofuran, dichloromethane and N,N-dimethylformamide.
7. The preparation method according to claim 3, characterized in that The initiator is an alcohol; preferably, the initiator is any one of methanol, ethanol, isopropanol, butanol, tert-butanol, benzyl alcohol, phenylethyl alcohol, phenylpropanol, diphenylmethanol and 2,2-diphenylethanol.
8. The preparation method according to claim 3, characterized in that The molar ratio of the amide functionalized lactone represented by formula IV, the catalyst and the initiator is (5-1000): (0.01-5): 1; preferably, the reaction temperature is 25-100° C.; and the reaction time is 1-2880 min.
9. Use of the bio-based polyester amide according to claim 1 or 2 or the bio-based polyester amide prepared by the method according to any one of claims 3 to 8 in the preparation of chemically recyclable materials.