Preparation method and application of polyesteramide compound
By exploiting the activity differences between amide-activated alkynes and ester-activated alkynes, and utilizing the stepwise click reaction between thiol and hydroxyl groups, polyesteramide compounds were prepared, solving the problem of multi-component polymerization reactions and realizing the preparation of efficient and controllable polymer materials with good thermal stability and processing performance.
Patent Information
- Application Number
- CN202511780244.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2025-11-21
- Filing Date
- 2025-11-28
- Publication Date
- 2026-02-13
AI Technical Summary
Existing technologies have failed to effectively utilize the activity differences of activated acetylene monomers to carry out multi-component polymerization reactions to prepare complex polymer materials. Furthermore, the polymerization reaction conditions are not mild enough, the yield is low, and it is difficult to achieve the functional transformation of polymer materials.
Polyesteramide compounds are prepared by utilizing the difference in activity between amide-activated alkynes and ester-activated alkynes through stepwise click reactions involving two nucleophilic groups, thiol and hydroxyl groups. The reaction is simple, efficient, and suitable for multi-component polymerization.
The tandem polymerization of multi-component activated acetylene monomers was achieved, the main chain structure sequence of the polymer material was controllable, and it had good thermal stability and processability, high yield, few by-products, and met the requirements of atom economy.
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Figure CN121517690A_ABST
Abstract
Description
Technical Field
[0001] This invention is designed in the fields of polymer chemistry and materials science, specifically designing a method for preparing polyesteramide compounds and their applications. Background Technology
[0002] Polymerization of acetylene monomers is an important method for preparing novel polymer materials. The raw materials are readily available, and the polymerized material retains unsaturated bonds in the main chain, thus often exhibiting unique photoelectric properties. Furthermore, functionalization can be achieved through post-modification. Therefore, the construction of polymer materials using acetylene monomers has significant technical and academic value. Selective reactions based on the reactivity differences of acetylene monomers, enabling rapid and efficient polymerization of different acetylene monomers, can lead to the development of more complex polymer materials.
[0003] Click polymerization has advantages such as readily available raw materials, simple and mild conditions, high efficiency, good regioselectivity, and atom economy. In recent years, Tang Benzhong's research group and others have developed a series of high-efficiency click polymerization reactions based on activated alkyne monomers. For example, the click polymerization of alkyne and hydroxyl monomers activated by ester groups can obtain poly(vinyl ether ester) with a weight average molecular weight of over 70,000 in an ultra-high yield of 99% after 1 hour of reaction. Moreover, the reaction is compatible with phenolic hydroxyl monomers, which greatly enriches the preparation methods of polymer materials (Si H.; Wang K.; Song B. et al. Organobase-catalysed Hydroxyl–yneClick Polymerization[J]. Polymer Chemistry, 2020, 11(14): 2568–2575.). Andrew P. Dove's research group utilized click polymerization of amide-activated alkynes with thiol monomers to achieve precise control over the stereochemical cis content of olefin double bonds in the main chain of the prepared materials within 35-82% under mild conditions (Worch JC; Weems AC; Yu J. et al. Elastomeric Polyamide Biomaterials with Stereochemically Tuneable Mechanical Properties and Shape Memory[J]. Nature Communications, 2020, 11(1): 3250.). Currently, research on polymerization reactions based on activated alkynes mainly focuses on the polymerization reaction between two components—activated alkynes and nucleophilic groups. There are no reports on the preparation of polymers by polymerizing various types of activated alkynes using differences in their reactivity. Therefore, it is foreseeable that developing simple and efficient multi-component polymerization reactions of activated alkynes to prepare polymer materials will have significant scientific and application value. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing polyesteramide compounds. This method is based on the activity difference between amide-activated alkynes and ester-activated alkynes, and uses a stepwise click reaction through two nucleophilic groups, thiol and hydroxyl groups. The reaction is simple, efficient and easy to operate.
[0005] Another object of the present invention is to obtain a polyesteramide compound by means of the above method, which has good processing properties and aggregation-induced emission properties.
[0006] The objective of this invention is achieved through the following technical solution: A method for preparing a polyesteramide compound includes the following steps: (1) The diamine alkynyl compound and 2-mercaptoethanol are reacted in a solvent to obtain an amide compound containing a dihydroxyl functional group, preferably for 5 hours.
[0007] (2) Add the diester alkynyl compound to the organic solvent system obtained in step (1) for polymerization reaction. After the reaction is complete, add methanol for precipitation, collect the precipitate, and dry it to constant weight to obtain polyester amide compound. The general structural formulas of the diamide alkynyl compounds and the diester alkynyl compounds are shown in formula (II) or (III), respectively: (II); (III); The structural formula of the 2-mercaptoethanol is shown in formula (IV): (IV); The general structural formula of the aforementioned polyesteramide compounds is shown in formula (I): (I); In equations (I)-(III), n is an integer ≥ 2, and R 1 R 2 These are the same or different organic groups.
[0008] As a preferred embodiment, in equations (I)-(III), R 1 Selected from any one of the following chemical structural formulas (1)-(3): R 2 Choose any one of the structural formulas (4)-(7): (1); (2); (3); (4); (5); (6); (7); Preferably, the organic solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, dimethyl sulfoxide, and N,N-dimethylamide.
[0009] Preferably, the reaction time in step (1) is 5-12 hours.
[0010] More preferably, the organic solvent is tetrahydrofuran, which results in a polyesteramide compound with a higher molecular weight, better solubility, and easier application in the next step.
[0011] The molar ratio of the diamide alkynyl compound, 2-mercaptoethanol, and diester alkynyl compound is 1:1:1, and the concentration of the diamide alkynyl compound, diester compound, and 2-mercaptoethanol in the organic solvent is 0.1-0.5 mol / L, preferably 0.5 mol / L.
[0012] The polymerization reaction in step (2) is carried out at a temperature of 25-55°C. o C, preferably 25 o C.
[0013] The polymerization reaction in step (2) takes 15-120 minutes, preferably 90 minutes.
[0014] The polymerization reaction described in step (2) needs to be carried out under the action of triethylenediamine, an organic base catalyst.
[0015] The amount of the organic base catalyst is 0.5%-2.5% of the molar amount of the diamide alkynyl compound and the diester alkynyl compound, preferably 2%.
[0016] Preferably, the polymerization reaction is carried out in an atmospheric atmosphere.
[0017] Preferably, after the polymerization reaction is completed, the reaction solution is dissolved in tetrahydrofuran for dilution, then added to methanol as a precipitant for precipitation, the precipitate is collected, and dried to constant weight.
[0018] This invention also provides a polyesteramide compound obtained by the above-described preparation method. This polyesteramide compound exhibits good thermal stability and excellent processability, and has high application value.
[0019] Compared with the prior art, the present invention has the following advantages: 1. The preparation method of the present invention realizes the tandem polymerization of multi-component activated acetylene monomers, and the main chain structure sequence of the obtained polymer material is controllable, which expands the types of polymerization reactions in which activated acetylene monomers participate, and therefore has important innovative significance and value.
[0020] 2. The raw materials for the preparation method of the present invention are readily available and can be purchased directly or prepared through simple reactions; the polymerization reaction conditions are simple and mild, the yield is high, no by-products are generated, it meets the requirements of atom economy, and a high molecular weight polymer can be obtained in just 90 minutes.
[0021] 3. The polymer prepared by this invention has good thermal stability and good processability. Attached Figure Description
[0022] Figure 1Comparison of the proton NMR spectra of the polyesteramide compound P1 and its corresponding monomer prepared in DMSO for Example 1 of this invention.
[0023] Figure 2 Comparison of the carbon NMR spectra of the polyesteramide compound P1 and its corresponding monomer prepared in DMSO for Example 1 of this invention.
[0024] Figure 3 The thermogravimetric curve of the polyesteramide compound P1 prepared in Example 1 of this invention.
[0025] Figure 4 The fluorescence emission spectrum of the polyesteramide compound P5 prepared in Example 1 of this invention in dimethyl sulfoxide with a water content of 0-40% is shown. Detailed Implementation
[0026] The present invention will be further described in detail below with reference to specific examples and accompanying drawings. However, the implementation and protection of the present invention are not limited thereto. For process parameters not specified, conventional techniques can be referred to.
[0027] The room temperature described in the following examples is 25°C. o C.
[0028] Example 1 A polyesteramide compound, the structural formula of which is shown in P1:
[0029] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0030] The monomer M1 can be synthesized according to the method described in the applicant's published literature (Nature Communications, 2020, 11(1): 3250.); the monomer M3 can be synthesized according to the method described in the applicant's published literature (Macromolecules, 2024, 57(5): 1970–1978.); 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example, they were purchased from Anaiji Chemical Co., Ltd.
[0031] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M1 (0.5 mmol, 89.096 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M3 (0.5 mmol, 111.12 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P1.
[0032] Analysis revealed that the final product, polyesteramide compound P1, had a yield of 93%, a weight-average molecular weight of 87,200, and a molecular weight distribution of 2.07. A comparison of the NMR spectra of this polyesteramide and its corresponding monomers (* represents solvent peaks) is shown below. Figure 1 , Figure 2 The figure confirms that the polymer is a polyesteramide compound. Figure 1 In the middle monomer M1 δ At position 2.12 and at the chemical shift of monomer M3 δ The ≡C–H resonance peak at 4.55 is located at... Figure 1 The corresponding positions in (C) and (D) have completely disappeared. Furthermore, the chemical shifts in the product diagram of the dihydroxyamide compound formed after the reaction of monomer M1 with 2-mercaptoethanol are also shown. δ 7.35 δ 6.92 δ 5.92 and δ A resonance peak appeared at position 5.84, exhibiting characteristics of cis-trans isomerism in olefins. The coupling constant of the E-type olefin peaks was 10.0 Hz, and the coupling constant of the Z-type olefin peaks was 15.0 Hz, with a ratio of approximately 2:1. In the 1H NMR spectrum of polymer P1, at chemical shift... δ 7.6 δ 5.3 and δ At position 5.27, an olefin resonance peak was observed, which is derived from the ≡C–H transformation of monomer M3. Figure 2 In the process, the carbon atoms in C≡C and ≡C–H of monomer M1 can be clearly observed. δ 78.77 and δ The resonance peak at 76.02 ppm has disappeared in polymer P1. Similarly, the carbon atoms in C≡C and ≡C–H of monomer M3... δ 79.10 and δThe resonance peak at 75.19 also disappeared in polymer P1. All of the above data indicate that, through this reaction process, the alkynyl groups in the monomer were completely consumed and converted into alkenyl double bonds. Based on the NMR spectrum results, the successful preparation of polyesteramide compounds can be confirmed.
[0033] from Figure 3 (Test conditions: nitrogen atmosphere, heating rate 10) o C / min, test range 30-800 o C) It can be seen that the 5% thermal weight loss temperature of this polyesteramide compound is 305°C. o C indicates that the compound has good thermal stability.
[0034] Example 2 A polyesteramide compound, the structural formula of which is shown on P2:
[0035] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0036] The synthesis methods of monomers M2 and M3 are the same as in Example 1; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0037] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M2 (0.5 mmol, 103.123 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were sequentially added to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M3 (0.5 mmol, 111.120 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P2.
[0038] Analysis showed that the final product, polyesteramide compound P2, had a yield of 97%, a weight-average molecular weight of 106,900, and a molecular weight distribution of 2.75.
[0039] Example 3 A polyesteramide compound, the structural formula of which is shown on page 3:
[0040] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0041] The synthesis methods of monomers M1 and M4 are the same as in Example 1; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0042] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M1 (0.5 mmol, 89.096 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M4 (0.5 mmol, 153.201 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P3.
[0043] Analysis showed that the final product, polyesteramide compound P3, had a yield of 86%, a weight-average molecular weight of 46,100, and a molecular weight distribution of 1.54.
[0044] Example 4: A polyesteramide compound with the structural formula shown on page 4:
[0045] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0046] The synthesis methods of monomers M2 and M4 are the same as in Example 1; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0047] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M2 (0.5 mmol, 103.123 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M4 (0.5 mmol, 153.201 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P4.
[0048] Analysis showed that the final product, polyesteramide compound P4, had a yield of 98%, a weight-average molecular weight of 165,100, and a molecular weight distribution of 2.47.
[0049] Example 5: A polyesteramide compound with the structural formula shown on page 5:
[0050] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0051] The synthesis method of monomer M1 is the same as that in Example 1; the synthesis method of monomer M5 can be synthesized according to the synthesis method of the applicant in the published literature (Macromolecules, 2025, 58(14): 7017–7025.); 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0052] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M1 (0.5 mmol, 89.096 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M5 (0.5 mmol, 234.254 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P5.
[0053] Analysis showed that the final product, polyesteramide compound P5, had a yield of 84%, a weight-average molecular weight of 43,500, and a molecular weight distribution of 1.70.
[0054] from Figure 4 (P5 in DMSO solution with 0-40% water content, concentration of 10) -5 As can be seen from the (mol / L) data, the fluorescence emission intensity of the system gradually increases with the increase of water content in the polymer solution, proving that the polyesteramide compound has a significant aggregation-induced emission effect and has certain application value in the optoelectronic field.
[0055] Example 6: A polyesteramide compound with the structural formula shown on page 6:
[0056] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0057] The synthesis method of monomer M2 is the same as in Example 1; the synthesis method of monomer M5 is the same as in Example 5; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0058] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M2 (0.5 mmol, 103.123 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M5 (0.5 mmol, 234.254 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P6.
[0059] Analysis showed that the final product, polyesteramide compound P6, had a yield of 82%, a weight-average molecular weight of 24,000, and a molecular weight distribution of 1.47.
[0060] Example 7: A polyesteramide compound with the structural formula shown on page 7:
[0061] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0062] The synthesis method of monomer M1 is the same as that in Example 1; the synthesis method of monomer M6 can be synthesized according to the synthesis method of the applicant in the published literature (Macromolecules, 2024, 57(5): 1970–1978.); 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0063] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M1 (0.5 mmol, 89.096 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M6 (0.5 mmol, 166.178 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P7.
[0064] Analysis revealed that the final product, polyesteramide compound P7, had a yield of 76%, a weight-average molecular weight of 11,600, and a molecular weight distribution of 1.46.
[0065] Example 8: A polyesteramide compound with the structural formula shown on page 8:
[0066] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0067] The synthesis method of monomer M2 is the same as in Example 1; the synthesis method of monomer M6 is the same as in Example 7; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0068] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M2 (0.5 mmol, 103.123 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were sequentially added to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M6 (0.5 mmol, 166.178 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P8.
[0069] Analysis showed that the final product, polyesteramide compound P8, had a yield of 86%, a weight-average molecular weight of 40,500, and a molecular weight distribution of 1.40.
[0070] Example 9: A polyesteramide compound with the structural formula shown on page 9:
[0071] The polyesteramide compounds are prepared by polymerization of amide-based alkynyl monomers, 2-mercaptoethanol, and ester-based alkynyl monomers in tetrahydrofuran under the catalysis of triethylenediamine (DABCO). The reaction equation is as follows:
[0072] The synthesis method of monomer M2 is the same as in Example 1; the synthesis method of monomer M6 is the same as in Example 7; 2-mercaptoethanol and triethylenediamine can be purchased from the market, and in this example they were purchased from Anaiji Chemical Co., Ltd.
[0073] The preparation steps of the aforementioned polyesteramide compounds are as follows: A magnetic stir bar, monomer M2 (0.5 mmol, 96.109 mg), and 2-mercaptoethanol (0.5 mmol, 78.129 mg) were added sequentially to a 10 mL polymerization tube, followed by stirring with 0.5 mL of THF. Triethylenediamine (0.01 mmol, 1.112 mg) was then dissolved in 0.5 mL of THF and added dropwise to the reaction solution. After stirring at room temperature for 5 h, monomer M6 (0.5 mmol, 166.178 mg) was slowly added, and the reaction was allowed to proceed for another 1.5 h at room temperature. After the reaction was complete, the reaction solution was diluted with 2 mL of THF. The polymer solution was then added dropwise through a cotton filter using a glass dropper to anhydrous methanol to allow the polymer to precipitate. The product was filtered and washed to obtain the polyesteramide compound P9.
[0074] Analysis showed that the final product, polyesteramide compound P9, had a yield of 79%, a weight-average molecular weight of 22,900, and a molecular weight distribution of 1.37.
Claims
1. A method for preparing a polyesteramide compound, characterized in that, Includes the following steps: (1) A diamine alkynyl compound and 2-mercaptoethanol are reacted in a solvent to obtain an amide compound containing a dihydroxyl functional group. (2) Add the diester alkynyl compound to the organic solvent system obtained in step (1) for polymerization reaction. After the reaction is complete, add methanol for precipitation, collect the precipitate, and dry it to constant weight to obtain polyester amide compound. The general structural formulas of the diamide alkynyl compounds and the diester alkynyl compounds are shown in formula (II) or (III), respectively: (II)) (III)) The structural formula of the 2-mercaptoethanol is shown in formula (IV): (IV); The general structural formula of the aforementioned polyesteramide compounds is shown in formula (I): (I); In equations (I)-(III), n is an integer ≥ 2, and R 1 R 2 These are the same or different organic groups.
2. The method for preparing a polyesteramide compound according to claim 1, characterized in that, In the formulas (I)-(III), R 1 Selected from any one of the following chemical structural formulas (1)-(3): R 2 Choose any one of the structural formulas (4)-(7): (1); (2); (3); (4); (5); (6); (7)。 3. The method for preparing a polyesteramide compound according to claim 1, characterized in that, The organic solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, dimethyl sulfoxide, and N,N-dimethylamide.
4. The method for preparing a polyesteramide compound according to claim 1, characterized in that, The reaction time described in step (2) is 5-12 hours.
5. The method for preparing a polyesteramide compound according to claim 1, characterized in that, The molar ratio of the diamide alkynyl compound, 2-mercaptoethanol, and diester alkynyl compound is 1:1:
1.
6. A method for preparing a polyesteramide compound according to claim 1, characterized in that, The concentration of the diamide compound and diester compound with 2-mercaptoethanol in the organic solvent is 0.1-0.5 mol / L.
7. A method for preparing a polyesteramide compound according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 25-55°C. o C, the reaction time is 15-120 minutes.
8. The method for preparing a polyesteramide compound according to claim 1, characterized in that, The polymerization reaction was carried out in an atmospheric atmosphere under the action of triethylenediamine, an organic base catalyst.
9. The method for preparing a polyesteramide compound according to claim 1, characterized in that, The amount of the organic base catalyst used is 0.5%-2.5% of the molar amount of the diamide compound and the diester compound.
10. A polyesteramide compound, characterized in that, It is prepared according to any one of claims 1-9.