Bio-based polyesteramide as well as preparation method and application thereof

Abstract

The invention discloses bio-based polyesteramide as well as a preparation method and application thereof, the preparation method of the bio-based polyesteramide comprises the following steps: (1) dissolving a furyl dicarboxylic acid ester derivative in an organic solvent I to obtain a first mixed solution; (2) dissolving 1, 3-diamino-2-propanol and a catalyst in an organic solvent II to obtain a second mixed solution; (3) simultaneously pumping the first mixed solution and the second mixed solution into a microreactor module for mixed reaction; and (4) collecting a crude product, and carrying out post-treatment to obtain the bio-based polyesteramide. The obtained bio-based polyesteramide can be used as an adhesive and applied to metal ion detection. Polyesteramide synthesized through a one-step method by utilizing a continuous flow technology not only combines the mechanical property of polyamide and the biocompatibility of polyester, but also has good adhesion property and aggregation-induced emission property, and is a bifunctional material integrating an adhesive and a metal ion detection agent.

Description

Technical Field

[0001] The present invention belongs to the technical field of bio-based polyester amides, and specifically relates to a bio-based polyester amide and a preparation method and application thereof. Background Art

[0002] Biomass is considered a very promising renewable alternative to petroleum due to its carbon neutrality, widespread distribution, and sustainability. Biomass-derived monomers and polymers are considered to be an ideal way to utilize biomass resources and address the environmental issues associated with traditional plastics. Polyesteramides (PEAs) contain ester and amide groups in their polymer backbone and exhibit improved thermal and mechanical properties compared to polyesters due to the increase in strong hydrogen bonding interactions between polymer chains. In the past few years, the application of PEAs in various fields such as drug delivery vehicles, smart materials, adhesives, and tissue engineering architectures has increased significantly.

[0003] Polyesteramide (PEAs) is a type of polyamide thermoplastic elastomer (TPAE), which is a segmented block copolymer with ester chains and amide bonds on its main molecular chain. Therefore, polyesteramide has both the excellent mechanical properties of polyamide and the biocompatibility and biodegradability of polyester, and is one of the thermoplastic elastomer products with excellent comprehensive performance. Polyesteramide is easy to process, and can be manufactured into films, wires, profiles, coating materials and other products by injection molding, extrusion molding, blow molding and other processing techniques. It can be widely used in the pharmaceutical, biomedical, telecommunications cable, automotive and other industries. In the medical field, it can be used as a drug controlled release material, tissue engineering material, etc.

[0004] There are many methods for preparing polyester amide, the main processes are: two-step method, first synthesizing ethanol phthalate monomer, and then reacting it with ethylene terephthalate to obtain it; one-step method, directly adding ethanolamine to the transesterification reaction to react to obtain it; ring-opening polymerization method, using caprolactone and aminocaproic acid as raw materials to carry out ring-opening and condensation reactions to prepare linear polyester amide; in addition, there is condensation polymerization method, etc. The preparation process of polyester amide is constantly improving. In the early days, condensation polymerization method was mainly used, which was gradually eliminated later. At present, ring-opening polymerization method is widely used in the preparation of linear polyester amide.

[0005] However, the preparation methods in the prior art often have some defects, such as long reaction time, low efficiency, and poor performance of the obtained polyester amide. Summary of the invention

[0006] Purpose of the invention: In view of the shortcomings of the prior art, the present invention provides a bio-based polyester amide and its preparation method and application. The polyester amide synthesized by the present invention through a one-step method using continuous flow technology not only combines the mechanical properties of polyamide and the biocompatibility of polyester, but also has good adhesion and aggregation-induced emission properties. It is a dual-functional material integrating adhesive and metal ion detector.

[0007] Technical solution: In order to solve the above technical problems, the present invention adopts the following technical solution:

[0008] A method for preparing a bio-based polyester amide comprises the following steps:

[0009] (1) dissolving a furanyl dicarboxylic acid ester derivative in an organic solvent I to obtain a first mixed solution;

[0010] (2) dissolving 1,3-diamino-2-propanol and a catalyst in an organic solvent II to obtain a second mixed solution;

[0011] (3) pumping the first mixed solution and the second mixed solution into the microreactor module for mixed reaction at the same time;

[0012] (4) collecting the crude product and performing post-treatment to obtain the bio-based polyester amide.

[0013] As a specific implementation scheme, in step (1), the furanyl dicarboxylic acid ester derivative is any one of 2,5-furandicarboxylic acid dimethyl ester, 2,4-furandicarboxylic acid dimethyl ester, or a combination of several thereof; the organic solvent I is any one of dimethyl sulfoxide, N-methylpyrrolidone, or N,N-diethylformamide or a combination of several thereof.

[0014] As a specific implementation scheme, in step (2), the catalyst is any one or a combination of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2.2.2]octane; the organic solvent II is any one or a combination of dimethyl sulfoxide, N-methylpyrrolidone, N,N-diethylformamide.

[0015] As a specific implementation scheme, in step (2), the amount of the catalyst added is determined by the total molar amount of the furanyl dicarboxylic acid ester derivatives and 1,3-diamino-2-propanol, and the amount added ranges from 6 to 12 mol%, preferably 10 mol%; that is, assuming that the total molar amount of the furanyl dicarboxylic acid ester derivatives and 1,3-diamino-2-propanol is 100 mol, the amount of the catalyst added is 6 to 12 mol, preferably 10 mol.

[0016] As a specific implementation scheme, in step (3), the microreactor module includes a microstructure mixer and a microstructure reactor which are sequentially connected by pipelines, and the first mixed liquid and the second mixed liquid are pumped into the microstructure mixer at the same time, and after mixing, they are passed into the microstructure reactor for reaction.

[0017] As a further embodiment, in the first mixed solution and the second mixed solution pumped into the microstructure mixer, the molar ratio of the furanyl dicarboxylic acid ester derivative to 1,3-diamino-2-propanol is in the range of (1.0-1.5):1, preferably 1.5:1.

[0018] As a further scheme, the flow rate of the first mixed liquid and the second mixed liquid pumped into the microstructure mixer is 40-250 μL / min, and the flow rates of the two are determined according to the molar ratio requirements between the furanyl dicarboxylic acid ester derivatives and 1,3-diamino-2-propanol. The residence time in the microstructure reactor is 0.25-2h, and the reaction temperature is 90-150°C. Preferably, the residence time is 0.5-2h, and the reaction temperature is 110-150°C. More preferably, the residence time is 0.5h.

[0019] As a specific implementation, in step (4), the post-treatment includes: dropping the reaction solution into an excess of ethyl acetate to obtain a polymer precipitate, collecting the precipitate, washing, and drying to obtain the bio-based polyester amide.

[0020] The present invention also provides a bio-based polyester amide, which is prepared by the above-mentioned preparation method.

[0021] The chemical structure of the bio-based polyester amide is shown in Formula I:

[0022]

[0023] Finally, the present invention provides the application of the bio-based polyester amide as an adhesive or in metal ion detection.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0025] (1) The present invention adopts a "one-step method" to prepare polyester amide materials, using bio-based monomers as raw materials, which are green bio-based compounds with a wide range of sources; polyester amide is effectively prepared by solution polymerization using a microreactor, wherein the micron-level mass transfer and heat transfer performance not only greatly shortens the reaction time, but also can easily achieve the enhancement of mass transfer-limited reactions. Therefore, the present invention explores a green continuous flow reaction technology to synthesize PEAs.

[0026] (2) The microreactor can be used to control the structure and properties of the polymer by simply controlling the feed molar ratio. The operation is simple and the reaction conditions can be quickly screened.

[0027] (3) Various hydrogen bonding interactions can be formed between different functional groups in PEAs, such as amide bonds, ester bonds, and hydroxyl groups, which can provide anchoring sites for the hydroxyl groups of stainless steel, have good mechanical properties and shear strength, and have great potential as a new type of adhesive in promoting long-lasting bonding of materials.

[0028] (4) The supramolecular enhanced charge transfer between the spatially separated amide and carboxyl groups in the PEA structure causes the polymer to produce fluorescence. PEAs in solid form or dissolved in NMP solution show bright blue under ultraviolet light, and the addition of metal ions causes obvious fluorescence quenching. Therefore, PEAs are expected to be used as metal ion detection reagents and have application potential in the field of environmental testing. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the H NMR spectrum of the bio-based polyester amide prepared in Example 1-4, wherein R represents the molar ratio of dimethyl furandicarboxylate to 1,3-diamino-2-propanol during the preparation process, and R=1.5, R=1.3, R=1.1 and R=1 represent that the molar ratios of the two are 1.5:1, 1.3:1, 1:1.1 and 1:1, respectively.

[0030] Figure 2 This is the infrared spectrum of the bio-based polyester amide obtained in Examples 1-4, wherein R represents the molar ratio of dimethyl furandicarboxylate to 1,3-diamino-2-propanol during the preparation process, and R=1.5, R=1.3, R=1.1 and R=1 represent that the molar ratios of the two are 1.5:1, 1.3:1, 1:1.1 and 1:1, respectively.

[0031] Figure 3 This is a shear strength diagram of the bio-based polyester amide prepared in Examples 1, 2, and 5, wherein the value of the abscissa represents the molar ratio of dimethyl furandicarboxylate to 1,3-diamino-2-propanol during the preparation process, and 1.5, 1.3, and 1.2 represent molar ratios of 1.5:1, 1.3:1, and 1:2.1, respectively.

[0032] Figure 4 This is the emission spectrum of the bio-based polyester amide solution prepared in Example 5 in the presence of different ions. DETAILED DESCRIPTION

[0033] 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.

[0034] If the specific techniques or conditions are not specified in the examples, they are carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased through regular channels.

[0035] The microreactor module in the following embodiment includes a microstructure mixer and a microstructure reactor connected in sequence by pipelines. The first mixed liquid and the second mixed liquid are pumped into the microstructure mixer at the same time, and after mixing, they are passed into the microstructure reactor for reaction; the microstructure mixer is a T-type mixer, and the first mixed liquid and the second mixed liquid are pumped into the microstructure mixer through different injection pumps respectively.

[0036] Example 1

[0037] A method for preparing a bio-based polyester amide comprises the following steps:

[0038] The first mixed solution was obtained by completely dissolving dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) in N-methylpyrrolidone (16 mL), and the second mixed solution was obtained by completely dissolving 1,3-diamino-2-propanol (0.0110 mol, 0.99 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.38 g, 10 mol%) in N-methylpyrrolidone (3.5 mL). The first and second mixed solutions were simultaneously pumped into the microreactor module for mixed reaction, respectively, with flow rates of 206 and 45 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1.5:1), the residence time of the reaction solution in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 130°C. Finally, the crude product was collected for post-treatment. The reaction solution was dropped into an excess of ethyl acetate, and the polymer precipitate was collected after standing. The precipitate was washed with water several times and then vacuum dried at 60°C for 3 days to obtain a bio-based polyester amide solid with a yield of 39%. Figure 1 As shown, the infrared spectrum is Figure 2 As shown, the glass transition temperature Tg is 114.7℃, the maximum decomposition rate temperature is about 330℃, and the shear strength diagram is as follows Figure 3 As shown, the shear strength is 1.5MPa.

[0039] Example 2

[0040] A method for preparing a bio-based polyester amide comprises the following steps:

[0041] The first mixed solution was obtained by completely dissolving dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) in N-methylpyrrolidone (16 mL), and the second mixed solution was obtained by completely dissolving 1,3-diamino-2-propanol (0.0127 mol, 1.14 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.40 g, 10 mol%) in N-methylpyrrolidone (3.5 mL). The first and second mixed solutions were simultaneously pumped into the microreactor module for mixed reaction, respectively, with flow rates of 207.0 and 45.3 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1.3:1), the residence time of the reaction solution in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 110°C. Finally, the crude product was collected for post-treatment. The reaction solution was dropped into an excess of ethyl acetate, and the polymer precipitate was collected after standing. The precipitate was washed with water several times and then vacuum dried at 60°C for 3 days to obtain a bio-based polyester amide solid with a yield of 42%. The NMR spectrum is shown in Figure 1 As shown, the infrared spectrum is Figure 2 As shown, the glass transition temperature Tg is 121.8℃, the maximum decomposition rate temperature is about 330℃, and the shear strength diagram is as follows Figure 3 As shown, the shear strength is 1.8MPa.

[0042] Example 3

[0043] A method for preparing a bio-based polyester amide comprises the following steps:

[0044] The first mixed solution was obtained by completely dissolving dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) in N-methylpyrrolidone (16 mL), and the second mixed solution was obtained by completely dissolving 1,3-diamino-2-propanol (0.0150 mol, 1.34 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.35 g, 8 mol%) in N-methylpyrrolidone (3.75 mL). The first and second mixed solutions were simultaneously pumped into the microreactor module for mixed reaction, respectively, with flow rates of 204.0 and 47.8 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1.1:1), the residence time of the reaction solution in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 150°C. Finally, the crude product was collected for post-treatment. The reaction solution was dropped into an excess of ethyl acetate, and the polymer precipitate was collected after standing. The precipitate was washed with water several times and then vacuum dried at 60°C for 3 days to obtain a bio-based polyester amide solid with a yield of 47%. The NMR spectrum is shown in Figure 1 As shown, the infrared spectrum is Figure 2 As shown, the glass transition temperature Tg is 144.2°C and the maximum decomposition rate temperature is about 330°C.

[0045] Example 4

[0046] A method for preparing a bio-based polyester amide comprises the following steps:

[0047] The first mixed solution was obtained by completely dissolving dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) in N-methylpyrrolidone (16 mL), and the second mixed solution was obtained by completely dissolving 1,3-diamino-2-propanol (0.0165 mol, 1.48 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.27 g, 6 mol%) in N-methylpyrrolidone (4 mL). The first and second mixed solutions were simultaneously pumped into the microreactor module for mixed reaction, respectively, with flow rates of 202.0 and 50.5 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1:1), the residence time of the reaction solution in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 110°C. Finally, the crude product was collected for post-treatment. The reaction solution was dropped into an excess of ethyl acetate, and the polymer precipitate was collected after standing. The precipitate was washed with water several times and then vacuum dried at 60°C for 3 days to obtain a bio-based polyester amide solid with a yield of 58%. Figure 1 As shown, the infrared spectrum is Figure 2 As shown, the glass transition temperature Tg is 112.4°C and the maximum decomposition rate temperature is about 330°C.

[0048] Example 5

[0049] A method for preparing a bio-based polyester amide comprises the following steps:

[0050] Dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) was completely dissolved in N-methylpyrrolidone (16 mL) to obtain a first mixed solution to obtain a second mixed solution, and 1,3-diamino-2-propanol (0.0138 mol, 1.24 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.40 g, 10 mol%) were completely dissolved in N-methylpyrrolidone (3.75 mL) to obtain a second mixed solution. The first and second mixed liquids were simultaneously pumped into the microreactor module for mixed reaction, with flow rates of 204.0 and 47.8 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivatives and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1.2:1), the residence time of the reaction liquid in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 110°C. Finally, the crude product was collected for post-treatment. The reaction solution was dripped into an excess of ethyl acetate, and the polymer precipitate was collected by standing. The precipitate was washed with water several times, and then vacuum dried at 60°C for 3 days to obtain a bio-based polyester amide solid with a yield of 45%. The NMR spectrum is shown as Figure 1 As shown, the infrared spectrum is Figure 2 As shown, the glass transition temperature Tg is 130.4℃, the maximum decomposition rate temperature is about 330℃, and the shear strength diagram is as follows Figure 3 As shown, the shear strength is 2.0 MPa.

[0051] Example 6

[0052] A method for preparing a bio-based polyester amide comprises the following steps:

[0053] The first mixed solution was obtained by completely dissolving dimethyl 2,5-furandicarboxylate (0.0165 mol, 3.04 g) in N-methylpyrrolidone (16 mL), and the second mixed solution was obtained by completely dissolving 1,3-diamino-2-propanol (0.0165 mol, 1.48 g) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.27 g, 6 mol%) in N-methylpyrrolidone (4 mL). The first and second mixed solutions were simultaneously pumped into the microreactor module for mixed reaction, respectively, with flow rates of 202.0 and 50.5 μL / min respectively (so that the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol in the solution entering the microstructure mixer was 1:1), the residence time of the reaction solution in the microreactor module was 0.5 h, and the entire polymerization reaction was carried out in an oil bath heated to 110°C. Finally, the crude product was collected for post-treatment. The reaction solution was dropped into an excess of ethyl acetate, and the polymer precipitate was collected by standing. The precipitate was washed with water several times and then vacuum dried at 60°C for 3 days to obtain bio-based polyester amide with a yield of 58%. PEAs were dissolved in NMP solution, and different ions were added to obtain different emission spectra at an excitation wavelength of 350nm, such as Figure 4 shown.

[0054] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a bio-based polyester amide, characterized in that: The steps include: (1) dissolving a furanyl dicarboxylic acid ester derivative in an organic solvent I to obtain a first mixed solution; (2) dissolving 1,3-diamino-2-propanol and a catalyst in an organic solvent II to obtain a second mixed solution; (3) pumping the first mixed solution and the second mixed solution into the microreactor module for mixed reaction at the same time; (4) collecting the crude product and performing post-treatment to obtain the bio-based polyester amide.

2. The method for preparing bio-based polyester amide according to claim 1, characterized in that: In step (1), the furanyl dicarboxylic acid ester derivative is any one of 2,5-furandicarboxylic acid dimethyl ester, 2,4-furandicarboxylic acid dimethyl ester, or a combination of several thereof; and the organic solvent I is any one of dimethyl sulfoxide, N-methylpyrrolidone, or N,N-diethylformamide or a combination of several thereof.

3. The method for preparing bio-based polyester amide according to claim 1, characterized in that: In step (2), the catalyst is any one or a combination of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicycloundec-7-ene, and 1,4-diazabicyclo[2.2.2]octane; the organic solvent II is any one or a combination of dimethyl sulfoxide, N-methylpyrrolidone, and N,N-diethylformamide.

4. The method for preparing bio-based polyester amide according to claim 1, characterized in that: In step (2), the amount of the catalyst added is determined by the total molar amount of the furanyl dicarboxylic acid ester derivatives and 1,3-diamino-2-propanol, and the amount added is in the range of 6-12 mol%.

5. The method for preparing bio-based polyester amide according to claim 1, characterized in that: In step (3), the microreactor module includes a microstructure mixer and a microstructure reactor which are sequentially connected by a pipeline. The first mixed liquid and the second mixed liquid are pumped into the microstructure mixer at the same time, and after mixing, they are passed into the microstructure reactor for reaction.

6. The method for preparing bio-based polyester amide according to claim 5, characterized in that: In the first mixed liquid and the second mixed liquid pumped into the microstructure mixer, the molar ratio between the furanyl dicarboxylic acid ester derivative and 1,3-diamino-2-propanol is in the range of (1.0-1.5):

1.

7. The method for preparing bio-based polyester amide according to claim 5, characterized in that: The flow rate of the first mixed liquid and the second mixed liquid pumped into the microstructure mixer is 40-250 μL / min, the residence time in the microstructure reactor is 0.25-2 h, and the reaction temperature is 90-150° C.

8. The method for preparing bio-based polyester amide according to claim 1, characterized in that: In step (4), the post-treatment includes: dropping the reaction solution into an excess of ethyl acetate to obtain a polymer precipitate, collecting the precipitate, washing, and drying to obtain the bio-based polyester amide.

9. A bio-based polyester amide, characterized in that: The bio-based polyester amide is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the bio-based polyester amide according to claim 9 as an adhesive or in metal ion detection.

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