Carbon dioxide / bio-based polymer with mechanical and fluorescent properties and preparation method thereof

Abstract

The invention discloses a carbon dioxide / bio-based polymer with mechanical and fluorescent properties and a preparation method thereof, and belongs to the field of functional polymer material synthesis. According to the preparation method of the carbon dioxide / bio-based polymer with the mechanical and fluorescent properties, carbon dioxide and a bio-based platform compound are adopted as substrates, and the carbon dioxide / bio-based polymer is prepared through a multi-component polymerization reaction. The preparation method has the advantages of green raw materials, no need of a catalyst, mild reaction conditions and high atom economy. The carbon dioxide / bio-based polymer shows good mechanical properties and fluorescence properties, the tensile strength can reach 7.69 MPa, the carbon dioxide / bio-based polymer has a strong fluorescence emission peak at the wavelength of 570-580 nm, and the carbon dioxide / bio-based polymer has wide application prospects in the field of functional polymer materials.

Description

Technical Field

[0001] The invention belongs to the field of functional polymer material synthesis, and in particular relates to a carbon dioxide / bio-based polymer with mechanical and fluorescent properties and a preparation method thereof. Background Art

[0002] While the large-scale application of polymer materials has brought great convenience to human production and life, it has also brought serious consequences to resources and the environment. Up to now, more than 95% of polymer materials are still derived from petrochemical resources, resulting in a large amount of resource consumption and carbon emissions. Based on the urgent demand for low-carbon raw materials in the polymer materials industry, in-depth research and development of polymer material synthesis technology based on low-carbon raw materials such as carbon dioxide (CO2) and bio-based compounds has become a hot topic in the field of polymer science. Using CO2 as a raw material to synthesize basic chemicals, energy chemicals and polymer materials is precisely a green route that meets the needs of low carbon and sustainable development. Among them, the use of carbon dioxide to synthesize polymer materials has become an international research hotspot because it can achieve the preparation of high-value-added fully degradable polycarbonates. However, up to now, research on carbon dioxide-based polymers is still mainly focused on the copolymerization reaction of CO2 and alkylene oxides. The structure of carbon dioxide-based polymer materials prepared by the above-mentioned route is relatively simple, and more importantly, the epoxy monomers used, such as propylene oxide, are still mainly derived from petrochemical resources, which hinders the rapid development of the carbon dioxide-based polymer materials industry. The development of bio-based synthetic polymer materials with diverse structures and higher biocarbon content has become a major trend in this research field.

[0003] Bio-based synthetic polymer materials are new bio-based materials that are different from natural polymers. Their preparation mainly depends on the development of bio-based compounds, namely bio-based monomer refining technology. In recent years, biorefining technology has attracted much attention, and the level of bio-based compound preparation technology has been rapidly improved. The emergence of a large number of bio-based compounds has brought huge opportunities to the field of polymer synthesis. At present, among bio-based platform compounds, 2,5-furandicarboxylic acid (FDCA) and ethylene glycol copolymerization with furfural as raw materials can prepare polyethylene 2,5-furandicarboxylate (PEF), which has great application prospects and is considered to be an ideal substitute for petroleum-based polyethylene terephthalate (PET). However, the application of new structural monomers brings about changes in the requirements for polymerization catalysts and polymerization processes. After years of research by scientists at home and abroad, great progress has been made, but large-scale application has not yet been achieved. Therefore, the development of a mild, efficient, and catalytic-free polymerization system is a difficult problem that needs to be solved in the field of synthetic polymer materials using CO2 and bio-based monomers.

[0004] The present invention uses carbon dioxide and bio-based platform compounds as raw materials and utilizes a multi-component polymerization reaction strategy to synthesize carbon dioxide / bio-based polymers. It has the advantages of green monomers, mild reaction conditions, easy operation, high atom economy, and relatively wide substrate applicability. It conforms to the concept of green chemical reactions and has good application prospects in the field of functional polymer materials. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing a carbon dioxide / bio-based polymer with mechanical and fluorescent properties, which overcomes the harsh synthetic conditions of existing carbon dioxide and bio-based platform compounds for preparing polymer materials and gives them high added value. The polymer has good mechanical properties and fluorescent luminescence properties.

[0006] The specific technical solution of the present invention is as follows: A carbon dioxide / biobased polymer with mechanical and fluorescent properties, the structural formula of which is as follows:

[0007]

[0008] Wherein, n is an integer from 2 to 200; R 1 R is selected from alkyl, furyl and phenyl groups having 1 to 6 carbon atoms; 2 R is selected from alkyl, furyl and phenyl groups having 1 to 12 carbon atoms; 3 R is selected from alkyl, furyl and phenyl groups having 1 to 6 carbon atoms; 4 It is selected from alkyl, cycloalkyl and benzyl groups with 1 to 6 carbon atoms; the carbon dioxide / bio-based polymer has mechanical properties and fluorescent properties.

[0009] Among them, R 1 The carbon dioxide / biobased polymer with furan group has the best tensile strength and fluorescence intensity, and the structure is shown below:

[0010]

[0011] Another object of the present invention is to provide a method for preparing a carbon dioxide / bio-based polymer with mechanical and fluorescent properties. Specifically, aldehyde and amine are used as starting materials, stirred in a reaction solvent, and reacted to form an imine intermediate; alcohol and isonitrile monomers are continuously added, and carbon dioxide monomers are introduced for polymerization; after the reaction is completed, the solvent is removed in vacuo, and the carbon dioxide / bio-based polymer is obtained after being dissolved in dichloromethane and precipitated with n-hexane; the aldehyde is OHC-R 1 -CHO, amine is NH2-R 2 -NH2, alcohol as R 3 -OH, isonitrile as R 4 -NC, the reaction formula is:

[0012]

[0013]

[0014] Preferably, the aldehyde OHC-R 1 -CHO is selected from any one of the following (1-5); amine NH2-R 2 -NH2 is selected from any one of the following (6-10); alcohol R 3 -OH is selected from any one of the following (11-15); isonitrile R 4 -NC is selected from any one of the following (16-20):

[0015]

[0016] Furthermore, the reaction solvent is any one or more of methanol, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran, and the preferred embodiment is methanol.

[0017] Furthermore, the aldehyde OHC-R 1 -CHO, amine NH2-R 2 -NH2, alcohol R 3 -OH, isonitrile R 4 The molar ratio of -NC is 1:1:(2-3):(2-3), and the pressure of the carbon dioxide is 0.5-10 MPa.

[0018] Furthermore, the reaction time of the aldehyde and the amine is 0.5 to 6 hours, the polymerization reaction time is 48 to 96 hours, and the polymerization reaction temperature is 0 to 60°C.

[0019] The preparation method provided by the present invention uses carbon dioxide and bio-based platform compounds as raw materials, and selects a multi-component polymerization reaction to prepare carbon dioxide / bio-based polymers. The material has good mechanical properties and fluorescent properties, and has good application prospects in the field of functional polymer materials. Compared with the prior art, the beneficial effects of the present invention are:

[0020] 1. The present invention uses carbon dioxide and bio-based platform compounds as monomers, which have the characteristics of wide raw material sources, rich structures, low prices and green renewable;

[0021] 2. The present invention utilizes a multi-component polymerization reaction to prepare carbon dioxide / bio-based polymers, which does not require a catalyst, has a simple synthesis method, mild reaction conditions, few by-products, and is easy to operate;

[0022] 3. The carbon dioxide / bio-based polymer prepared by the present invention has good mechanical properties and high-efficiency fluorescent properties, with a tensile strength of up to 7.69 MPa and a maximum emission wavelength of 570-580 nm, and is expected to be widely used in the field of functional polymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / bio-based polymer synthesized in Example 1 of the present invention;

[0024] Figure 2 is a hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / bio-based polymer synthesized in Example 2 of the present invention;

[0025] Figure 3 is a hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / bio-based polymer synthesized in Example 3 of the present invention;

[0026] Figure 4 is the Fourier transform infrared spectrum of the carbon dioxide / bio-based polymer synthesized in Examples 1-3 of the present invention;

[0027] Figure 5 is the DSC curve of the carbon dioxide / bio-based polymer synthesized in Examples 1-3 of the present invention;

[0028] Figure 6 is the stress-strain curve of the carbon dioxide / bio-based polymer synthesized in Examples 1-3 of the present invention;

[0029] Figure 7 It is the fluorescence spectrum of the carbon dioxide / bio-based polymer synthesized in Examples 1-3 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0031] Embodiment 1:

[0032] Using carbon dioxide, methanol, 2,5-furandicarboxaldehyde, decanediamine and tert-butyl isonitrile as raw materials, the reaction formula and experimental steps are as follows:

[0033]

[0034] Monomers of carbon dioxide, methanol, 2,5-furandicarboxaldehyde, decanediamine and tert-butyl isonitrile can be purchased; 2,5-furandicarboxaldehyde (148.9 mg, 1.2 mmol) and decanediamine (206.8 mg, 1.2 mmol) were added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isonitrile (299.3 mg, 3.6 mmol) was added, carbon dioxide was introduced, and the pressure was maintained at 1.5 MPa for 48 hours. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 46%, a weight average molecular weight of 14400 g / mol, and a molecular weight distribution index of 2.29.

[0035] The hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / biobased polymer P1 prepared in this example is as follows Figure 1 As shown, from Figure 1 It can be seen that the proton chemical shift of the aldehyde group in the monomer 2,5-furandicarboxaldehyde has disappeared, and the -CH- shift directly connected to the furan ring in the monomer 2,5-furandicarboxaldehyde has been reduced to 5.30-6.75 ppm. The infrared absorption spectrum of the carbon dioxide / bio-based polymer P1 prepared in this example is shown in FIG. Figure 4 As shown, from Figure 4 It can be seen that the characteristic peaks of the amide and urethane structures in P1 appear at 1750-1600 cm -1 The stretching vibration peaks of NH in amide appear at 3415 and 3317 cm -1 , which indicates that the polymerization reaction proceeds smoothly. The DSC curve of the carbon dioxide / bio-based polymer P1 prepared in this example under a nitrogen atmosphere is as follows Figure 5 shown. Figure 5 The glass transition temperature of the obtained polymer is 50.5° C. The stress-strain curve of the carbon dioxide / bio-based polymer P1 prepared in this example is shown in FIG. Figure 6 As shown, the tensile strength of the polymer is 4.97 MPa and the elongation at break is 366.9%. The fluorescence emission spectrum of the carbon dioxide / bio-based polymer P1 prepared in this example is shown in Figure 7 As shown, under an excitation wavelength of 496 nm, the maximum emission wavelength of the polymer appears at 575 nm.

[0036] Embodiment 2:

[0037] Using carbon dioxide, methanol, 2,5-furandicarboxaldehyde, octanediamine and tert-butyl isocyanide as raw materials, the reaction formula and experimental steps are as follows:

[0038]

[0039] Monomers of carbon dioxide, methanol, 2,5-furandicarboxaldehyde, octanediamine and tert-butyl isocyanide can be purchased; 2,5-furandicarboxaldehyde (148.9 mg, 1.2 mmol) and octanediamine (173.1 mg, 1.2 mmol) were added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isocyanide (299.3 mg, 3.6 mmol) was added, carbon dioxide was introduced, and the pressure was maintained at 1.5 MPa for 48 hours. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 50%, a weight average molecular weight of 9500 g / mol, and a molecular weight distribution index of 1.86.

[0040] The hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / biobased polymer P2 prepared in this example is as follows Figure 2 As shown, from Figure 2 It can be seen that the proton chemical shift of the aldehyde group in the monomer 2,5-furandicarboxaldehyde has disappeared, and the -CH- shift directly connected to the furan ring in the monomer 2,5-furandicarboxaldehyde has been reduced to 5.40-6.85ppm. The infrared absorption spectrum of the carbon dioxide / bio-based polymer P2 prepared in this example is shown in Figure 4 As shown in Figure 2, the characteristic peaks of the amide and aminoester structures in P2 appeared at 1750-1600 cm -1 The stretching vibration peaks of NH in amide appear at 3415 and 3317 cm -1 , which indicates that the polymerization reaction proceeds smoothly. The DSC curve of the bio-based fluorescent polyamide prepared in this example under nitrogen atmosphere is shown in Figure 5 shown. Figure 5 The glass transition temperature of the obtained polymer is 67.1° C. The stress-strain curve of the carbon dioxide / bio-based polymer P2 prepared in this example is shown in FIG. Figure 6 As shown, the tensile strength of the polymer is 2.61 MPa and the elongation at break is 346.5%. The fluorescence emission spectrum of the bio-based fluorescent polyamide prepared in this embodiment is shown in Figure 7 As shown, Figure 7 It shows that the maximum emission wavelength of the obtained polymer appears at 570nm under the excitation wavelength of 496nm.

[0041] Embodiment 3:

[0042] Using carbon dioxide, methanol, 2,5-furandicarboxaldehyde, 1,12-diaminododecane and tert-butyl isonitrile as raw materials, the reaction formula and experimental steps are as follows:

[0043]

[0044] Monomers of carbon dioxide, methanol, 2,5-furandicarboxaldehyde, 1,12-diaminododecane and tert-butyl isonitrile can be purchased; 2,5-furandicarboxaldehyde (148.9 mg, 1.2 mmol) and 1,12-diaminododecane (240.4 mg, 1.2 mmol) were added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isonitrile (299.3 mg, 3.6 mmol) was added, carbon dioxide was introduced, and the pressure was maintained at 1.5 MPa for 48 hours. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 41%, a weight average molecular weight of 12500 g / mol, and a molecular weight distribution index of 2.02.

[0045] The hydrogen nuclear magnetic resonance spectrum of the carbon dioxide / biobased polymer P3 prepared in this example is as follows Figure 3 As shown, from Figure 3 It can be seen that the proton chemical shift of the aldehyde group in the monomer 2,5-furandicarboxaldehyde has disappeared, and the -CH- shift directly connected to the furan ring in the monomer 2,5-furandicarboxaldehyde has been reduced to 5.40-6.75 ppm. The infrared absorption spectrum of the carbon dioxide / bio-based polymer P3 prepared in this example is shown in FIG. Figure 4 As shown in Figure 2, the characteristic peaks of the amide and aminoester structures in P3 appeared at 1750-1600 cm -1 The stretching vibration peaks of NH in amide appear at 3415 and 3317 cm -1 , which indicates that the polymerization reaction proceeds smoothly. The DSC curve of the bio-based fluorescent polyamide prepared in this example under nitrogen atmosphere is shown in Figure 5 shown. Figure 5 The glass transition temperature of the obtained polymer is 26.7° C. The stress-strain curve of the carbon dioxide / bio-based polymer P3 prepared in this example is shown in FIG. Figure 6 As shown, the tensile strength of the polymer is 7.69 MPa and the elongation at break is 245.3%. The fluorescence emission spectrum of the bio-based fluorescent polyamide prepared in this embodiment is shown in Figure 7 As shown, Figure 7 It shows that the maximum emission wavelength of the obtained polymer appears at 580nm under the excitation wavelength of 496nm.

[0046] Embodiment 4:

[0047] Using carbon dioxide, methanol, 2,5-furandicarboxaldehyde, 2,5-furandimethylamine and tert-butyl isonitrile as raw materials, the reaction formula and experimental steps are as follows:

[0048]

[0049] Monomers of carbon dioxide, methanol, 2,5-furandicarboxaldehyde, 2,5-furandimethylamine and tert-butyl isocyanide can be purchased; 2,5-furandicarboxaldehyde (148.9 mg, 1.2 mmol) and 2,5-furandimethylamine (151.4 mg, 1.2 mmol) were added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isocyanide (299.3 mg, 3.6 mmol) was added, carbon dioxide was introduced, and the pressure was maintained at 1.5 MPa for 48 hours. After the reaction was completed, the solvent was removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 55%, a weight average molecular weight of 11600 g / mol, and a molecular weight distribution index of 2.00.

[0050] Embodiment 5:

[0051] Using carbon dioxide, methanol, glutaraldehyde, 2,5-furandimethylamine and tert-butyl isocyanide as raw materials, the reaction formula and experimental steps are as follows:

[0052]

[0053] Monomers of carbon dioxide, methanol, glutaraldehyde, 2,5-furandimethylamine and tert-butyl isocyanide can be purchased; glutaraldehyde (120.1 mg, 1.2 mmol) and 2,5-furandimethylamine (151.4 mg, 1.2 mmol) are added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isocyanide (299.3 mg, 3.6 mmol) is added, carbon dioxide is introduced, and the pressure is maintained at 1.5 MPa for 48 hours. After the reaction is completed, the solvent is removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 65%, a weight average molecular weight of 13300 g / mol, and a molecular weight distribution index of 2.08.

[0054] Embodiment 6:

[0055] Using carbon dioxide, methanol, glutaraldehyde, decanediamine and tert-butyl isonitrile as raw materials, the reaction formula and experimental steps are as follows:

[0056]

[0057] Monomers of carbon dioxide, methanol, glutaraldehyde, decanediamine and tert-butyl isonitrile can be purchased; glutaraldehyde (120.1 mg, 1.2 mmol) and decanediamine (206.8 mg, 1.2 mmol) are added to a 10 mL reaction tube containing 2.4 mL methanol and 2.4 mL dichloromethane, stirred at room temperature for 1 hour, then tert-butyl isonitrile (299.3 mg, 3.6 mmol) is added, carbon dioxide is introduced, and the pressure is maintained at 1.5 MPa for 48 hours. After the reaction is completed, the solvent is removed by rotary evaporation, dissolved in dichloromethane, precipitated with n-hexane, and dried to obtain carbon dioxide / bio-based polymer, with a yield of 56%, a weight average molecular weight of 9600 g / mol, and a molecular weight distribution index of 2.13.

[0058] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various equivalent transformations can be made to the technical scheme of the present invention, and these equivalent transformations all belong to the protection scope of the present invention.

Claims

1. A carbon dioxide / bio-based polymer with mechanical and fluorescent properties, characterized in that: Has the following structure: Wherein, n is an integer from 2 to 200; R 1 R is selected from alkyl, furyl and phenyl groups having 1 to 6 carbon atoms; 2 is selected from alkyl, furyl and phenyl groups having 1 to 12 carbon atoms; R 3 R is selected from alkyl, furyl and phenyl groups having 1 to 6 carbon atoms; 4 It is selected from alkyl, cycloalkyl and benzyl groups with 1 to 6 carbon atoms; the carbon dioxide / bio-based polymer has mechanical properties and fluorescent properties.

2. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 1, characterized in that: The steps include: The aldehyde and amine monomers are dissolved in a reaction solvent, reacted for a period of time, and then alcohol and isonitrile monomers are added, and carbon dioxide monomers are introduced for polymerization, and then treated to obtain carbon dioxide / biobased polymers; the aldehyde is OHC-R 1 -CHO, amine is NH2-R 2 -NH2, alcohol as R 3 -OH, isonitrile as R 4 -NC, the reaction formula is:

3. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 2, characterized in that: Aldehyde OHC-R 1 -CHO is selected from any one of the following (1-5); amine NH2-R 2 -NH2 is selected from any one of the following (6-10); alcohol R 3 -OH is selected from any one of the following (11-15); isonitrile R 4 -NC is selected from any one of the following (16-20):

4. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 2, characterized in that: The reaction solvent is selected from any one or more of methanol, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.

5. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 2, characterized in that: The aldehyde OHC-R 1 -CHO, amine NH2-R 2 -NH2, alcohol R 3 -OH, isonitrile R 4 The molar ratio of -NC is 1:1:(2-3):(2-3), and the pressure of carbon dioxide is 0.5-10 MPa.

6. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 2, characterized in that: The reaction time of aldehyde and amine is 0.5 to 6 hours, the polymerization time is 48 to 96 hours, and the polymerization temperature is 0 to 60°C.

7. The method for preparing carbon dioxide / bio-based polymer with mechanical and fluorescent properties according to claim 2, characterized in that: The subsequent treatment means that after the reaction is completed, the reaction solution is decompressed to remove the solvent, dissolved in dichloromethane, and then precipitated in n-hexane to obtain carbon dioxide / bio-based polymer.

Images