A furanyl polyester compound containing an olefin structure, and a preparation method and application thereof

Abstract

The application discloses a furan-based polyester compound containing an olefin structure, a preparation method and application thereof, and belongs to the technical field of furan-based polymers. The furan-based polyester compound containing the olefin structure has a structure shown in formula (I), R is selected from one or more of C1-C20 linear or branched alkyl, aryl, heteroaryl, and n is a repeating unit. 48 The furan-based polyester compound containing the olefin structure is novel in structure and can be further converted into other furan-based polyester compounds with other structures, so that the structure type of the furan-based polyester compound is greatly enriched.

Description

Technical Field

[0001] This invention relates to the technical field of furan-based polymers, and more particularly to a furan-based polyester compound containing an olefin structure, its preparation method, and its applications. Background Technology

[0002] Since the advent of the Ziegler-Natta process in the early 1950s, polyolefins (especially polyethylene) have been widely used in transportation, construction, agriculture, and medicine due to their superior performance and cost-effectiveness, comparable to traditional materials. However, their excellent biochemical stability and high durability make their biodegradation extremely slow, leading to continuous accumulation in the environment and increasing "white pollution." Polyester structures are commonly used in textiles, film materials, and engineering plastics, but since most polyester structures on the market contain benzene rings, their corresponding polymer monomers, such as terephthalic acid, are derived from petrochemical products. The environmental pollution, climate change, and resource and energy crises caused by the large-scale use of petrochemical resources have become a focus of attention for the global academic and industrial communities. Therefore, there is a great interest in producing "degradable" green polymer materials. Developing green and renewable biomass resources is a top priority in current research, and converting renewable biomass resources into high-value-added chemicals is of great significance for the sustainable development of chemistry.

[0003] 2,5-Furfurandicarboxylic acid (FDCA), as the only compound containing an aromatic ring among promising bio-based platform compounds, can be prepared from biomass such as starch and cellulose through hydrolysis, dehydration, and oxidation. It possesses structural and physical properties similar to the petroleum-based monomer terephthalic acid (TPA) and is considered the most promising bio-based monomer to replace TPA, capable of synthesizing high-performance polyesters, polyamides, and epoxy resins. As early as 1946, a patent co-authored by Drewitt and Lincoln first mentioned the polymerization of dimethyl 2,5-furandicarboxylate (DMFD) and ethylene glycol (EG) to prepare polyethylene 2,5-furandicarboxylate (PEF). With continuous exploration and development, the synthesis of furan-based polyesters currently mainly includes solution polymerization, direct esterification, transesterification, and other methods (such as interfacial polymerization, ring-opening polymerization, and enzyme-catalyzed polymerization). However, the processes or product purification and separation procedures of these synthetic methods are often quite complex, and the synthesized furanyl polyester compounds have limited structural types, which restricts the industrial production and application of furanyl polyester compounds. Therefore, it is crucial to develop new synthetic methods for furanyl polyester compounds. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a furan-based polyester compound containing an olefin structure, its preparation method, and its application. The furan-based polyester compound containing an olefin structure described in the present invention has a novel and unique structure and can undergo further transformation, thus enriching the structural types of furan-based polyester compounds.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] This invention provides a furanyl polyester compound containing an olefin structure, having the structure shown in formula (I):

[0007]

[0008] Preferably, R is selected from C1 to C2. 48 One or more of the following: straight-chain or branched alkyl groups, substituted or unsubstituted aryl groups, and heteroaryl groups.

[0009] The n is a repeating unit, preferably 10 to 100.

[0010] The C1~C 48 The straight-chain or branched alkyl group is more preferably C2-C3. 16 A straight-chain or branched alkyl group. In a specific embodiment of the invention, R is -(C9H 18 )- or -(C4H8)-.

[0011] Preferably, the substituents of the aryl and heteroaryl groups are selected from one or more of alkoxy, alkyl, and halogen groups.

[0012] Preferably, the aryl group is selected from phenyl or benzyl.

[0013] Preferably, the heteroaryl group is selected from one or more of pyridyl, furanyl, thiophene, pyrrole, pyranyl, and pyrimidinyl.

[0014] Preferably, the alkoxy group has 1 to 10 carbon atoms.

[0015] Preferably, the alkyl group has 1 to 10 carbon atoms.

[0016] The present invention also provides a method for preparing a furan-based polyester compound containing an olefin structure, wherein a diene monomer containing a furan group and a catalyst are mixed and polymerized to obtain a furan-based polyester compound containing an olefin structure.

[0017] Preferably, the structure of the diene monomer containing the furan group is shown in formula (II):

[0018]

[0019] The R1 Selected from C3~C 50 One or more of the following: a straight-chain or branched olefinic group, an aryl group containing an olefinic substituent, or a heteroaryl group.

[0020] The C3~C 50 Straight-chain or branched olefinic groups are more preferably C4-C5. 18 A straight-chain or branched olefinic group. In a specific embodiment of the invention, R 1 It is 10-undecenyl.

[0021] The double bonds in the above-mentioned straight-chain or branched olefin groups can be located at the terminal position or in the middle of the chain.

[0022] Preferably, the aryl or heteroaryl substituent containing the olefin substituent further includes one or more of alkoxy, alkyl, and halogen groups.

[0023] Preferably, the olefin substituent is selected from C3-C8 straight-chain or branched olefin groups; more preferably, the olefin substituent is selected from one or more of allyl, allyl, and allyl.

[0024] Preferably, the aryl group is selected from phenyl or benzyl.

[0025] Preferably, the heteroaryl group is selected from one or more of pyridyl, furanyl, thiophene, pyrrole, pyranyl, and pyrimidinyl.

[0026] Preferably, the alkoxy group has 1 to 10 carbon atoms.

[0027] Preferably, the alkyl group has 1 to 10 carbon atoms.

[0028] Preferably, the structure of the diene monomer containing the furan group includes, but is not limited to, the following structures:

[0029]

[0030] Preferably, the catalyst is selected from one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst, and Hoveyda-Grubbs II catalyst.

[0031] Preferably, the mass ratio of the catalyst to the furan-containing diene monomer is 1:(500-1000).

[0032] Preferably, the reaction is carried out under vacuum.

[0033] Preferably, the vacuum degree of the reaction is 0.01 to 0.05 MPa.

[0034] Preferably, the reaction employs a programmed temperature ramp process.

[0035] Preferably, the programmed heating process is as follows: first, react at 50°C for 2–18 hours; then, react at 80°C for 2–24 hours; and finally, react at 120°C for 2–48 hours.

[0036] Preferably, the stirring rate during the programmed heating process is 50–850 r / min; more preferably, the stirring rate is 50–350 r / min.

[0037] The present invention adopts the above-mentioned temperature-increasing process for reaction, with the aim of achieving prepolymerization at a low temperature first, and then increasing the degree of polymerization of furan-based polyester compounds containing olefin structures by gradually increasing the temperature.

[0038] Because the polymerization reaction of the above-mentioned furanyl polyester compounds containing olefin structures is a bulk polymerization without solvent, the stirring rate is faster when the monomer melt is relatively thin in the initial stage, but the liquid gradually becomes viscous in the later stage, and the stirring rate is too fast to stir. Therefore, it is necessary to reduce the stirring rate until stirring is possible.

[0039] Preferably, the reaction further includes filtration and washing post-treatment.

[0040] Preferably, the washing solution is selected from one or more of methanol, ethanol, ethyl acetate, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, and chloroform; more preferably, the washing solution is selected from methanol.

[0041] After the above reaction is completed, the reaction solution is cooled to room temperature, methanol is added for washing, and then the process of filtration and washing is repeated several times to obtain the furanyl polyester compound containing the olefin structure.

[0042] This invention prepares furan-based polyester compounds with olefin structures by olefin metathesis polymerization of diene monomers containing furan groups through programmed temperature rise. The products can be further structurally modified to develop furan-based polyester compounds with diverse structures. This not only helps to overcome the limitation of the single structural type of furan-based polyester compounds, but also facilitates the comprehensive utilization of biomass raw materials.

[0043] In addition, the preparation method of the furan-based polyester compound containing an olefin structure described in this invention is simple to operate, uses renewable raw materials, produces few by-products, has a short process, and has a high product yield. The reaction conditions are mild and environmentally friendly, which provides a new approach for the industrial production and application of furan-based polyester compounds.

[0044] This invention also provides a furanyl polyester compound containing a saturated alkyl structure, which is prepared by catalytic hydrogenation from the above-mentioned furanyl polyester compound containing an olefin structure or the furanyl polyester compound containing an olefin structure prepared by the above-mentioned preparation method, and has the structure shown in formula (III):

[0045]

[0046] Preferably, R is selected from C1 to C2. 48 One or more of the following: straight-chain or branched alkyl groups, substituted or unsubstituted aryl groups, and heteroaryl groups.

[0047] The n is a repeating unit, preferably 10 to 100.

[0048] Preferably, the catalyst for the reaction is selected from one or more of Pd / C, Raney Ni, and nickel boride. In a specific embodiment of the present invention, 10% Pd / C is selected as the catalyst.

[0049] Preferably, the solvent for the reaction is selected from one or more of hexafluoroisopropanol, dichloromethane, and methanol.

[0050] Preferably, the reaction is carried out in the presence of hydrogen.

[0051] Preferably, the reaction temperature is room temperature. Specifically, it can be 20℃ to 30℃.

[0052] Preferably, the reaction time is 2 to 30 hours.

[0053] This invention also provides a furanyl polyester compound containing an propylene oxide structure, which is prepared by an epoxidation reaction from the above-mentioned furanyl polyester compound containing an olefin structure or the furanyl polyester compound containing an olefin structure prepared by the above-mentioned preparation method, and has the structure shown in formula (IV):

[0054]

[0055] Preferably, R is selected from C1 to C2. 48 One or more of the following: straight-chain or branched alkyl groups, substituted or unsubstituted aryl groups, and heteroaryl groups.

[0056] The n is a repeating unit, preferably 10 to 100.

[0057] Preferably, the oxidant in the reaction is selected from one or more of m-chloroperoxybenzoic acid, peracetic acid, and dimethyldioxane.

[0058] Preferably, the solvent for the reaction is selected from one or more of dichloromethane, N,N-dimethylformamide, trichloromethane, and toluene.

[0059] Preferably, the reaction is carried out under a protective gas atmosphere.

[0060] Preferably, the protective gas includes nitrogen or an inert gas. In a specific embodiment of the present invention, the reaction is carried out under an argon atmosphere.

[0061] Preferably, the reaction temperature is room temperature. Specifically, it can be 20℃ to 30℃.

[0062] Preferably, the reaction time is 1 to 24 hours.

[0063] Compared with the prior art, the furanyl polyester compound containing an olefin structure provided by the present invention has the structure shown in formula (I), wherein R is selected from C1 to C2. 48 The furanyl polyester compound of the present invention comprises one or more of alkyl, aryl, and heteroaryl groups, either linear or branched, wherein n is a repeating unit. The furanyl polyester compound containing an olefin structure of the present invention has a novel structure and can be further transformed into furanyl polyester compounds with other structures, greatly enriching the structural types of furanyl polyester compounds. Attached Figure Description

[0064] Figure 1 The 1H NMR spectrum of polymer 1a is shown.

[0065] Figure 2 The image shows the carbon NMR spectrum of polymer 1a.

[0066] Figure 3 The 1H NMR spectrum of polymer 2a is shown.

[0067] Figure 4 The image shows the carbon NMR spectrum of polymer 2a.

[0068] Figure 5 Comparison of the 1H NMR spectra of polymers 3a and 1a;

[0069] Figure 6 The image shows the proton NMR spectrum of polymer 1b.

[0070] Figure 7 Thermogravimetric analysis (TGA) characterization spectra of polymers 1a, 2a, and 3a. Detailed Implementation

[0071] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, describes the furanyl polyester compounds containing olefin structures provided by the present invention, their preparation methods, and their applications.

[0072] The substrates and solvents used in the following examples are all commercially available products (analytical grade reagents) and have not been further purified.

[0073] 1H NMR (400MHz), 13 C10 NMR (101 MHz) was performed using CDCl3 as the deuterated solvent and TMS as the internal standard.

[0074] Multiplicity is defined as follows: s (single); d (doublet); t (triplet); q (quartet); and m (multiplet). The coupling constant is J (Hertz).

[0075] Example 1

[0076] Preparation of furanyl polyester compound 1a containing olefin structure

[0077] (1) After adding 1g of furan group-containing diene monomer (1), 2mg of GrubbsI catalyst and magnetic stir bar to the reaction tube, the reaction tube is sealed and vacuumed.

[0078] The structure of the diene monomer (1) containing a furan group is shown below:

[0079]

[0080] (2) Heat and stir at 50°C for 5 hours until the reaction liquid changes from a molten state to a solid state; then raise the temperature to 80°C and heat and stir for 16 hours until no bubbles emerge in the system; then raise the temperature to 120°C and heat and stir for 24 hours until almost no bubbles are generated; the stirring rate is controlled at 50-850 r / min throughout the reaction.

[0081] (3) Cool the reaction solution obtained in step (2) to room temperature, add methanol for washing, and then filter and wash with methanol to remove the solvent to obtain a light yellow solid, which is the furanyl polyester compound 1a with an olefin structure as shown in the following structural formula, with a mass yield of 74%.

[0082]

[0083] 1 H NMR (400MHz, Chloroform-d) δ7.19 (s, 2H), 5.33-5.39 (m, 2H), 4.32 (t, J=6.8Hz, 4H), 2.08-1.91 (m, 4H), 1.75 (p, J=6.8Hz, 4H), 1.45-1.18 (m, 24H).

[0084] 13 C NMR (101MHz, Chloroform-d) δ158.2, 146.9, 130.3, 118.2, 65.7, 32.6, 29.7, 29.5, 29.4, 29.3, 29.2, 28.6, 27.2, 25.9.

[0085] Example 2

[0086] Hydrogenation conversion of furanyl polyester compound 1a containing olefin structure

[0087] (1) After adding 40 mg of polymer 1a, 40 mg of 10% Pd / C and a magnetic stir bar to the reaction tube, the reaction tube was sealed and subjected to vacuuming-hydrogen filling operation, repeated 3 times. The hydrogen balloon was inserted into the reaction tube through a long needle tube.

[0088] (2) Hexafluoroisopropanol solvent was added to the reaction tube, and the reaction was stirred at room temperature for 24 h. After the reaction was completed, the reaction solution was purified by passing it through a short silica gel column. The washing solution was dichloromethane. The solvent was removed by rotary evaporation, and a white solid was finally obtained, which is the furanyl polyester compound 2a with a saturated alkyl structure shown in the following structural formula. The yield was 80%.

[0089]

[0090] 1 H NMR (400MHz, Chloroform-d) δ7.18 (s, 2H), 4.32 (t, J=6.8Hz, 4H), 1.75 (p, J=6.8Hz, 4H), 1.49-1.16 (m, 36H).

[0091] 13 C NMR (101MHz, Chloroform-d) δ158.1, 146.9, 118.1, 65.7, 29.7, 29.6, 29.5, 29.5, 29.2, 28.6, 25.8.

[0092] Example 3

[0093] Epoxidative transformation of furanyl polyester compound 1a containing olefin structure

[0094] (1) After adding 40 mg of polymer 1a, 21 mg of m-chloroperoxybenzoic acid (m-CPBA) and a magnetic stir bar into the reaction tube, seal the reaction tube and perform a vacuum-argon purging operation, repeating 3 times to make the reaction tube under an argon atmosphere.

[0095] (2) Dichloromethane solvent was added to the reaction tube and stirred at room temperature for 24 h. After the reaction was completed, the reaction solvent was removed by rotary evaporation to obtain a white solid, which is the furanyl polyester compound 3a containing the propylene oxide structure shown below, with a mass yield of 71%.

[0096]

[0097] 1H NMR (400MHz, Chloroform-d) δ7.19 (s, 2H), 4.32 (t, J=6.7Hz, 4H), 2.68 (m, 2H), 1.87-1.63 (m, 4H), 1.52 (m, 4H), 1.35 (m, 24H).

[0098] 13 C NMR (101MHz, Chloroform-d) δ158.1, 146.9, 118.2, 65.6, 59.0, 32.0, 29.4, 29.3, 29.1, 29.1, 28.5, 26.0, 25.8.

[0099] Example 4

[0100] Preparation of furanyl polyester compound 1b containing olefin structure

[0101] (1) After adding 1g of a furan-containing diene monomer (2), 2mg of Grubbs I catalyst and a magnetic stir bar to the reaction tube, the reaction tube is sealed and a vacuum is applied.

[0102] The structure of the diene monomer (2) containing a furan group is shown below:

[0103]

[0104] (2) Heat and stir at 50°C for 4 hours until the reaction liquid changes from a molten state to a solid state; then raise the temperature to 80°C and heat and stir for 12 hours until no bubbles emerge in the system; then raise the temperature to 120°C and heat and stir for 24 hours until almost no bubbles are generated; the stirring rate is controlled at 50-850 r / min throughout the reaction.

[0105] (3) Cool the reaction solution obtained in step (2) to room temperature, add methanol for washing, and then filter and wash with methanol to remove the solvent to obtain a slightly yellow solid, which is the furanyl polyester compound 1b with an olefin structure as shown below, with a mass yield of 76%.

[0106]

[0107] 1 H NMR (400MHz, Chloroform-d) δ7.19 (s, 2H), 5.48-5.33 (m, 2H), 4.32 (t, J=6.5Hz, 4H), 2.26-1.96 (m, 4H), 1.87-1.67 (m, 4H), 1.54-1.23 (m, 4H).

[0108] Figures 1-4The above are the proton and carbon NMR spectra of polymers 1a and 2a. Figure 5 Comparison of the 1H NMR spectra of polymers 3a and 1a; Figure 6 The 1H NMR spectrum of polymer 1b is shown. Figure 7 Thermogravimetric analysis (TGA) characterization spectra of polymers 1a, 2a, and 3a.

[0109] from Figure 6 It can be seen that the obtained olefin polymer 1a has good thermal stability, with only a 5% mass loss (i.e., thermal decomposition temperature) at 359.28℃. The hydrogenated polymer 2a is more stable than 1a, with a thermal decomposition temperature reaching 363.79℃; the epoxidized polymer 3a has reduced thermal stability, and begins thermal decomposition at 257.80℃.

[0110] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A furanyl polyester compound containing an olefin structure, characterized in that, It has the structure shown in equation (Ⅰ): Equation (I); The R is selected from C1~C 48 Straight-chain or branched alkyl groups; n is the number of repeating units.

2. A method for preparing a furanyl polyester compound containing an olefin structure, characterized in that, A polymerization reaction is carried out by mixing a diene monomer containing a furan group and a catalyst to obtain a furan-based polyester compound containing an olefin structure; The structure of the diene monomer containing the furan group is shown in formula (II): Formula (II); The R 1 Selected from C3~C 50 A straight-chain or branched olefinic group.

3. The method for preparing the furanyl polyester compound containing an olefin structure according to claim 2, characterized in that, The catalyst is selected from one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst, and Hoveyda-Grubbs II catalyst; The mass ratio of the catalyst to the furan-containing diene monomer is 1:(500~1000).

4. The method for preparing the furanyl polyester compound containing an olefin structure according to claim 2, characterized in that, The reaction is carried out under vacuum. The vacuum degree of the reaction is 0.01~0.05 MPa; The reaction employs a programmed temperature ramping process; The specific temperature ramping process is as follows: first, react at 50℃ for 2~18 h; then, react at 80℃ for 2~24 h; and finally, react at 120℃ for 2~48 h. The stirring rate during the programmed heating process is 50~850 r / min.

5. The method for preparing the furanyl polyester compound containing an olefin structure according to claim 2, characterized in that, The reaction also includes filtration and washing post-treatment; The washing solution is selected from one or more of methanol, ethanol, ethyl acetate, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, and trichloromethane.

6. The application of the furanyl polyester compound containing an olefin structure as described in claim 1 or the furanyl polyester compound containing an olefin structure prepared by the preparation method according to any one of claims 2 to 5 to prepare a furanyl polyester compound containing a saturated alkyl structure by catalytic hydrogenation reaction; The furanyl polyester compound containing a saturated alkyl structure has the structure shown in formula (Ⅲ): Formula (Ⅲ); The R is selected from C1~C 48 Straight-chain or branched alkyl groups; n is the number of repeating units.

7. A furanyl polyester compound containing an epoxy propylene structure, characterized in that, The furanyl polyester compound containing an olefin structure as described in claim 1 or the furanyl polyester compound containing an olefin structure prepared by the preparation method described in any one of claims 2 to 5 is prepared by an epoxidation reaction, and has the structure shown in formula (IV): Formula (Ⅳ); The R is selected from C1~C 48 Straight-chain or branched alkyl groups; n is the number of repeating units.

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