Polyester material containing pyrrole and furan groups and preparation method thereof
By copolymerizing pyrrole dicarboxylic acid with diol and using specific catalysts and condensation activators, polyester materials containing pyrrole and furan groups were prepared, which solved the problem of fragile performance of existing materials and achieved improved versatility and stability of the materials.
Patent Information
- Application Number
- CN202311743266.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-18
- Publication Date
- 2025-06-20
AI Technical Summary
Existing biomass-based pyrrole dicarboxylic acid polymers have relatively brittle properties and are difficult to meet the requirements of versatility and stability.
By copolymerizing pyrrole dicarboxylic acid with diol, and using catalysts such as EDCI, DCC, DIC and condensation activators such as DMAP, HOBt, and HOAt, polyester materials containing pyrrole and furan groups were prepared.
The performance of polyester materials is improved, including simple operation, gentleness, high efficiency, greenness, and the ultraviolet transmittance in the wavelength range of 0-380nm is reduced to 0-20%, enhancing the material's ultraviolet resistance.
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Figure CN120173224A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a polyester material containing pyrrole and furan groups and a preparation method thereof, belonging to the technical field of polymer materials. Background Art
[0002] In recent years, various bio-based polymers have been developed to address the environmental problems caused by the consumption of petroleum resources. Pyrroledicarboxylic acid derived from biomass is considered a promising compound due to the characteristics of its structure. It can be used to design polymers with various functions, such as metal recovery, ion recognition, solid electrolyte membranes, etc. However, due to its relatively brittle structure, its modification is also the main research direction for us. Summary of the Invention
[0003] The present application is based on a copolymer synthesized from biomass-derived pyrroledicarboxylic acid and two diols, and relates to a copolyester material of pyrroledicarboxylic acid and diol and a preparation method thereof.
[0004] The object of the present invention is to provide a copolyester material of pyrroledicarboxylic acid and diol and a preparation method thereof to improve its performance.
[0005] According to one aspect of the present application, there is provided a polyester material containing pyrrole and furan groups, and the polyester material containing pyrrole and furan groups has a structure shown in Formula I:
[0006]
[0007] n is a repeating structural unit, and 1 ≤ n ≤ 99;
[0008] R1 is selected from one of the structures shown in Formula II-1 and Formula II-2;
[0009]
[0010] In Formula II-1, k is a repeating structural unit, and 1 ≤ k ≤ 20;
[0011] R2 is selected from one of methyl, phenyl, and tert-butyl;
[0012] R3 is selected from one of hydrogen, tolyl, phenyl, and ethyl;
[0013] R4 is selected from one of Cl, F, and Br.
[0014] Optionally, the ultraviolet transmittance of the polyester material containing pyrrole and furan groups in the wavelength range of 0 to 380 nm is 0 to 20%.
[0015] According to another aspect of the present application, there is provided a preparation method of the above-mentioned polyester material containing pyrrole and furan groups, and the preparation method includes:
[0016] React a mixture containing a pyrroledicarboxylic acid compound, a diol, a compound of the structure shown in Formula IV, a catalyst, and a condensation activator to obtain the polyester material containing pyrrole and furan groups;
[0017] The compound of the structure shown in Formula IV is selected from one of the structures shown in IV-1, IV-2, IV-3, IV-4, and IV-5;
[0018]
[0019] Optionally, the pyrroledicarboxylic acid compound is selected from at least one of 2,5-pyrroledicarboxylic acid, phenyl-2,5-pyrroledicarboxylic acid, 3-methyl-2,5-pyrroledicarboxylic acid, 3-chloro-2,5-pyrroledicarboxylic acid, and p-methylphenyl-2,5-pyrroledicarboxylic acid.
[0020] Optionally, the diol is selected from at least one of ethylene glycol, p-phenylenediol, pentanediol, and 1,8-octanediol.
[0021] Optionally, the molar ratio of the pyrroledicarboxylic acid compound to the diol is 1:0.1 to 1:1.
[0022] Optionally, the molar ratio of the pyrroledicarboxylic acid compound to the compound of the structure shown in Formula IV is 1:0.1 to 1:1.
[0023] Optionally, the catalyst is selected from at least one of EDCI, DCC, and DIC.
[0024] Preferably, the catalyst is EDCI.
[0025] Optionally, the amount of the catalyst is 0.01% to 500% of the molar percentage of the pyrroledicarboxylic acid compound.
[0026] Preferably, the amount of the catalyst is 200% of the molar percentage of the pyrroledicarboxylic acid compound.
[0027] Optionally, the amount of the catalyst, as the molar percentage of the pyrroledicarboxylic acid compound, is independently selected from any value of 0.01%, 0.1%, 1%, 10%, 50%, 100%, 200%, 300%, 400%, 500% or the range value between any two of the above.
[0028] Optionally, the condensation activator is selected from at least one of DMAP, HOBt, and HOAt.
[0029] Preferably, the condensation activator is DMAP.
[0030] Optionally, the molar ratio of the pyrrolic dicarboxylic acid compound to the condensation activator is 1:2 to 1:10.
[0031] Optionally, the mixture further includes a solvent.
[0032] Optionally, the solvent is selected from at least one of water, chloroform, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, toluene, N,N-dimethylacetamide, and γ-valerolactone.
[0033] Preferably, the solvent is selected from γ-valerolactone.
[0034] Optionally, the molar volume ratio of the pyrrolic dicarboxylic acid compound to the solvent is 1:0.01 to 1 mol / L.
[0035] Optionally, the dosage of the solvent is 0.1 to 10 mol / L of the molar concentration of the pyrrolic dicarboxylic acid compound.
[0036] Preferably, the dosage of the solvent is 10 mol / L of the molar concentration of the pyrrolic dicarboxylic acid compound.
[0037] Optionally, the dosage of the solvent independently selected from any value of 0.1 mol / L, 0.2 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 5 mol / L, 8 mol / L, 10 mol / L of the molar concentration of the pyrrolic dicarboxylic acid compound or a range value between any two of the above.
[0038] Optionally, the temperature of the reaction is -50 to 200 °C.
[0039] Preferably, the temperature of the reaction is 25 °C.
[0040] Optionally, the temperature of the reaction independently selected from any value of -50 °C, -20 °C, 0 °C, 25 °C, 50 °C, 100 °C, 150 °C, 200 °C or a range value between any two of the above.
[0041] Optionally, the time of the reaction is 0.5 to 72 h.
[0042] Preferably, the reaction time is 10 h.
[0043] Optionally, the time of the reaction independently selected from any value of 0.5 h, 1 h, 2 h, 5 h, 12 h, 24 h, 36 h, 48 h, 60 h, 72 h or a range value between any two of the above.
[0044] This application uses pyrroledicarboxylic acid and two kinds of diols as reaction raw materials, is catalyzed by common catalysts such as EDCI, DCC, DIC, etc., adds common condensation activators such as DMAP, HOBt, HOAt, etc., and reacts in a solvent to synthesize the target pyrroledicarboxylic acid and diol copolyester material. Taking 2,5-pyrroledicarboxylic acid as an example, its reaction formula is as follows:
[0045]
[0046] Among them, R1 = aryl, C1-C 20 alkyl; R2 = aryl, C1-C 20 alkyl.
[0047] The structure of Compound 1 is but not limited to the following structures:
[0048] etc.;
[0049] The structure of Compound 2 is but not limited to the following structures:
[0050]
[0051] The structure of Compound 3 is but not limited to the following structures:
[0052]
[0053] In this application, the term "alkyl" refers to the group formed by removing any one hydrogen atom from the alkane compound molecule.
[0054] In this application, the term "aryl" refers to the group formed by removing one hydrogen atom on the aromatic ring from the aromatic compound molecule; for example, the p-tolyl group formed by removing the hydrogen atom at the para position of the methyl group on the benzene ring of toluene.
[0055] In this application, "EDCI" refers to 1-ethyl-(3-dimethylaminopropyl)carbodiimide.
[0056] In this application, "DCC" refers to diisopropylcarbodiimide.
[0057] In this application, "DIC" refers to diisopropylcarbodiimide.
[0058] In this application, "DMAP" refers to 4-dimethylaminopyridine.
[0059] In this application, "HOBt" refers to 1-hydroxybenzotriazole.
[0060] In this application, "HOAt" refers to 1-hydroxy-7-azabenzotriazole.
[0061] The beneficial effects that this application can produce include:
[0062] The preparation method of the polyesters of pyrrole dicarboxylic acid and two diols provided by this application is simple, mild, efficient and green in operation; the prepared polyester material containing pyrrole groups has an ultraviolet transmittance of 0-20% in the wavelength range of 0-380 nm. Description of the Drawings
[0063] Figure 1 It is the ultraviolet transmittance diagram of Example 1 and the comparative example of this application.
[0064] Figure 2 It is the 1H NMR spectrum of Example 1 of this application. Detailed Description of the Invention
[0065] The following describes this application in detail with reference to the examples, but this application is not limited to these examples.
[0066] Unless otherwise specified, the raw materials in the examples of this application are all purchased through commercial channels.
[0067] This application uses a UV spectrophotometer to test the ultraviolet transmittance.
[0068] Preparation of Pyrrole Dicarboxylic Acid Compounds
[0069] Using furan dicarboxylic acid derivatives and primary amines from biomass sources as reaction raw materials, and using catalysts such as solid acids, Bronsted acids, Lewis acids, or rare earth-doped titanium dioxide for catalysis, the target pyrrole dicarboxylic acid compounds are synthesized by reaction in a solvent; the specific preparation general formula is as follows:
[0070]
[0071] The structure of Compound 1 is but not limited to the following structures:
[0072]
[0073] Diethyl 2,5-furandicarboxylate, etc.;
[0074] The structure of Compound 2 is but not limited to the following:
[0075] NH3, etc.
[0076] Example 1
[0077]
[0078] Step 1: Put 1 mmol of 2,5-pyrroledicarboxylic acid, 0.5 mmol of ethylene glycol, and 0.5 mmol of the compound with the structure shown in Formula IV-1 into a reaction vessel, add a catalyst, add 2 mmol (2 eq) of the condensation activator EDCI and 0.2 mmol of DMAP, add 20 mL of the solvent γ-valerolactone, and introduce nitrogen gas;
[0079] Step 2: Set the reaction temperature to 25 °C and the time to 48 h;
[0080] Step 3: Carry out post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product; obtain a polyester material, and after pressing into a film, conduct tests under the conditions of 200 - 800 nm using an ultraviolet tester, and the ultraviolet transmittance test T 320 is 0.68%, T 350 is 0.55%, T 400 is 19.9%.
[0081] Example 2
[0082]
[0083] Step 1: Put 1 mmol of phenyl-2,5-pyrroledicarboxylic acid, 0.7 mmol of hydroquinone, and 0.3 mmol of the compound with the structure shown in Formula IV-2 into a reaction vessel, add a catalyst, add 2 mmol (2 eq) of the condensation activator DCC and 0.2 mmol of HOBt, add 15 mL of the solvent dichloroethane, and introduce nitrogen gas;
[0084] Step 2: Set the reaction temperature to 15 °C and the time to 72 h;
[0085] Step 3: Carry out post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product.
[0086] Through the ultraviolet transmittance test T 320 is 0.80%, T 350 is 0.56%, T 400 is 14.9%.
[0087] Example 3
[0088]
[0089] Step 1: Put 1 mmol of 3-methyl-2,5-pyrroledicarboxylic acid, 0.6 mmol of ethylene glycol, and 0.4 mmol of the compound with the structure shown in Formula IV-3 into a reaction vessel, add a catalyst, add 2 mmol (2 eq) of the condensation activator DIC and 0.2 mmol of HOAt, add 20 mL of the solvent γ-valerolactone, and introduce nitrogen gas;
[0090] Step 2: Set the reaction temperature to 0 °C and the time to 48 h;
[0091] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product.
[0092] Test T by ultraviolet transmittance 320 is 0.60%, T 350 is 0.43%, T 400 is 13.2%.
[0093] Example 4
[0094]
[0095] Step 1: Put 1 mmol of 3-chloro-2,5-pyrroledicarboxylic acid, 0.2 mmol of pentanediol, and 0.8 mmol of the compound shown in Formula IV-4 into a reaction vessel, add a catalyst, add 2 mmol (2 eq) of the condensation activator EDCI and 0.2 mmol of DMAP, add 25 mL of the solvent chloroform, and introduce nitrogen;
[0096] Step 2: Set the reaction temperature to 10 °C and the time to 36 h;
[0097] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product.
[0098] Test T by ultraviolet transmittance 320 is 0.40%, T 350 is 0.2%, T 400 is 1.4%.
[0099] Example 5
[0100]
[0101] Step 1: Put 1 mmol of p-methylphenyl-2,5-pyrroledicarboxylic acid, 0.3 mmol of ethylene glycol, and 0.7 mmol of the compound shown in Formula IV-5 into a reaction vessel, add a catalyst, add 2 mmol (2 eq) of the condensation activator DCC and 0.2 mmol of DMAP, add 5 mL of the solvent γ-valerolactone, and introduce nitrogen;
[0102] Step 2: Set the reaction temperature to 18 °C and the time to 72 h;
[0103] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product.
[0104] Test T by ultraviolet transmittance 320 is 0.22%, T 350 is 0.11%, T 400 is 7.3%.
[0105] Comparative Example 1
[0106] Put the homopolymer of 1 mol of pyrrole dicarboxylic acid and 1.5 mol of ethylene glycol between polytetrafluoroethylene plates with a 0.2-mm-thick aluminum spacer and hot press at 100 °C for 3 minutes under a pressure of 5 MPa. Take out the formed film, put it in a vacuum oven at 60 °C for reaction for 7 hours, and then store the obtained polymer network material 6 at room temperature. Test the ultraviolet transmittance T of the polymer 320 is 11.07%, T 350 is 55.02%, T 400 is 74.59%. It can be seen from Examples 1-5 that the alcohol of the compound with the structure shown in Formula IV can improve the ultraviolet resistance of the polyester. From Figure 1 it can be seen that the ultraviolet shielding effect of the examples is much higher than that of the comparative examples; Figure 2 is the 1H NMR spectrum of Example 1. From the 1H NMR spectrum, we can see that there are obvious hydrogens on the side-chain benzene ring at δ 7.84 - 6.98, obvious hydrogens on the furan ring at δ 6.83 - 6.27, and an obvious peak of ethylene glycol at δ 4.81.
[0107] The above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the technical content disclosed above, which are equivalent to equivalent implementation cases and all belong to the scope of the technical solution.
Claims
1. A polyester material containing pyrrole and furan groups, characterized in that, The polyester material containing pyrrole and furan groups has the structure shown in Formula I: n is the repeating structural unit, 1 ≤ n ≤ 99; R1 is selected from one of the structures shown in Formula II-1 and Formula II-2; In Formula II-1, k is the repeating structural unit, 1 ≤ k ≤ 20; R2 is selected from one of methyl, phenyl, and tert-butyl; R3 is selected from one of hydrogen, tolyl, phenyl, and ethyl; R4 is selected from one of Cl, F, and Br.
2. The polyester material containing pyrrole and furan groups according to claim 1, characterized in that, The ultraviolet transmittance of the polyester material containing pyrrole and furan groups in the wavelength range of 0 - 380 nm is 0 - 20%.
3. A preparation method of the polyester material containing pyrrole and furan groups according to any one of claims 1 to 2, characterized in that, The preparation method includes: Reacting a mixture containing a pyrrole dicarboxylic acid compound, a diol, a compound with the structure shown in Formula IV, a catalyst, and a condensation activator to obtain the polyester material containing pyrrole and furan groups; The compound with the structure shown in Formula IV is selected from one of the structures shown in IV-1, IV-2, IV-3, IV-4, and IV-5; 4. The preparation method according to claim 3, characterized in that, The pyrrole dicarboxylic acid compound is selected from at least one of 2,5-pyrrole dicarboxylic acid, phenyl-2,5-pyrrole dicarboxylic acid, 3-methyl-2,5-pyrrole dicarboxylic acid, 3-chloro-2,5-pyrrole dicarboxylic acid, and p-methylphenyl-2,5-pyrrole dicarboxylic acid; Preferably, the diol is selected from at least one of ethylene glycol, p-phenylenediol, pentanediol, and 1,8-octanediol; Preferably, the molar ratio of the pyrrole dicarboxylic acid compound to the diol is 1:0.1 - 1:1; Preferably, the molar ratio of the pyrrole dicarboxylic acid compound to the compound with the structure shown in Formula IV is 1:0.1 - 1:
1.
5. The preparation method according to claim 3, characterized in that, The catalyst is selected from at least one of EDCI, DCC, and DIC; Preferably, the dosage of the catalyst is 0.01% - 500% of the molar percentage of the pyrrole dicarboxylic acid compound.
6. The preparation method according to claim 3, characterized in that, The condensation activator is selected from at least one of DMAP, HOBt, and HOAt; Preferably, the molar ratio of the pyrrole dicarboxylic acid compound to the condensation activator is 1:2 - 1:
10.
7. The preparation method according to claim 3, characterized in that, The mixture further includes a solvent; Preferably, the solvent is selected from at least one of water, chloroform, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, toluene, N,N-dimethylacetamide, and γ-valerolactone.
8. The preparation method according to claim 7, characterized in that, The molar volume ratio of the pyrrole dicarboxylic acid compound to the solvent is 1:0.01 - 1 mol / L.
9. The preparation method according to claim 3, characterized in that, The temperature of the reaction is -50 - 200 °C.
10. The preparation method according to claim 3, characterized in that, The time of the reaction is 0.5 - 72 h.