Polyester material and preparation method thereof

Abstract

The invention discloses a polyester material and a preparation method thereof. The polyester material is obtained through condensation reaction of pyrrole dicarboxylic acid and dihydric alcohol. The invention provides a method for preparing the pyrrole dicarboxylic acid and dihydric alcohol homo-polyester material, which is simple to operate, mild, efficient and green, and the prepared polyester material has higher glass transition temperature.

Description

Technical Field

[0001] This application relates to a polyester material 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 brought about 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. Summary of the Invention

[0003] This application is based on a linear polymer synthesized from biomass-derived pyrroledicarboxylic acid and diols, and relates to a homopolyester material of pyrroledicarboxylic acid and diols and a preparation method thereof.

[0004] According to one aspect of this application, a polyester material is provided, and the polyester material has a structure shown in Formula I:

[0005]

[0006] n is a repeating structural unit, 1 ≤ n ≤ 99;

[0007] R is selected from one of the structures shown in Formula II-1, Formula II-2, and Formula II-3;

[0008]

[0009] In Formula II-2, R3 is selected from one of phenyl and C3-C20 alkyl;

[0010] R1 is selected from one of hydrogen, phenyl, tolyl, and tert-butyl;

[0011] R2 is selected from one of Cl, Br, and F.

[0012] Optionally, the glass transition temperature of the polyester material is 70-120 °C.

[0013] According to another aspect of this application, a preparation method of the above-mentioned polyester material is provided, and the preparation method includes:

[0014] In an inert atmosphere, a mixture containing a pyrroledicarboxylic acid derivative, a diol compound, a condensation activator, a catalyst, and a solvent is reacted to obtain a polyester material.

[0015] Optionally, the pyrrolidine dicarboxylic acid derivative is selected from at least one of 3-chloro-2,5-pyrrolidine dicarboxylic acid, 2,5-pyrrolidine dicarboxylic acid, p-methylphenyl-2,5-pyrrolidine dicarboxylic acid, phenyl-2,5-pyrrolidine dicarboxylic acid, and 3-methyl-2,5-pyrrolidine dicarboxylic acid.

[0016] Optionally, the diol compound is selected from at least one of ethylene glycol, p-phenylenediol, and pentanediol.

[0017] Optionally, the molar ratio of the pyrrolidine dicarboxylic acid derivative to the diol compound is 1:1 to 1:5.

[0018] Optionally, the catalyst is selected from at least one of EDCI, DCC, and DIC.

[0019] Optionally, the catalyst is EDCI.

[0020] Optionally, the amount of the catalyst is 0.01% to 500% of the molar percentage of the pyrrolidine dicarboxylic acid derivative.

[0021] Optionally, the amount of the catalyst is independently selected from any value of 0.01%, 0.05%, 1%, 5%, 10%, 100%, 180%, 200%, 220%, 500% of the molar percentage of the pyrrolidine dicarboxylic acid derivative or a range value between any two of the above.

[0022] Optionally, the amount of the catalyst is 180% to 220% of the molar percentage of the pyrrolidine dicarboxylic acid derivative.

[0023] Optionally, the condensation activator is selected from at least one of DMAP, HOBt, and HOAt.

[0024] Optionally, the condensation activator is DMAP.

[0025] Optionally, the molar ratio of the condensation activator to the pyrrolidine dicarboxylic acid derivative is 2 to 8:1.

[0026] Optionally, the solvent is selected from at least one of water, toluene, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, tetrahydropyran, methyl tert-butyl ether, N,N-dimethylformamide, and dimethyl sulfoxide.

[0027] Optionally, the molar volume ratio of the pyrrolidine dicarboxylic acid derivative to the solvent is 1:0.01 to 1 mol / L.

[0028] Optionally, the amount of the solvent is 0.1 to 10 mol / L of the molar concentration of the pyrrolidine dicarboxylic acid derivative.

[0029] Optionally, the dosage of the solvent is any value independently selected from 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 5 mol / L, 10 mol / L or a range value between any two of the above for the molar concentration of the pyrrolidine dicarboxylic acid derivative.

[0030] Optionally, the temperature of the reaction is -50 to 200 °C.

[0031] Optionally, the temperature of the reaction is independently selected from any value of -50 °C, -25 °C, 0 °C, 25 °C, 50 °C, 100 °C, 150 °C, 200 °C or a range value between any two of the above.

[0032] Optionally, the temperature of the reaction is 0 to 200 °C.

[0033] Optionally, the time of the reaction is 0.5 to 72 h.

[0034] Optionally, the time of the reaction is independently selected from any value of 0.5 h, 1 h, 4 h, 8 h, 12 h, 24 h, 30 h, 40 h, 50 h, 60 h, 72 h or a range value between any two of the above.

[0035] Optionally, the time of the reaction is 0.5 to 24 h.

[0036] Optionally, the inert atmosphere is selected from at least one of nitrogen, argon, and helium.

[0037] The polyester material disclosed in this application uses pyrrolidine dicarboxylic acid and diol as reaction raw materials, is catalyzed by at least one of common catalysts such as EDCI, DCC, and DIC, and at least one of common condensation activators such as DMAP, HOBt, and HOAt is added, and is synthesized by reaction in a solvent to obtain the target pyrrolidine dicarboxylic acid and diol copolyester material. Taking 2,5-pyrrolidine dicarboxylic acid as an example, the reaction general formula is as follows:

[0038]

[0039] In the formula, R = aryl, alkyl with C3 - C20.

[0040] The structure of Compound 1 is but not limited to the following structures:

[0041] etc.

[0042] The structure of Compound 2 is but not limited to the following structures:

[0043] etc.

[0044] In this application, the term "alkyl" refers to a group formed by removing any one hydrogen atom from a hydrocarbon compound molecule.

[0045] In this application, the term "aryl" refers to a group formed by removing one hydrogen atom from an aromatic ring of an aromatic compound molecule; for example, p-tolyl formed by removing the hydrogen atom at the para position of the methyl group on the benzene ring of toluene.

[0046] The beneficial effects that can be produced by this application include:

[0047] The pyrrole dicarboxylic acid and diol copolyester material provided by this application and its preparation method are simple, mild, efficient, and green in operation; the glass transition temperature of the prepared polyester material is 70-120 degrees Celsius. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 It is the 1H NMR spectrum of poly(ethylene 2,5-pyrrole dicarboxylate) synthesized in Example 1 of this application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0049] The following describes this application in detail with reference to the embodiments, but this application is not limited to these embodiments.

[0050] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0051] This application uses a nuclear magnetic resonance instrument to characterize the prepared polyester material.

[0052] This application uses a differential scanning calorimeter to test the glass transition temperature.

[0053] Preparation of pyrrole dicarboxylic acid derivatives

[0054] Using biomass-derived furan dicarboxylic acid derivatives and primary amines as reaction raw materials, and using solid acids, Bronsted acids, Lewis acids, rare earth-doped titanium dioxide, etc. as catalysts for catalysis, the target pyrrole dicarboxylic acid derivatives are synthesized by reaction in a solvent; the specific preparation general formula is as follows:

[0055]

[0056] The structure of Compound 1 is but not limited to the following structures:

[0057]

[0058] Diethyl 2,5-furandicarboxylate, etc.;

[0059] The structure of Compound 2 is but not limited to the following:

[0060] etc.

[0061] Example 1

[0062] Step 1: Put 1 mmol of 2,5-pyrroledicarboxylic acid and 1 mmol of ethylene glycol into a reaction vessel, add 2 mmol (2 eq) of catalyst EDCI and 0.2 mmol of DMAP, add 15 mL of solvent γ-valerolactone, and introduce nitrogen gas.

[0063] Step 2: Set the reaction temperature to 25 °C and the time to 48 h.

[0064] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product to obtain polyethylene glycol 2,5-pyrroledicarboxylate.

[0065] Polyethylene glycol 2,5-pyrroledicarboxylate 1 H NMR (400 MHz, ) δ 7.33 (s, 2H), 5.07 (s, 4H). The glass transition temperature was measured using a differential scanning calorimeter. The glass transition temperature of polyethylene glycol 2,5-pyrroledicarboxylate was 103 °C.

[0066] Example 2

[0067] Step 1: Put 1 mmol of phenyl-2,5-pyrroledicarboxylic acid and 1 mmol of hydroquinone into a reaction vessel, add 2 mmol (2 eq) of catalyst DCC and 0.2 mmol of HOBt, add 20 mL of solvent dichloroethane, and introduce nitrogen gas.

[0068] Step 2: Set the reaction temperature to 15 °C and the time to 72 h.

[0069] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product to obtain polyphenyl-2,5-pyrroledicarboxylate phenyl glycol ester.

[0070] As Figure 1 shown, polyphenyl-2,5-pyrroledicarboxylate phenyl glycol ester 1 H NMR (400 MHz, ) δ 7.49 (m, 5H), 7.33 (s, 2H), 6.97 (m, 4H), 5.13 (s, 4H). Tested according to the glass transition temperature test conditions in Example 1, the glass transition temperature of polyphenyl-2,5-pyrroledicarboxylate phenyl glycol ester was 112 °C.

[0071] Example 3

[0072] Step 1: Put 1 mmol of 3-methyl-2,5-pyrroledicarboxylic acid and 1 mmol of ethylene glycol into a reaction vessel, add 2 mmol (2 eq) of catalyst DIC and 0.2 mmol of HOAt, add 10 mL of solvent γ-valerolactone, and introduce nitrogen gas.

[0073] Step 2: Set the reaction temperature to 0 °C and the time to 48 h;

[0074] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product to obtain poly(ethylene glycol 3-methyl-2,5-pyrroledicarboxylate).

[0075] Poly(ethylene glycol 3-methyl-2,5-pyrroledicarboxylate) 1 H NMR (400 MHz,) δ 7.30 (s, 2H), 5.07 (s, 4H), 2.38 (s, 3H). Tested according to the test conditions of the glass transition temperature in Example 1, the glass transition temperature of poly(ethylene glycol 3-methyl-2,5-pyrroledicarboxylate) is 96 °C.

[0076] Example 4

[0077] Step 1: Put 1 mmol of 3-chloro-2,5-pyrroledicarboxylic acid and 1 mmol of pentanediol into a reaction vessel, add 2 mmol (2 eq) of catalyst EDCI and 0.2 mmol of DMAP, add 25 mL of solvent chloroform, and introduce nitrogen;

[0078] Step 2: Set the reaction temperature to 10 °C and the time to 36 h;

[0079] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product; poly(pentanediol 3-chloro-2,5-pyrroledicarboxylate).

[0080] Poly(pentanediol 3-chloro-2,5-pyrroledicarboxylate) 1 H NMR (400 MHz,) δ 7.30 (s, 2H), 5.07 (s, 4H), 4.48 (m, 4H), 1.83 (m, 6H). Tested according to the test conditions of the glass transition temperature in Example 1, the glass transition temperature of poly(pentanediol 3-chloro-2,5-pyrroledicarboxylate) is 96 °C.

[0081] Example 5

[0082] Step 1: Put 1 mmol of p-methylphenyl-2,5-pyrroledicarboxylic acid and 1 mmol of ethylene glycol into a reaction vessel, add 2 mmol (2 eq) of catalyst DCC and 0.2 mmol of DMAP, add 5 mL of solvent γ-valerolactone, and introduce nitrogen;

[0083] Step 2: Set the reaction temperature to 18 °C and the time to 72 h;

[0084] Step 3: Perform post-treatments such as dialysis, rotary evaporation, drying, and performance testing on the reacted product, poly(ethylene glycol p-methylphenyl-2,5-pyrroledicarboxylate).

[0085] Ethylene glycol bis(2,5-dicarboxy-p-methylphenyl)pyrrole 1 H NMR (400 MHz, ) δ 7.51 (m, 5H), 7.30 (s, 2H), 5.09 (s, 4H), 2.88 (s, 3H). Test was carried out according to the test conditions of the glass transition temperature in Example 1. The glass transition temperature of ethylene glycol bis(2,5-dicarboxy-p-methylphenyl)pyrrole was 112 °C.

[0086] As mentioned above, these 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 with preferred embodiments as above, 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, making some changes or modifications using the disclosed technical content are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A polyester material, characterized in that, The polyester material has the structure shown in Formula I: n is a repeating structural unit, 1 ≤ n ≤ 99; R is selected from one of the structures shown in Formula II-1, Formula II-2, and Formula II-3; In Formula II-2, R3 is selected from one of phenyl and C3-C20 alkyl; R1 is selected from one of hydrogen, phenyl, tolyl, and tert-butyl; R2 is selected from one of Cl, F, and Br.

2. The polyester material according to claim 1, characterized in that, The glass transition temperature of the polyester material is 70-120 °C.

3. A method for preparing the polyester material according to any one of claims 1 to 2, characterized in that, The preparation method includes: In an inert atmosphere, a mixture containing a pyrrole dicarboxylic acid derivative, a diol compound, a condensation activator, a catalyst, and a solvent is reacted to obtain a polyester material.

4. The preparation method according to claim 3, characterized in that, The pyrrole dicarboxylic acid derivative is selected from at least one of 3-chloro-2,5-pyrrole dicarboxylic acid, 2,5-pyrrole dicarboxylic acid, p-methylphenyl-2,5-pyrrole dicarboxylic acid, phenyl-2,5-pyrrole dicarboxylic acid, and 3-methyl-2,5-pyrrole dicarboxylic acid; Preferably, the diol compound is selected from at least one of ethylene glycol, p-phenylenediol, and pentanediol; Preferably, the molar ratio of the pyrrole dicarboxylic acid derivative to the diol compound is 1:1 to 1:

5.

5. The preparation method according to claim 3, characterized in that, The catalyst is selected from at least one of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, dicyclohexylcarbodiimide, and diisopropylcarbodiimide; Preferably, the amount of the catalyst is 0.01% to 500% of the molar percentage of the pyrrole dicarboxylic acid derivative; Preferably, the amount of the catalyst is 180% to 220% of the molar percentage of the pyrrole dicarboxylic acid derivative.

6. The preparation method according to claim 3, characterized in that, The condensation activator is selected from at least one of 4-dimethylaminopyridine, 1-hydroxybenzotriazole, and 1-hydroxy-7-azabenzotriazole; Preferably, the molar ratio of the condensation activator to the pyrrole dicarboxylic acid derivative is 2-8:

1.

7. The preparation method according to claim 3, characterized in that, The solvent is selected from at least one of water, toluene, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, tetrahydropyran, methyl tert-butyl ether, N,N-dimethylformamide, and dimethyl sulfoxide; Preferably, the molar volume ratio of the pyrrole dicarboxylic acid derivative to the solvent is 1:0.01 to 1 mol / L.

8. The preparation method according to claim 3, characterized in that, The temperature of the reaction is -50 to 200 °C; Preferably, the temperature of the reaction is 0 to 200 °C.

9. The preparation method according to claim 3, characterized in that, The time of the reaction is 0.5 to 72 h; Preferably, the time of the reaction is 0.5 to 24 h.

10. The preparation method according to claim 3, characterized in that, The inert atmosphere is selected from at least one of nitrogen, argon, and helium.

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