An anion-coordinated supramolecular foldamer material and its preparation method

Abstract

The present invention discloses an anionic coordination supramolecular foldamer material in the field of polymer materials and a preparation method thereof, comprising the following steps: S1, reacting aniline with o-nitroisocyanate to obtain a polyurea compound 1; S2, adding a catalyst to compound 1 under stirring conditions to obtain compound 2; S3, uniformly mixing 4-(9-decenyloxy)benzoic acid and diphenylphosphoryl azide, and adding a catalyst under stirring conditions to obtain chain extender 1; S4, uniformly mixing compound 2 and chain extender 1, and reacting to obtain a ligand; S5, uniformly mixing the ligand and tetrabutylammonium chloride to obtain a monomer, and uniformly mixing the monomer and trimethylolpropane tris(3-mercaptopropionate), adding a catalyst, and removing the residual solvent after light irradiation. The present invention introduces an anionic coordination foldamer structure into a photocurable polymer, which is different from traditional photocurable polymers and has excellent mechanical properties and a unique energy dissipation mechanism.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and particularly relates to an anion-coordinated supramolecular foldamer material and a preparation method thereof. Background Art

[0002] Anion coordination chemistry has developed rapidly and has become a mature branch of supramolecular chemistry. Related research is very extensive. For example, anion recognition and separation, sensing and their applications in smart materials, transmembrane transport and catalysis; in particular, it has unique advantages for constructing a series of supramolecular structures including folds, helical structures, cages, etc.

[0003] Supramolecular polymers are aggregates in which monomers are connected by highly directional and reversible non-covalent bond interactions and exhibit polymer properties in solution and the bulk phase. The non-covalent bond interactions involved include hydrogen bonding, metal coordination, host-guest recognition, π-π stacking, and hydrophilic-hydrophobic interactions, etc. Due to the weak bond connection mode of non-covalent bonds, supramolecular polymers are usually highly dynamic, and their structures can undergo reversible dissociation and formation under the influence of environmental factors such as temperature and pH. Therefore, supramolecular polymers possess properties that are difficult for general covalent polymers to possess, such as easy processing, self-adaptation, and self-healing. However, supramolecular polymers also have the defect of "excessive dynamics and insufficient mechanical properties" and are difficult to adapt to occasions with high requirements for mechanical properties and stability.

[0004] Traditional photocurable polymers usually use multifunctional acrylates as monomers. Fast curing and good spatial resolution are the advantages of these systems, but brittleness and poor impact resistance caused by uneven polymer structure and high crosslinking density are serious disadvantages. Summary of the Invention

[0005] The purpose of the present invention is to provide an anion-coordinated supramolecular foldamer material and a preparation method thereof to solve the deficiencies of the prior art in the background art.

[0006] To achieve the above purpose, the technical solution of the present invention is as follows:

[0007] The first aspect of the present invention provides a preparation method of an anion-coordinated supramolecular foldamer material, including the following steps:

[0008] S1. React aniline with o-nitroisocyanate to obtain a polyurea compound 1;

[0009] S2. Add a catalyst to compound 1 under stirring conditions and react to obtain compound 2;

[0010] S3. Mix 4-(9-decenyloxy)benzoic acid and diphenylphosphoryl azide evenly, add a catalyst under stirring conditions, and react to obtain a chain extender 1;

[0011] S4. Mix compound 2 and chain extender 1 evenly and react to obtain a ligand;

[0012] S5. Mix the ligand and tetrabutylammonium chloride evenly to obtain a monomer; then mix the monomer and trimethylolpropane - tris(3 - mercaptopropionate) evenly, add a catalyst, and after light irradiation, remove the residual solvent to obtain an anion - coordinated supramolecular foldamer material.

[0013] Further, in step S1, the aniline is selected from one of o - phenylenediamine and 1,2 - bis-(2 - aminophenyl - urea)-benzene; the solvent is tetrahydrofuran; the molar ratio of aniline to o - nitroisocyanate is 1:(2 - 2.5); the reaction temperature is 70 - 90 °C; the reaction time is 2 - 6 hours.

[0014] Further, in step S2, the catalyst is palladium - carbon, and the dosage is 5 - 10% of the total mass of the reactants; the reaction temperature is 70 - 90 °C; the reaction time is 2 - 6 hours.

[0015] Further, in step S3, the catalyst is triethylamine; the molar ratio of 4-(9 - decenyloxy)benzoic acid, diphenylphosphoryl azide and triethylamine is 1:(1 - 2):1; diphenylphosphoryl azide is added dropwise under an ice bath; the reaction temperature is room temperature, and the reaction time is 6 - 8 hours.

[0016] Further, in step S4, the molar ratio of compound 2 and compound 4 to chain extender 1 is 1:(2 - 3); the reaction temperature is 70 - 80 °C; the reaction time is 12 - 24 hours.

[0017] Further, in step S5, the molar ratio of the ligand to tetrabutylammonium chloride is 1:2; the stirring time is 2 - 12 hours, and the temperature is 25 °C.

[0018] Further, in step S5, the molar ratio of the monomer to trimethylolpropane - tris(3 - mercaptopropionate) is 2:3; the catalyst is benzoin dimethyl ether (DMPA), and the dosage is 3 - 5% of the mass of the monomer; the light irradiation wavelength is 365 nm; the residual solvent is removed at 60 °C using a vacuum oven.

[0019] The second aspect of the present invention provides an anion - coordinated supramolecular foldamer material, which is prepared by the preparation method of the above - mentioned anion - coordinated supramolecular foldamer material.

[0020] The following beneficial effects are achieved by adopting the above - mentioned scheme:

[0021] 1. The anionic coordination supramolecular foldamer material and its preparation method of the present invention crosslink the anionic coordination foldamer structure with trimethylolpropane tris(3-mercaptopropionate) through the thiol-ene click reaction. The thiol-ene click reaction has the advantages of fast rate, high selectivity, quantitative and site-specific reaction, and environmental friendliness.

[0022] 2. The anionic coordination supramolecular foldamer material and its preparation method of the present invention realize excellent mechanical properties and energy consumption by introducing the anionic coordination foldamer structure into the photocurable polymer material. The preparation process of this material is simple, easy to operate, and suitable for commercial production.

[0023] 3. The anionic coordination supramolecular foldamer material of the present invention not only has the characteristic of high strength like traditional photocurable polymers, but also has excellent toughness and elasticity.

[0024] 4. The anionic coordination supramolecular foldamer material of the present invention successfully realizes the self-healing performance of supramolecules. Different from traditional photocurable polymers, the anionic coordination supramolecular foldamer material can return to its original state within a short time after being deformed under external force. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is the route diagram for synthesizing ligand L4U in Example 1 of the anionic coordination supramolecular foldamer material and its preparation method of the present invention;

[0026] Figure 2 It is the route diagram for synthesizing ligand L6U in Example 2 of the anionic coordination supramolecular foldamer material and its preparation method of the present invention;

[0027] Figure 3 It is the stress-strain curve of the anionic coordination supramolecular foldamer material prepared in Example 1 and Example 2 of the anionic coordination supramolecular foldamer material and its preparation method of the present invention;

[0028] Figure 4 It is the route diagram for synthesizing ligand L4U in Example 1 of the anionic coordination supramolecular foldamer material and its preparation method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0029] The embodiments of the present invention are described in detail below. The examples are shown in the accompanying drawings, where the same or similar reference numerals represent the same or similar elements or elements with the same or similar functions from beginning to end. The embodiments described below by referring to the accompanying drawings are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention.

[0030] In the description of the present invention, it should be understood that the orientation or positional relationships indicated by the terms "longitudinal", "transverse", "vertical", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientation or positional relationships shown in the drawings. These are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the present invention.

[0031] In the description of the present invention, unless otherwise specified and defined, it should be noted that the terms "installation", "connection", and "coupling" should be understood in a broad sense. For example, they can be mechanical connections or electrical connections, or the communication inside two elements. They can be directly connected or indirectly connected through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms can be understood according to specific circumstances.

[0032] The following is a further detailed description through specific embodiments:

[0033] Example 1:

[0034] Basically as shown in the attached Figure 1 and attached Figure 3 and attached Figure 4 shown: This example provides a preparation method of an anion-coordinated supramolecular foldamer material. The reaction route is as shown in attached Figure 1 shown, and includes the following steps:

[0035] Step 1: Add o-phenylenediamine (1.61 g, 14.91 mmol) and o-nitroisocyanate (5.14 g, 31.32 mmol) into a flask, add 50 mL of tetrahydrofuran, and reflux at 80 °C for about 12 h. A yellow precipitate is formed. After the reaction is completed, filter, and vacuum dry the solid to obtain Compound 1 (1,2-bis-(2-nitrophenyl-urea)-benzene).

[0036] Step 2: Add Compound 1 (2.00 g, 4.58 mmol) into a three-necked flask, add 200 mL of ethanol as a solvent, and then add 0.20 g of Pd / C (10% of the reactant mass). Drop 15 mL of hydrazine hydrate at 60 °C. Reflux at 80 °C for about 5 h. After the reaction is completed, filter off the Pd / C with a Buchner funnel and diatomaceous earth, wash the product with N,N-dimethylformamide, introduce it into water to precipitate a solid, filter and dry the solid to obtain Compound 2 (1,2-bis-(2-aminophenyl-urea)-benzene).

[0037] Step 3: In a 100 mL single-necked round-bottom flask of a heat-collecting constant-temperature heating magnetic stirrer, first add 1.01 g of 4-(9-decenoxy)benzoic acid and 0.78 mL of triethylamine, and then add 20 mL of anhydrous tetrahydrofuran. While under ice bath, add 0.78 mL of diphenylphosphoryl azide dropwise (the molar ratio of 4-(9-decenoxy)benzoic acid, triethylamine and diphenylphosphoryl azide is 1:1.2:1), and stir at room temperature for 8 hours. Separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate = 100:1). After removing the organic solvent by vacuum concentration, 4-(9-decenoxy)benzoyl azide (chain extender 1) is obtained.

[0038] Step 4: Add compound 2 (0.34 g, 0.90 mmol) and 4-(9-decenoxy)benzoyl azide (0.54 g, 1.82 mmol) to 15 mL of tetrahydrofuran as the solvent, and reflux at 80 °C for 12 h. Concentrate the solution and drop it into a large amount of water to obtain an orange solid. Filter by suction and dry to obtain ligand L4U.

[0039] Step 5: Take 100 mg of ligand L4U and 64 mg of tetrabutylammonium chloride, add 0.5 mL of tetrahydrofuran and stir for 2 hours. Add 8 mg of benzoin dimethyl ether (DMPA) and 28.8 mg of trimethylolpropane-tris(3-mercaptopropionate), stir evenly, pour into a polytetrafluoroethylene mold, irradiate with ultraviolet light at 365 nm for 0.5 hour, and then dry in vacuum for 12 hours to obtain an anion-coordinated supramolecular foldamer material 4U (monomer).

[0040] Example 2:

[0041] Basically as shown in the attached Figure 2 and the attached Figure 3 shown: This example provides a preparation method of an anion-coordinated supramolecular foldamer material. The reaction route is as shown in the attached Figure 2 shown, including the following steps:

[0042] Step 1: Add compound 2 (0.77 g, 2.05 mmol) and o-nitroisocyanate (0.81 g, 2.12 mmol) to a flask, add 20 mL of tetrahydrofuran, and reflux at 80 °C for 12 h. After the reaction is completed, filter and dry to obtain compound 3 (1-(2-(3-(2-nitrophenyl)ureido)phenyl)-3-(2-(3-2-[3-[2-nitrophenyl]ureido]phenyl]ureido)phenyl)urea).

[0043] Step 2: Take compound 3 (1.26 g, 1.78 mmol) in a three-necked flask, add 200 mL of ethanol as the solvent, and then add 0.12 g of Pd / C (10% of the reactant mass). Drop 15 mL of hydrazine hydrate at 60 °C and reflux at 80 °C for about 5 h. After the reaction is completed, filter off the Pd / C with diatomaceous earth using a Buchner funnel, wash the product with N,N-dimethylformamide, introduce it into water to precipitate a solid, filter and dry the solid to obtain compound 4 (1-(2-(3-(2-aminophenyl)ureido)phenyl)-3-(2-(3-2-[3-[2-aminophenyl]ureido]phenyl]ureido)phenyl)urea).

[0044] Step 3: In a 100 mL single-necked round-bottom flask in a thermostatic heating magnetic stirrer with a condenser, first add 1.01 g of 4-(9-decenoxy)benzoic acid and 0.78 mL of triethylamine, and add 20 mL of anhydrous tetrahydrofuran. Drop 0.78 mL of diphenylphosphoryl azide at ice bath temperature (the molar ratio of 4-(9-decenoxy)benzoic acid, triethylamine and diphenylphosphoryl azide is 1:1.2:1), and stir at room temperature for 8 hours. Separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate = 100:1), and remove the organic solvent by vacuum concentration to obtain 4-(9-decenoxy)benzoyl azide (chain extender 1).

[0045] Step 4: Add compound 4 (0.34 g, 0.53 mmol) and 4-(9-decenoxy)benzoyl azide (0.40 g, 1.32 mmol) to 15 mL of tetrahydrofuran as the solvent, and reflux at 80 °C for 24 h. Concentrate the solution and drop it into a large amount of water to obtain a yellow solid, filter by suction and dry to obtain ligand L6U.

[0046] Step 5: Take 100 mg of ligand L6U and 50 mg of tetrabutylammonium chloride, add 0.5 mL of tetrahydrofuran and stir for 2 hours. Add 8 mg of benzoin dimethyl ether (DMPA) and 22.2 mg of trimethylolpropane-tris(3-mercaptopropionate), stir evenly, pour into a polytetrafluoroethylene mold, irradiate with 365 nm ultraviolet light for 0.5 hours, and then dry in vacuum for 12 hours to obtain an anion-coordinated supramolecular foldamer material 6U (monomer).

[0047] Tensile property test:

[0048] Perform tensile tests on the anion-coordinated supramolecular foldamer materials 4U and 6U prepared in Example 2 and Example 3 at a tensile rate of 100 mm min-1 at room temperature, as shown in the appendix Figure 3As shown. The maximum elongation rates of 4U and 6U are 300% and 260% respectively, the Young's moduli are 39.97 MPa and 108.92 MPa respectively, the toughnesses are 9.9 MJ / m3 and 16.02 MJ / m3 respectively, and the strengths (maximum tensile stresses) are 6.7 MPa and 11.2 MPa. After stretching the material by 50%, it can fully recover to its initial length in about 7 minutes (as shown in the appendix Figure 4 shown).

[0049] The above are only embodiments of the present invention, and common knowledge such as specific structures and / or characteristics known in the art are not described in detail herein. It should be noted that for those skilled in the art, without departing from the structure of the present invention, several deformations and improvements can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the implementation effect of the present invention and the practicality of the patent. The protection scope required by this application should be based on the content of its claims, and the specific implementation manners described in the specification can be used to interpret the content of the claims.

Claims

1. A preparation method of an anion-coordinated supramolecular foldamer material, characterized in that: It includes the following steps: S1. React aniline with o-nitroisocyanate to obtain a polyurea compound 1; S2. Add a catalyst to compound 1 under stirring conditions and react to obtain compound 2; S3. Mix 4-(9-decenyloxy)benzoic acid and diphenylphosphoryl azide evenly, add a catalyst under stirring conditions and react to obtain chain extender 1; S4. Mix compound 2 and chain extender 1 evenly and react to obtain a ligand; S5. Mix the ligand and tetrabutylammonium chloride evenly to obtain a monomer; and mix the monomer and trimethylolpropane-tris(3-mercaptopropionate) evenly, add a catalyst, and remove the residual solvent after light irradiation to obtain an anion-coordinated supramolecular foldamer material; In step S2, the catalyst is palladium on carbon; in step S3, the catalyst is triethylamine; in step S5, the catalyst is benzoin dimethyl ether.

2. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 1, wherein: In step S1, the aniline is selected from one of o-phenylenediamine or (1,2-bis-(2-aminophenyl-urea)-benzene); the solvent is tetrahydrofuran; the molar ratio of aniline to o-nitroisocyanate is 1:(2-2.5); the reaction temperature is 70-90 °C; the reaction time is 2-6 hours.

3. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 2, wherein: In step S2, the amount of palladium on carbon used is 5-10% of the total mass of the reactants; the reaction temperature is 70-90 °C; the reaction time is 2-6 hours.

4. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 3, wherein: In step S3, the molar ratio of 4-(9-decenyloxy)benzoic acid, triethylamine and diphenylphosphoryl azide is 1:1.2:1; diphenylphosphoryl azide is added dropwise under ice bath; the reaction temperature is room temperature and the reaction time is 6-8 hours.

5. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 4, wherein: In step S4, the molar ratio of compound 2 and compound 4 to chain extender 1 is 1:(2-3); the reaction temperature is 70-80 °C; the reaction time is 12-24 hours.

6. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 5, characterized in that: In step S5, the molar ratio of the ligand to tetrabutylammonium chloride is 1:2; the stirring time is 2-12 hours and the temperature is 25 °C.

7. The preparation method of the anion-coordinated supramolecular foldamer material according to claim 6, characterized in that: In step S5, the molar ratio of the monomer to trimethylolpropane-tris(3-mercaptopropionate) is 2:3; the amount of benzoin dimethyl ether used is 3-5% of the mass of the monomer; the light irradiation wavelength is 365 nm; the residual solvent is removed using a vacuum oven at 60 °C.

8. An anion-coordinated supramolecular foldamer material, characterized in that: It is prepared by the preparation method of the anion-coordinated supramolecular foldamer material described in any one of claims 1 to 7.

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