Amino-functionalized polyester and preparation method thereof

Abstract

The invention discloses amino functional polyester and a preparation method thereof. The amino-functionalized polyester has a structure as shown in a formula (I): # imgabs0 #, wherein n is equal to 10 to 2000; t1 is tert-butyl or benzyl; and T2 has the following structure: # imgabs 1 #. According to the present invention, the efficient catalysis rate and the polymerization controllability are considered, the high polymerization rate and the narrow molecular weight distribution are provided, and the molecular weight distribution index of the amino-functionalized polyester is 1.01-1.20.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer synthesis, and specifically, to an amino-functionalized polyester and a preparation method thereof. Background Art

[0002] Degradable polyesters are polymer materials whose structural units are connected by ester groups. Such materials are safe and non-toxic, have excellent biodegradability, can be decomposed under the action of microorganisms, enzymes or chemistry, and are ultimately degraded into water and carbon dioxide. As environmentally friendly materials, they are widely used in the fields of food packaging and agriculture, making important contributions to solving environmental pollution problems. At the same time, degradable polyesters have good biocompatibility and have broad application prospects in the fields of biomedicine, nanomaterials, etc.

[0003] The properties of traditional degradable polyesters are single and cannot meet the requirements of multiple fields. Therefore, it is necessary to design an effective synthesis method to regulate the polymer structure and physical properties, realize the customized synthesis of polymers, and obtain polyester materials with different properties. The introduction of specific functional groups into polyesters can endow the polymer materials with rich functionality and adjust the physical and mechanical properties of the materials.

[0004] Amino groups can introduce a variety of functional groups, facilitating the modification of polymer properties; at the same time, cationic polymers can be prepared, which have important application prospects in the field of gene therapy. However, the main chain of polyesters has hydrolytic reactivity, and the introduction of functional groups will lead to a decrease in molecular weight and a change in material properties. Therefore, the functionalization of polyesters still faces great challenges. The present invention can catalyze the preparation of amino-functionalized polyesters by using an efficient catalytic system. Summary of the Invention

[0005] In view of the above deficiencies of the prior art, the present invention provides an amino-functionalized polyester and a preparation method thereof.

[0006] One of the purposes of the present invention is to provide an amino-functionalized polyester having the structure shown in formula (I):

[0007]

[0008] wherein, n = 10 - 2000; T1 is tert-butyl or benzyl;

[0009] T2 has the following structure:

[0010]

[0011] The number-average molecular weight of the amino-functionalized polyester is 1000 - 600000 g / mol, preferably 2000 - 100000 g / mol.

[0012] The molecular weight distribution index of the amino-functionalized polyester is 1.01 to 1.2, and can be, for example, 1.01, 1.05, 1.10, 1.13, 1.15, 1.18, 1.2, etc.

[0013] The second object of the present invention is to provide a method for preparing an amino-functionalized polyester, which includes adding an initiator and a monomer to a catalyst and a solvent, and reacting to obtain the amino-functionalized polyester.

[0014] Wherein the monomer has the structure shown in formula (II) or formula (III):

[0015]

[0016]

[0017] Wherein, the catalyst includes compound (a) and compound (b), and compound (a) and compound (b) have the structures shown in the following formula (a) and formula (b) respectively:

[0018]

[0019] R1 is tert-butyl, isopropyl, phenyl, p-tolyl, m-tolyl, mesityl;

[0020]

[0021] R2 is tert-butyl, isopropyl, phenyl, mesityl(trifluoromethyl)phenyl, p-trifluoromethylphenyl, m-trifluoromethylphenyl, p-chlorophenyl.

[0022] During the reaction process, compound (a) and compound (b) react in situ to form a catalyst.

[0023] Wherein, the initiator is at least one of benzyl alcohol, 3-phenyl-1-propanol, diphenylmethanol, 2,2-diphenylethanol, 1,4-benzenedimethanol.

[0024] Wherein, the solvent is at least one of toluene, tetrahydrofuran, chloroform, dichloromethane, deuterated chloroform, N,N-dimethylformamide, and acetonitrile for in-situ reaction.

[0025] Wherein, the molar ratio of the monomer, initiator, compound (a), and compound (b) is (10 to 2000):1:(1 to 20):(1 to 20).

[0026] Preferably, the molar ratio of the monomer, initiator, compound (a), and compound (b) is (10 to 600):1:(1 to 6):(1 to 6).

[0027] Among them, the reaction temperature is 0 to 100 °C. Preferably, the reaction temperature is 25 to 50 °C. For example, it can be any value among 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, or any value between any two numerical ranges.

[0028] Among them, the reaction time is 1 to 21,600 seconds. Preferably, the reaction time is 10 to 1,800 seconds. For example, it can be any value among 1 second, 10 seconds, 50 seconds, 100 seconds, 200 seconds, 300 seconds, 400 seconds, 500 seconds, 600 seconds, 700 seconds, 800 seconds, 900 seconds, 1,000 seconds, 1,200 seconds, 1,500 seconds, 1,700 seconds, 2,000 seconds, 5,000 seconds, 8,000 seconds, 10,000 seconds, 15,000 seconds, 20,000 seconds, 21,600 seconds, or any value between any two numerical ranges.

[0029] The preparation method further includes adding a benzoic acid / deuterated chloroform solution to terminate the reaction after the reaction ends, and then precipitating the amino-functionalized polyester in a methanol solution, followed by filtration and separation.

[0030] The number-average molecular weight of the amino-functionalized polyester prepared by the present invention is 1,000 to 600,000 g / mol, and the molecular weight distribution index is 1.01 to 1.20.

[0031] For traditional polyester polymerization methods, the polymerization reaction time is long, generally 24 hours or more; although a superbase catalytic system can shorten the time, the molecular weight distribution is wide and the polymerization controllability is poor. The present invention takes into account both high catalytic rate and polymerization controllability, achieving both high polymerization rate and narrow molecular weight distribution.

[0032] All publications, patent applications, patents, and other references mentioned in this specification are hereby incorporated by reference in their entirety. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0033] When this specification uses prefixes such as "well-known to those skilled in the art", "prior art", or their similar terms to introduce materials, substances, methods, steps, devices, or components, etc., the objects introduced by such prefixes cover those commonly used in the art at the time when this application is filed, but also include those that are not commonly used at present but will become recognized by the art as suitable for similar purposes.

[0034] In the context of this specification, any matter or thing not mentioned, except as expressly stated, shall directly apply those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas thus formed shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider such combination to be obviously unreasonable.

[0035] The present invention will be further described below by way of examples, but not limited to these examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 1H NMR spectrum of the amino-functionalized polyester prepared for Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] The present invention will be specifically described below in conjunction with specific drawings and examples. It is necessary to point out here that the following examples are only for further illustration of the present invention and cannot be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0038] In addition, it should be noted that, in the following detailed description, the various specific technical features described can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0039] Furthermore, any arbitrary combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention. The technical solutions thus formed belong to part of the original disclosure content of this specification and also fall within the protection scope of the present invention.

[0040] According to a preferred embodiment of the present invention, the preparation method may include the following steps:

[0041] Add the catalyst and solvent into an ampoule bottle that has been treated under anhydrous and anaerobic conditions. After mixing evenly, add the initiator and monomer, and stir and react for a period of time. After the reaction is completed, add benzoic acid / deuterated chloroform solution to terminate the reaction, take it out and add it to a cold methanol solution, and a polymer will precipitate. Filter and separate to obtain a white solid of amino-functionalized polyester, and transfer it to a vacuum drying oven for drying.

[0042] Among them, the structural formula of the monomer is any one of the structural formulas shown in (II) or formula (III):

[0043]

[0044] Among them, the catalyst may include a combination of any one of compound (a) and any one of compound (b).

[0045]

[0046] Among them, R1 is tert-butyl, isopropyl, phenyl, p-tolyl, m-tolyl, mesityl; R2 is tert-butyl, isopropyl, phenyl, mesityl tris(trifluoromethyl)phenyl, p-trifluoromethylphenyl, m-trifluoromethylphenyl, p-chlorophenyl.

[0047] Among them, the initiator is at least one of benzyl alcohol, 3-phenyl-1-propanol, diphenylmethanol, 2,2-diphenylethanol, 1,4-benzenedimethanol.

[0048] According to a preferred embodiment of the present invention, the molar ratio of the monomer to the initiator is (10 - 2000):1, preferably (10 - 600):1. For example, it can be any value among 10:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1500:1, 2000:1 or a value between any two numerical ranges.

[0049] According to a preferred embodiment of the present invention, the molar ratio of compound (a) to the initiator is (1 - 20):1, preferably (1 - 6). For example, it can be any value among 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1 or a value between any two numerical ranges.

[0050] According to a preferred embodiment of the present invention, the molar ratio of compound (b) to the initiator is (1 - 20):1, preferably (1 - 6). For example, it can be any value among 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1 or a value between any two numerical ranges.

[0051] There is no particular limitation on the concentration of benzoic acid in the benzoic acid / deuterated chloroform solution, and preferably it can be 5 - 15 mg / mL.

[0052] In the following examples, the experimental methods, unless otherwise specified, are all conventional methods; the reagents and materials, unless otherwise specified, can all be obtained from commercial sources.

[0053] In the following examples, the number-average molecular weight and the molecular weight distribution index of the polymer were determined by GPC.

[0054] In the following examples, the concentration of the benzoic acid / deuterated chloroform solution was 10 mg / mL.

[0055] Example 1

[0056] 1,3-Di-tert-butylimidazol-2-ylidene (0.1 mmol), diisopropylthiourea (0.1 mmol), benzyl alcohol (0.1 mmol), and toluene (3.2 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (5 mmol) was added for polymerization reaction. After reacting for 10 seconds at 25 °C, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, and then the solution was taken out and added to a cold methanol solution, whereupon a polymer precipitated. The polymer was obtained as a white solid by filtration and separation, and then transferred to a vacuum drying oven for drying.

[0057] The conversion rate was calculated from the reaction solution by 1H NMR, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 99%, the number-average molecular weight of the polymer was 11050 g / mol, and the molecular weight distribution index was 1.02.

[0058] Example 2

[0059] 1,3-Dimesitylimidazol-2-ylidene (0.3 mmol), diisopropylthiourea (0.3 mmol), benzyl alcohol (0.1 mmol), and toluene (15 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (50 mmol) was added for polymerization reaction. After reacting for 10 minutes at 25 °C, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, and then the solution was taken out and added to a cold methanol solution, whereupon a polymer precipitated. The polymer was obtained as a white solid by filtration and separation, and then transferred to a vacuum drying oven for drying.

[0060] The conversion rate was calculated from the reaction solution by 1H NMR, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 99%, the number-average molecular weight of the polymer was 11980 g / mol, and the molecular weight distribution index was 1.09.

[0061] Example 3

[0062] 1,3 - Di - mesitylimidazol - 2 - ylidene (0.8 mmol), di - tert - butylthiourea (0.8 mmol), benzyl alcohol (0.1 mmol), and toluene (80 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (150 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 40 minutes, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. A polymer precipitated out. The white solid was obtained by filtration and separation, transferred to a vacuum drying oven for drying, and the polymer was obtained.

[0063] The conversion rate was calculated from the reaction solution by 1H NMR, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 99%, the number - average molecular weight of the polymer was 325190 g / mol, and the molecular weight distribution index was 1.16.

[0064] Example 4

[0065] 1,3 - Di - isopropylimidazol - 2 - ylidene (0.3 mmol), diphenylthiourea (0.3 mmol), diphenylmethanol (0.1 mmol), and toluene (20 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (III) (20 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 15 minutes, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. A polymer precipitated out. The white solid was obtained by filtration and separation, transferred to a vacuum drying oven for drying, and the polymer was obtained.

[0066] The conversion rate was calculated from the reaction solution by 1H NMR, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 99%, the number - average molecular weight of the polymer was 47260 g / mol, and the molecular weight distribution index was 1.13.

[0067] Example 5

[0068] 1,3 - Di - isopropylimidazol - 2 - ylidene (0.3 mmol), diphenylthiourea (0.9 mmol), benzyl alcohol (0.1 mmol), and toluene (20 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (60 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 6 minutes, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. A polymer precipitated out. The white solid was obtained by filtration and separation, transferred to a vacuum drying oven for drying, and the polymer was obtained.

[0069] The conversion rate was calculated by 1H NMR of the reaction solution, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 99%, the number-average molecular weight of the polymer was 12708 g / mol, and the molecular weight distribution index was 1.17.

[0070] Comparative Example 1

[0071] 1,8-Diazabicyclo[5.4.0]undec-7-ene (0.1 mmol), benzyl alcohol (0.1 mmol), and chloroform (3.2 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (5 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 24 hours, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. A polymer precipitated out. The white solid was obtained by filtration and separation, transferred to a vacuum drying oven for drying to obtain the polymer.

[0072] The conversion rate was calculated by 1H NMR of the reaction solution, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 97%, the number-average molecular weight of the polymer was 12060 g / mol, and the molecular weight distribution index was 1.08.

[0073] Comparative Example 2

[0074] 4-Dimethylaminopyridine (0.3 mmol), diphenylthiourea (0.3 mmol), benzyl alcohol (0.1 mmol), and toluene (20 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (10 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 60 minutes, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. No polymer precipitated out.

[0075] The conversion rate was calculated by 1H NMR of the reaction solution, and the monomer conversion rate was 0%. This catalytic system had no catalytic performance.

[0076] Comparative Example 3

[0077] 1,8-Diazabicyclo[5.4.0]undec-7-ene (0.1 mmol), 1,3-bis(3,5-bis(trifluoromethyl)phenyl)thiourea (0.1 mmol), benzyl alcohol (0.1 mmol), and toluene (20 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (5 mmol) was added to carry out the polymerization reaction. After reacting at 25 °C for 120 minutes, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, which was then taken out and added to a cold methanol solution. No polymer precipitated out.

[0078] The conversion rate was calculated by 1H NMR of the reaction solution, and the monomer conversion rate was 8%.

[0079] Comparative Example 4

[0080] 1,3-Di-tert-butylimidazol-2-ylidene (0.1 mmol), benzyl alcohol (0.1 mmol), and toluene (20 mL) were added to an ampoule that had been treated under anhydrous and anaerobic conditions. The mixture was mechanically stirred for 1 minute to mix evenly, and then monomer (II) (5 mmol) was added for polymerization reaction. After reacting for 120 minutes at 25 °C, a benzoic acid / deuterated chloroform solution was added to dissolve the mixture, and the resulting solution was taken out and added to a cold methanol solution, whereupon a polymer precipitated. The white solid was obtained by filtration and separation, transferred to a vacuum drying oven for drying to obtain the polymer.

[0081] The conversion rate was calculated by 1H NMR of the reaction solution, and the molecular weight and molecular weight distribution index of the polymer were determined by GPC. The monomer conversion rate was 67%, the number-average molecular weight of the polymer was 7030 g / mol, and the molecular weight distribution index was 1.41.

[0082] For those of ordinary skill in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be encompassed by the present invention.

Claims

1. An amino-functionalized polyester having the structure shown in formula (I): Among them, n = 10 - 2000; T1 is tert-butyl or benzyl; T2 has the structure shown below:

2. The amino-functionalized polyester according to claim 1, wherein: The number-average molecular weight of the amino-functionalized polyester is 1000 - 600000 g / mol, preferably 2000 - 100000 g / mol; and / or, The molecular weight distribution index of the amino-functionalized polyester is 1.01 - 1.

2.

3. A method for preparing an amino-functionalized polyester, comprising adding an initiator and a monomer to a catalyst and a solvent, and reacting to obtain the amino-functionalized polyester, wherein the monomer has the structure shown in formula (II) or formula (III):

4. The method for preparing an amino-functionalized polyester according to claim 3, wherein: The catalyst comprises compound (a) and compound (b), and compound (a) and compound (b) have the structures shown in formula (a) and formula (b) below respectively: Wherein, R1 is tert-butyl, isopropyl, phenyl, p-tolyl, m-tolyl, mesityl; R2 is tert-butyl, isopropyl, phenyl, mesityl(trifluoromethyl)phenyl, p-trifluoromethylphenyl, m-trifluoromethylphenyl, p-chlorophenyl.

5. The method for preparing an amino-functionalized polyester according to claim 3, wherein: The initiator is at least one of benzyl alcohol, 3-phenyl-1-propanol, diphenylmethanol, 2,2-diphenylethanol, 1,4-benzenedimethanol.

6. The method for preparing an amino-functionalized polyester according to claim 3, wherein: The solvent is at least one of toluene, tetrahydrofuran, chloroform, dichloromethane, deuterated chloroform, N,N-dimethylformamide, acetonitrile.

7. The method for preparing an amino-functionalized polyester according to claim 4, wherein: The molar ratio of the monomer, initiator, compound (a), and compound (b) is (10 - 2000):1:(1 - 20):(1 - 20), preferably (10 - 600):1:(1 - 6):(1 - 6).

8. The method for preparing an amino-functionalized polyester according to claim 3, wherein: The reaction temperature is 0 - 100 °C, preferably 25 - 50 °C; and / or, The reaction time is 1 - 21600 seconds, preferably 10 - 1800 seconds.

9. The method for preparing an amino-functionalized polyester according to any one of claims 3 - 8, wherein: The preparation method further comprises adding a benzoic acid / deuterated chloroform solution to terminate the reaction after the reaction is completed, and then precipitating the amino-functionalized polyester in a methanol solution, followed by filtration and separation.

10. The amino-functionalized polyester obtained by the preparation method according to any one of claims 3 - 9.

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