CN114409879B - Furyl-terminated hyperbranched polyester and preparation method and application thereof - Google Patents
Furyl-terminated hyperbranched polyester and preparation method and application thereof Download PDFInfo
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract
The invention discloses a furyl-terminated hyperbranched polyester and a preparation method and application thereof. The structure of the terminal furyl hyperbranched polyester is shown as a formula (I), and the terminal furyl hyperbranched polyester has a non-traditional luminous fluorescent response characteristic because a molecular skeleton contains a large number of groups containing active hydrogen such as hydroxyl, secondary amine and the like and ester groups; the terminal contains a large amount of rigid furan structures, so that the hyperbranched polyester has better thermal stability, biocompatibility and the like, and can further react with diene such as maleimide and the like to form a self-repairable functional polymer with reversible covalent DA bonds, and the reactivity of the hyperbranched polyester is also maintained; the preparation method is suitable for the fields of biological fluorescence imaging, medical drug sustained release, biosensing, light-emitting diodes and the like, mainly adopts bio-based raw materials, is low in cost, high in reproducibility of the preparation method, and is easy for industrial mass production.
Description
Technical Field
The invention belongs to the field of high-molecular luminescent materials, and relates to a furyl-terminated hyperbranched polyester, and a preparation method and application thereof.
Background
In recent years, organic light emitting materials have attracted the interest of many researchers due to their special photophysical properties and their use in biological monitoring, cell imaging, drug delivery, and the like. The traditional fluorescent polymer is generally prepared by doping or grafting luminescent molecules on a polymer substrate, the luminescent molecules usually have structures such as large pi-delocalized conjugated unsaturated groups, benzene rings or heterocycles, or the like, or the organic-inorganic luminescent crystals are directly doped, the substances can generate strong fluorescent effect after being combined with the polymer, and the fluorescent polymer is widely applied in the fields of fluorescence, biosensing and light emitting diodes, but the conjugated benzene rings have high specific gravity, so that the toxicity of the conjugated benzene rings cannot be ignored in the application of biomedicine, and the application of the conjugated benzene rings in the aspects of bioluminescence imaging, medical drug slow release and the like is limited.
Hyperbranched polymers have a structure similar to that of dendrimers, both of which contain a large number of reactive end groups and internal pores. Compared with the complicated synthesis process of the dendritic macromolecule, the synthesis method of the hyperbranched polymer is simple, does not need repeated purification, and is beneficial to large-scale production. In addition, hyperbranched polymers have more excellent rheological properties and reactivity and unique fluorescence characteristics than linear polymers of the same molecular weight, which makes hyperbranched polymers one of the hot areas for polymer research. The hyperbranched polymer does not contain large-area luminescent conjugated groups, has good biocompatibility and environmental protection, and has wider application in the luminescent field of biomedicine. Hyperbranched polymers without characteristic luminescent groups, such as polyamino ester, polyethyleneimine, hydroxyl-terminated, amino, epoxy polyester, polycarbonate and the like, all indicate the unconventional luminescent phenomenon.
The patent document with the application number of 201710073938.X discloses hyperbranched fluorescent aliphatic polyamide-imide and a preparation method and application thereof, wherein thiolactone-maleimide is used as a raw material, an intermediate with the chain end being sulfydryl and alkynyl is firstly synthesized, then the hyperbranched fluorescent aliphatic polyamide-imide is synthesized through sulfydryl-alkyne click reaction, and the fluorescent characteristic of the hyperbranched fluorescent aliphatic polyamide-imide in a solution state is researched.
The patent document 201810526643.8 discloses hyperbranched polyaminoester capable of emitting multicolor fluorescence and a preparation method thereof, wherein citric acid and triethanolamine are used as raw materials to be directly subjected to polycondensation to form the hyperbranched polyaminoester, and the fluorescence intensities of hyperbranched polyaminoester solution and pure hyperbranched polyaminoester under different wavelengths are studied.
Rigid groups are not introduced into hyperbranched polymer chains synthesized by the two technologies, and the terminal amino or hydroxyl keeps the reactivity of the polymer, but greatly reduces the heat resistance of the hyperbranched polymer.
Therefore, it is highly desirable to develop a hyperbranched polymer having good heat resistance, biocompatibility and fluorescence responsiveness.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a furyl-terminated hyperbranched polyester with good heat resistance, biocompatibility and fluorescence responsiveness, and a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a furyl-terminated hyperbranched polyester, which has a structure represented by formula (i):
wherein R is 1 The core of the furan-terminated hyperbranched polyester contains more than two carboxyl groups or more than one anhydride or contains more than one carboxyl group and anhydride simultaneously; r 2 The branch of the furan-terminated hyperbranched polyester contains one hydroxyl and more than two carboxyl; n is a natural number greater than 4.
The terminal furyl hyperbranched polyester has the non-traditional luminescent fluorescent response characteristic because the molecular skeleton contains a large number of groups containing active hydrogen such as hydroxyl, secondary amine and the like and ester groups; meanwhile, the terminal contains a large amount of rigid furan structures, so that the hyperbranched polyester has better thermal stability, biocompatibility and the like, and can further react with diene such as maleimide and the like to form a self-repairable functional polymer with reversible covalent diels-alder (DA) bonds, thereby also maintaining the reactivity of the hyperbranched polyester.
In the end furyl hyperbranched polyester, the value of n is determined according to the content of R in the selected raw materials 1 And compounds containing R 2 Number of terminal functional groups of the compound of (1), and the compound containing R 1 And compounds containing R 2 The charge ratio of the compound (c) is different. Preferably, n =9 to 81.
In a second aspect, the present invention provides a method for preparing the furyl-terminated hyperbranched polyester, which comprises the following steps:
s1, reacting at least one of a first polycarboxylic acid and a first polybasic acid anhydride with a second monohydroxy polycarboxylic acid in a first organic solvent in the presence of a water-carrying agent and a catalyst to obtain carboxyl-terminated hyperbranched polyester;
s2, reacting the carboxyl-terminated hyperbranched polyester with epoxy chloropropane in a protective gas atmosphere, and removing unreacted epoxy chloropropane after the reaction is finished to obtain an intermediate; reacting the intermediate in a second organic solvent in the presence of inorganic base, and purifying to obtain epoxy-terminated hyperbranched polyester;
s3, reacting the epoxy-terminated hyperbranched polyester with 2-furanmethylamine to obtain the furyl-terminated hyperbranched polyester,
wherein the structure of the intermediate is shown as the formula (II):
herein, "polycarboxylic acid" means a dicarboxylic or higher carboxylic acid, such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, etc.; "polybasic acid anhydride" refers to more than two-membered acid anhydrides, such as dibasic acid anhydride, tribasic acid anhydride, tetrabasic acid anhydride, and the like.
The epoxy-terminated hyperbranched polyester obtained in the step S2 reacts with 2-furanmethylamine, a large number of rigid furan structures are introduced at the tail end, so that the thermal stability, the biocompatibility and the like are better, the epoxy-terminated hyperbranched polyester can further react with diene such as maleimide and the like to form a self-repairable functional polymer with reversible covalent DA bonds, and the reactivity of the hyperbranched polyester is also maintained. Preferably, in step S1, the reaction is carried out for 5 to 7 hours at 90 to 110 ℃ and then for 4 to 6 hours at 115 to 135 ℃; the ratio of the total molar amount of the first polycarboxylic acid and the first polybasic acid anhydride to the molar amount of the second monohydroxy polycarboxylic acid is 1:3-39.
Preferably, in step S1, the first polycarboxylic acid includes at least one of oxalic acid, adipic acid, terephthalic acid, trimesic acid, and the like; the first polybasic acid anhydride comprises at least one of succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride and the like; the second monohydroxy polycarboxylic acid comprises at least one of citric acid, malic acid, and the like; the water-carrying agent comprises at least one of toluene, xylene and the like; the catalyst is p-toluenesulfonic acid; the first organic solvent includes at least one of dioxane, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.
Preferably, in the step S2, the temperature of the reaction between the carboxyl-terminated hyperbranched polyester and the epichlorohydrin is 125 to 145 ℃, and the time is 3 to 5 hours; the reaction temperature for generating the epoxy-terminated hyperbranched polyester by the intermediate is normal temperature, and the reaction time is 5-6 h; the molar ratio of the epoxy chloropropane to the terminal carboxyl of the second organic solvent to the inorganic base to the carboxyl-terminated hyperbranched polyester is epichlorohydrin: a second organic solvent: inorganic base: terminal carboxyl = 2-8 of carboxyl-terminated hyperbranched polyester: 5 to 8:6 to 9:1.
the protective gas can be at least one of nitrogen and inert gas.
As used herein, "ambient temperature" means room temperature, and may be without heating or cooling, e.g., 5-35 ℃.
Preferably, in step S2, the inorganic base includes at least one of sodium hydroxide and the like; the second organic solvent includes at least one of ethyl acetate and the like.
Preferably, in step S2, the reaction between the carboxyl-terminated hyperbranched polyester and the epichlorohydrin is a heating reflux reaction.
The epoxy-terminated hyperbranched polyester is a light yellow low-viscosity liquid.
Preferably, in step S2, the purification comprises the steps of: extracting with water, and drying the upper organic phase to obtain the epoxy-terminated hyperbranched polyester. The extraction times and the water consumption can be adjusted according to the needs; the method and temperature of drying are not limited as long as the target substance is not denatured.
Preferably, in step S3, the molar ratio of the epoxy-terminated hyperbranched polyester to the 2-furanmethanamine is that of the epoxy-terminated hyperbranched polyester: 2-furanmethanamine =1:1.2 to 2, the reaction temperature is 40 to 60 ℃, and the reaction time is 6 to 10 hours.
The end furyl hyperbranched polyester is brownish black viscous liquid.
Preferably, in step S3, after the reaction is finished, unreacted 2-furanmethanamine is removed by rotary evaporation, and then drying treatment is performed, so as to obtain the furyl-terminated hyperbranched polyester. The rotary evaporation temperature can be selected from 70-90 ℃ and the like; the method and temperature of drying are not limited as long as the target substance is not denatured.
In a third aspect, the invention provides an application of the terminal furyl hyperbranched polyester in the fields of bioluminescence imaging, medical drug sustained release, biosensing or light emitting diodes.
Compared with the prior art, the invention has the beneficial effects that: the terminal furyl hyperbranched polyester has the fluorescent response characteristic of non-traditional luminescence because a molecular skeleton contains a large number of groups (such as hydroxyl, secondary amine and the like) containing active hydrogen and ester groups; compared with the existing hyperbranched polyester, the hyperbranched polyester has better thermal stability, biocompatibility and the like because the tail end contains a large amount of rigid furan structures; the terminal furan structure can further react with diene such as maleimide and the like to form a self-repairable functional polymer with reversible DA bonds, so that the reactivity of the hyperbranched polyester is maintained. The end furyl hyperbranched polyester is suitable for the fields of biological fluorescence imaging, medical drug sustained release, biosensing, light-emitting diodes and the like. In addition, the preparation raw materials used by the end-furyl-hyperbranched polyester are mainly bio-based raw materials, the cost is low, the reproducibility of the preparation method is high, and the industrial mass production is easy to realize.
Drawings
FIG. 1 is an IR spectrum of an epoxy-terminated hyperbranched polyester of comparative example 1;
FIG. 2 is an infrared spectrum of the hyperbranched polyester with furyl group at the end of example 1;
FIG. 3 is a thermogravimetric plot of the epoxy-terminated hyperbranched polyester of comparative example 1;
FIG. 4 is a thermogravimetric plot of the hyperbranched furan-terminated polyester of example 1;
FIG. 5 is a thermogravimetric plot of the example 3 end-furyl hyperbranched polyester;
FIG. 6 is a fluorescence spectrum of the end-furyl hyperbranched polyester of example 1.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reagents, methods and equipment used in the invention are conventional in the technical field unless otherwise specified.
Example 1
This example provides an algebraic 1-terminated furyl hyperbranched polyester, which has the following structural formula:
wherein R is 1 Is the core of the furan-terminated hyperbranched polyester and contains 1 carboxyl and 1 anhydride; r 2 Is a branch of the furyl-terminated hyperbranched polyester and contains one hydroxyl and 3 carboxyl; n is 9. The preparation method comprises the following steps:
s1, carboxyl-terminated hyperbranched polyester
Adding 0.04mol of trimellitic anhydride, 0.12mol of citric acid, 0.31g of p-toluenesulfonic acid, 100mL of toluene and 100mL of dioxane into a reaction vessel provided with a reflux device, a nitrogen protection device and a mechanical stirring device, stirring for 6h at 100 ℃, and reacting for 5h at 125 ℃ to obtain carboxyl-terminated hyperbranched polyester;
s2. Epoxy-terminated hyperbranched polyester
Adding 0.008mol of the carboxyl-terminated hyperbranched polyester obtained in the step S1 into 0.54mol of epoxy chloropropane, and heating and refluxing for 3h at 135 ℃ in a nitrogen atmosphere; after the reaction is finished, removing excessive epichlorohydrin by rotary evaporation to obtain an intermediate; adding 250mL of ethyl acetate and 27g of sodium hydroxide into the intermediate, and stirring for 5-6 h at normal temperature; after the reaction is finished, adding 75mL of ultrapure water to dissolve sodium hydroxide, separating and extracting, taking an upper organic phase, extracting for 3 times by using 5mL of ultrapure water respectively, and drying the extracted upper organic clear liquid in a drying oven at 80 ℃ to obtain the epoxy-terminated hyperbranched polyester in a light yellow low-viscosity liquid;
s3, end furyl hyperbranched polyester
And (3) adding 0.003mol of the epoxy-terminated hyperbranched polyester obtained in the step (S2) and 0.054mol of 2-furanmethylamine into a round-bottomed flask, reacting for 15 hours at 45 ℃, removing excessive 2-furanmethylamine by rotary evaporation after the reaction is finished, and drying in an oven at 80 ℃ for 48 hours to obtain the brown-black viscous liquid-terminated furyl-hyperbranched polyester.
Example 2
This example provides an algebraic 2 furan-terminated hyperbranched polyester, whose structural formula is as follows:
wherein R is 1 Is the core of the furan-terminated hyperbranched polyester and contains 1 carboxyl and 1 anhydride; r 2 Is a branch of the furyl-terminated hyperbranched polyester, and contains one hydroxyl and 3 carboxyl; n is 27. The preparation method is different from that of the embodiment 1 in that the raw materials in the step S1 are 0.04mol of trimellitic anhydride, 0.48mol of citric acid, 1g of p-toluenesulfonic acid, 100mL of toluene and 100mL of dioxane; in the step S2, the consumption of the epoxy chloropropane is 1.6mol, and the consumption of the sodium hydroxide is 42.3g; in the step S3, the using amount of the 2-furanmethanamine is 0.162mol.
Example 3
This example provides an algebraic 3-terminated furan-terminated hyperbranched polymer, which has the following structural formula:
wherein R is 1 Is the core of the furan-terminated hyperbranched polyester and contains 1 carboxyl and 1 anhydride; r 2 Is a branch of the furyl-terminated hyperbranched polyester and contains one hydroxyl and 3 carboxyl; n is 81. The preparation method is different from that of the embodiment 1 in that the raw materials in the step S1 are 0.04mol of trimellitic anhydride, 1.56mol of citric acid, 3.07g of p-toluenesulfonic acid, 100mL of toluene and 100mL of dioxane; in the step S2, the consumption of the epoxy chloropropane is 4.85mol, and the consumption of the sodium hydroxide is 41.7g; in the step S3, the using amount of the 2-furanmethanamine is 0.486mol.
Comparative example 1
This comparative example provides an epoxy-terminated hyperbranched polyester of generation number 1, which is prepared by a method different from that of example 1 in that only steps S1 and S2 are performed without passing through step S3.
Comparative example 2
This comparative example provides an epoxy-terminated hyperbranched polyester of generation number 2, which is prepared by a method different from that of example 2 in that only steps S1 and S2 are performed without passing through step S3.
Comparative example 3
This comparative example provides an epoxy-terminated hyperbranched polyester of generation number 3, which is prepared by a method different from that of example 3 in that only steps S1 and S2 are performed without passing through step S3.
Examples of effects
The furan-terminated hyperbranched polyester prepared in each example and the epoxy-terminated hyperbranched polyester prepared in each proportion are subjected to characterization tests, and the test method is as follows:
(1) Gel permeation chromatography test
Molecular weights and their distributions of the samples to be tested were characterized using Breeze 2 GPC system from Waters corporation, usa. The test temperature was 25 ℃, tetrahydrofuran as the mobile phase, PS (polystyrene) as the standard, and the flow rate was 1mL/min.
(2) Thermogravimetric testing
The thermal weight loss temperature of the sample to be tested was characterized using the PE Pyris1 TGA system from Perkinelmer, USA. The heating rate was 10 ℃/min.
(3) Fluorescence spectroscopy test
The fluorescence spectrum of the sample to be tested is tested by adopting a fluorescence spectrophotometer F-4500 of Hitachi, japan, the scanning speed is 1200nm/min, and the size of the grating is 5.0nm multiplied by 5.0nm.
The specific test results are shown in table 1.
TABLE 1
| Sample(s) | Td,5％/℃ | Td,max/℃ | Mn | Mw | DP (polydispersity) |
| Comparative example 1 | 102.0 | 170.19 | 1413 | 1443 | 1.02 |
| Example 1 | 186.68 | 252.52 | 1419 | 1447 | 1.02 |
| Comparative example 2 | 99.21 | 194.58 | 1399 | 1422 | 1.02 |
| Example 2 | 146.62 | 245.34 | 1744 | 1967 | 1.13 |
| Comparative example 3 | 108.01 | 203.0 | 1683 | 1858 | 1.10 |
| Example 3 | 135.96 | 242.77 | 2485 | 3812 | 1.53 |
As can be seen from the thermogravimetric results in table 1, compared with the epoxy-terminated hyperbranched polyester, the furan-terminated hyperbranched polyester has higher weight loss starting temperature and maximum weight loss temperature, which indicates that the heat resistance of the furan-terminated hyperbranched polyester is improved, because the terminal of the hyperbranched polyester contains more rigid furan groups, the overall heat resistance of the hyperbranched polyester is improved. The number average molecular weight, weight average molecular weight and polydispersity of the two types of hyperbranched polymers, as measured using gel permeation chromatography, are also listed in table 1, with a large difference from the theoretical molecular weight, possibly due to the fact that GPC uses linear PS as a standard, while the hyperbranched polymers are three-dimensional and extend all around. In addition, the maximum excitation wavelength of the furan-terminated hyperbranched polyester obtained in each example is 410nm, and the maximum emission wavelength is 450nm.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The furyl-terminated hyperbranched polyester is prepared by a preparation method comprising the following steps:
s1, reacting at least one of a first polycarboxylic acid and a first polybasic acid anhydride with a second monohydroxy polycarboxylic acid in a first organic solvent in the presence of a water-carrying agent and a catalyst to obtain carboxyl-terminated hyperbranched polyester;
s2, reacting the carboxyl-terminated hyperbranched polyester with epoxy chloropropane in a protective gas atmosphere, and removing unreacted epoxy chloropropane after the reaction is finished to obtain an intermediate; reacting the intermediate in a second organic solvent in the presence of inorganic base, and purifying to obtain epoxy-terminated hyperbranched polyester;
s3, reacting the epoxy-terminated hyperbranched polyester with 2-furanmethylamine to obtain the furyl-terminated hyperbranched polyester,
the structure of the intermediate is shown as a formula (II), wherein n is a natural number more than 4 in the formula (II):
2. the furyl-terminated hyperbranched polyester of claim 1, wherein in step S1, the reaction is performed at 90 to 110 ℃ for 5 to 7 hours, and then at 115 to 135 ℃ for 4 to 6 hours; the ratio of the total molar amount of the first polycarboxylic acid and the first polybasic acid anhydride to the molar amount of the second monohydroxy polycarboxylic acid is 1:3-39.
3. The furyl-terminated, hyperbranched polyester of claim 1, wherein in step S1, the first polycarboxylic acid comprises at least one of oxalic acid, adipic acid, terephthalic acid, and trimesic acid; the first polybasic acid anhydride comprises at least one of succinic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride; the second monohydroxy polycarboxylic acid comprises at least one of citric acid and malic acid; the water-carrying agent comprises at least one of toluene and xylene; the catalyst is p-toluenesulfonic acid; the first organic solvent includes at least one of dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.
4. The furyl-terminated hyperbranched polyester of claim 1, wherein in step S2, the carboxyl-terminated hyperbranched polyester is reacted with the epichlorohydrin at a temperature of 125 to 145 ℃ for 3 to 5 hours; the reaction temperature of the intermediate for generating the epoxy-terminated hyperbranched polyester is normal temperature, and the reaction time is 5-6 h; the molar ratio of the epoxy chloropropane to the terminal carboxyl of the second organic solvent to the inorganic base to the carboxyl-terminated hyperbranched polyester is epichlorohydrin: a second organic solvent: inorganic base: terminal carboxyl = 2-8 of carboxyl-terminated hyperbranched polyester: 5 to 8:6 to 9:1.
5. the furyl-terminated, hyperbranched polyester of claim 1, wherein in step S2, the inorganic base comprises sodium hydroxide; the second organic solvent comprises ethyl acetate.
6. The furyl-terminated, hyperbranched polyester of claim 1, wherein in step S2, the purifying comprises the steps of: extracting with water, and drying the upper organic phase to obtain the epoxy-terminated hyperbranched polyester.
7. The furyl-terminated hyperbranched polyester of claim 1, wherein in step S3 the molar ratio of the hydroxyl-terminated hyperbranched polyester to the 2-furanmethanamine is that of the hydroxyl-terminated hyperbranched polyester: 2-furanmethanamine =1:1.2 to 2, the reaction temperature is 40 to 60 ℃, and the reaction time is 6 to 10 hours.
8. The furyl-terminated hyperbranched polyester of claim 1, wherein in step S3, after the reaction is finished, unreacted 2-furanmethanamine is removed by rotary evaporation, and then the furyl-terminated hyperbranched polyester is obtained after drying treatment.
9. The use of the furyl-terminated hyperbranched polyester as defined in claim 1 in the fields of bioluminescence imaging, medical drug release, biosensing, or light emitting diodes.
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