A METHOD FOR PREPARING MULTI-COMPONENT POLYMERS THROUGH POST-POLYMERIZATION MODIFICATION

Abstract

The present disclosure provides a method for preparing multi-component polymers through post-polymerization modification, used to functionalize polysulfonyl imidate polymer including a dispersing polymer reactant, an electrophilic substitution reagent and a catalyst in an organic dispersant; adding acid-binding agent to react at room temperature for 4-48 h; obtaining the precipitate when the reaction finished; washing and drying the obtained precipitate to get the functionalized multi-component polymers. The present disclosure involves a low polymerization temperature, allowing for the reaction to occur at room temperature. Additionally, the conversion rate is high, and the applicable electrophilic substitution monomer reagents have a wide selection. Besides that, the synthesis cost of the reaction is low due to the widespread availability of common chemical reagents such as catalysts, organic dispersants, acid binding agents, and other reaction reagents. The ease of access to these raw materials contributes to the overall affordability of the synthesis process.

Claims

1. A method for preparing a multi-component polymer through post-polymerization modification, used to functionalize a polysulfonyl imidate polymer, comprising: dispersing a polymer reactant, an electrophilic substitution reagent and a catalyst in an organic dispersant; adding an acid-binding agent to react at room temperature for 4-48 h; obtaining a precipitate when the reaction is completed; washing and drying the obtained precipitate to get the functionalized multi-component polymers; wherein the polymer reactant includes a structure as shown below: ##STR00018## n is an integer from 1 to 50; the electrophilic substitution reagent is a para-substituted aromatic ring of trans-nitracrine with a formula structure as shown below, ##STR00019## or an ester with glyoxylate group with a formula structure as shown below, ##STR00020## or a Baylis-Hillman addition derivative with a formula structure as shown below, ##STR00021## wherein R.sub.1, R.sub.2 and R.sub.3 are electron-donating groups or electron-withdrawing groups; a molar ratio of the polymer reactant to the electrophilic reagent is 1:1-2; the multi-component polymers further include a structure selected from the group consisting of: ##STR00022## wherein the multi-component polymer has a molecular weight of 8000-31000 g/moL.

2. The method of claim 1, wherein the electrophilic substitution reagent is selected from the group consisting of ##STR00023## ##STR00024## ##STR00025##

3. The method of claim 1, wherein the organic dispersant is tetrahydrofuran or N,N′-dimethylformamide.

4. The method of claim 1, wherein a monomer concentration of the electrophilic substitution reagent in the organic dispersant is 0.1 M-0.4 M.

5. The method of claim 1, wherein the catalyst comprises cuprous bromide, an amount of copper bromide ranges from 0.01 M-0.1 M

6. The method of claim 1, wherein the acid binding agent comprises triethylamine, and the amount of triethylamine ranges from 0.05 M-1 M.

7. A method of further functionalizing the multi-component polymer prepared by the method of claim 1, comprising: dispersing the multi-component polymers with the formula structure as shown below and the acid binding agent in the organic dispersant; ##STR00026## adding electrophilic addition reagent and reacting at room temperature for 4 h; obtaining the precipitate when the reaction is completed; drying and washing the precipitate to obtain the further functionalized polymers with a formula structure as shown below: ##STR00027## the acid binding agent is triethylamine, the organic dispersant is tetrahydrofuran or N,N′-dimethylformamide, and the electrophilic addition reagent is benzyl mercaptan.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 shows a schematic diagram of the process for preparing the functionalized polymer in Embodiment 1 of this disclosure.

[0038] FIG. 2 shows a schematic diagram of the process for preparing the functionalized polymer in Embodiment 2 of this disclosure.

[0039] FIG. 3 shows a schematic diagram of the process for preparing the functionalized polymer in Embodiment 3 of this disclosure.

[0040] FIG. 4 shows the nuclear magnetogram of the functionalized polymer P1 prepared in Embodiment 1 of this disclosure.

[0041] FIG. 5 shows the nuclear magnetogram of the functionalized polymer P2 prepared in Embodiment 2 of this disclosure.

[0042] FIG. 6 shows the nuclear magnetogram of the functionalized polymer P3 prepared in Embodiment 3 of this disclosure.

[0043] FIG. 7 shows the nuclear magnetogram of the functionalized polymer P4 prepared in Embodiment 4 of this disclosure.

DETAILED DESCRIPTION OF THE SPECIFIC EMBODIMENTS

[0044] Referring to the drawings, to the following detailed description, detailed information about this disclosure is provided including the description of the specific embodiments. The detailed description serves to explain the principles of this disclosure, and this disclosure is not limited to the particular forms disclosed. This disclosure covers all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the claim.

[0045] All chemical reagents and solvents are purchased from Aladdin Chemical Reagent Co. The solvent specifications are all analytical purity, and the reagent purity is 99%.

[0046] The polysulfonyl imidate polymer applied in this disclosure includes a formula as shown below, wherein n is an integer from 1 to 50. Such polymer is synthesized through three monomers, sulfonyl azide, bis-alkyne and bis-hydroxy compound, by monovalent copper-catalyzed polymerization at room temperature. The synthesis process can be found in the publication “Multicomponent polymerization toward biodegradable polymers with diverse responsiveness in tumor microenvironments,” Polymer Chemistry, 2020, 11(6): 1198-1210.

##STR00010##

[0047] Nuclear magnetic resonance hydrogen spectroscopy (′H-NMR) was tested by Bruker AV 500 NMR instrument from Bruker, Germany.

Embodiment 1

[0048] The polysulfonyl imidate polymer (0.2 mmol, 116.2 mg), CuBr (0.04 mmol, 5.6 mg) and trans-nitrostyrene 1 (0.2 mmol, 29.8 mg) were dissolved in 1 mL of anhydrous N,N′-dimethylformamide solvent; then triethylamine (1 mmol, 140 μL) was slowly added to the reaction system and the reaction was carried out at room temperature for 8-48 h with magnetic stirring. After the reaction finished, the product was purified by sedimentation with methanol and dried under vacuum at room temperature to obtain polymer P1 with the structural formula as shown below. Referring to FIG. 4, the hydrogen on the polymer was characterized by 1H NMR, wherein the NMR spectra clearly show that each hydrogen atom on the polymer can be distinguished and analyzed individually. It indicates that the functionalized polymer has been successfully prepared.

##STR00011##

[0049] Other trans-nitrostyrene derivatives including but not limiting the compounds represented by structural formulas 2-5 below, could also be applied in the hereinabove reaction. See FIG. 1 for the reaction equation.

##STR00012##

Embodiment 2

[0050] The polysulfonyl imidate polymer (0.2 mmol, 116.2 mg), CuBr (0.04 mmol, 5.6 mg) and ethyl glyoxylate as shown in structural formula 6 (0.2 mmol, 29.8 mg) were dissolved in 1 mL of anhydrous N,N′-dimethylformamide solvent; then triethylamine (1 mmol, 140 μL) was slowly added to the reaction system and the reaction was carried out at room temperature with magnetic stirring for 8-48 h. After the reaction finished, the product was purified by sedimentation with methanol and dried under vacuum at room temperature to obtain polymer P2 with the structural formula as shown below.

##STR00013##

[0051] When the polysulfonyl imidate polymer reacts with ethyl glyoxylate 6 in a 1:2 reaction molar ratio, a bimolecular substitution reaction occurs. As shown in FIG. 5, this bimolecular substitution product is characterized by 1H NMR, wherein the hydrogens in the polymer match their respective attributions on the NMR spectrum, indicating that the functionalized polymer has been successfully prepared.

[0052] As used herein, other esters including glyoxylate groups, including but not limited to methyl glyoxylate (for example, the structural formula 7 as shown below), could also be appropriate for the hereinabove reaction. See FIG. 2 for the reaction equation.

##STR00014##

Embodiment 3

[0053] The polysulfonyl imidate polymer (0.2 mmol, 116.2 mg), CuBr (0.04 mmol, 5.6 mg) and Baylis-Hillman addition derivative as shown in structural formula 8 (0.2 mmol, 29.8 mg) were dissolved in 1 mL of anhydrous N,N′-dimethylformamide solvent; then triethylamine (1 mmol, 140 μL) was slowly added to the reaction system and the reaction was carried out at room temperature with magnetic stirring for 8-48 h. After the reaction, the product was purified by sedimentation with methanol and dried under vacuum at room temperature to obtain the polymer P3 with the structural formula as shown below. As shown in FIG. 6, this product is characterized by 1H NMR, wherein the hydrogens in the polymer match their respective attributions on the NMR spectrum, indicating that the functionalized polymer has been successfully prepared.

##STR00015##

[0054] As used herein, other Baylis-Hillman addition including but not limiting to methyl glyoxylate, (for example, the structural formula 9 as shown below) could also be appropriate for the hereinabove reaction. See FIG. 3 for the reaction equation.

##STR00016##

[0055] In hereinabove embodiments 1, 2, and 3, the amount of catalyst, cuprous bromide, could vary between 0.01 M and 0.1 M, while the amount of acid binding agent, triethylamine, could range from 0.05 M to 1 M. Moreover, the molecular weight of the synthesized functionalized polymer falls between 8000 and 31000 g/mol.

Embodiment 4

[0056] Polymer P3 (40.5 mg) and triethylamine (0.03 mmol, 5 μL) were dissolved in 1 mL of anhydrous N,N′-dimethylformamide solvent, and then benzyl mercaptan (0.18 mmol, 23 mg) was added slowly dropwise and stirred at room temperature for 4 h. After the reaction, the reaction solution was added to a large amount of methanol, the crude product was washed three times with methanol, the purified product was collected by centrifugation, and finally the polymer was dried in vacuum to obtain polymer P4 whose structural formula is shown below. As shown in FIG. 7, this product is characterized by 1H NMR, wherein the hydrogens in the polymer match their respective attributions on the NMR spectrum, indicating that the functionalized polymer has been successfully prepared.

##STR00017##

[0057] The present disclosure involves a low polymerization temperature, allowing for the reaction to occur at room temperature. Additionally, the conversion rate is high, and the applicable electrophilic substitution monomer reagents have a wide selection. Besides that, the synthesis cost of the reaction is low due to the widespread availability of common chemical reagents such as catalysts, organic dispersants, acid binding agents, and other reaction reagents. The ease of access to these raw materials contributes to the overall affordability of the synthesis process. Moreover, the polymers functionalized through the present invention can undergo further functionalization via addition reactions with other electrophilic reagents within this reaction system through proper reaction design. This ability allows for the preparation of intricate polymers and enhances reaction efficiency.

[0058] The technical features of the embodiments described above can be combinable in any manner. While all possible combinations of the technical features have not been exhaustively described to maintain brevity, any combination of these features that does not contradict their intended use should be considered within the scope of this specification.

[0059] In the foregoing specification, this disclosure has been described with reference to specific embodiments thereof. The specification should be regarded in an illustrative rather than a restrictive sense. It will, however, be evident that various modifications and changes can be made thereto without departing from the broader spirit and scope of the disclosure as set forth in the appended claims. Therefore, the scope of this disclosure should be limited on by the appended claims.