Preparation and application of a light-induced reversible mediated heterogeneous polymerization catalyst

Abstract

The application discloses a preparation and application of a light-induced reversible mediated heterogeneous phase catalyst, wherein the heterogeneous phase light catalyst is a conjugated microporous polymer (CMP), and when the CMP is used as a catalyst, light-induced reversible complex-mediated (RCMP) polymerization can be carried out without a solvent; the obtained polymer has low dispersity (PDI=1.04-1.25); when the CMP is used as the catalyst to carry out the RCMP polymerization, the CMP has strong stability and can be repeatedly used for many times; the CMP can be induced by full spectrum light, has strong applicability and is suitable for large-scale application.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer material preparation, and more specifically, relates to a conjugated microporous polymer and a preparation method thereof, as well as an application thereof in visible light-induced controlled free radical polymerization. Background Art

[0002] In recent years, controlled radical polymerization (CRP) has been widely developed and applied to prepare polymer materials with precise structures, controllable molecular weights, and uniform molecular weight distribution. Methods for controlled radical polymerization have also been continuously developed, such as nitroxide-stabilized radical polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer radical polymerization (RAFT), reversible chain transfer catalytic polymerization (RTCP), and reversible complexation-mediated polymerization (RCMP). These polymerization techniques have opened up new avenues for achieving structural and functional diversity in polymers. Compared to traditional thermally initiated polymerization processes, photoinduced radical polymerization operates under milder conditions, providing an important approach for achieving a wider range of polymer applications.

[0003] Compared to other controlled living radical polymerization methods, reversible complexation-mediated polymerization (RCMP) offers advantages not only in its diverse catalyst options but also in its suitability for the controlled polymerization of a wide range of functional monomers. RCMP can be used to synthesize polymers with well-defined compositions, controllable molecular weights, and relatively uniform molecular weights. These polymers are widely used in clinical medicine, biomedicine, healthcare, cosmetics, and pesticide release.

[0004] Conjugated microporous polymers (CMPs) are a highly promising class of organic porous materials. They possess advantages such as π-conjugation, large specific surface area, high stability, precisely tunable micropore size and volume, and high chemical and thermal stability. They are reusable, highly efficient, and adaptable for large-scale applications. They have found important applications in a wide range of fields, including gas adsorption, chemical sensing, heterogeneous catalysis, and energy storage and conversion. Because the π-conjugation of conjugated microporous polymers affects the conduction of electrons and holes, CMPs hold great promise for application in photoinduced RCMP processes.

[0005] Purpose of the Invention

[0006] The purpose of the present invention is to broaden the application of CMPs materials in the field of light-induced RCMP polymerization, and for the first time improve the conversion rate of CMPs materials for RCMP by increasing the π conjugation degree of CMPs materials and modifying the pore wall structure of CMPs materials.

[0007] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0008] Preparation and application of a light-induced reversible complex-mediated heterogeneous catalyst with conjugated microporous structure (CMP S ), and the specific molecular structure is as follows:

[0009]

[0010] Wherein the dotted line represents the bonding position.

[0011] Preferably, the conjugated microporous polymer is obtained by condensation of an aldehyde monomer and an amino monomer in the presence of a solvent A and a catalyst;

[0012] Preferably, the solvent A is one or more of 1,2-dichlorobenzene, n-butanol, mesitylene, 1,4-dioxane, toluene, p-xylene, N,N-dimethylformamide, and N,N-dimethylacetamide;

[0013] Preferably, the catalyst is an acetic acid solution with a concentration of one of 3M, 4M, and 6M;

[0014] Preferably, the aldehyde monomer M is one or more of 4'4-biphenyldicarboxaldehyde, 1,4-bis(4-formylphenyl)benzene, 4,4'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde, 1,3,5-benzene tricarboxaldehyde, and 2,4,6-trichloro-1,3,5-benzene tricarboxaldehyde;

[0015] Preferably, the amino monomer is 1,3,5-tris(4-aminophenyl)benzene;

[0016] Preferably, the condensation reaction temperature is 80-180°C.

[0017] Application: the catalyst, monomer, and initiator are used for reversible complex-mediated polymerization under the action of visible light in a nitrogen or argon atmosphere, and the monomer is one or more of methyl methacrylate (MMA), methoxyethyl methacrylate (MEMA), glycidyl methacrylate (GMA), 2-(diethylamino)ethyl methacrylate (HEA), N,N-dimethylacrylamide (DMA), dimethylaminoethyl methacrylate (DEAEMA), and polyethylene glycol methyl ether acrylate (PEGMA);

[0018] Preferably, when the catalyst is used for reversible complex-mediated polymerization, the initiator is one of 2-iodo-2-methylpropionitrile, 2-iodopropionitrile, ethyl α-iodophenylacetate, α-iodophenylacetonitrile, and diethyl 2-iodo-2-methylmalonate.

[0019] The beneficial effects and outstanding advantages of the present application are:

[0020] 1. The catalyst can be used in the RCMP polymerization reaction to achieve controllable free radical polymerization under the condition of nitrogen or argon atmosphere, and the obtained polymer has low dispersity (PDI = 1.04-1.25).

[0021] 2. The catalyst can be used in the RCMP polymerization without solvent, which is more environmentally friendly.

[0022] 3. The catalyst can maintain considerable catalytic activity in multiple RCMP polymerization cycles. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The monomer conversion, dispersity and GPC elution profile of the monomer obtained by using the catalysts described in Example 3, Example 6 and Example 9 for RCMP polymerization under white light LED irradiation;

[0024] Figure 2 The infrared spectra of the catalyst described in Example 4 placed in MMA solution for 0h and 24h;

[0025] Figure 3 The XRD pattern of the catalyst described in Example 6;

[0026] Figure 4 The SEM pattern of the catalyst described in Example 7;

[0027] Figure 5 The polymerization kinetics curve of performance test Example 17;

[0028] Figure 6 The graph of the relationship between the molecular weight (Mn) and the conversion rate of performance test Example 17. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the present application clearer and more obvious, the following embodiments are combined to describe the present application in detail. The specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0030] Example 1

[0031] Synthesis of TAPB-S1-CMPs:

[0032] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 1,4-di(4-formylphenyl)benzene (18.33 mg) followed by 1,2-dichlorobenzene (1.9 mL), n-butanol (0.1 mL) and acetic acid solution (0.2 mL, 6M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 150 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 65%.

[0033] The structure of TAPB-S1-CMPs is as follows:

[0034]

[0035] Example 2

[0036] Synthesis of TAPB-S1-CMPs:

[0037] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 1,4-di(4-formylphenyl)benzene (18.33 mg) followed by 1,2-dichlorobenzene (1.5 mL), toluene (0.5 mL) and acetic acid solution (0.2 mL, 3M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 150 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 50%.

[0038] Example 3

[0039] Synthesis of TAPB-S1-CMPs:

[0040] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 1,4-di(4-formylphenyl)benzene (18.33 mg) followed by 1,2-dichlorobenzene (0.5 mL), n-butanol (0.5 mL) and acetic acid solution (0.2 mL, 6M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 150 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 65%.

[0041] Example 4

[0042] Synthesis of TAPB-S2-CMPs:

[0043] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 4,4'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (22 mg), followed by 1,2-dichlorobenzene (1.5 mL), n-butanol (0.5 mL) and acetic acid solution (0.1 mL, 6 M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 120 °C for 3 days, a yellow precipitate was produced. Washing with tetrahydrofuran, tetrahydrofuran was Soxhlet extracted for 1 day. Vacuum dried to give the final product with a yield of 72%.

[0044] The structure of TAPB-S2-CMPs is as follows:

[0045]

[0046] Example 5

[0047] Synthesis of TAPB-S2-CMPs:

[0048] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 4,4'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (26 mg), followed by 1,2-dichlorobenzene (1.5 mL), mesitylene (0.5 mL) and acetic acid solution (0.1 mL, 6 M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 150 °C for 3 days, a yellow precipitate was produced. Washing with tetrahydrofuran, tetrahydrofuran was Soxhlet extracted for 1 day. Vacuum dried to give the final product with a yield of 69%.

[0049] Example 6

[0050] Synthesis of TAPB-S2-CMPs:

[0051] Into a Schlenk tube was introduced 1,3,5-tri(4-aminophenyl)benzene (15 mg) and 4,4'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (18.33 mg), followed by 1,2-dichlorobenzene (0.5 mL), n-butanol (0.5 mL) and acetic acid solution (0.1 mL, 6 M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 150 °C for 3 days, a yellow precipitate was produced. Washing with tetrahydrofuran, tetrahydrofuran was Soxhlet extracted for 1 day. Vacuum dried to give the final product with a yield of 69%.

[0052] Example 7

[0053] Synthesis of TAPB-S3-CMPs:

[0054] TAPB (15 mg) and 4'4-biphenyldicarboxaldehyde (17.5 mg) were introduced into a Schlenk tube followed by mesitylene (1.5 mL), p-xylene (0.5 mL) and acetic acid solution (0.2 mL, 3M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 120 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 77%.

[0055] The structure of TAPB-S3-CMP is as follows:

[0056]

[0057] Example 8

[0058] Synthesis of TAPB-S3-CMPs:

[0059] TAPB (15 mg) and 4'4-biphenyldicarboxaldehyde (13.5 mg) were introduced into a Schlenk tube followed by mesitylene (0.5 mL), methanol (0.5 mL) and acetic acid solution (0.2 mL, 6M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 120 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 77%.

[0060] Example 9

[0061] Synthesis of TAPB-S3-CMPs:

[0062] TAPB (15 mg) and 4'4-biphenyldicarboxaldehyde (13.5 mg) were introduced into a Schlenk tube followed by mesitylene (0.5 mL), methanol (0.5 mL) and acetic acid solution (0.2 mL, 6M) as catalyst. After 3 minutes of sonication, a quick freeze with liquid nitrogen, freeze-pump-thaw 3 times. Heating at 120 °C for 3 days produced a yellow precipitate. Washing with tetrahydrofuran, tetrahydrofuran Soxhlet extraction washing for 1 day. Vacuum drying gave the final product with a yield of 77%.

[0063] The following are performance tests

[0064] Example 10

[0065] MMA (2 mL), a-iodobenzonitrile (12 μL), TAPB-S1-CMP (10 mg) were added into a 3 ml glass vial, which was tightly capped with a rubber stopper and degassed with a nitrogen balloon for 30 min, the resulting mixture was irradiated under white light LED (13 W m -1 , 15 mW cm-2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 5600 g mol -1 And Mw / Mn=1.08.

[0066] Example 11

[0067] MEMA (2 mL), 2-iodo-2-methylpropionitrile (21 μL), and TAPB-S1-CMP (10 mg) were added to a 3 mL glass bottle. The glass bottle was tightly plugged with a rubber stopper and degassed with a nitrogen balloon for 30 min. The resulting mixture was then illuminated by a white light LED (13 W m -1 ,15mW cm -2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 6900 g mol -1 And Mw / Mn=1.09.

[0068] Example 12

[0069] BZMA (2 mL), ethyl α-iodophenylacetate (26 μL), and TAPB-S1-CMP (10 mg) were added to a 3 mL glass bottle. The glass bottle was tightly plugged with a rubber stopper and degassed with a nitrogen balloon for 30 min. The resulting mixture was then illuminated by a white light LED (13 W m -1 ,15mW cm -2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 6500 g mol -1 And Mw / Mn=1.15.

[0070] Example 13

[0071] BZMA (2 mL), ethyl α-iodophenylacetate (26 μL), and TAPB-S2-CMP (5 mg) were added to a 3 mL glass bottle. The glass bottle was tightly plugged with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was then illuminated by a white light LED (13 W m -1 ,15mW cm -2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 6300 g mol -1 And Mw / Mn=1.20.

[0072] Example 14

[0073] DEAEMA (2 mL), 2-iodo-2-methylmalonate diethyl ester (19 μί), TAPB-S2-CMP (5 mg) were added to a 3 ml glass vial, which was tightly closed with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was irradiated under white light LED (13 W m -1 , 15 mW cm -2 -2) at room temperature, and samples were collected every hour for GPC analysis to characterize the molecular weight (Mn) and molecular weight dispersity (Mw / Mn). After 10 h of reaction, Mn was 6100 g mol -1 and Mw / Mn = 1.05, as measured by GPC.

[0074] Example 15

[0075] GMA (2 mL), 2-iodopropionitrile (27 μί), TAPB-S2-CMP (5 mg) were added to a 3 ml glass vial, which was tightly closed with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was irradiated under white light LED (13 W m -1 , 15 mW cm -2 -2) at room temperature, and samples were collected every hour for GPC analysis to characterize the molecular weight (Mn) and molecular weight dispersity (Mw / Mn). After 10 h of reaction, Mn was 5500 g mol -1 and Mw / Mn = 1.20, as measured by GPC.

[0076] Example 16

[0077] MEMA (2 mL), 2-iodopropionitrile (30 μί), TAPB-S3-CMP (5 mg) were added to a 3 ml glass vial, which was tightly closed with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was irradiated under white light LED (13 W m -1 , 15 mW cm -2 -2) at room temperature, and samples were collected every hour for GPC analysis to characterize the molecular weight (Mn) and molecular weight dispersity (Mw / Mn). After 10 h of reaction, Mn was 6700 g mol -1 and Mw / Mn = 1.10, as measured by GPC.

[0078] Example 17

[0079] MMA (2 mL), 2-iodo-2-methylpropionitrile (21 μί), TAPB-S3-CMP (5 mg) were added to a 3 ml glass vial, which was tightly closed with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was irradiated under white light LED (13 W m -1 , 15 mW cm-2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 5300 g mol -1 And Mw / Mn=1.16.

[0080] Example 18

[0081] MMA (2 mL), 2-iodopropionitrile (50 μL), and TAPB-S3-CMP (10 mg) were added to a 3 mL glass bottle. The glass bottle was tightly plugged with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was then illuminated by a white light LED (13 W m -1 ,15mW cm -2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 6000 g mol -1 And Mw / Mn=1.07.

[0082] Example 19

[0083] DEAEMA (2 mL), 2-iodo-2-methylpropionitrile (25 μL), and TAPB-S3-CMP (10 mg) were added to a 3 mL glass bottle. The glass bottle was tightly plugged with a rubber stopper and degassed with a nitrogen balloon for 30 min. The mixture was then illuminated by a white LED (13 W m -1 ,15mW cm -2 ) and samples were collected at room temperature at regular intervals. GPC analysis was used to characterize the molecular weight (Mn) and molecular weight dispersion (Mw / Mn). After 10 h of reaction, the Mn measured by GPC was 6900 g mol -1 And Mw / Mn=1.25.

[0084] Figure 1 The monomer conversion, dispersion and GPC elution curves obtained when RCMP polymerization was carried out using the catalysts described in Examples 3, 6 and 9 under white light LED irradiation; Figure 1 The results of the polymerization experiment show that compared with the catalyst TAPB-S3-CMP (conversion rate is 50%), TAPB-S1-CMP with a higher π-conjugation degree has a higher conversion rate (conversion rate is 54%). In addition, the introduction of nitrogen-containing groups at the pore wall of the material TAPB-S1-CMP, namely the catalyst TAPB-S2-CMP, shows higher catalytic performance (conversion rate reaches 67%).

[0085] Figure 2IR spectra of the catalyst described in Example 4 placed in MMA solution for 0h and 24h; Figure 2 The IR characteristic peaks of the catalyst TAPB-S2-CMP after being immersed in MMA for 24h basically remain unchanged, indicating that the catalyst TAPB-S2-CMP has good stability when used in MMA bulk polymerization.

[0086] Figure 3 XRD pattern of the catalyst described in Example 6; Figure 3 The XRD pattern of the catalyst TAPB-S2-CMP shows no obvious diffraction peaks, which is consistent with the characteristics of amorphous materials (CMPs materials are amorphous materials).

[0087] Figure 4 SEM pattern of the catalyst described in Example 7; the catalyst TAPB-S3-CMP is composed of spherical objects with uneven sizes, which is consistent with the characteristics of amorphous materials.

[0088] Figure 5 Polymerization kinetics curve of Example 17; ln([M]0 / [M] t ) vs time is linear, indicating that the polymerization process is consistent with the characteristics of free radical controllable polymerization.

[0089] Figure 6 Molecular weight (Mn) vs conversion of Example 17; Figure 6 The relationship between the number average molecular weight M n and the conversion (Conversion) of the polymer obtained by using the catalyst TAPB-S3-CMP is shown in the figure, the dotted line is the theoretical line, and it can be seen that the molecular weight of the polymer increases with the increase of the conversion, in addition, M n is basically consistent with M n，theo , and the controllability of the polymerization is high.

[0090] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application are all covered by the present application.

Claims

1. A photoinduced reversible mediated polymerization heterogeneous catalyst, characterized in that: The photoinduced reversible mediated polymerization heterogeneous catalyst is a conjugated microporous polymer TAPB-M-CMP, which has the following structure: ； The dotted lines indicate the bond connection positions; The conjugated microporous polymer is obtained by condensing an aldehyde monomer and an amino monomer in the presence of solvent A and a catalyst; The solvent A is one or more of 1,2-dichlorobenzene, n-butanol, mesitylene, 1,4-dioxane, toluene, p-xylene, N,N-dimethylformamide, and N,N-dimethylacetamide; The catalyst is an acetic acid solution with a concentration of 3M, 4M, or 6M; The aldehyde monomer is one or more of 4'4-biphenyl dicarboxaldehyde, 1,4-di(4-formylphenyl)benzene, and 4,4'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde; The amino monomer is 1,3,5-tris(4-aminophenyl)benzene; The condensation reaction temperature is 80-180°C.

2. The use of a photoinduced reversible mediated polymerization heterogeneous catalyst according to claim 1, characterized in that: The catalyst, monomer, and initiator are subjected to a reversible complexation-mediated polymerization reaction under nitrogen or argon atmosphere and the action of visible light; the monomer is one or more of methyl methacrylate, methoxyethyl methacrylate, glycidyl methacrylate, 2-(diethylamino)ethyl methacrylate, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, and polyethylene glycol methyl ether acrylate.

3. The use according to claim 2, characterized in that: The initiator is one of 2-iodo-2-methylpropionitrile, 2-iodopropionitrile, α-iodophenylacetic acid ethyl ester, α-iodophenylacetonitrile and diethyl 2-iodo-2-methylmalonate.

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