Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines

Abdollah Omrani; Zeynep Deliballi; Kerem Kaya; Baris Kiskan; Mert Akgun

doi:10.1021/acsapm.3c01902

Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines

Abdollah Omrani^*, Zeynep Deliballi, Kerem Kaya, Baris Kiskan^*, Mert Akgun

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

The influence of nanoscale confinement on the thermally induced ring-opening polymerization (ROP) of three different monofunctional benzoxazines (Bzs) was highlighted for the first time. The Bzs were solution-loaded or blended in/with a titanium-based metal-organic framework (MOF), i.e., MIL-125-based. The successful infiltration of the Bzs within the MOF was confirmed through comprehensive analyses using FTIR, BET, and DSC techniques. Remarkably, the nanoconfinement exhibited exceptional promotion of the Bzs ROP, resulting in a significant decrease in the onset temperature of the corresponding exotherms of as much as 127 °C for the nonsubstituted monomer. GPC traces revealed that high-molecular-weight polybenzoxazines (PBzs) were formed when fluorine-substituted Bz polymerized in the MOF-confined nanospaces. The catalytic role of nanoconfinement was further supported by analyzing the effective activation energy through the isoconversional method of Starink. ROP of the Bz-MIL-125 blend, where the effect of nanoconfinement was absent, demonstrated the catalytic role of MIL-125 with a less pronounced impact compared to the nanoconfined system.

Original language	English
Pages (from-to)	253-264
Number of pages	12
Journal	ACS Applied Polymer Materials
Volume	6
Issue number	1
DOIs	https://doi.org/10.1021/acsapm.3c01902
Publication status	Published - 12 Jan 2024

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.

Keywords

Benzoxazine
MIL-125(Ti)
activation energy
catalysis
metal−organic frameworks (MOFs)
nanoconfinement
ring-opening polymerization

Access to Document

10.1021/acsapm.3c01902

Cite this

@article{6886b68ebfe24dbf8cada4ae4c59f3f6,

title = "Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines",

abstract = "The influence of nanoscale confinement on the thermally induced ring-opening polymerization (ROP) of three different monofunctional benzoxazines (Bzs) was highlighted for the first time. The Bzs were solution-loaded or blended in/with a titanium-based metal-organic framework (MOF), i.e., MIL-125-based. The successful infiltration of the Bzs within the MOF was confirmed through comprehensive analyses using FTIR, BET, and DSC techniques. Remarkably, the nanoconfinement exhibited exceptional promotion of the Bzs ROP, resulting in a significant decrease in the onset temperature of the corresponding exotherms of as much as 127 °C for the nonsubstituted monomer. GPC traces revealed that high-molecular-weight polybenzoxazines (PBzs) were formed when fluorine-substituted Bz polymerized in the MOF-confined nanospaces. The catalytic role of nanoconfinement was further supported by analyzing the effective activation energy through the isoconversional method of Starink. ROP of the Bz-MIL-125 blend, where the effect of nanoconfinement was absent, demonstrated the catalytic role of MIL-125 with a less pronounced impact compared to the nanoconfined system.",

keywords = "Benzoxazine, MIL-125(Ti), activation energy, catalysis, metal−organic frameworks (MOFs), nanoconfinement, ring-opening polymerization",

author = "Abdollah Omrani and Zeynep Deliballi and Kerem Kaya and Baris Kiskan and Mert Akgun",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2024",

month = jan,

day = "12",

doi = "10.1021/acsapm.3c01902",

language = "English",

volume = "6",

pages = "253--264",

journal = "ACS Applied Polymer Materials",

issn = "2637-6105",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines

AU - Omrani, Abdollah

AU - Deliballi, Zeynep

AU - Kaya, Kerem

AU - Kiskan, Baris

AU - Akgun, Mert

PY - 2024/1/12

Y1 - 2024/1/12

N2 - The influence of nanoscale confinement on the thermally induced ring-opening polymerization (ROP) of three different monofunctional benzoxazines (Bzs) was highlighted for the first time. The Bzs were solution-loaded or blended in/with a titanium-based metal-organic framework (MOF), i.e., MIL-125-based. The successful infiltration of the Bzs within the MOF was confirmed through comprehensive analyses using FTIR, BET, and DSC techniques. Remarkably, the nanoconfinement exhibited exceptional promotion of the Bzs ROP, resulting in a significant decrease in the onset temperature of the corresponding exotherms of as much as 127 °C for the nonsubstituted monomer. GPC traces revealed that high-molecular-weight polybenzoxazines (PBzs) were formed when fluorine-substituted Bz polymerized in the MOF-confined nanospaces. The catalytic role of nanoconfinement was further supported by analyzing the effective activation energy through the isoconversional method of Starink. ROP of the Bz-MIL-125 blend, where the effect of nanoconfinement was absent, demonstrated the catalytic role of MIL-125 with a less pronounced impact compared to the nanoconfined system.

AB - The influence of nanoscale confinement on the thermally induced ring-opening polymerization (ROP) of three different monofunctional benzoxazines (Bzs) was highlighted for the first time. The Bzs were solution-loaded or blended in/with a titanium-based metal-organic framework (MOF), i.e., MIL-125-based. The successful infiltration of the Bzs within the MOF was confirmed through comprehensive analyses using FTIR, BET, and DSC techniques. Remarkably, the nanoconfinement exhibited exceptional promotion of the Bzs ROP, resulting in a significant decrease in the onset temperature of the corresponding exotherms of as much as 127 °C for the nonsubstituted monomer. GPC traces revealed that high-molecular-weight polybenzoxazines (PBzs) were formed when fluorine-substituted Bz polymerized in the MOF-confined nanospaces. The catalytic role of nanoconfinement was further supported by analyzing the effective activation energy through the isoconversional method of Starink. ROP of the Bz-MIL-125 blend, where the effect of nanoconfinement was absent, demonstrated the catalytic role of MIL-125 with a less pronounced impact compared to the nanoconfined system.

KW - Benzoxazine

KW - MIL-125(Ti)

KW - activation energy

KW - catalysis

KW - metal−organic frameworks (MOFs)

KW - nanoconfinement

KW - ring-opening polymerization

UR - http://www.scopus.com/inward/record.url?scp=85180084493&partnerID=8YFLogxK

U2 - 10.1021/acsapm.3c01902

DO - 10.1021/acsapm.3c01902

M3 - Article

AN - SCOPUS:85180084493

SN - 2637-6105

VL - 6

SP - 253

EP - 264

JO - ACS Applied Polymer Materials

JF - ACS Applied Polymer Materials

IS - 1

ER -

Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Fingerprint

Cite this