Visible-Light-Induced Cationic Polymerization of Isobutylene: A Route toward the Synthesis of End-Functional Polyisobutylene#

Maksim Hulnik; Diana Trofimuk; Pavel A. Nikishau; Hüseyin Cem Kiliclar; Baris Kiskan; Sergei V. Kostjuk

doi:10.1021/acsmacrolett.3c00384

Visible-Light-Induced Cationic Polymerization of Isobutylene: A Route toward the Synthesis of End-Functional Polyisobutylene#

Maksim Hulnik, Diana Trofimuk, Pavel A. Nikishau, Hüseyin Cem Kiliclar, Baris Kiskan, Sergei V. Kostjuk^*

^*Corresponding author for this work

Department of Chemistry

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

3 Citations (Scopus)

Abstract

The visible-light-induced cationic polymerization of isobutylene with a dimanganese decacarbonyl (Mn₂(CO)₁₀)/diphenyl iodonium hexafluorophosphate (Ph₂I⁺PF₆^-) photoinitiating system in a CH₂Cl₂/n-hexane mixture at −30 °C was reported. It was shown that polymerization is initiated by chloromethylisobutyl carbocations generated by the oxidation of chloromethylisobutyl radicals by Ph₂I⁺PF₆^-. The latter are formed via chlorine abstraction from solvent (CH₂Cl₂) by MnCO₅· radicals, which are generated by the photoinduced decomposition of Mn₂(CO)₁₀, followed by single isobutylene addition. This initiating system allowed us to synthesize valuable low molecular weight polyisobutylene with a relatively low polydispersity (M_n = 2000-3000 g mol^-1; Đ < 1.7) and high content of exo-olefin end groups (up to 90%). The molecular weight of polyisobutylenes could be easily controlled in the range from 2000 to 12000 g mol^-1 by changing the diphenyl iodonium salt concentration. Poly(β-pinene) with M_n = 5000 g mol^-1 and Đ ∼ 2.0 was successfully synthesized using the same photoinitiating system.

Original language	English
Pages (from-to)	1125-1131
Number of pages	7
Journal	ACS Macro Letters
Volume	12
Issue number	8
DOIs	https://doi.org/10.1021/acsmacrolett.3c00384
Publication status	Published - 15 Aug 2023

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.

Funding

The authors would like to acknowledge the financial support from the joint project between Belarus and Turkey BRFFR-TUBITAK (Project Number: X21TYB-008), the Scientific and Technological Research Council of Turkey (TUBITAK) (Project Number: 220N159), and the Council of Higher Education (YÖK) - Istanbul Technical University Research Fund YAP (Project Number: TGA-2023-44004). The authors also would like to acknowledge the financial support from BASF SE and, partially, from State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03).

Funders	Funder number
Belarus and Turkey BRFFR-TUBITAK	X21TYB-008
State Program for Scientific Research of Belarus	2.1.01.03
BASF
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu	220N159
Yükseköğretim Kurulu
Istanbul Teknik Üniversitesi	TGA-2023-44004

Access to Document

10.1021/acsmacrolett.3c00384

Cite this

@article{b337a22ecbcc4c25be452eba32b14a99,

title = "Visible-Light-Induced Cationic Polymerization of Isobutylene: A Route toward the Synthesis of End-Functional Polyisobutylene#",

abstract = "The visible-light-induced cationic polymerization of isobutylene with a dimanganese decacarbonyl (Mn2(CO)10)/diphenyl iodonium hexafluorophosphate (Ph2I+PF6-) photoinitiating system in a CH2Cl2/n-hexane mixture at −30 °C was reported. It was shown that polymerization is initiated by chloromethylisobutyl carbocations generated by the oxidation of chloromethylisobutyl radicals by Ph2I+PF6-. The latter are formed via chlorine abstraction from solvent (CH2Cl2) by MnCO5· radicals, which are generated by the photoinduced decomposition of Mn2(CO)10, followed by single isobutylene addition. This initiating system allowed us to synthesize valuable low molecular weight polyisobutylene with a relatively low polydispersity (Mn = 2000-3000 g mol-1; {\D} < 1.7) and high content of exo-olefin end groups (up to 90%). The molecular weight of polyisobutylenes could be easily controlled in the range from 2000 to 12000 g mol-1 by changing the diphenyl iodonium salt concentration. Poly(β-pinene) with Mn = 5000 g mol-1 and {\D} ∼ 2.0 was successfully synthesized using the same photoinitiating system.",

author = "Maksim Hulnik and Diana Trofimuk and Nikishau, {Pavel A.} and Kiliclar, {H{\"u}seyin Cem} and Baris Kiskan and Kostjuk, {Sergei V.}",

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

year = "2023",

month = aug,

day = "15",

doi = "10.1021/acsmacrolett.3c00384",

language = "English",

volume = "12",

pages = "1125--1131",

journal = "ACS Macro Letters",

issn = "2161-1653",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Visible-Light-Induced Cationic Polymerization of Isobutylene

T2 - A Route toward the Synthesis of End-Functional Polyisobutylene#

AU - Hulnik, Maksim

AU - Trofimuk, Diana

AU - Nikishau, Pavel A.

AU - Kiliclar, Hüseyin Cem

AU - Kiskan, Baris

AU - Kostjuk, Sergei V.

PY - 2023/8/15

Y1 - 2023/8/15

N2 - The visible-light-induced cationic polymerization of isobutylene with a dimanganese decacarbonyl (Mn2(CO)10)/diphenyl iodonium hexafluorophosphate (Ph2I+PF6-) photoinitiating system in a CH2Cl2/n-hexane mixture at −30 °C was reported. It was shown that polymerization is initiated by chloromethylisobutyl carbocations generated by the oxidation of chloromethylisobutyl radicals by Ph2I+PF6-. The latter are formed via chlorine abstraction from solvent (CH2Cl2) by MnCO5· radicals, which are generated by the photoinduced decomposition of Mn2(CO)10, followed by single isobutylene addition. This initiating system allowed us to synthesize valuable low molecular weight polyisobutylene with a relatively low polydispersity (Mn = 2000-3000 g mol-1; Đ < 1.7) and high content of exo-olefin end groups (up to 90%). The molecular weight of polyisobutylenes could be easily controlled in the range from 2000 to 12000 g mol-1 by changing the diphenyl iodonium salt concentration. Poly(β-pinene) with Mn = 5000 g mol-1 and Đ ∼ 2.0 was successfully synthesized using the same photoinitiating system.

AB - The visible-light-induced cationic polymerization of isobutylene with a dimanganese decacarbonyl (Mn2(CO)10)/diphenyl iodonium hexafluorophosphate (Ph2I+PF6-) photoinitiating system in a CH2Cl2/n-hexane mixture at −30 °C was reported. It was shown that polymerization is initiated by chloromethylisobutyl carbocations generated by the oxidation of chloromethylisobutyl radicals by Ph2I+PF6-. The latter are formed via chlorine abstraction from solvent (CH2Cl2) by MnCO5· radicals, which are generated by the photoinduced decomposition of Mn2(CO)10, followed by single isobutylene addition. This initiating system allowed us to synthesize valuable low molecular weight polyisobutylene with a relatively low polydispersity (Mn = 2000-3000 g mol-1; Đ < 1.7) and high content of exo-olefin end groups (up to 90%). The molecular weight of polyisobutylenes could be easily controlled in the range from 2000 to 12000 g mol-1 by changing the diphenyl iodonium salt concentration. Poly(β-pinene) with Mn = 5000 g mol-1 and Đ ∼ 2.0 was successfully synthesized using the same photoinitiating system.

UR - http://www.scopus.com/inward/record.url?scp=85167885099&partnerID=8YFLogxK

U2 - 10.1021/acsmacrolett.3c00384

DO - 10.1021/acsmacrolett.3c00384

M3 - Article

AN - SCOPUS:85167885099

SN - 2161-1653

VL - 12

SP - 1125

EP - 1131

JO - ACS Macro Letters

JF - ACS Macro Letters

IS - 8

ER -

Visible-Light-Induced Cationic Polymerization of Isobutylene: A Route toward the Synthesis of End-Functional Polyisobutylene#

Abstract

Bibliographical note

Funding

Access to Document

Other files and links

Fingerprint

Cite this