Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis

Du, Tianyi1; Shen, Boming2,3; Dai, Jieyu1; Zhang, Miaomiao1; Chen, Xingjian1; Yu, Peiyuan2,3; Liu, Yun1

2023-11-21

10.1021/jacs.3c10708

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S-S bond is highly reactive in the presence of the sulfide (RS-) anion, imposing a persistent challenge to control the polymerization. Here, we report an anion-binding approach to arrest the high reactivity of the RS- chain end to control the synthesis of linear poly(disulfide)s, realizing a rapid, living ring-opening polymerization of 1,2-dithiolanes with narrow dispersity and high regioselectivity (M-w/M-n similar to 1.1, P-s similar to 0.85). Mechanistic studies support the formation of a thiourea-base-sulfide ternary complex as the catalytically active species during the chain propagation. Theoretical analyses reveal a synergistic catalytic model where the catalyst preorganizes the protonated base and anionic chain end to establish spatial confinement over the bound monomer, effecting the observed regioselectivity. The catalytic system is amenable to monomers with various functional groups, and semicrystalline polymers are also obtained from lipoic acid derivatives by enhancing the regioselectivity.

SCI ; EI

英语

NI论文

通讯

Basic and Applied Basic Research Foundation of Guangdong Province[22271005] ; Beijing National Laboratory for Molecular Sciences[2021A1515010387]

Chemistry

Chemistry, Multidisciplinary

WOS:001128744000001

AMER CHEMICAL SOC

20234915173777

Binding energy ; Functional materials ; Ions ; Living polymerization ; Regioselectivity ; Ring opening polymerization ; Sulfur compounds

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Polymerization:815.2 ; Materials Science:951

2-s2.0-85178549820

Web of Science

1.Peking Univ, Beijing Natl Lab Mol Sci, Ctr Soft Matter Sci & Engn, Coll Chem & Mol Engn,Key Lab Polymer Chem & Phys,M, Beijing 100871, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Du, Tianyi,Shen, Boming,Dai, Jieyu,et al. Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(50):27788-27799.

Du, Tianyi.,Shen, Boming.,Dai, Jieyu.,Zhang, Miaomiao.,Chen, Xingjian.,...&Liu, Yun.(2023).Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(50),27788-27799.

Du, Tianyi,et al."Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.50(2023):27788-27799.