Molecular dynamics of pegylated multifunctional polyhedral oligomeric silsesquioxane

Yu Bian, Jovan Mijovic

Research output: Contribution to journalArticle

Abstract

Here we report a study of molecular dynamics of (1) four different poly(propylene oxide)/poly (ethylene oxide) (PPO/PEO) copolymers, two amorphous and two semicrystalline, and (2) the product of the chemical reaction between these copolymers and a multifunctional polyhedral oligomeric silsesquioxane (POSS). We refer to the latter group of compounds as "PEGylated POSS". Experimental results were generated using broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequencies and temperatures. Amorphous copolymers exhibit the segmental process (α), the normal mode process (α N), and two local processes (β and γ), while semicrystalline copolymers possess segmental (α) and two local relaxations (β and γ). The β process is a secondary relaxation and the γ process is due to the combination of the local motions in PPO and PEO blocks. PEGylated POSS was synthesized by chemical reaction between the functional end groups on the PPO block (amine) and the POSS side chain (epoxy). Dynamics of PEGylated POSS were investigated and contrasted with the dynamics of the corresponding neat copolymers. Covalent bonding between POSS and copolymer slows down the segmental and the normal mode process but does not affect the time scale of the β or the y process. A detailed account of the effect of molecular weight, PPO/PEO mole ratio, copolymer morphology and covalent bonding between POSS and copolymer on the molecular origin, temperature dependence, and spectral characteristics of relaxation processes in copolymers and PEGylated POSS is provided.

Original languageEnglish (US)
Pages (from-to)4181-4190
Number of pages10
JournalMacromolecules
Volume42
Issue number12
DOIs
StatePublished - Jun 23 2009

Fingerprint

Molecular dynamics
Copolymers
Polyethylene oxides
Polypropylene oxides
Polyphenylene oxides
Chemical reactions
Spectroscopy
Dielectric relaxation
Relaxation processes
Amines
Molecular weight
Temperature

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Molecular dynamics of pegylated multifunctional polyhedral oligomeric silsesquioxane. / Bian, Yu; Mijovic, Jovan.

In: Macromolecules, Vol. 42, No. 12, 23.06.2009, p. 4181-4190.

Research output: Contribution to journalArticle

@article{2be0573383be44f98d9b7da9f38f1af8,
title = "Molecular dynamics of pegylated multifunctional polyhedral oligomeric silsesquioxane",
abstract = "Here we report a study of molecular dynamics of (1) four different poly(propylene oxide)/poly (ethylene oxide) (PPO/PEO) copolymers, two amorphous and two semicrystalline, and (2) the product of the chemical reaction between these copolymers and a multifunctional polyhedral oligomeric silsesquioxane (POSS). We refer to the latter group of compounds as {"}PEGylated POSS{"}. Experimental results were generated using broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequencies and temperatures. Amorphous copolymers exhibit the segmental process (α), the normal mode process (α N), and two local processes (β and γ), while semicrystalline copolymers possess segmental (α) and two local relaxations (β and γ). The β process is a secondary relaxation and the γ process is due to the combination of the local motions in PPO and PEO blocks. PEGylated POSS was synthesized by chemical reaction between the functional end groups on the PPO block (amine) and the POSS side chain (epoxy). Dynamics of PEGylated POSS were investigated and contrasted with the dynamics of the corresponding neat copolymers. Covalent bonding between POSS and copolymer slows down the segmental and the normal mode process but does not affect the time scale of the β or the y process. A detailed account of the effect of molecular weight, PPO/PEO mole ratio, copolymer morphology and covalent bonding between POSS and copolymer on the molecular origin, temperature dependence, and spectral characteristics of relaxation processes in copolymers and PEGylated POSS is provided.",
author = "Yu Bian and Jovan Mijovic",
year = "2009",
month = "6",
day = "23",
doi = "10.1021/ma900090j",
language = "English (US)",
volume = "42",
pages = "4181--4190",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Molecular dynamics of pegylated multifunctional polyhedral oligomeric silsesquioxane

AU - Bian, Yu

AU - Mijovic, Jovan

PY - 2009/6/23

Y1 - 2009/6/23

N2 - Here we report a study of molecular dynamics of (1) four different poly(propylene oxide)/poly (ethylene oxide) (PPO/PEO) copolymers, two amorphous and two semicrystalline, and (2) the product of the chemical reaction between these copolymers and a multifunctional polyhedral oligomeric silsesquioxane (POSS). We refer to the latter group of compounds as "PEGylated POSS". Experimental results were generated using broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequencies and temperatures. Amorphous copolymers exhibit the segmental process (α), the normal mode process (α N), and two local processes (β and γ), while semicrystalline copolymers possess segmental (α) and two local relaxations (β and γ). The β process is a secondary relaxation and the γ process is due to the combination of the local motions in PPO and PEO blocks. PEGylated POSS was synthesized by chemical reaction between the functional end groups on the PPO block (amine) and the POSS side chain (epoxy). Dynamics of PEGylated POSS were investigated and contrasted with the dynamics of the corresponding neat copolymers. Covalent bonding between POSS and copolymer slows down the segmental and the normal mode process but does not affect the time scale of the β or the y process. A detailed account of the effect of molecular weight, PPO/PEO mole ratio, copolymer morphology and covalent bonding between POSS and copolymer on the molecular origin, temperature dependence, and spectral characteristics of relaxation processes in copolymers and PEGylated POSS is provided.

AB - Here we report a study of molecular dynamics of (1) four different poly(propylene oxide)/poly (ethylene oxide) (PPO/PEO) copolymers, two amorphous and two semicrystalline, and (2) the product of the chemical reaction between these copolymers and a multifunctional polyhedral oligomeric silsesquioxane (POSS). We refer to the latter group of compounds as "PEGylated POSS". Experimental results were generated using broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequencies and temperatures. Amorphous copolymers exhibit the segmental process (α), the normal mode process (α N), and two local processes (β and γ), while semicrystalline copolymers possess segmental (α) and two local relaxations (β and γ). The β process is a secondary relaxation and the γ process is due to the combination of the local motions in PPO and PEO blocks. PEGylated POSS was synthesized by chemical reaction between the functional end groups on the PPO block (amine) and the POSS side chain (epoxy). Dynamics of PEGylated POSS were investigated and contrasted with the dynamics of the corresponding neat copolymers. Covalent bonding between POSS and copolymer slows down the segmental and the normal mode process but does not affect the time scale of the β or the y process. A detailed account of the effect of molecular weight, PPO/PEO mole ratio, copolymer morphology and covalent bonding between POSS and copolymer on the molecular origin, temperature dependence, and spectral characteristics of relaxation processes in copolymers and PEGylated POSS is provided.

UR - http://www.scopus.com/inward/record.url?scp=67649196746&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67649196746&partnerID=8YFLogxK

U2 - 10.1021/ma900090j

DO - 10.1021/ma900090j

M3 - Article

AN - SCOPUS:67649196746

VL - 42

SP - 4181

EP - 4190

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 12

ER -