Heterotelechelic silicones: Facile synthesis and functionalization using silane-based initiators
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Jan 14, 2024 version files 67.78 MB
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README.md
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Abstract
The synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives is limited due to challenges in preparing materials with high chain-end fidelity. In this study, anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D3) monomer using a specifically designed silyl hydride (Si–H)-based initiator provides a versatile approach towards a library of heterotelechelic PDMS polymers. A novel initiator, where the Si–H terminal group is connected to a C atom (H–Si–C) and not an O atom (H–Si–O) as in traditional systems, suppresses intermolecular transfer of the Si–H group, leading to heterotelechelic PDMS derivatives with a high degree of control over chain-ends. In-situ termination of the D3 propagating chain end with commercially available chlorosilanes (alkyl chlorides, methacrylates, and norbornenes) yields an array of chain-end functionalized PDMS derivatives. This diversity can be further increased by hydrosilylation with functionalized alkenes (alcohols, esters, and epoxides) to generate a library of heterotelechelic PDMS polymers. Due to the living nature of ring opening polymerization and efficient initiation, narrow-dispersity (Đ < 1.2) polymers spanning a wide range of molar masses (2 – 11 kg mol−1) were synthesized. With facile access to α-Si–H and ω-norbornene functionalized PDMS macromonomers (H–PDMS–Nb), the synthesis of well-defined super-soft (Gʹ = 30 kPa) PDMS bottlebrush networks, which are difficult to prepare using established strategies, was demonstrated.
README: Heterotelechelic silicones: Facile synthesis and functionalization using silane-based initiators
https://doi.org/10.5061/dryad.cjsxksncm
Data files are organized into one folder: with the manuscript and supporting information. This folder is related to the publication which includes the manuscript and supporting information document.
All data can be opened as a .csv file using Excel or google sheets (free alternative)
Data files are organized as follows:
manuscript -> Figure number -> figure sub-category
Within each data file, there are tabs for each unique trace. The tab is denoted as the trace identifier. Some trace identifiers are label names.
Compounds are denoted as such: hexamethylcyclotrisiloxane (D3), Polydimethylsiloxane (PDMS), Methacrylate (MA), Norborene (Nb), Chloropropyl (Cl), Hydride (H), Polystyrene (PS).
Figures that are pictures and illustrations will not be included in the folders. This includes Figure 1, Scheme 1, Figure 5, and Figure 8.
All data is supplied in two columns (x,y) these columns refer to the x and y axis on each graph. Please refer to the manuscript and to the original graph for appropriate legends.
All SEC data supplied is normalized to the peak being analyzed.
Description of the data and file structure
The following describes Figure X; The parameters used for each figure are listed at the end.
2a: 1H-NMR of H–PDMS–MA
2b: 29Si-NMR of H–PDMS–MA
3a: MALDI-tof
3b: MALDI-tof
4a: conversion plot of H–PDMS–MA
4b: SEC of H–PDMS–MA
6: SEC of ATRP-PDMS-Cl and PS-PDMS-Cl
7: SEC of PDMS bottlebrush
S1: 1H-NMR
S2: 13C-NMR
S3: 29Si-NMR
S4: 1H-NMR
S5: 13C-NMR
S6: 29Si-NMR
S7: FT-IR
S8: SEC
S9: MALDI-tof
S10: 1H-NMR
S11: 13C-NMR
S12: 29Si-NMR
S13: FT-IR
S14: SEC
S15: MALDI-tof
S16a: MALDI-tof
S16b: MALDI-tof
S17: 1H-NMR
S18: 13C-NMR
S19: 29Si-NMR
S20: FT-IR
S21: SEC
S22: MALDI-tof
S23: 1H-NMR
S24: 13C-NMR
S25: 29Si-NMR
S26: FT-IR
S27: SEC
S28: MALDI-tof
S29: 1H-NMR
S30: 13C-NMR
S31: 29Si-NMR
S32: FT-IR
S33: SEC
S34: MALDI-tof
S35: 1H-NMR
S36: 13C-NMR
S37: 29Si-NMR
S38: FT-IR
S39: SEC
S40: MALDI-tof
S41: 1H-NMR
S42: 13C-NMR
S43: 29Si-NMR
S44: FT-IR
S45: SEC
S46: MALDI-tof
S47: 1H-NMR
S48: 13C-NMR
S49: 29Si-NMR
S50: FT-IR
S51: SEC
S52: MALDI-tof
S53: 1H-NMR
S54: 13C-NMR
S55: 29Si-NMR
S56: FT-IR
S57: SEC
S58: MALDI-tof
S59: 1H-NMR
S60: 13C-NMR
S61: 29Si-NMR
S62: SEC
S63: 1H-NMR
S64: 13C-NMR
S65: 29Si-NMR
S66: FT-IR
S67: SEC
S68: 1H-NMR
S69: 13C-NMR
S70: 29Si-NMR
S71: FT-IR
S72: SEC
S73: MALDI-tof
S74: 1H-NMR
S75: 13C-NMR
S76: 29Si-NMR
S77: FT-IR
S78: SEC
S79: Curing profile
S80: Frequency sweep
Methods
Nuclear magnetic resonance spectroscopy
1H-, 13C- and 29Si-NMR spectra were collected on a Bruker Avance NEO 500 MHz using chloroform as a deuterated solvent. IR spectra was measured with a Thermo Nicolet iS10 FTIR spectrometer equipped with a Smart Diamond attenuated total reflectance (ATR) accessory.
Size exclusion chromatography
Size exclusion chromatography (SEC) was measured using Waters e2695 separation module with a Waters 2414 differential refractive index detector equipped with two columns (PLgel, 5 μm MiniMIX-D, 250×4.6 mm columns + guard) with chloroform containing 0.25% TEA at 35 °C as the mobile phase.
Matrix assisted laser desorption ionization-time of flight mass spectrometry
MALDI-TOF MS spectrometry was measured using a Bruker Microflex LRF MALDI TOF mass spectrometer in positive reflection mode; the analyte, matrix (DCTB) were dissolved in chloroform at the concentration of 2.5 and 10 mg/mL respectively, and cationization agent (NaTFA) was dissolved in chloroform at concentrations of 1 mg/mL, then mixed in a volume ratio of 20 : 1 : 1 (DCTB : NaTFA : sample). 0.5 μL of this mixed solution was spotted onto a ground steel target plate and the solvent was allowed to evaporate prior to analysis.
Mechanical analysis
Frequency sweeps and isochronal temperature sweeps were obtained on a TA Instruments ARES G2 in oscillatory shear mode with an 8 mm parallel-plate geometry and a nitrogen-purged forced–convection oven.