Precise synthesis of linear polysiloxanes with a polar side-chain structure by organocatalytic controlled/living ring-opening polymerization of (3-cyanopropyl)pentamethylcyclotrisiloxane
- 11 May 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Polymer Chemistry
- Vol. 12 (22), 3321-3331
- https://doi.org/10.1039/d1py00391g
Abstract
The organocatalytic controlled/living ring-opening polymerization (ROP) of (3-cyanopropyl)pentamethylcyclotrisiloxane (CNPD2) using water or a silanol as the initiator, 1,3-trimethylene-2-methylguanidine (TMMG) as the catalyst, and organochlorosilanes as the end-capping agents produced linear polysiloxanes with a controlled number-average molecular weight (Mn), narrow molecular-weight dispersity (ĐM), the desired terminal structures, and good distribution of the 3-cyanopropyl side-chains. CNPD2 was obtained from the reaction of 1,3-dihydroxy-1,1,3,3-tetramethyldisiloxane with diacetoxy(3-cyanopropyl)methylsilane. The composition and monomeric sequence of the resulting side-chain-functionalized polysiloxanes were conveniently controlled by using either polymerization of CNPD2 or copolymerization of CNPD2 and another cyclotrisiloxanes and by varying the initial feed ratio of the two monomers and the monomer addition timing, i.e., using either premix or two-stage methods in the copolymerizations. An analysis of the monomeric sequences using 29Si{1H} NMR measurements revealed that the polymerizations proceeded almost completely in the statistical propagation mode. Plausible monomeric sequences and chain-length distributions of the resulting side-chain-functionalized polysiloxanes were visualized using two simulation methods. The solubility and thermal properties of the resulting polysiloxanes with cyanopropyl group side chains were investigated. Importantly, the poly[dimethylsiloxane-co-3-cyanopropyl(methyl)siloxane] (p(DMS-co-CNPMS)) segments behave independently in the copolymer synthesized from hexamethylcyclotrisiloxane and CNPD2 using the two-stage method.Keywords
Funding Information
- New Energy and Industrial Technology Development Organization
This publication has 35 references indexed in Scilit:
- 3-Chloropropyl Functionalized Dendrigraft Polysiloxanes and Dendritic PolyelectrolytesMacromolecules, 2007
- Reactions of tertiary hydroxyalkylamines with 3-halogenopropyl substituted polysiloxanes: a route to water soluble and amphiphilic siliconesReactive and Functional Polymers, 2004
- Tunable block copolymers based on a polysiloxane backbone by anionic ring‐opening polymerizationJournal of Polymer Science Part A: Polymer Chemistry, 2004
- Amphiphilic block and statistical siloxane copolymers with antimicrobial activityJournal of Polymer Science Part A: Polymer Chemistry, 2003
- Synthesis of Branched Polysiloxanes with Controlled Branching and Functionalization by Anionic Ring-Opening PolymerizationMacromolecules, 2003
- Formation of cobalt nanoparticle dispersions in the presence of polysiloxane block copolymersPolymer, 2002
- Controlled synthesis of vinylmethylsiloxane–dimethylsiloxane gradient, block and alternate copolymers by anionic ROP of cyclotrisiloxanesPolymer, 2002
- Preparation of functionalized block copolymers based on a polysiloxane backbone by anionic ring‐opening polymerizationJournal of Polymer Science Part A: Polymer Chemistry, 2002
- Side-Chain Liquid-Crystalline Polysiloxanes via Anionic Polymerization: (n-Undecyloxy)arenecarboxylic Acid Mesogens Linked to Poly(dimethylsiloxane-co-methylvinylsiloxane)Macromolecules, 1997
- Polysiloxane based CHEMFETs for the detection of heavy metal ionsJournal of the Chemical Society, Perkin Transactions 2, 1996