Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

Abstract

A one‐pot procedure for the synthesis of hyperbranched polyethylenes tethered with ATRP initiating sites by chain walking ethylene copolymerization with an acrylate‐type ATRP inimer, 2‐(2‐bromoisobutyryloxy) ethyl acrylate (BIEA) is reported. Because of its ability to incorporate acrylate‐type comonomers and tolerance toward the α‐bromoester group, the chain walking Pd‐diimine catalyst, [(ArNC(Me)(Me)CNAr)Pd(CH3)(NCMe)]SbF6 (Ar = 2,6‐(iPr)2C6H3), allowed the successful synthesis of a series of hyperbranched copolymers tethered with 2‐bromoisobutyryl groups at different densities. These copolymers may serve as polyfunctional macroinitiators for the ATRP of functional monomers to further synthesize core‐shell structured functionalized copolymers with a hyperbranched polyethylene core grafted with side chains of the functional monomers.magnified image

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

“…The specific concept of "active site transfer" has also been investigated in the RAFT polymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) [44]; anionic SCVP of divinylbenzene (DVB) and 1,3-isopropenylenebenzene [45]; AT-SCVP of DVB and (1-bromoethyl)benzene [46]; AT-SCVP of EGDMA and bisphenol A dimethacrylate [47]; and deactivation-enhanced AT-SCVP of commercially available multifunctional vinyl monomers [48]. A remarkable approach using Pd(II) and Ni(II) catalysts and very bulky chelating diimine ligands [49][50][51], has been reported for the formation of hyperbranched polyethylene at low pressure (a so-called "chain walking" process). The mechanism of active site transfer occurring predominantly among intra-chain provides a facile approach for controlling the topology of polyethylene.…”

Efficient, robust surface functionalization and stabilization of gold nanorods with quaternary ammonium-containing ionomers as multidentate macromolecular ligands

“…Figure 5 shows the 1 H NMR spectrum, along with that of pure CTAB in the same solvent mixture. Strong signals attributable to the hyperbranched polyethylene skeletons (0.75, 1.14, and 1.18 ppm for methyl, methine, and methylene protons, respectively) 45,46,[48][49][50][51][52][53][54][55] are present in the spectrum of I-GNR2. Signals characteristic of CTAB are absent within the detection limit of 1 H NMR spectroscopy.…”

“…[48][49][50][51][52][53][54][55] The acrylate comonomers, including AETA + BF 4 -, BIEA, and PMA, were synthesized according to the procedures reported in our earlier papers. 49 Representatively, the following is the procedure employed for the synthesis of HPEI3 in Table 1.…”

“…45 The highly compact dendrimer-like hyperbranched polymer skeleton results from the characteristic chain walking mechanism of the Pd-diimine catalysts. 45,46 We have previously synthesized a large class of such polymers 45,46,[48][49][50][51][52][53][54] and have recently demonstrated, in particular, the synthesis of hyperbranched polyethylene ionomers by direct copolymerization of ethylene with acrylate-type quaternary ammonium-containing ionic liquid comonomers. 55 To demonstrate that this ionomer functionalization strategy is general and not just limited to the hyperbranched polyethylene-based ionomers, we have also synthesized a quaternary ammoniumcontaining, linear poly(n-butyl acrylate)-based ionomer (PBAI) by free radical terpolymerization of n-butyl acrylate (BA), AETA + BF 4 -, and PMA (see Scheme 1b).…”

Geometry Constrained N-(5,6,7-Trihydroquinolin-8-ylidene)arylaminopalladium Dichloride Complexes: Catalytic Behavior toward Methyl Acrylate (MA), Methyl Acrylate-co-Norbornene (MA-co-NB) Polymerization and Heck Coupling

“…The extensive use have driven the price of palladium higher and higher, making it is necessary to enhance the catalytic efficiency by designing simpler and general palladium catalyst systems which can work under accessible reaction conditions. On the other hand, commercial copolymerization processes plays a key role in the production of new materials, which is indispensable in all fields of human life [24][25][26][27][28][29][30]. For instance, the copolymerization of polar monomers, particularly methyl acrylate (MA), with olefins confers novel properties on the resulting polymers: improved thermal stability, superior etch resistance, good adhesion due to the ester groups and a hydrophobic character derived from the C-C backbone [31][32][33].…”