Easy Access to Amphiphilic Heterografted Poly(2-oxazoline) Comb Copolymers

Weber, C.; Wagner, Michael R.; Baykal, Duygu; Hoeppener, Stephanie; Paulus, Renzo M.; Festag, Grit; Altuntaş, Esra; Schacher, Felix H.; Schubert, Ulrich S.

doi:10.1021/ma400947r

Cited by 42 publications

(30 citation statements)

References 44 publications

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“…Termination of the living POx chains with (meth‐)acrylic acid has been emerged as the method of choice to generate POx macromonomers (oligo(Ox)MA), which have been polymerized by free radical polymerization (FRP),[33d,62] group transfer polymerization (GTP), reversible addition‐fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP) and Cu(0)‐mediated polymerization (Figure A). [33c] A range of monomers including MeOx, EtOx,[33c,64] iPrOx[33d,65] and 2‐nonyl‐2‐oxazoline (NonOx) have been used to tailor the properties of the corresponding comb POx and their aqueous solution behavior have been studied in detail by the groups of Hoogenboom, Schubert and Jordan (Figure B) . Recently, we copolymerized oligo(EtOx)MA with other vinyl monomers bearing alkyne and epoxide moieties which allowed for the post‐polymerization modification of the comb polymers.…”

Section: Poly(cyclic Imino Ether)s (Poly(cie)s) Via Cationic Ring‐opementioning

confidence: 99%

Chain and Step Growth Polymerizations of Cyclic Imino Ethers: From Poly(2‐oxazoline)s to Poly(ester amide)s

Kempe

2017

Macromol. Chem. Phys.

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Cyclic imino ethers (CIEs), such as 2‐oxazolines and 2‐oxazines are a unique class of monomers, which because of their manifold reactivities can be polymerized via multiple techniques. Most prominent, the living cationic ring‐opening polymerization (CROP) of CIEs enables the synthesis of well‐defined tailor‐made poly(CIEs), which have tremendous importance as functional and biocompatible polymers. On the other hand, CIEs are also powerful monomers in polyadditions resulting in the formation of a variety of biodegradable polyamide‐based systems. In this contribution, the enormous potential of CIEs as functional building blocks is discussed, which goes well beyond the CROP. Besides trends in the CROP of CIEs, recent developments in step‐growth polymerizations of CIEs are highlighted, including the spontaneous zwitterionic copolymerization (SZWIP) which provides access to functional alternating N‐acylated poly(amino ester)s (NPAEs) and polyadditions of multifunctional CIEs which give main‐chain poly(ester amide)s (PEAs).

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Section: Poly(cyclic Imino Ether)s (Poly(cie)s) Via Cationic Ring‐opementioning

confidence: 99%

Chain and Step Growth Polymerizations of Cyclic Imino Ethers: From Poly(2‐oxazoline)s to Poly(ester amide)s

Kempe

2017

Macromol. Chem. Phys.

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“…17 Additionally their solubility and aggregation behavior can be finetuned by structural and compositional variation of the poly(2-oxazoline)s by usage of easy accessible monomers. 49 FRP of macromonomers results in molecular brushes with a very long backbone (P w ~ 1050) but a broad molar mass distribution. 7,[21][22][23][24][25][26][27][28][29][30] After early approaches 31,32 yielding a variety of POx-based comb polymers, [33][34][35][36][37][38][39][40][41][42][43][44][45][46] POx molecular brushes have been synthesized recently by several routes.…”

Section: Introductionmentioning

confidence: 99%

Poly(2-oxazoline) molecular brushes by grafting through of poly(2-oxazoline)methacrylates with aqueous ATRP

Gieseler

Jordan

2015

Polym. Chem.

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Molecular brushes of poly(2-oxazoline)s (POx) are an intriguing class of polymers as they combine a unique architecture with the properties of POx as a biomaterial. Here, the synthesis of several POx macromonomers with methacrylate end groups and consecutive grafting through polymerization by aqueous atom transfer radical polymerization (ATRP) at room temperature is reported. 1 H-NMR spectroscopy and size exclusion chromatography (SEC) confirmed the synthesis of POx molecular brushes with maximum side chain grafting densities, narrow molar mass distributions (Ð ≤ 1.16) and final molar masses corresponding to the initial macromonomer : initiator ratio. Chain extension experiments show high end group fidelity, formation of block copolymer molecular brushes and kinetic studies revealed a polymerization behavior of oligo(2methyl-2-oxazoline methacrylate) very similar to the frequently used oligo(ethylene glycol) methacrylate (OEGMA 475 ). Aqueous solutions of POx molecular brushes with poly(2-ethyl-and 2-isopropyl-2-oxazoline) side chains exhibit the typically defined thermoresponsive behavior with a tunable, very narrow and reversible phase transition. P(MeOx 7 -MA) 52 0.118 P(MeOx 7 -MA) 104 0.116 P(MeOx 7 -MA) 202 0.114 P(MeOx 21 -MA) 50 0.146 P(MeOx 21 -MA) 91 0.153 P(EtOx 21 -MA) 50 0.149 P(EtOx 21 -MA) 92 0.156 P(EtOx 21 -MA) 183 0.153 Macromonomer synthesis Macromonomer MeOx 7 -MA: In a glove box, 5.7774 g (35.2 mmol, 1 eq) methyltriflate was dissolved in 45 mL acetonitrile and 14.9237 g (175.4 mmol, 5.0 eq) 2-methyl-2-oxazoline were added slowly at r.t.. The solution was stirred at 90 °C for 20 min. Afterwards the solution was

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“…In 2009, Schubert et al reported homopolymerization of PEtOx via the reversible addition‐fragmentation chain transfer (RAFT) polymerization . Subsequently, a heterografted brush with PEtOx and oligo(2‐ n ‐nonyl‐2‐oxazoline) side chains and a cylindrical brush with sugar‐functionalized PEtOx side chains were prepared by them using the similar method . Recently, Jordon et al explored aqueous atom transfer radical polymerization of POx macromonomers to yield the brushes with long backbone (DP up to 820).…”

Section: Introductionmentioning

confidence: 99%

Uni‐molecular nanoparticles of poly(2‐oxazoline) showing tunable thermoresponsive behaviors

Chu

Huang

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Herein, cylindrical molecular bottlebrushes grafted with poly(2‐oxazoline) (POx) as a shaped tunable uni‐molecular nanoparticle were synthesized via the grafting‐onto approach. First, poly(glycidyl methacrylate) (PGMA) backbones with azide pendant units were prepared via reversible addition fragmentation transfer (RAFT) polymerization followed by post‐modification. The degree of polymerization (DP) of the backbones was tuned in a range from 20 to 800. Alkynyl‐terminated POx side chains were synthesized by living cationic ring opening polymerization (LCROP) of 2‐ethyl‐2‐oxazoline (EtOx) and 2‐methyl‐2‐oxazoline (MeOx), respectively. The DP of side chains was varied between 20 and 100. Then, the copper‐catalyzed azide‐alkynyl cycloaddition (CuAAC) click chemistry was conducted with a feed ratio of [alkynyl]:[azide] = 1.2:1 to yield a series of brushes. Depending on the DP of side chains, the grafting density ranged between 47 and 85%. The resulting brushlike nanoparticles exhibited shapes of sphere, rod and worm. Aqueous solutions of PEtOx brushes demonstrated a thermoresponsive behavior as a function of the length of backbones and side chains. Surprisingly, it was found that the lower critical solution temperature of PEtOx brushes increased with a length increase of backbones. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 174–183

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Easy Access to Amphiphilic Heterografted Poly(2-oxazoline) Comb Copolymers

Cited by 42 publications

References 44 publications

Chain and Step Growth Polymerizations of Cyclic Imino Ethers: From Poly(2‐oxazoline)s to Poly(ester amide)s

Chain and Step Growth Polymerizations of Cyclic Imino Ethers: From Poly(2‐oxazoline)s to Poly(ester amide)s

Poly(2-oxazoline) molecular brushes by grafting through of poly(2-oxazoline)methacrylates with aqueous ATRP

Uni‐molecular nanoparticles of poly(2‐oxazoline) showing tunable thermoresponsive behaviors

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