More participants, yet efficient reactions: Multicomponent reactions (MCRs) have found application in polymer chemistry both the synthesis of multifunctional monomers and post-polymerization modification. Examples include Passerini three-component reaction, Ugi four-component copper-catalyzed MCR (see scheme).

A Kabachnik-Fields postpolymerization modification reaction (KF-PMR) was conducted on poly(4-vinyl benzaldehyde) (poly(St-CHO)) with amines and phosphites. Successful KF-PMR demonstrated by precise structural analysis of the obtained polymers kinetic investigation processes, making it a powerful tool for modifications that lead to α-amino phosphonates as side groups.

The living ring-opening polymerization of δ-valerolactone (VL) initiated from 6-azide-1-hexanol using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea (BCT) was carried out to prepare the poly(δ-valerolactone)s (N3−PVL−OH) bearing azide groups at α-chain ends with Mn,NMRs (PDIs) 2600 (1.08), 4700 (1.11), 9900 (1.09). acetylene functionality introduced ω-end N3−PVL-OH 5-hexynoyl chloride afford telechelic poly(δ-valerolactone) group α-end...

A Cu-catalyzed multi-component reaction (CuMCR) of terminal alkynes, sulfonyl azides, and amines was employed in a post-polymerization modification process. The conducted on polystyrene bearing 20 mol % alkyne groups with 4-toluenesulfonyl azide dihexylamine the presence Cu(PPh3)3Br/diisopropylethylamine catalyst. CuMCR polymer proceeded efficiently, as confirmed by obvious gas evolution during reaction, conversion moiety reached almost 100%, yielding polymeric N-sulfonylamidine derivatives,...

We have established a new cellulose modification protocol without any additional catalysts and corrosive chemicals.

The polymerization of δ-valerolactone (δ-VL) using 3-phenyl-1-propanol (3-Ph-PrOH) as the initiator and trifluoromethanesulfonimide (HNTf2) catalyst in CH2Cl2 at 27 °C with [δ-VL]0/[3-Ph-PrOH]0/[HNTf2]0 ratio 100:1:0.1 proceeded homogeneously to afford a poly(δ-valerolactone) (PVL) narrow polydispersity index. molecular weight determined from 1H NMR analysis, Mn = 9600 g mol−1, fairly agreed that estimated initial [δ-VL]0/[3-Ph-PrOH]0, Mn,theo 9400 mol−1. In addition, kinetic chain extension...

Poly(phenylacetylene) with rationally designed urea groups was demonstrated to be a superior anion receptor possessing both colorimetric response ability and positive homotropic allosteric binding mode. The target polymer, poly(phenylacetylene) [bis(trifluoromethyl)phenyl]urea pendants (poly-1), synthesized by the stereoselective polymerization Rh(nbd)BPh4 (nbd = norbornadiene) in high yield. sensing of poly-1 evaluated using tetra-n-butylammonium (TBA) salts series anions THF. Upon addition...

Kabachnik-Fields reaction was employed as a new method for polycondensation. For this purpose, polymers were prepared from mixture of dialdehydes, diamines, and phosphites. Variation different starting monomers allowed the synthesis with tunable properties. It not only variation glass transition temperatures but also enabled highly functional including zwitterionic polymers. Further, photodegradable have been realized by utilizing photolabile dialdehyde monomer, which renders obtained...

Abstract The 2‐chloropropionamide derivative featuring an azido group is used as the initiator for ATRP of N‐ isopropylacrylamide (NIPAM) with copper( I ) chloride (CuCl) and tris[2‐(dimethylamino)ethyl]amine (Me 6 TREN) to produce PNIPAM end‐functionalized group. Subsequently, ‘click’ reaction between end‐group acetylene derivatives demonstrated in which end‐groups are modified by phenyl, 4‐phenoxyphenyl, butyl, octyl, carboxylic acid, hydroxymethyl groups. resulting show a LCST that ranges...

The Brønsted acid, trifluoromethanesulfonimide (HNTf2), was revealed to act as a highly efficient activator for group transfer polymerization (GTP) of methyl methacrylate (MMA) at ambient temperature. HNTf2-catalyzed GTP MMA initiated by 1-methoxy-1-trimethylsilyloxy-2-methyl-propene (MTS) proceeded in living manner produce poly(methyl methacrylate)s (PMMA) with controlled molecular weights and narrow weight distributions. Kinetic measurement postpolymerization experiment further supported...

A colorimetric detection susceptible to the dimensions of guest counteranions has been demonstrated by using poly(phenylacetylene) with L-leucine and urea functionalities (poly-PA-Leu). Poly-PA-Leu was prepared from N-(4-ethynylphenylcarbamoyl)-L-leucine ethyl ester (PA-Leu) [Rh(+){eta(6)-C(6)H(5))B(-)(C(6)H(5))(3)}(2,5-norbornadiene)] as a catalyst. The biased helical conformation poly-PA-Leu through Cotton effects in circular dichroism (CD) spectra. addition ammonium salts, including...

The successful sequence-controlled installation of an activated ester using a newly designed monomer pentafluorophenyl 4-maleimidobenzoate is demonstrated. Pentafluorophenyl kinetically installed at different stages nitroxide-mediated polymerization, namely, near the α-chain end and in middle PS chain. In addition, apolar polar functional groups achieved via post-polymerization functionalization, which demonstrated versatility synthesis universal precursor for locally functionalized polymers.

Mechanistic insights into organocatalytic properties of imidazolium-based ionic liquids led to improvements cellulose modification reactions in liquids.

Cellulose triacetate was synthesised by the transesterification reaction of mild acid-pretreated lignocellulosic biomass with a stable acetylating reagent (isopropenyl acetate, IPA) in an ionic liquid (1-ethyl-3-methylimidazolium EmimOAc) which enabled dissolution lignocellulose as well organocatalytic reaction. The homogeneous acetylation pretreated sugar-cane bagasse carried out under conditions (80 °C, 30 min), and subsequent reprecipitation processes led to enriched cellulose high degree...

Abstract A poly(phenylacetylene) bearing a polycarbohydrate ionophore as graft chain (copolymer 4 ) was synthesized by the copolymerization of end‐functionalized (1→6)‐2,5‐anhydro‐3,4‐di‐ O ‐ethyl‐ D ‐glucitol with 4‐ethynylbenzoyl group (macromonomer 2 phenylacetylene. Copolymer showed split‐type circular dichroism (CD) in long absorption region conjugated polymer backbone (280–500 nm), and CD pattern varied response to external stimuli, such solvents temperature. This suggested that had...

Three-dimensionally organized sulfonamide groups have been demonstrated to show an anion signaling ability using poly(phenylacetylene) with l-aspartic acid and functionalities (poly-1). The polymerization of N-(4-ethynylphenylsulfonyl)-l-aspartic diethyl ester (1) was carried out Rh+(2,5-norbornadiene)[(η6-C6H5)B−(C6H5)3] (Rh(nbd)BPh4) as a catalyst afford poly-1. biased helical conformation poly-1 through Cotton effects in the circular dichroism (CD) spectra. addition anions including...

ABSTRACT In this study, we succeeded in the situ activation of nonactivated ester moieties embedded polymer structures. Although poly(pentafluorophenyl methacrylate) (PPFPMA) can react with 2‐ethylhexylamine at 50 °C presence proton scavenger such as NEt 3 , conditions were not suitable for poly(phenyl (PPhMA). Nevertheless, combination organo‐activating agents, namely 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) and 1,2,4‐triazole (TZ) led to a facile conversion from amide PPhMA. The reaction...

A new sequential post-polymerization modification process was developed, which comprised a sulfonamidation reaction between poly(pentafluorophenyl 4-vinylbenzenesulfonate) (poly(PFP-4VS)) and amines subsequent Mitsunobu on NH moieties of the obtained polymeric sulfonamides. We have successfully demonstrated utilization this by synthesizing library functional polymers.

Polystyrene-block-poly(maleimide pentafluorophenyl ester-co-styrene)-block-poly(ethylene oxide) with an o-nitrobenzyl ester junction was synthesized by "one-step" RAFT polymerization. Highly ordered and locally reactive nanoporous thin films were obtained from the photocleavable triblock copolymer after spin coating, solvent annealing, UV exposure, washing methanol/water to remove minor block PEO. The local reactivity in demonstrated fabrication of iron oxide nanotori post-modification...

The role of 1-ethyl-3-methylimidazolium (Emim) carboxylate-type ionic liquid (IL) as the solvent and organocatalyst for transesterification reaction cellulose was investigated. reported method using Emim acetate vinyl ester caused an undesired side reaction: anion derived from EmimOAc introduced into ester. To improve system, ILs with a high solubility, degree substitution (DS) value, low side-reaction were systematically explored. Newly synthesized p-anisate mixed system achieved DS value...

Cis-transoidal poly(4'-ethynylbenzo-15-crown-5) (2) prepared by the polymerization of 4'-ethynylbenzo-15-crown-5 with Rh(nbd)BPh4 has been used as a thermoresponsive material chiral on−off switching property. In circular dichroism (CD) spectrum 2 in presence perchloric acid salt l-phenylglycine (l-Pgly·HClO4) at −30 °C, large Cotton effect an intensity +2.96 × 104 deg cm2 dmol-1 was observed range from 300 to 550 nm corresponding absorption conjugated polymer backbone, indicating that formed...