Polyether Core-Shell Cylinder-Polymerization of Polyglycidol Macromonomers

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. The radical polymerization of the macromonomers was carried out in water with addition of a non-polar solvent (benzene) and AIBN as initiator. Co…

Star-Like Polymers of tert -Butyl Acrylate via Controlled Radical Polymerization - Synthesis and Properties

Summary: Star polymers with different numbers and lengths of poly(tert-butyl acrylate) arms were obtained by the core-first method via atom transfer and iodine mediated radical polymerization. Multifunctional initiators with different numbers of initiating groups (from 3 to 28) were used to initiate the polymerization of tert-butyl acrylate, yielding stars with different numbers of arms. The structures of the stars were characterized by NMR and gel permeation chromatography with refractive index, multiangle laser light scattering and viscosimetric detectors.

Core-shell polyacrylate and polystyrene-block-polyacrylate stars

The polymerization of p-(iodomethyl)styrene (PIMS) yields well-defined branched polymers with reactive iodomethyl groups. The branched poly[p-(iodomethyl)styrene] was used as the transfer agent in the iodine mediated radical polymerization of vinyl monomers. The polymerization proceeds in a controlled way and yields polystyrene and poly(t-butyl acrylate) star polymers with reactive groups at the end of their arms. Polymers so obtained were also used to prepare stars with block copolymer arms: polystyrene-block-poly(t-butyl acrylate). The characterization of star structures was performed by NMR and gel permeation chromatography with absolute molar mass detection (MALLS). Preliminary characte…

Loading of polymer nanocarriers: Factors, mechanisms and applications

Abstract The progress in synthetic polymer chemistry has allowed the precise design of hybrid and multifunctional colloidal particles, which differ in type, size and shape, thus enhancing their possible applications as target-oriented carriers of low and high molar mass active species. This survey discusses the basic principles and factors, associated with the process of loading of polymeric nanoparticles. For the purpose of this review, the polymeric nano-carriers are divided into five most studied types: micelles, nanogels, capsules (incl. vesicles), dendrimers, and hybrid nanoparticles with porous cores. Factors influencing the loading are described and their importance discussed. An imp…

Polyfunctional chloroformates were applied to the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline. The use of a trifunctional initiator, viz. the chloroformate of 2,2-bis(hydroxymethyl)-1-butanol, led to three-arm star polymers of 2-oxazolines. Two macromolecular initiators, viz. poly(ethylene oxide) with two chloroformate end groups (α-chloroformyl-ω-chloroformyloxypoly(oxyethylene)) with number-average molar masses 350 g/mol ≤ Mn ≤ 6000 g/mol and α-chloroformyl-ω-methoxypoly(oxyethylene) with Mn = 350 and 750 g/mol were applied for the synthesis of poly(2-oxazoline)-block-poly(ethylene oxide)-block-poly(2-oxazoline) and poly(2-oxazoline)-block-poly(ethylene oxide) copolyme…

Synthesis and thermoresponsive properties of four arm, amphiphilic poly(tert-butyl-glycidylether)-block-polyglycidol stars

Abstract A series of four arm stars with copolymer arms composed of poly(tert-butyl-glycidylether)-b-polyglycidol were prepared using a multi-step process based on anionic ring-opening polymerization. Control of the length of the arms and the number of functional (hydroxyl) reactive groups was achieved by anionic polymerization. Stars with molar masses up to 12200 g/mol were prepared. The amphiphilic character of the star structure was varied using different polyglycidol block lengths. The star structure and molar mass of the obtained stars were characterized by SEC–MALLS and NMR spectroscopy. The temperature behavior of an aqueous solution of the obtained polymers was also investigated. Th…

The influence of hydrophobic substitution on self-association of poly(ethylene oxide)-b-poly(n-alkyl glycidyl carbamate)s-b-poly(ethylene oxide) triblock copolymers in aqueous media

Abstract A series of amphiphilic poly(ethylene oxide)-b-poly(n-alkyl glycidyl carbamate)s-b-poly(ethylene oxide) triblock copolymers were synthesized by reaction between poly(ethylene oxide)-b-polyglycidol-b-poly(ethylene oxide) precursor copolymer and four n-alkyl isocyanates: ethyl, propyl, butyl and pentyl. After dissolution in water at room temperature the copolymers spontaneously form micelles. The critical micellization concentrations were determined by UV–VIS spectroscopy. The dimensions of the micelles, the aggregation numbers, and in some cases the micellar shape were determined by dynamic and static light scattering in a relatively broad temperature range. Special attention has be…

Core‐shell nanoparticles with hyperbranched poly(arylene‐oxindole) interiors

Opracowano synteze wysoce rozgalezionego poli(aryleno-oksyndolu) na drodze reakcji polimeryzacji pochodnej 5-bromoizatyny, a nastepnie modyfikacji terminalnych jednostek izatynowych. Tak przygotowany polimerowy rdzen, charakteryzujący sie stopniem rozgalezienia 100 %, byl substratem do rodnikowej polimeryzacji z przeniesieniem atomu (z ang. ATRP) w reakcji z akrylanem tert-butylu. Otrzymane kopolimery zawierające hydrofobowy rdzen i alkilowe lancuchy zakonczone wolnymi grupami karboksylowymi tworzą sferyczne nanocząstki. Przedstawiono wstepne wyniki badan dotyczących ich wlaściwości fizykochemicznych oraz potencjalnych zastosowan.

Polymerization of methyl and phenyl oxazoline initiated with alkyl chloroformates

It has been shown that alkyl chloroformates are capable of initiating the polymerization of oxazolines. Esters itself initiate rather slowly and the polymerization proceeds via covalent growing species. Exchange of counter ions with triflate or iodide anions leads to faster initiation and higher reaction rates. The polymerization is of living character.

Branched polymers starting from ethylene-vinyl acetate copolymers

Abstract Polyethylene-graft-poly-2-phenyl-2-oxazoline, polyethylene-graft-poly-2-methyl-2-oxazoline and polyethylenegraft-poly(ethylene oxide) were prepared using poly(ethylene-co-vinyl chloroformate) as macroinitiator or polyfunctional precursor. The vinyl acetate groups of ethylene-vinyl acetate copolymer were hydrolyzed, the corresponding alcohol functions were converted into chloroformate, which in turn was used for grafting of oxazolines. Comb-like polymers with hydrophilic poly(ethylene oxide) grafts with definite length were synthesized as well. The resulting graft copolymers were characterized by GPC, IR, and 1 H-NMR spectroscopy and differential scanning calorimetry.

High molecular arborescent polyoxyethylene with hydroxyl containing shell

Abstract Arborescent polyoxyethylene of high molar mass (2×10 5  g/mol) and narrow molar mass distribution was synthesized in a three-stage process. In the first stage a triblock copolymer of ethylene oxide (central block, DP ca. 90) and 2,3-epoxypropanol-1 (short flanking blocks, DP ca. 5) was synthesized. The potassium alcoholate derived from this copolymer was used to initiate the polymerization of ethylene oxide and the subsequent addition of protected glycidol (1-etoxyethyl glycidyl ether). After deprotection the short polyglycidol blocks were used as branching units for the next generation. Repeated step by step process leads to the ‘pom-pom like’ branched polyoxyethylene macromolecul…

Block and graft copolymers of 2-oxazolines

The cationic ring-opening polymerization of 2-oxazolines is known to be initiated by alkyl halides, Lewis acids and esters of strong acids. The polymerization proceeds by a living mechanism. Numerous block and graft copolymers have already been described. Recently it was found that chloroformates (R-O-CO-CI) are also useful initiators. The mechanism of the initiation and propagation is discussed. This type of initiators allows the synthesis of different novel two-block and three-block copolymers, star-shape polymers, and a graft copolymer with a polyvinylacetate backbone.

Solution behavior of 4-arm poly(tert-butyl acrylate) star polymers

Abstract This paper reports the synthesis of 4-arm poly( tert -butyl acrylate) stars of different molar masses up to 10 6  g/mol by the “core-first” method using ATRP. All obtained stars have a monomodal and narrow molar-mass distribution ( The dilute-solution properties of these star polymers were investigated in good solvents (tetrahydrofuran and acetone). Gel permeation chromatography and dynamic and static light scattering were used to measure the hydrodynamic properties including intrinsic viscosity [ η ], radius of gyration R g , hydrodynamic radius R h , second virial coefficient A 2 and diffusion coefficient D 0 . These data were used to establish relationships between these paramet…

Photodegradation of polyglycidol in aqueous solutions exposed to UV irradiation

The photodegradation of polyglycidol in aqueous solution with UV wavelength of 254 nm was investigated. The experiments were carried out in air at a constant temperature and the photodegradation of polyglycidol (PGl) was compared to that of poly(ethylene oxide) (PEO), the most widely studied polyether. Size exclusion chromatography with multiangle light scattering detection (SEC-MALLS) was used to measure the changes in the molar masses and molar mass dispersities of polymers during degradation. The molar mass of PGl decreased dramatically during the first period of UV irradiation and then gradually approached a limiting value of 17,000 g/mol, regardless of the initial polymer concentration…

Synthesis of polyvinyl acetate-graft-poly-2-oxazolines

Poly(vinyl acetate-co-vinyl chloroformate) (1) was synthesized via phosgenation of poly(vinyl acetate-co-vinyl alcohol). It was shown that (1) is capable of initiating the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline, when the counter ion is exchanged using potassium iodide. Polyvinyl acetate-graft-poly-2-phenyl-2-oxazoline and polyvinyl acetate-graft-poly-2-methyl-2-oxazoline are obtained in the grafting reaction.

Synthesis, characterization and properties of functional star and dendritic block copolymers of ethylene oxide and glycidol with oligoglycidol branching units

Abstract Well-defined, four-arm star block copolymers of ethylene oxide and glycidol were prepared via controlled anionic polymerization using protected glycidol. The length of the poly(ethylene oxide) block was varied from DP = 10 to 50, while the length of the short polyglycidol block remained nearly constant, at DP = 4–6. Star block copolymers with hydroxyl groups at the ends of the arms after conversion to the corresponding alkoxides were used as multifunctional macroinitiators for the sequential polymerization of ethylene oxide and protected glycidol. After deprotection, the branched block copolymers of ethylene oxide and glycidol had narrow molar mass distributions and multiple hydrox…

Star poly(2-ethyl-2-oxazoline)s-synthesis and thermosensitivity

A series of star-shaped poly(2-ethyl-2-oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4-nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. …