Search results for "polymers"
showing 10 items of 3567 documents
Alternating, all-trans polyenynes: Model compounds for poly(diacetylene)s with defined conjugation length
1994
The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v(CC) = 2108–2128 cm−1 and v(CC) = 1505–1532 cm−1 were calculated after extrapolation. Similarly sp-C13C NMR data yielded a shift of δ = 100 ppm. These data are…
Aminal Protection of Epoxide Monomer Permits the Introduction of Multiple Secondary Amine Moieties at Poly(ethylene glycol).
2019
In contrast to acetal groups, aminal moieties are almost unknown in polymer chemistry. The aminal-protected isopropyl-hexahydro-pyrimidine glycidyl amine (PyGA) for the anionic ring-opening polymerization (AROP) is introduced. The monomer is prepared in a two-step synthesis and can be polymerized in a well-controlled manner under AROP conditions. Several poly(ethylene glycol) block and triblock copolymers are synthesized in a molecular weight range from 2 700 to 11 400 g mol-1 with up to 11 mol% PyGA. The molecular weight distributions are monomodal with low dispersity (Đ = Mw /Mn ) below 1.2. After the polymerization, the acid-labile hexahydro-pyrimidine rings can be conveniently cleaved i…
An Analysis of the Concentration Effects on Elution Volumes by Using the Preferential Solvation Parameter in Two SEC Packings
2002
Size exclusion chromatography (SEC) elution behavior of different solvent/polymer systems has been analyzed from chromatographic, thermodynamic, and hydrodynamic points of view in two organic column packings based on polystyrene/divinylbenzene (PS/DVB) copolymer, μ-styragel and TSK-Gel H HR . Although both packings present similar chromatographic properties, some differences arise when eluting the same systems. The values of the adsorption distribution coefficients, K p , have been correlated with the preferential solvation coefficient, λ (see Figure), for both packings, showing that those systems with lower and negative λ values (denoting higher preferential solvation of the polymer by the…
Estimation of Number-Average Molecular Weights of Copolymers by Gel Permeation Chromatography−Light Scattering
1996
The true number-average molecular weight, Mn, of copolymers is obtained by GPC coupled with a light-scattering detector even if the composition and therefore the refractive index increment varies with elution volume, provided slices taken are monodisperse with respect to molecular weight and composition. In contrast, only an apparent weight-average molecular weight, can be obtained by the conventional GPC−light scattering combination, even for a perfect chromatographic resolution. The errors in Mn associated with nonhomogeneous slices are estimated. Experimental data with mixtures of linear polystyrene and poly(methyl methacrylate) confirm these estimations and indicate that the error in Mn…
Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles
2016
The synthesis of high-molecular-weight, well-defined poly(vinylferrocene)-block-poly(ethylene glycol) (PVFc-b-PEG) diblock copolymers (Mn = 13 000–44 000 g mol–1; Đ = 1.29–1.34) with precisely one allyl group at the junction point is introduced. Allyl glycidyl ether (AGE) was used to end-functionalize PVFc, resulting in hydroxyl functional macroinitiators for the oxyanionic polymerization of ethylene oxide. The self-assembly behavior of the amphiphilic PVFc-b-PEG copolymers in water has been investigated in a detailed manner, using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The redox activity of the PVFc block was confirmed by UV/vis spectroscopy, while cyclo…
Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity …
2022
Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ 1H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (rEO = 1.05 ± 0…
A Challenging Comonomer Pair: Copolymerization of Ethylene Oxide and Glycidyl Methyl Ether to Thermoresponsive Polyethers
2014
Motivated by the oxygen-rich and fully amorphous structure of poly(glycidyl methyl ether) (PGME), a series of thermoresponsive poly(glycidyl methyl ether-co-ethylene oxide) copolymers P(GME-co-EO) with molecular weights in the range of 3000–20 000 g mol–1 were synthesized by the activated monomer polymerization technique. Tetraoctylammonium bromide (NOct4Br) was employed as an initiator in combination with triisobutylaluminum (i-Bu3Al) as a catalyst under mild conditions. Polyethers with varying GME content between 31 and 100 mol % were obtained. Triad sequence analysis using 13C NMR spectroscopy proved that no pronounced block structure was obtained. Differential scanning calorimetry (DSC)…
Vinyl ferrocenyl glycidyl ether: an unprotected orthogonal ferrocene monomer for anionic and radical polymerization
2015
The first orthogonal ferrocene monomer, vinyl ferrocenyl glycidyl ether (VfcGE), for both anionic and radical polymerization – without the need of a protection group – is presented. Anionic ring-opening copolymerization of VfcGE and ethylene oxide (EO) generates stimuli-responsive, multifunctional poly[(vinyl ferrocenyl glycidyl ether)-co-(ethylene oxide)] (P[VfcGE-co-EO]) copolymers (molecular weights of ca. 7500 g mol−1 and low molecular weight dispersities (Đ ≤ 1.14)). The amount of the equimolar ferrocenyl and vinyl groups are controlled by the comonomer ratio up to 15.4 mol% VfcGE. The pendant vinyl groups of P[VfcGE-co-EO] were post-modified with 3-mercaptopropionic acid via thiol–ene…
Multi-olefin containing polyethers and triazolinediones: a powerful alliance
2019
Multi-functional polyethers with ene or diene moieties were prepared via the polymerisation of tailored functional glycidyl ether monomers to create a platform for click chemistry with triazolinediones (TADs). Specifically, two novel monomers (i) 2,4-hexadien-1-yl glycidyl ether (HDEGE) and (ii) citronellyl glycidyl ether (CitroGE), designed to undergo a Diels–Alder or Alder–Ene reaction with TADs, respectively, were synthesized and subsequently transformed into a variety of tailored polyethers, either via the monomer activated method or anionic ring opening polymerisation. Multi-functional copolymers of HDEGE with ethylene oxide, propylene oxide and ethoxy ethyl glycidyl ether as well as A…
Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block
2008
The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were em…