Search results for "End-group"

Ring opening polymerization of d,l-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(ii) carboxylate complexes

2021

1,2-Bis{(3,5-dimethylpyrazol-1-yl)methyl}benzene (L) reacts with [Cu(OAc)2] and C6H5COOH, 4-OH-C6H4COOH, 2-Cl-C6H4COOH and (3,5-NO2)2-C6H3COOH to afford the copper complexes [Cu2(C6H5COO)4(L)2] (1), [Cu2(4-OH-C6H4COO)4(L)2] (2), [Cu2(2-Cl-C6H4COO)4(L)2]n (3) and [Cu{(3,5-NO2)2-C6H3COO}2L]n (4) which are characterised by IR, mass spectrometry, elemental analyses, and X-ray crystallography. The structural data revealed two geometries that are adopted by the complexes: (i) paddle wheel in 1, 2·7H2O, 3 and (ii) regular chains in 3 and 4. Magnetic studies show strong antiferromagnetic couplings in the paddle wheel complexes and a weak antiferromagnetic coupling in the monometallic chain one. Cat…

Double Thermoresponsive Block Copolymers Featuring a Biotin End Group

2010

A poly(oligo(ethylene glycol) monomethyl ether methacrylate)-block-poly(N-isopropyl methacrylamide) (POEGMA-b-PNIPMAM) block copolymer with a biotin end group on the PNIPMAM block as a biotarget was synthesized as a model system for temperature-controlled polymer immobilization. The synthesis was based on RAFT polymerization followed by postpolymerization modification of an activated ester precursor block and an exchange of the dithioester end group within one step. NMR, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidimetry measurements were performed to investigate the stimulus-responsive properties. The double thermoresponsive POEGMA-b-PNIPMAM with biot…

Hyperbranched Polyglycerol-Based Lipids via Oxyanionic Polymerization: Toward Multifunctional Stealth Liposomes

2010

We describe the synthesis of linear-hyperbranched lipids for liposome preparation based on linear poly(ethylene glycol) (PEG) and hyperbranched polyglycerol (PG). Molecular weights were adjusted to values around 3000 g/mol with varying degrees of polymerization of the linear and the branched segments in analogy to PEG-based stealth lipids; polydispersities were generally low and below 1.3. The hydrophobic anchors were introduced into the lipid structures as initiators for the anionic polymerization of ethylene oxide and are either based on cholesterol or on different aliphatic glyceryl ethers. Complete incorporation of the apolar initiators was evidenced by MALDI-ToF analysis at all stages …

Aliphatic Hyperbranched Copolyesters by Combination of ROP and AB2-Polycondensation

2005

Hyperbranched aliphatic copolyesters have been prepared by the copolymerization of e-caprolactone and 2,2-bis(hydroxymethyl)butyric acid (AB 2 -monomer), catalyzed by (i) HfCl 4 (THF) 2 and (ii) diphenylammonium trifluoromethanesulfonate (DPAT), respectively. In both cases, copolymerization by combined ROP/AB 2 -Polycondensation was achieved. The degree of branching (DB) and consequently the density of functional groups of the resulting copolyesters were controlled by the comonomer ratio in the feed. Molecular weights in the range M n =22 000-166 000 g mot -1 (GPC, PS standards) were obtained, with apparent polydispersity indices of 1.20 to 1.95. The DB was in the range 0.03-0.35. Remarkabl…

Dispersion Polymerization of Vinylidene Fluoride in Supercritical Carbon Dioxide

2006

The dispersion polymerization of vinylidene fluoride in supercritical carbon dioxide is investigated using two ammonium carboxylate perfluoropolyether stabilizers of different molecular weights. Under suitable operating conditions a polymer made of well-dispersed spherical particles has been obtained up to relatively high conversion. The experimental data of polymerization rate and molecular weight distribution are in good agreement with the predictions of a model previously developed. Such an agreement supports the conclusion that the polymerization kinetics is dominated by the interphase transport of the active radicals between the continuous phase and the polymer particles.

Metal-free polymerization of phenylsilane: tris(pentafluorophenyl)borane-catalyzed synthesis of branched polysilanes at elevated temperatures.

2013

The strong organoborane Lewis acid B(C6F5)3 catalyzes the polymerization of phenylsilane at elevated temperatures forming benzene and SiH4 as side-products. The resulting polymer is a branched polysilane with an irregular substitution pattern, as revealed by 2D NMR spectroscopy. Having explored the mechanism of this novel metal-free polymerization by computational chemistry methods at the DFT level, we have suggested that unusual cationic active species, namely monomer-stabilized silyl cations, propagate the polymerization. Hydride abstraction of SiH3 moiety by the catalyst in the initiation step was found to be kinetically preferred by around 9 kcal mol(-1) over activation by coordination …

End-Group-Dominated Molecular Order in Self-Assembled Monolayers

1995

Polymerisation von äthylenoxid mit dem kaliumalkoholat von 4-benzolazo-benzylalkohol. II. Die quantitative bestimmung einer übertragungsreaktion

1966

Die Untersuchung von Polyathylenoxiden, die mit dem Kaliumalkoholat von 4-Benzolazo-benzylalkohol und Athylenoxid erhalten wurden, ergab, das nicht jedes Polyathylenoxidmolekul eine Endgruppc aus dein Polymerisationsstarter enthielt. Die vermutete Ubertragungsreaktion mit Wasserspuren wurde folgendermasen nachgewiesen und quantative bestimint. Eine quantitative Umsetzung der Polyathylenoxide mit(4-Benzolazobenzoesa-)anhydrid gab mittels colorimetrischer Messungen den Gehalt an HO-Endgruppen. Der Vergleich des Gehaltes an Endgruppen aus dem Starter mit dem HO-Endgruppengehalt zeigte ein starkes Uberwiegen der HO-Endgruppen. Die Zahlenmittel der Molekulargewichte (Mn) von Polyathylenoxidfrakt…

1992

The kinetics and the molecular weight distributions (MWD) in the anionic polymerization of tert-butyl acrylate (tBuA) in tetrahydrofuran at 23 ± 3°C were investigated. Tert-butyl α-lithioisobutyrate (tBiB-Li) was used as the initiator in the absence and presence of the additives lithium chloride and lithium tert-butoxide (tBuOLi). A flow tube reactor was used which allowed very rapid mixing of reagents, within milliseconds. The polymerization is extremely fast, half-lives being 0,01 s for the system without additive, 0,05 s for LiCl and 3 s for tBuOLi as an additive. The rate of termination was estimated from the strong UV absorption of the enolized β-oxoester end group formed. The number-a…

Tail and Head Group Interactions in Phospholipid Monolayers

1996

Abstract The order/disorder transition of the phospholipid 1,2-dihexadecyl-sn-glycero-3-phosphocholine and its derivatives was studied by X-ray reflection and thermodynamic measurements. We find that increasing the length of an ethylene oxide spacer (zero to three EO groups) between the phosphate group and the hydrophobic chains (i) induces a slight shift of the main transition, (ii) reduces the influence of the head groups on the chain lattice, and (iii) increases the head group length and promotes its hydration. For DH(EO)3PC in the ordered phase we find that the small phosphate groups (which are the main source of contrast in X-ray reflectivity) are homogeneously distributed within the h…