0000000000037324
AUTHOR
Helmut Schlaad
showing 12 related works from this author
Mechanism of anionic polymerization of methyl methacrylate in the presence of aluminium alkyls
1995
Methyl methacrylate was polymerized with tert-butyl lithium in the presence of triethylaluminium or triisobutylaluminium at 78°C in toluene. As indicated by GPC and MALDI-TOF mass spectrometry, the polymerization is accompanied by side reactions. The lower oligomers were fractionated by distillation and characterised by NMR, FT-IR, UV and electron impact (EI) mass spectrometry. All these data show that part of the polymer chains are carrying exactly one tert-butyl isoprenyl ketone unit. In order to avoid the formation of tert-butyl isoprenyl ketone a molar ratio of Al/Li>2 is necessary.
Mechanism of Anionic Polymerization of (Meth)acrylates in the Presence of Aluminum Alkyls, 6. Polymerization of Primary and Tertiary Acrylates
1998
The kinetics of the polymerization of n-butyl acrylate initiated by lithiated ester enolates in the presence of aluminum alkyls was investigated in toluene and in toluene/Lewis base mixed solvents at −78 °C. In pure toluene, curved time−conversion plots, incomplete monomer conversion, and broad molecular weight distributions (Mw/Mn ≈ 2) are observedin the absence of aluminum alkyls the molecular weight distributions are significantly broader (Mw/Mn > 14). High monomer conversions and narrower molecular weight distributions (Mw/Mn ≈ 1.5) are obtained when using Lewis bases (e.g., methyl pivalate) as cosolvents. The polymerization of tert-butyl acrylate rapidly reaches full monomer conversion…
Mechanism of Anionic Polymerization of (Meth)acrylates in the Presence of Aluminium Alkyls IV. Formation of a Co-ordinative Polymer Network via the L…
1996
The polymerization of methyl methacrylate in the presence of aluminium alkyls in toluene deviates from conventional kinetics. This results predominantly from the formation and precipitation of a co-ordinative polymer gel or network. Due to the lower reactivity and accessibility of the living chains in the gel, they are regarded as ’dormant’ and thus the concentration of active species decreases during polymerization. The network formation occurs via co-ordination of the living aluminate chain end group with in-chain ester carbonyl groups. Part of the chains are deactivated by a termination process but they are free of cyclic β-ketoesters which would result from the common ’back-biting’ reac…
Tuning the surface of nanoparticles: Impact of poly(2-ethyl-2-oxazoline) on protein adsorption in serum and cellular uptake
2016
Item does not contain fulltext Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asym…
Quantitative analysis of broad molecular weight distributions obtained by matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry
1996
In order to quantify the error of matrix-assisted laser desorption ionisation (MALDI) time-of-flight (TOF) mass spectrometry in the determination of broad molecular weight distributions, different mixtures by weight of two poly(methyl methacrylate) standards were prepared. These mixtures, with well-defined bimodal molecular weight distributions were analysed by MALDI-TOF mass spectrometry using different matrices (2,4,6-trihydroxyacetophenone and 2,5-dihydroxybenzoic acid) and different cations (Li+, Na+, K+, Rb+ and Cs+) for doping the analyte. From the MALDI-TOF mass spectrometric data, the weight fractions of the two polymers of all mixtures were determined and compared to the values mea…
Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls
1995
Summary Methyl methacrylate was polymerized with tert-butyl lithium in the presence of triethylaluminum or triisobutylaluminium at -78~ in toluene. As indicated by GPC and MALDI-TOF mass spectrometry, the polymerization is accompanied by side reactions. The lower oligomers were fractionated by distillation and characterised by NMR, FT-IR, UV and electron impact (EI) mass spectrometry. All these data show that part of the polymer chains are carrying exactly one tert-butyl isoprenyl ketone unit. In order to avoid the formation of tert-butyl isoprenyl ketone a molar ratio of A1/Li > 2 is necessary.
Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls, 2. Kinetic investigations with methyl methacrylate in tol…
1995
The kinetics of the polymerization of methyl methacrylate initiated by lithium alkyls (tert-butyllithium or ethyl α-lithiobutyrate) was investigated in the presence of aluminium alkyls (triethylaluminium or triisobutylaluminium) in toluene at −78°C. The rate of polymerization decreases considerably once the living dimer is formed. This suggests that the aluminate end-group coordinates with the penultimate ester group of the polymer chain, thus decreasing reactivity. The results are at variance with an activated monomer mechanism.
Effect of bulkiness and lewis acidity of aluminium compounds on the anionic polymerization of methyl methacrylate in toluene
1996
The bulkiness and the Lewis acidity of added aluminium compounds strongly affect the polymerization of methyl methacrylate in toluene at −78°C. The polymerization strongly deviates from ‘ideal’ first-order kinetics, i.e. the first-order time-conversion plots are kinked at low monomer conversions. Additionally, for the more bulky and more Lewis-acid aluminium alkyls, the time-conversion plots show a further downward curvature. This curvature is not the result of a termination reaction because the polymers are free of side products like β-ketoesters or vinyl ketone units. The molecular weight distributions and tacticities of the resulting polymers are also affected. Dependent on the aluminium…
NMR and Quantum-Chemical Study on the Structure of Ester Enolate−Aluminum Alkyl Complexes as Models of the Active Center in the Anionic Polymerizatio…
1999
6Li and 13C NMR on ethyl α-lithioisobutyrate (EiBLi) and quantum-chemical (DFT) calculations on methyl α-lithioisobutyrate (MiBLi) were used to elucidate the structure of the active center in the anionic polymerization of methacrylates in the presence of triethylaluminum (AlEt3) in toluene. This study reveals ester enolate/aluminum alkyl complexes with different degrees of association, (MiBLi·AlEt3)n (n = 1, 2, 4), and different stoichiometries, MiBLi·xAlEt3 (x = 1, 2). In the presence of methyl pivalate (MPiv), which is taken as a model compound for the monomer and polymer, complexes such as (MiBLi·MPiv·AlEt3)n (n = 1, 2) are formed. These complexes can dissociate into MiBLi·2AlEt3 and MPi…
Living and Controlled Anionic Polymerization of Methacrylates and Acrylates in the Presence of Tetraalkylammonium Halide-Alkylaluminum Complexes in T…
1997
The size of both the cation and the anion of added NR4 X influences the rate of living polymerization of acrylates and methacrylates with alkylaluminum compounds. This controlled reaction, which occurs near to room temperature, provides unimodal polymers with narrow molecular-weight distributions. The complex shown to the right is suggested as a possible active species. R=Me, Et, nBu; R'=Me, Et; X=Cl, Br, I.
Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls, 1. 13C NMR studies of model compounds in toluene
1994
The bimetallic ate complex [(CH 3 ) 2 C=C(OEt)(O - AlR 3 )]Li + is regarded to be the model of the active centre of the polymerization of methyl methacrylate in the presence of aluminium alkyls. This complex is detectable by 13 C NMR up to 273 K. At ambient temperature irreversible decomposition takes place. Apart from the formation of the ate complex, excess aluminium chloride coordinates to the ester carbonyl groups of both the monomer and the polymer chain
Novel initiating systems for the living polymerization of acrylates and methacrylates
1998
The polymerization of methyl methacrylate with lithiated initiators in the presence of aluminium alkyls in toluene has living character but it deviates from conventional first-order kinetics and the polymers have fairly broad molecular weight distributions. This results from the formation and precipitation of a coordinative polymer network in which the lithium ions of the living chain ends are coordinated to the in-chain ester carbonyl groups. Thus, the network formation can be prevented by adding Lewis bases like methyl pivalate which coordinate to the living chain ends instead ofthe polymer. Alternatively, one can introduce tetraalkylammonium salts aiming at an exchange of the lithium ion…