0000000000213958
AUTHOR
Kamil Maciol
showing 6 related works from this author
Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends
2019
Highly efficient stoichiometric coupling of sterically hindered polystyryllithium (PS-Li) chain ends was achieved using tetra[3-(chloro-dimethylsilyl)propyl]silane (TCDMSPS) as the linking agent. Based on the disparate reactivities of isoprene (I, rI = 11.0) and styrene (S, rS = 0.049) in the anionic copolymerization in nonpolar media, poly(isoprene0.5-grad-styrene0.5) (P(I0.5-grad-S0.5)) tapered 4-arm star copolymers were synthesized in only two steps. The tapered 4-arm star copolymers (Mtargetedw = 40 to 160 kg mol−1) were synthesized with high star functionalities f (Mw,star/Mw,arm = 3.68–3.98), low dispersity (Đ = 1.06–1.15) and minimal residual precursor content (2–8 wt%), avoiding fra…
Copolymerization of Isoprene with p-Alkylstyrene Monomers: Disparate Reactivity Ratios and the Shape of the Gradient
2019
The statistical copolymerization of isoprene with p-ethyl- (p-ES), p-isopropyl- (p-iPS), and p-tert-butylstyrene (p-tBS) initiated by sec-butyllithium in cyclohexane was investigated with respect to kinetics, reactivity ratios, and formation of tapered block copolymers with pronounced monomer gradient. An efficient synthetic route to the monomers was developed on a multigram scale, relying on the precipitation of the side-product triphenylphosphine oxide at low temperature. The copolymerization kinetics and resulting molecular weight distributions were analyzed. The dispersity, Đ, of the copolymers depends on the p-alkyl substituent, the the degree of polymerization Pn and the comonomer mol…
The poly(propylene oxide-co-ethylene oxide) gradient is controlled by the polymerization method: determination of reactivity ratios by direct compari…
2019
An investigation of the highly relevant copolymerization of ethylene oxide (EO) and propylene oxide (PO) by in situ1H NMR spectroscopy shows striking differences in the copolymerization kinetics, depending on the polymerization method. Examination of the EO/PO copolymerization kinetics using iBu3Al for the monomer-activated anionic ring opening polymerization (AROP) confirmed a strong monomer gradient of the microstructure (rEO = 6.4, rPO = 0.16) in contrast to the known weak gradient in the conventional AROP (rEO = 2.8, rPO = 0.25). The first study via in situ1H-NMR kinetics of the copolymerization of PO and EO under heterogeneous double metal cyanide (DMC) catalysis, a method that produce…
Poly(ethylene glycol) with Multiple Aldehyde Functionalities Opens up a Rich and Versatile Post-Polymerization Chemistry
2019
Two novel epoxide monomers 3,3-dimethoxy-propanyl glycidyl ether (DMPGE) and 3,3-dimethoxy-2,2-dimethylpropanyl glycidyl ether (DDPGE) were developed for the introduction of multiple aldehyde functionalities into the poly(ethylene glycol) (PEG) backbone. The acetal protecting group for the aldehyde functionality is stable against the harsh, basic conditions of the anionic ring-opening polymerization. Both monomers could be homopolymerized as well as copolymerized randomly with ethylene oxide (EO) in a controlled fashion. Copolymers with molecular weights (Mn) in the range of 4500–20100 g/mol and low dispersity (Mw/Mn) between 1.06 and 1.14 were obtained. The polymers were characterized by s…
Ester Functional Epoxide Monomers for Random and Gradient Poly(ethylene glycol) Polyelectrolytes with Multiple Carboxylic Acid Moieties
2020
The tailormade ester functional epoxides, methyl 4,5-epoxypentenoate (MEP) and tbutyl 4,5-epoxypentenoate (tBEP), were synthesized in good overall yields (60–65%) in short reaction sequences. Both ...
Synthesis of linear polyglycerols with tailored degree of methylation by copolymerization and the effect on thermorheological behavior
2017
Abstract We introduce a two-step strategy for the synthesis of linear polyglycerols (linPG-OHx/OMey) with an adjustable degree of methylation ( y = D M 100 ). Ethoxy ethyl glycidyl ether (EEGE) and glycidyl methyl ether (GME) were copolymerized via the “activated monomer” polymerization technique, using tetraoctylammonium bromide (NOct4Br) as an initiator and triisobutylaluminum (i-Bu3Al) as a catalyst under mild conditions. Subsequent acidic cleavage of the acetal protective groups generates linear polyglycerols with different degree of methylation (DM) by varying the GME comonomer content between 10 and 91%. Size exclusion chromatography (SEC) evidenced good control over molecular weight …