Cyclodextrins in Polymer Synthesis:  Free-Radical Polymerization of Methylated β-Cyclodextrin Complexes of Methyl Methacrylate and Styrene Controlled by N-Acetyl-l-cysteine as a Chain-Transfer Agent in Aqueous Medium

Cyclodextrins in polymer chemistry: Influence of methylated β-cyclodextrin as host on the free radical copolymerization reactivity ratios of isobornyl acrylate and butyl acrylate as guest monomers in aqueous medium

Methylated β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers isobornyl acrylate (1) and butyl acrylate (2) yielding the water-soluble host/guest complexes isobornyl acrylate/me-β-CD (1a) and butyl acrylate/me-β-CD (2a). The included monomers were copolymerized in water by free-radical mechanism and the kinetics were studied. In order to evaluate these results, the corresponding uncomplexed monomers 1 and 2 were also copolymerized in organic solution. The reactivity ratios of 1a and 2a (r1a = 0.3, r2a = 1.7) differ significantly from the reactivity ratios of the corresponding uncomplexed acrylates 1 and 2 in organic solution (r1 = 1.3, r2 = 1.0). In addition, we found tha…

Cyclodextrins in Polymer Synthesis:  Influence of Acrylate Side Groups on the Initial Rate of Radical Polymerization of Various Acrylate/Methylated β-cyclodextrin Complexes in Water

Methylated β-cyclodextrin was used to complex the hydrophobic monomers n-propyl acrylate (1), n-butyl acrylate (2), n-pentyl acrylate (3), n-hexyl acrylate (4), and cyclohexyl acrylate (5) respectively yielding the corresponding water-soluble host/guest-complexes 1a−5a. The complexes were polymerized in water by free radical mechanism and the initial polymerization rates (v0) determined. We found that v0 increases as follows:  1a (12.5), 2a (27.5), 3a (44.2), 5a (49.4), 4a (75.8 × 10-6 mol·L-1·s-1). To investigate the influence of the hydrophobic character of the guest monomers on the reaction rate, the water solubilities of the uncomplexed monomers 1−5 were determined by HPLC measurements.…

Cyclodextrins in polymer synthesis: photocrosslinkable films via free radical copolymerization of methylated β-cyclodextrin-complexed styrene with sodium 4-(acrylamido)-phenyldiazosulfonate in aqueous medium

The copolymerization of a methylated-β-cyclodextrin (m-β-CD) 1:1 host-guest compound of styrene (1a) with various molar ratios of sodium 4-(acrylamido)-phenyldiazosulfonate (2) is described. The copolymerization of complex 1a with 2 was carried out in water with 2,2′-azobis(N,N′-dimethyleneisobutyramidine)-dihydrochloride as the free radical initiator at 40°C. Depending on the amount of 2 incorporated in the copolymer, water- or DMF-soluble copolymers of high molar mass were obtained. Irradiation of the copolymers with UV light in solution resulted in rapid decomposition of the azo chromophore, and irradiation of the polymers as films led to crosslinking and thus to insolubility.

Cyclodextrins in polymer synthesis: Influence of methylated β-cyclodextrin as host on the free radical copolymerization reactivity ratios of hydrophobic acrylates as guest monomers in aqueous medium

Methylated (β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers n-butyl acrylate (1), n-hexyl acrylate (2) and cyclohexyl acrylate (3) yielding the corresponding water soluble host/guest complexes 1a–3a. The complexes were copolymerized in water by free radical mechanism and the reactivity ratios were determined by measuring the monomer consumption by HPLC. The following reactivity ratios were found: copolymerization of 1a and 2a: r1= 1.01 ± 0.01; r2= 1.04 ± 0.01; copolymerization of 3a and 2a: r1= 0.74; r2= 1.28; copolymerization of 3a and 1a: r1= 0.75 ± 0.04; r2= 1.13 ± 0.01. In contrast to that, the copolymerization of the uncomplexed monomers 1–3 in organic medium (DMF…

Effect of weathering on physical properties of clearcoats

Aim of the investigations was to explore the weatherability performance of selected polymer films. The results were correlated with each other, so that measurable changes can be attributed to chemical and/or physical effects. Therefore, polyols with different aromatic content were produced. The resins were crosslinked with melamine-formaldehyde resin (1K system) and polyisocyanurate (2K system), respectively. The analyses resulted after each 100 h accelerated weathering in a period of total 1000 h. Chemical degradation processes were analysed by means of FT-IR spectroscopy. For the physical investigations were used: dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC),…

Cyclodextrins in polymer synthesis: Free radical polymerization of methylated β-cyclodextrin complexes of methyl methacrylate and styrene, controlled by dodecanethiol as the chain-transfer agent in aqueous medium

Methylated β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers methyl methacrylate (1) or styrene (2) yielding the water-soluble 1 : 1-host/guest complexes methyl methacrylate/me-β-CD (1 a) and styrene/me-β-CD (2 a), respectively. In addition, the hydrophobic chain-transfer agent dodecanethiol (3) was complexed by two equivalents of me-β-CD yielding the water-soluble dodecanethiol/me-β-CD (3 a). The included monomers were polymerized in water by a free-radical mechanism in the presence of 3 a as the chain-transfer agent. The chain-transfer constants were determined. In order to evaluate these results, the chain-transfer constants of 3 were also determined in the case of th…

Cyclodextrins in Polymer Synthesis:  Free Radical Copolymerization of Methylated β-Cyclodextrin Complexes of Hydrophobic Monomers with N-Isopropylacrylamide in Aqueous Medium

Methylated β-cyclodextrin (me-β-CD) was used to form water-soluble host/guest complexes with the hydrophobic monomers n-butyl methacrylate (1), cyclohexyl methacrylate (2), isobornyl acrylate (3), isobornyl methacrylate (4), and styrene (5), respectively. The free-radical copolymerizations of the water-soluble N-isopropylacrylamide (NIPAAm) with these complexed monomers were carried out in water at different molar ratios.