Cyclodextrins in polymer synthesis: free radical polymerization of cyclodextrin complexes with oxazoline‐functionalized vinyl monomers as guest molecules in aqueous medium

The synthesis of five new oxazoline functionalized vinyl monomers N‐[4‐(4′,5′‐dihydrooxazol‐2‐yl)phenyl]acrylamide ( 3 a ), N‐[4‐(4′,5′‐dihydrooxazol‐2‐yl)phenyl]‐2‐methylacrylamide ( 3 b ), N‐{10‐[4‐(4′,5′‐dihydrooxazol‐2‐yl)phenylcarbamoyl]decyl}‐2‐acrylamide ( 5 a ), N‐{10‐[4‐(4′,5′‐dihydrooxazol‐2‐yl)phenylcarbamoyl]decyl}‐2‐methylacrylamide ( 5 b ) and N‐[4‐(4′,5′‐dihydrooxazol‐2‐yl)‐phenyl]‐4‐vinylbenzamide ( 7 ) is described. With an equimolar amount of 2,6‐dimethyl‐β‐cyclodextrin (DMCD) these monomers formed hydrophilic inclusion complexes 3 a,b‐DMCD , 5 a,b‐DMCD and 7‐DMCD . These complexes were polymerized radically in an aqueous medium. Resulting polymers P‐(3 a, b) , P‐(5 a, b) and P‐(7) precipitated during the polymerization due to unthreading of the cyclodextrin from the growing polymer chain. The remaining oxazoline moiety offers possibilities of further modification of the polymers, e. g. grafting in a cationic ring opening polymerization with commercially available alkyloxazolines.     

Association thickener by host guest interaction of a β-cyclodextrin polymer and a polymer with hydrophobic side-groups

A host polymer with pending β-cyclodextrin side-groups and a guest polymer with pending hydrophobic 4-tert-butylanilide side groups were synthesized by polymeranalogous reactions starting from poly[(maleic anhydride)-alt-(isobutene)] (M̄_w = 60000). The inclusions of both polymers with complementary monomeric guests and hosts are proven by microcalorimetry. The interaction of the host polymer and the guest polymer in aqueous solution is accompanied by a tremendous increase in viscosity.     

Solvent effects on the free‐radical copolymerization of styrene with butyl acrylate. I. Monomer reactivity ratios

The free‐radical copolymerization of styrene with butyl acrylate was carried out in benzene and benzonitrile at 50°C. Differences between the apparent reactivity ratios determined in this work and those previously reported in bulk indicated noticeable solvent effects. This is explained by a qualitative bootstrap effect. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 60–67, 2000     

Octadecyl maleamic acid salt as a microreactor for its copolymerization reaction with butyl acrylate in aqueous medium

The hydrogelator, octadecyl maleamic acid salt (ODMAS), has been shown to perform as a microreactor in copolymerization reaction with butyl acrylate in aqueous medium thereby providing functionalized latex. The evidence for occurrence of controlled polymerization reaction inside the microreactor is drawn from the composition and the polydispersity index of the copolymers. The copolymers generated under microreactor conditions or in other words, from emulsion phase provided by the hydrogelator exhibit significant incorporation of ODMAS with narrow polydispersity index. For example, a copolymer with ODMAS as high as 0.62 m and polydispersity index at 1.39 could be achieved. On the contrary, the solution copolymerization reactions in THF resulted in low yield of polymers with molecular weight at 10(3) order and polydispersity index in range of 2.53-2.91. The particle size distribution of the latexes remains almost invariant at 74 +/- 4 nm, over the concentration range of 0.12-0.62m with standard deviation (sigma) of 0.12-0.22. The surface area/molecule of ODMAS on the latex particle has been estimated to be 0.21 nm(2)/molecule. The polymerized latexes exhibit zeta potential at 64 +/- 3 mV and surface tension in range of 42.8-47.9 mN m(-)(1) respectively. This is indicative of coverage of latex with ODMAS.     

Cyclodextrins in polymer synthesis: free radical polymerisation of cyclodextrin complexes of cyclohexyl and phenyl methacrylate in aqueous medium

The polymerisation mechanism of 2,6-dimethyl-β-cyclodextrin (Me₂-β-CD) complexes of phenyl methacrylate ( 1 ) and cyclohexyl methacrylate ( 2 ) is described. The polymerisation of the complexes 1 a and 2a was carried out in water with potassium peroxodisulfate/potassium hydrogensulfite as initiator. The unthreading of the Me₂-β-CD during the polymerisation led to water-insoluble poly(phenyl methacrylate) ( 1b ) and poly(cyclohexyl methacrylate) ( 2b ). By comparison, analogously prepared polymers from uncomplexed monomers 1 and 2 in homogeneous organic solvent (THF) with AIBN as radical initiator showed significantly lower viscosities and were obtained in lower yields in both cases.     

Radical polymerization and copolymerization of methyl α-(2-carbomethoxyethyl)acrylate,a dimer of methyl acrylate,as a polymerizable α-substituted acrylate

Polymerization and copolymerization of methyl α-(2-carbomethoxyethyl)acrylate (MMEA), which is known as a dimer of methyl acrylate, were studied in relation to steric hindrance-assisted polymerization. The propagating polymer radical from MMEA was detected as a five-line spectrum and quantified by ESR spectroscopy during the bulk polymerization at 40–80°C. The absolute rate constants of propagation and termination (κ_p and κ_t) for MMEA at 60°C (κ_p = 19 L/mol s and κ_t = 5.1 × 10⁵ L/mol s) were evaluated using the concentration of the propagating radical at the steady state. The balance of the propagation and termination rates allows polymer formation from MMEA. The polymerization rate of MMEA at 60°C was less than that of MMA by a factor of about 4 at a constant monomer concentration. Although no influence of ceiling temperature was observed at a temperature ranging from 40 to 70°C, addition-fragmentation in competition with propagation reduced the molecular weight of the polymer. The content of the unsaturated end group was estimated to be 0.1% at 60°C to the total amount of the monomer units consisting of the main chain. MMEA exhibited reactivities almost similar to those of MMA toward polymer radicals. It is concluded that MMEA is one of the polymerizable acrylates bearing a substituted alkyl group as an α-substituent. Characterization of poly(MMEA) was also carried out. © 1996 John Wiley & Sons, Inc.     

Application of poly(N-isopropylacrylamide) with pendent β-cyclodextrin to separation of a guest substance in an aqueous solution

Poly(N-isopropylacrylamide) with pendent β-cyclodextrin (PNI-PAAm-CD) was prepared by copolymerization of acryloyl-β-CD and NIPAAm. During the temperature-induced phase separation of an aqueous solution of PNIPAAm-CD, Toluidine Blue dye in the solution was separated into the precipitate of PNIPAAm-CD by way of inclusion complex formation.     

ESR single-crystal study of radical and radical-pair formation in some γ-irradiated vinyl monomers

Single crystals of methyl methacrylate (MMA), methyl acrylate (MA), and acrolein (A) have been prepared by a low-temperature technique. After irradiation with γ-rays at 77°K the paramagnetic species were identified by ESR spectroscopy. MMA gave a seven-line single spectrum from radicals formed by hydrogen addition. The hyperfine coupling constants are slightly anisotropic with a mean value of 22 G. Radical pairs were observed as ΔM_s = 1 and ΔM_s = 2 transitions; the hyperfine coupling was 11 G. From the strongly anisotropic dipolar interaction, upper limits for the distances between the pair components were calculated to be 5.45 Å and 6.3 Å. MA gave a five-line main spectrum with the same hyperfine coupling values and two radical pairs, one with a distance 5.9 Å between the components. In a there was also a strongly anisotropic interaction. The hyperfine coupling of the ΔM_s = 2 transition was 9.8 G. The number of radical pairs compared to the total number of radicals increases only slightly with the radiation dose. This makes it likely that pair formation occurs in the spurs and blobs formed by the γ-radiation. At an increased temperature the radical pairs disappeared; the spectrum of MMA changed to that characteristic of propagating polymer radicals.     

Controllability of radical copolymerization of maleimide and ethyl α‐(n‐propyl)acrylate using 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy) ethane as initiator

The radical copolymerization of maleimide (MI) and ethyl α‐propylacrylate was performed using 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy) ethane (TPSE) as initiator. The whole copolymerization process might be divided into two stages: in the first stage, the copolymerization was carried out on the common radical mechanism, the molecular weight of the copolymer increased rapidly in much lower conversion (< 85%), and did not depend on the polymerization time and conversion; in the second stage, molecular weight of the copolymer increased linearly with the conversion and the polymerization time. It was found, however, when the conversion was higher than a certain value, for example, more than 36%, the molecular weight of the copolymer was nearly unchangeable with the polymerization time and the molecular weight distribution was widened. The effect of reaction conditions on copolymerization was discussed and the reactivity ratios were calculated by the Kelen–Tudos method, the values were r_MI = 0.13 ± 0.03, r_EPA = 0.58 ± 0.06 for TPSE system and r_MI = 0.12 ± 0.03, r_EPA = 0.52 ± 0.06 for AIBN system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2872–2878, 2000     

Cyclodextrins as chiral stationary phases in capillary gas chromatography. Part VI: Octakis (2,3,6-tri-O-pentyl)-γ-cyclodextrin

Perpentylated γ-cyclodextrin is a very hydrophobic liquid which exhibits enantioselectivity toward a number of non-polar chiral substrates including the saturated hydrocarbons cis- and trans-pinane, β-chiral olefins, iron(O) tricarbonyl complexes of prochiral olefins and 3,3,8,8-tetramethyl-trans-cyclooctene, a compound with planar chirality.     

Cyclodextrins as chiral stationary phases in capillary gas chromatography. Part V: Octakis(3-O-butyryl-2,6-di-O-pentyl)-γ-cyclodextrin

γ-Cyclodextrin with 3-O-butyryl and 2,6-di-O-pentyl residues is a very versatile chiral stationary phase for enantiomer separation. Most of the common and many uncommon amino acids can be separated as well as α- and β-hydroxy acids, chiral alcohols, diols, triols, ketones, bicyclic, and tricyclic acetals, amines, alkyl halides, lactones, and functionalized cyclopropane derivatives.     

Determination of absolute rate constants for free radical polymerization of ethyl α-fluoroacrylate and characterization of the polymer

The absolute rate constants for propagation (k_p) and for termination (k_t) of ethyl α-fluoroacrylate (EFA) were determined by means of the rotating sector method; k_p = 1120 and k_t = 4.8 × 10⁸ L/mol.s at 30°C. The monomer reactivity ratios for the copolymerizations with various monomers were obtained. By combining the k_p values for EFA from the present study and those for common monomers with the monomer reactivity ratios, the absolute values of the rate constants for cross-propagations were also evaluated. Reactivities of EFA and poly(EFA) radical, being compared with those of methyl acrylate and its polymer radical, were found to be little affected by the α-fluoro substitution. Poly(EFA) prepared with the radical initiator was characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Although the glass transition temperature obtained by DSC for poly(EFA) resembled that of poly(ethyl α-chloroacrylate), its TGA thermogram showed fast chain de polymerization to EFA that was distinct from complicated degradation of poly(ethyl α-chloroacrylate).     

Host/guest complex of β-cyclodextrin/5-thia pentacene-14-one for photoinitiated polymerization of acrylamide in water

β-Cyclodextrin (β-CD) was used to complex the photoinitiator, 5-thia pentacene-14-one (TX-A), yielding a water-soluble host/guest complex. IR, UV–Vis and fluorescence spectroscopy were employed to characterize complexed β-CD/TX-A. Photoinitiated polymerization of acrylamide in water was achieved with β-CD/TX-A in the presence of N-methyldiethanolamine (MDEA). Excellent polymerization yields were observed in air saturated solutions when MDEA was added.