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

Abstract

Abstract-The copolymerization of a methylated-¯-cyclodextrin (m-¯-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 0 -azobis-(N,N 0 -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 lms led to crosslinking and thus to insolubility.

Towards Green Routes for Polymer Synthesis: Polymerization of Cyclodextrin Host‐Guest Complexed Diethyl Fumarate and Copolymerization with Complexed Styrene in Homogenous Aqueous Solution

“…[1,2] For these reasons our group is focused on the use of cyclodextrins in polymer chemistry, a field that has recently received a great deal of industrial attention. [3][4][5][6][7][8][9][10][11][12][13][14] Cyclodextrins (CD) are cyclic oligomers of amylose consisting of six, seven or eight glucose units (a-, b-, g-cyclodextrin, respectively). The cyclodextrin molecules resemble a hollow truncated cone, with primary hydroxy groups at the narrower end and secondary hydroxy groups at the broader end.…”

“…This methylated b-CD, which is also used in consumer products, is synthesized industrially on a large scale and is therefore readily available. [15] We have recently investigated the free-radical [3][4][5][6][7][8][9][10][11][12][13][14] and controlled-''living'' [16] polymerizations of various CDcomplexed vinyl derivatives and also some other types of monomers under surfactant-free conditions. For example, the synthesis of conducting polymers under oxidative conditions [11,17] from aqueous media was described.…”

Cyclodextrins in Polymer Modification: Diels–Alder Addition of Cyclopentadiene/Methylated‐β‐Cyclodextrin Complex on Unsaturated Polyester and Formation of a New Type of Polypseudorotaxane

“…For example, in our group, the radical polymerization in aqueous solution of some hydrophobic monomers that were solubilized by complexation with methylated-b-CD was investigated and it was shown that higher monomer conversions were obtained as compared with the radical polymerization of uncomplexed monomers. [4][5][6][7][8] This concept has been also applied, for example, to the free-radical copolymerization of a water-soluble monomer (sodium 4-(acrylamido)-phenyldiazosulfonate) [9] or N-isopropylacrylamide) [10] with styrene, in aqueous solution using CD as solubilizer. Recently, the cross-linking reaction in a homogeneous aqueous medium of a watersoluble unsaturated polyester by use of a styrene/methylated-b-CD complex was reported.…”

Cyclodextrins in polymer synthesis: Steric retardation of the free-radical polymerization in aqueous medium of 4-vinylbenzaldehyde/methylated -cyclodextrin complex

“…In almost all examples studied before, water insoluble polymers were obtained in a high yield. [8][9][10][11][12][13][14][15][16][17][18] It was demonstrated that, generally during the propagation steps, the CD-host slips off from the monomer and the resulting polymer precipitates. Because of the high water solubility of the methylated CDs this component remains in solution.…”

“…One of several potential applications of this method is the possibility to copolymerize water soluble and completely water insoluble monomers via formation of CD-complexes. [18] We normally found that the polymerization rate of the complexed hydrophobic monomers is increased by the CD-host because of a drastic increase of concentration of the molecularly dispersed monomer complexes in the water phase.…”