Method for Hydroxylation and Esterification of Interior Sites of Polyolefinic Films

Abstract

A method is described to functionalize specifically the interior portions of polyolefinic films with chromophoric/lumophoric groups. In the first step, a film doped with dibenzothiophene 5-oxide (DBTO) is irradiated (λ > 300 nm) to produce O(3P) atoms that oxidize nearby C−H bonds of the polymer. Covalent attachment of acid chlorides (containing chromophoric/lumophoric groups) to the hydroxy bonds (via ester linkages) provides films that retain their absorption and luminescence in water or air for long periods. The esterified films have been characterized using UV/vis absorption spectroscopy and static and dynamic fluorescence techniques. Fluorescence from native or modified and then esterified films in 1.0 M methanolic 2-(dimethylamino)ethanol, a surface quencher, indicates that the vast majority of the chromophores/lumophores are located inside the films. Selective modification of the film surfaces by an analogous method was not efficient. However, a very low concentration of hydroxy groups is present throughout the native films. Their esterification reduces the fluorescence contrast between undoped/irradiated and DBTO-doped/irradiated parts of a film.

Synthesis and photophysical properties of a poly(methyl methacrylate) polymer with carbazolyl side groups

“…[1][2][3] One approach to this end involves copolymerizations in which a small mole fraction of a second monomer is used to introduce a new property that is absent in the homopolymer.…”

Photochemical and Photophysical Studies of and in Bulk Polymers

“…These methods include grafting, surface blending, copolymerization with functionalized monomers, and chemical modifi cation of preformed polymers. 64 Whereas doped host -guest systems report only an average environment due to the mobility of the guest molecules and their translocation among sites, covalent attachment of reporter groups ensures that they sense a specifi c environment over long periods. As mentioned in the section on " Polymers to Determine the Kinetic Energy of High -Energy Particles, " polycyclic aromatic hydrocarbons, such as pyrene, can be covalently attached to the chains of PE fi lms when exposed to UV or ionizing radiation.…”

“…Azobenzene moieties can be attached to chains of PE24 fi lms by esterifi cation of 4 -(phenylazo)benzoyl chloride at interior sites that have been modifi ed to contain a hydroxyl group (Scheme 11.25 ). 64 In this method, PE chains are derivatized by irradiating ( λ > 300 nm) fi lms doped with dibenzothiophene -5 -oxide ( DBTO ). Ground -state oxygen atoms ( 3 O P ) are formed, and they insert into nearby C -H bonds of the polymer.…”

The effect of dye-polymer interactions on the kinetics of the isomerization of 4-dimethylaminoazobenzene and mercury dithizonate

“…1,2,[5][6][7][8][9][10][11][12][13] There are two general methodologies to incorporate dyes into polymeric materials: one produces a solid-state solution where the dye is a guest in a polymer host. 15,16 Usually, for technological purposes this is a less employed methodology since very low concentrations of the dye can be incorporated into the material. 1 The second methodology uses chemical attachment of the dye in the polymer chain either by chemical modification of the pre- formed polymer or by polymerization reactions using a monomer labeled with the azo-dye.…”

“…1 The second methodology uses chemical attachment of the dye in the polymer chain either by chemical modification of the pre- formed polymer or by polymerization reactions using a monomer labeled with the azo-dye. 1,9,10,[13][14][15][16] For both types of materials films can be prepared by casting, spin coating, self-assembly or Langmuir-Blodgett monolayer deposition. 1,9,10,12,13 Moreover, the alignment of the azodyes in polymer matrices should be induced by several types of methodologies including poling, 17 deposition by self-assembling 1,6 or by Langmuir-Blodgett, 1,6,13 by macroscopic stretching 18,19 or by photoinduction.…”