Photochemical reactions of polymers bearing O‐acryloxyimino groups in the solid phase. Effects of main‐chain structure on the formation of pendent amino groups

Abstract

IntroductionIn a previous paper') we reported that pendent amino groups can be introduced by photolysis of pendent acryloxyimino (AOI) groups *) followed by hydrolysis, and that the pendent amino groups are effective in crosslinking of epoxides. In the course of the studies of the formation of pendent amino groups, described above, we noticed that the efficiency of their formation depends on the main chain structure (R in 3; see Scheme I ) , which shows the outline of the photoreactions of polymers bearing A01 groups.This paper describes the effect of main chain structure on the formation of amino groups.Experimental part 0-acryloyl acetophenone oxime (la) and 0-methacryloyl acetophenone oxime (1 b) were prepared by reaction of acetophenone oxime with acryloyl chloride and methacjloyl chloride, respectively, by a method similar to that described in the previous paper*). l a : m. p. 59 -60°C; 1 b: m. p. 46-47 "C. Styrene (2) was purified by the usual way.Copolymerization: Copolymers. poly(1 a-co-2) (3 a) and poly(1 b-co-2) (3 b), were prepared by solution polymerization in benzene under nitrogen at 60°C in the dark, using 0,2 wt.-Yo 2,2'azoisobutyronitrile (AIBN) as initiator. Molecular weights of the prepared polymers were measured by GPC. The contents of monomeric units of l a and 1 b in the copolymers 3a, b were determined by their elemental analyses. Composition and physical properties of the copolymers are shown in Tab. 1. Films were prepared from a polymer solution in benzene in a Petri dish. Benzophenone (BP) (10 wt.-To) was added as sensitizer to the polymer solution. The thickness of the films was about 30-40 pm.Photoreactions: A high pressure mercury lamp (Ushio UM102) was used as a light source. The applied wavelength was 366 nm (separated by the use of a Toshiba UV-DlB filter). The distance between films and lamp was 7 cm, and the films were irradiated at room temperature. The degree of decomposition of A01 groups was determined by following the change of the *) Strictly: Alkylideneiminooxycarbonyl groups. 0173-2803/88/$01 .oO 520 K.-H. Song, M. Tsunooka, M. Tanakaabsorbance of the carbonyl groups at 1760 cm-' in the IR spectra of the polymer films before and after irradiation. Samples for elemental analyses were prepared by precipitation of the irradiated copolymers from THF/CH30H solutions to remove the sensitizer and lowmolecular-weight compounds formed after irradiation. The alkylideneimino groups formed after irradiation easily change to amino groups by hydrolysis with water. The contents of double bonds were determined by comparing the ratio of the absorbance of double bonds (1 640 cm-' or 970 cm-I) to that of the monomeric units of styrene (1495 cm-I) as an internal standard with a working curve, prepared by the use of the model compounds 2-ethyl-1-hexene (1 640 cm-I) or 2-octene (970 cm-I), in polystyrene.The contents of amino groups in the irradiated polymers were determined by calculation based on the contents of undecomposed A01 groups and double bonds, determined by the IR spectra, assuming...

Photochemical reactions of quaternary ammonium dithiocarbamates as photobase generators and their use in the photoinitiated thermal crosslinking of poly(glycidyl methacrylate)

“…Still, resulting bases that are generated from PBGs do not have such unfavorable properties and may be used as crosslinkers of epoxy compounds and as catalysts for the imidization of poly(amic acid)4 and the surface modification of polymers 5, 6. Thus far, Co‐amine complexes,7 carbamates,8–12 O ‐acyloximes,5, 6, 13–16 O ‐carbamoyloximes,17–19 formamide,20 and onium salts21–23 are known as PBGs, and several reviews have been published 3, 24–27. Most articles on them, however, describe photoproduction of primary or secondary amines from them, and PBGs that generate tertiary amines are scarcely reported.…”

Effects of crosslinking by quinones on dyeing of irradiated films of copolymers bearing photobase generating groups

“…7,8 Since the irradiated (BQ) (Tokyo Kasei, Tokyo, Japan) were recrystalarea became hydrophilic by the conversion of the lized from hexane. C.I.…”

“…the degree of dyeing and the hydrophilicity of the AAPO was prepared as described in a previous films by the transformation of AOI groups into article. 7 ammonio groups or the coexistence of comonomCopolymers were prepared by radical polymerers.…”

<title>Controlling actin motility on microfabricated linear channels</title>

“…6,7 This polymer was chosen primarily because it was susceptible to laser ablation at 337 nm and because it has proven an appropriate substrate for protein attachment 8 .…”