Synthesis of α,ω-Bis Epoxy Oligo (1‘H,1‘H,2‘H,2‘H-Perfluoroalkyl Siloxane)s and Properties of Their Photo-Acid Cross-Linked Films

Abstract

3′-trifluoropropyl)cyclotrisiloxane (II), and hexamethylcyclotrisiloxane (D 3 ) (III), respectively, in 1,1,3,3-tetramethyldisiloxane (TMDS). Solutions of a UV-sensitive diaryliodonium salt (0.5 wt %) and oligomers VII-IX were cast as uniform layers onto clean glass microscope slides and steel coupons. UV irradiation of these liquid layers rapidly converted them to cross-linked films (X-XII). Thermal stability of these films was determined by thermogravimetric analysis (TGA). Glass transition temperatures (T g s) were measured by dynamic mechanical thermal analysis (DMTA). Static contact angles of distilled water on the air-film interfaces of X-XII have been determined with a goniometer. Dynamic contact angle (DCA) measurements have also been carried out on free-standing films. Corrosion protection of steel coupons by X-XII was evaluated by electrochemical impedance spectroscopy (EIS) during exposure to 0.5 N NaCl. Antifoul and foul-release properties of X-XII were studied by settlement and removal tests with the barnacle Balanus amphitrite and with spores and sporelings of the green alga Enteromorpha.

Synthesis of 1,9-bis[glycidyloxypropyl]penta(1′H,1′H,2′H,2′H-perfluoroalkylmethylsiloxane)s and copolymerization with piperazine

“…Our synthetic sequence begins with the known acidcatalyzed ring-opening of hexamethylcyclotrisiloxane (D 3 ), 1,3,5-tris(3 0 ,3 0 ,3 0 -trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane, and 1,3,5-tris(1 0 H,1 0 H,2 0 H,2 0 H-perfluorooctyl)-1,3,5-trimethylcyclotrisiloxane in tetramethyldisiloxane (TMDS) to yield I -III, respectively [4,25,26]. This was followed by Pt-catalyzed (Karstedt) hydrosilyation of allyl glycidyl ether and I -III to yield 1,9-bis[glycidyloxypropyl]decamethylpentasiloxane (IV), 1,9-bis[glycidyloxypropyl]-3,5,7-tris(3 0 ,3 0 ,3 0 -trifluoropropyl)heptamethylpentasiloxane (V), and 1,9-bis[glycidyloxypropyl]-3,5,7-tris(1 0 H,1 0 H,2 0 H,2 0 H-perfluorooctyl)heptamethylpentasiloxane (VI), respectively.…”

“…3.6.4. 1,9-Dihydrido-3,5,7-tris(3 0 ,3 0 ,3 0 -trifluoropropyl)-heptamethylpentasiloxane (II) II was prepared by the triflic acid catalyzed ring opening of 1,3,5-trimethyl-1,3,5-tris(3 0 ,3 0 ,3 0 -trifluoropropyl)cyclotrisiloxane in TMDS [26]. 13 V was prepared from II (10 g, 16.6 mmol) and allyl glycidyl ether (6.6 g, 57.9 mmol) as above.…”

Preparation and physical properties of films prepared by crosslinking 1,9‐bis(glycidyloxypropyl)pentasiloxanes with α,ω‐bis(3‐aminopropyl)polydimethylsiloxane and their settlement and release properties

“…23 1,9-Dihydrido-3,5,7-tris(3Ј,3Ј,3Ј-trifluoropropyl)heptamethylpentasiloxane (IV) was prepared by the triflic acid-catalyzed ring opening of D 3 F in TMDS. 16 1,9-Bis[glycidyloxypropyl]decamethylpentasiloxane (I) 18 was obtained by Pt-catalyzed hydrosilylation of III and allyl glycidyl ether in the presence of a small amount of triethylamine. 1 .…”

“…We have previously utilized both photoacid-catalyzed ring opening polymerization of ␣,-bis(epoxy)oligosiloxanes 16 and crosslinking of ␣,-bis(epoxy)oligosiloxanes with ␣,-diamines to prepare siloxane films. 17 Herein, we report our recent work on the preparation and properties of siloxane films produced by this latter approach.…”

Crosslinking of 1,9‐bis[glycidyloxypropyl]penta‐ (1′H,1′H,2′H,2′H‐perfluoroalkylmethylsiloxane)s with α,ω‐diaminoalkanes: The cure behavior and film properties

“…40 1,9-Dihydrido-3,5,7-tris(3Ј,3Ј,3Ј-trifluoropropyl)-heptamethylpentasiloxane was prepared by the triflic acid catalyzed ring opening of 1,3,5-trimethyl-1,3,5-tris-(3Ј,3Ј,3Ј-trifluoropropyl)cyclotrisiloxane in TMDS. 41 1,9-Dihydrido-3,5,7-tris(1ЈH,1ЈH,2ЈH,2ЈH-perfluorooctyl)heptamethylpentasiloxane was prepared by the triflic acid catalyzed ring opening of 1,3,5-trimethyl-1,3,5-tris(1ЈH,1HЈ,2HЈ,2HЈ-perfluorooctyl)-cyclotrisiloxane in TMDS.…”