Synthesis and properties of ultraviolet‐curable resins via a thio–ene (thiol and allyl) addition reaction

Abstract

Benzophenone diallyl ester (I) and benzophenone tetraallyl ester (II) based on 3,3Ј,4,4Ј-benzophenone tetracarboxylic dianhydride (BTDA) with allyl alcohol (AAL) were synthesized. Glycidyl methacrylate (GMA) was added to I and formed diallyl diglycidyl methacrylate (III). These BTDA-based allyl-containing compounds (II and III) reacted with 1,4-butanedithiol and 4,4Ј-thiol-bisbenzenethiol to produce ultraviolet (UV)-curable resins via a thioene addition reaction. The ester (III) was cured easily when exposed to UV or sunlight radiation without any photoinitiator and only required a lower thermal curing temperature. The diallyl ester (I) and tetraallyl ester (II) required the addition of benzophenone to increase the photosensitivity, which reduced the exposition time. These resins used AAL as a monomer to successfully reduce the oxygen effect of the photocuring. The resin BTDA-2Allyl-2GMA had a glasstransition temperature of 166°C and a hardness of 6H. The resultant UV-curable coatings had excellent hardness, chemical resistance, adhesion, and tensile properties.

Synthesis of a new photoreactive gelatin with BTDA and HEMA derivatives

“…This reaction scheme relied on the formation of peptide bond between the amino groups of glycine and the carboxylic acid groups of BTHE. The BTHE used in this study has been previously synthesized in our laboratory 14. BTDA reacted with HEMA in ring‐opening reaction.…”

“…All the materials utilized in this synthesis are nontoxic to human according to the published reports. 6,7,12,14 Many related papers were focused in this field to develop suitable bioglues for the substituents of suture, but mostly failed on achieving the adequate curing time and enough tensile strength. For confirmation of the reaction of GE-BTHE, a model reaction with simple amino-acid (Glycine) was used to forecast the possibility of reaction.…”

“…Once the BTDA solution was cooled to 30°C, 1.30 g (0.01 mol) of HEMA was added and the mixture was stirred for 15 min in an opaque device. By the ring‐opening reaction, a BTDA derivative, dimethacrylate dicarboxylic acid monomer (BTHE), was generated 14. DCC (0.001 mol) and DMAP (0.0001 mol) in 1 mL of methanol was then added to the transparent BTHE solution.…”

“…The making of photocurable gelatin is not a new idea, but there is still room for improvement in preparation. In this article, the synthesis of a novel gelatin derivative using photoreactive agent dimethacrylate dicarboxylic acid of BTDA1 and HEMA14 was reported, where gelatin was grafted with BTDA photocurable monomers bonded with HEMA hydrogel for the creation of a photocurable, bioadhering and water swellable multi‐functional gel.…”

Photopolymerization Reactions: On the Way to a Green and Sustainable Chemistry

“…For example, the development of sunlight photosensitive formulations (see, e.g., [77][78][79][80][81][82][83][84][85] and references therein; see also the patent literature aiming at industrial applications) for the drying of paints for crack-bridging applications, anti-soiling properties, the manufacture of interpenetrating polymer networks (IPN) usable as protective coatings and glues, the fabrication of glass fiber reinforced composites, hard and rigidified four layer glass cloth laminate, clearcoats and polymer-clay composites has been realized in the past, but these systems, except some of them (e.g., those described in [79,80,84]) suffer from oxygen inhibition and a relatively low photosensitivity.…”