Study of photopolymers. XXX. Syntheses of new di(meth) acrylate oligomers by addition reactions of epoxy compounds with active esters

Abstract

SynopsisSome dimethacrylate oligomers were synthesized by new addition reactions of 2,2-(4-hydroxy-pheny1)propane diglycidyl ether (BPGE) or glycidyl methacrylate (GMA) with phenyl methacrylates such as phenyl methacrylate (PMA), 4-nitrophenyl methacrylate (NPMA), 2,4-dichlorophenyl methacrylate (DCPMA), 4-methoxyphenyl methacrylate (MPMA), and (4-cinnamoy-1oxy)phenyl methacrylate (CIPMA) using tetrabutylammonium bromide as a catalyst a t 120°C. The other new dimethacrylate or diacrylate oligomers were also prepared by the addition reactions of GMA or glycidyl acrylate with active esters such as di(S-pheny1)thioisophthalate (PTIP), di(4-nitropheny1)isophthalate (NPIP), di(4-nitropheny1)adipate (NPAD), and di(4-nitropheny1)sebacate (NPSB) under similar reaction conditions. Furthermore, the rates of photochemical reaction of the obtained dimethacrylate oligomers were measured with 3 mol % of various photosensitizers such as benzoin Iso-propyl ether (BIPE), 2-ethylanthraquinone (EAQ), and benzophenone (BP). The rate of photochemical reaction of BPGE-DCPMA oligomer was higher than those of BPGE-PMA, BPGE-NPMA, and BPGE-MPMA oligomers using BIPE as a photosensitizer. However, the photochemical reactivity of the unsensitized BPGE-CIPMA was almost the same as that of the sensitized BPGE-DCPMA. On the other hand, when EAQ was used as a photosensitizer, GMA-PTIP oligomer showed much higher reactivity than GMA-NPAD, GMA-NPSB, and GMA-NPIP oligomers. Also it was shown that the activity of EAQ as a sensitizer was higher than BIPE and BP in the photochemical reaction of BPGE-DCPMA oligomer.

The Effect of Diglyme on the Kinetics of Chromium(III) Ethanoate-Catalyzed Reactions of Carboxylic Acids with Epichlorohydrin

“…Products of addition of carboxylic acids to epichlohydrin are raw materials in the synthesis of glycidyl esters then used as epoxy resins themselves or as reactive solvents for the bisphenol A or novolac-based epoxy resins. , Glycidyl (meth)acrylate readily polymerizes or copolymerizes, and it is often used as a modifier of physical or chemical properties of engineering or commodity polymers. They are also used in manufacturing of reactive polymers. − Adducts of unsaturated carboxylic acid to commercial epoxy resins, the so-called vinyl-ester resins, exhibit an enhanced chemical resistance when cured in the same way as the less chemically stable classical unsaturated polyester resins. − Hence, the adducts are used for manufacturing laminates or other products reinforced with glass fibres…”

Synthesis and Polymerization of Epoxy Methacrylates, 2. Acylated Epoxy Methacrylates and their Copolymers

“…[8] BisGMA acylated with a phenylsubstituted aliphatic acid was of considerably lower viscosity than pure BisGMA and resulted in composites of comparable polymerization shrinkage and E-modulus like composites from pure BisGMA. [8] Nishikubo et al [11] used two different transesterification reactions as single step reactions to synthesize modified epoxy methacrylate monomers from i) phenyl methacrylates and the diglycidyl ether of bisphenol A (DGEBA) ii) glycidyl methacrylate and diesters of bisphenol A where the hydroxyl groups were etherified (i) and esterified (ii), respectively.…”

Synthesis and characterization of photosensitive methacrylates to give heat-resistant polymers

“…Among them, the polymers having acryloyloxy group (acrylate-type photopolymer [1][2][3][4][5][6][7][8]) surpassed the others in terms of the extent of utilizing fields and consumption, because of their advantages to form transparent, flexible, strong, and thick films. One of their uses is solder resist [9][10][11][12] in which the key structure is epoxyacrylate [13][14][15][16]. 'Epoxyacrylate' is an idiomatic expression and, precisely expressing, it should be referred to as epoxymethacrylate compound.…”