Ultraviolet stabilizing monomers and polymers. I. Synthesis and polymerization of phenyl 5‐methacryloxymethylsalicylate

Abstract

synopsisWith a view to permanently incorporating ultraviolet stabilizing moieties into polymer systems, monomew containing the phenyl salicylate structure have been prepared and polymerized. Phenyl 5acryloxymethylsalicylate and phenyl 5methacryloxymethyl-salicylate were prepared by the chloromethylation of phenyl salicylate and subsequent reaction with sodium acrylate or methacrylate. Homopolymers and copolymers of the methacryloxymethyl monomer were prepared and studied. The ultraviolet spectra of the chloromethyl derivative, the monomers, and the homopolymers were essentially similar to that of the starting material, phenyl salicylate. Copolymers of the ultraviolet-absorbing monomers (2%) with vinyl acetate, vinylidene chloride, and vinyl chloride were prepared. The ultraviolet stability of these copolymers was then compared to that of an unstabilized control series and a series containing phenyl salicylate. While there were some differences in the behavior of the copolymerized absorber it was a t least as effective m phenyl salicylate in stabilizing the polymers.The advantage of an ultraviolet stabilizing moiety chemically attached to the substrate has been generally recognized in the past few years. Such problems as migration, volatility on prolonged exposure to exterior conditions, compatibility, and toxicity should be minimized by this approach. Recent patent literature' cites examples, wherein vinyl and ally1 esters of salicylic acid are copolymerized and thus permanently attached to the polymeric substrate. The use of salicylates as ultraviolet absorbers is well known12+ and phenyl salicylate has, in particular, been extensively used for the stabilization of poly(viny1idene chloride)6 and to a more limited extent for poly(viny1 chloride) 2 and polyolefins.I n this work, the approach to the preparation of ultraviolet absorbing monomers has been to use the phenyl salicylate moiety, and to attach onto it, by fairly simple organic reactions, acrylate and methacrylate groups [es. (1) 1.

Preparation and characterization of a high molecular weight UV‐stabilizer based on a derivative of 2,4‐dihydroxybenzophenone and its application in polymer materials

“…The conversion of polymerization is very high as shown in Table I, and it confirms that BPMA and MMA can react with each other easily. This is a better result than solution polymerization, 3,4 which has a low conversion about 10%. The molecular weights of the copolymers are listed in Table I.…”

“…Hydrogen atoms of poly(MMA-co-BPMA) are marked using 1, 2, 3, 4, 5, 6, 7, 8, a, b, c, d. The peaks at ␦ ϭ 7.39 -7.49 ppm are due to aromatic protons, and they belong to H 1,2,3,4,5,6 , and the peaks at ␦ ϭ 6.46 -6.57 ppm are also ascribed to aromatic protons H 7,8 . From Figure 1, it is also realized that peaks But, in poly(MMA-co-BPMA), this effect is weakened by the -MMA-section.…”

“…It leads to a strong diminution of the materials' utilization. To resolve such problems, many approaches have been developed, such as preparing reactive UV-stabilizer, [2][3][4][5][6][7][8][9][10][11] introducing compatible side chains, or chemically anchoring of the additive to the polymer backbone, 12-15 etc. Among these methods, preparing high molecular weight UVstabilizer is a highlight because, for most of the polymer materials, blending is the first choice to enhance their UV-resistance.…”

Transparent ultraviolet‐barrier coatings

“…(4) Polymers based on Diphenolic Acid carboxylic acid derivatives as monomers demonstrate the following solubility relationship : aliphatic ester > piperidide (amide) >> acid (compare polymers A34, A38, A39, and A41 with A44 and with B8 and B9). (5) The additional presence of an ether oxygen in the Diphenolic Acid ester side chain produces a second separate solubility parameter range in medium hydrogen-bonding solvents. The original medium solubility parameter range apparently illustrah polymer solution via main chain solubilization.…”

Studies on stable free radicals. XVIII. Stabilizing effect of copolymers of N‐oxyl biradical with xylylene on photooxidation of polypropylene

“…Attempts have been made to polymerize synthetic polymer additives such as antioxidants (AO) ( 2 ) and W absorbers (3), with the a i m of improving the physical properties, such as volatility, of the additives.…”