Phosphonated methacrylate

Figure 10.1 shows an almost linear trend for the evolution of corrosion as a function of time when the diblock copolymer is used as additive. As expected, virgin poly(VDF) alone is not able to prevent the metal from corrosion as the surface is almost completely corroded after only 48 h. Figure 10.1 also shows a high improvement when poly(VDF) is blended with poly(MMA)-b-poly(phosphonate methacrylate) diblock copolymer additive, although the statistical copolymer seems to afford better adhesion towards the metallic surface and hence better anticorrosion properties. 

Alkoxy titanium acylate derivatives coordinated with a phosphite diester (phosphonate diester) can be prepared by reaction of a tetraalkyl titanate and an equal molar amount of a carboxyUc acid, such as methacrylic acid or isostearic acid, and a phosphite or phosphonate diester, such as dibutyl hydrogen phosphite (103). These materials reduce the viscosity of a composite system, improve... 

There is a wide variety of commercially available chiral stationary phases and mobile phase additives.32 34 Preparative scale separations have been performed on the gram scale.32 Many stationary phases are based on chiral polymers such as cellulose or methacrylate, proteins such as human serum albumin or acid glycoprotein, Pirkle-type phases (often based on amino acids), or cyclodextrins. A typical application of a Pirkle phase column was the use of a N-(3,5-dinitrobenzyl)-a-amino phosphonate to synthesize several functionalized chiral stationary phases to separate enantiomers of... 

The compositions of copolymers of styrene, methyl methacrylate, acrylonitrile and acrylamide with diethyl vinyl phosphonate (S-DEVP, MMA-DEVP, AN-DEVP and AM-DEVP), with incorporated FR functionality, were analysed by means of 11 1-NMR in CDC13, DMSO-d6 and D20 [217],... 

Phosphodiesters, 17 625 Phosphoethyl methacrylate, 16 242 Phosphogypsum, 4 593 23 511 Phospholipids, 10 804, 822 24 53 in cosmetics, 24 159 Phospholipid surfactants, 24 161 Phosphomolybdic acid (PMA), 19 438 Phosphomycin calcium, registered for use in aquaculture in Japan, 3 22 It Phosphonate esters, 19 37 Phosphonate finishes, 11 498 Phosphonates... 

Spontaneous polymerization of 4-vinyl pyridine in the presence of polyacids was one of the earliest cases of template polymerization studied. Vinyl pyridine polymerizes without an additional initiator in the presence of both low molecular weight acids and polyacids such as poly(acrylic acid), poly(methacrylic acid), polyCvinyl phosphonic acid), or poly(styrene sulfonic acid). The polyacids, in comparison with low molecular weight acids, support much higher initial rates of polymerization and lead to different kinetic equations. The authors suggested that the reaction was initiated by zwitterions. The chain reaction mechanism includes anion addition to activated double bonds of quaternary salt molecules of 4-vinylpyridine, then propagation in the activated center, and termination of the growing center by protonization. The proposed structure of the product, obtained in the case of poly(acrylic acid), used as a template is ... 

A similar concept was used in the development of artificial chymotrypsin mimics [54]. The esterase-site was modeled by using the phosphonate template 75 as a stable transition state analogue (Scheme 13.19). The catalytic triad of the active site of chymotrypsin - that is, serine, histidine and aspartic acid (carboxy-late anion) - was mimicked by imidazole, phenolic hydroxy and carboxyl groups, respectively. The catalytically active MIP catalyst 76 was prepared using free radical polymerization, in the presence of the phosphonate template 75, methacrylic acid, ethylene glycol dimethacrylate and AIBN. The template removal conditions had a decisive influence on the efficiency of the polymer-mediated catalysis, and best results were obtained with aqueous Na2CC>3. 

D. Price, L.K. Cunliffe, K.J. Bullett (formerly Pyrah), T.R. Huh, G.J. Milnes, J.R. Ebdon, B.J. Hunl, and P. Joseph, Thermal behavior of covalently bonded phosphonate flame retarded poly(methyl methacrylate) systems. Polym. Adv. Technol., 19 (6), 710-723 (2008) and previous references therein. 

SCHEME 5.3 Suggested mechanism for char formation in methacrylate/phosphonate ester copolymer. 

Ebdon, J. R Hunt, B. J., Joseph, P Konkel, C. S Price,D Pyrah, K Hull,T. R Milnes, G. J., Hill, S.B Lindsay, C. I., McCluskey, J., and Robinson, I., Thermal degradation and flame retardance in copolymers of methyl methacrylate with diethyl(methacryloyloxymethyl)phosphonate, Polym. Degrad. Stab., 2000, 70, 425 136. 

Price, D., Pyrah, K., Hull, T. R., Milnes, G. J., Wooley, W. D., Ebdon, J. R., Hunt, B. J., and Konkel, C. S., Ignition temperatures and pyrolysis of a flame-retardant methyl methacrylate copolymer containing diethyl(methacryloyloxymethyl)-phosphonate units, Polym. Int., 2000, 49, 1164-1168. 

Banks, M., Ebdon, J. R., and Johnson, M., The flame-retardant effect of diethylvinyl phosphonate in copolymers with styrene, methyl methacrylate, acrylonitrile and acrylamide, Polymer, 1994, 35, 3470-3473. 

In contrast to stabilizers, fire retardants must be added in much higher concentrations, which affect thermal and mechanical properties as well as cost. Sherr and co-workers report that novel derivatives of phosphine oxides, phosphonic acids, phosphinic acid, and phosphonium halides may be used generally in concentrations as low as 2.5-5 p.p.h. to be effective fire retardants in polyethylene and poly (methyl methacrylate). 

In our studies we found that phosphonic acids (16), phosphinic acids (25), and phosphine oxides (17) are additives capable of imparting fire retardant properties to thermoplastic polymers. Tables I and II present data for some of these compounds when added to polyethylene or to poly (methyl methacrylate). The concentration reported is not necessarily the lowest effective concentration for the additive in the polymer. These additives also were effective in other thermoplastic polymers such as polystyrene, impact polystyrene, polypropylene and ABS. The compounds were completely compatible with the polymers. 

Methyl methacrylate phosphonate (24 mmol) and 18-crown-6 (57 mmol) dissolved in 300 ml THF were cooled to -78°C, then treated with 50 ml 0.5 M in toluene potassium hexamethyldisilazide, and stirred 30 minutes. The Step 8 product was added as powder to this mixture and stirred 6 hours at -78°C and then overnight at ambient temperature. The mixture was then diluted with 1.21 EtOAc, washed four times with 500 ml water, dried, and concentrated. The residue consisted of a mixture of 10 g of E/7, 1 10, respectively, isomer mixture, and the Z-isomer isolated after recrystallization in EtOAc. 

Some other interesting copolymers having properties of PVC thermal stabUizers, like poly[Af-(a-benzothiazolonylmethyl)methacrylate-co-methyl methacrylate] [45], of flame retardants like a terpolymer of styrene, acrylonitrile and a polymerizable perbrominated phenol [76] or poly[4-methacryloyloxy-2,3,5,6-tetrabromobenzyldi-phenyl phosphonate-co-methyl methacrylate] [104] (93), bioddes, mostly copolymers of monomers containing tris(n-butyl tin) or triphenyl tin moieties and alkyl acrylates, methacrylates, vinyl acetate, acrylonitrile, styrene or A-vinylpyrrolidone [105], e.g. a terpolymer of styrene, MMA and tri(n-butyl tin) itaconate [106] (94),... 

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