Phenoxy-containing monomers

Synthesis of the Phenoxy-Containing Monomers. Perfluoro(2-phe-noxpropyl vinyl ether) is prepared by the route shown in Figure 6 (3). The 2-phenoxy compound requires the least-involved synthesis of the various monomers. The first two steps were carried out in ordinary glass equipment. The last reaction was carried out using a bed of dried sodium carbonate. 

Properties and Applieations. Aryloxyphosphazene elastomers using phenoxy and J-ethylphenoxy substituents have found interest in a number of appHcations involving fire safety. This elastomer has a limiting oxygen index of 28 and contains essentially no halogens. It may be cured using either peroxide or sulfur. Peroxide cures do not require the allyhc cute monomer. Gum physical properties are as follows (17) ... 

Occupational and environmental exposure to chemicals can take place both indoors and outdoors. Occupational exposure is caused by the chemicals that are used and produced indoors in industrial plants, whereas nonoccupa-tional (and occupational nonindustrial) indoor exposure is mainly caused by products. Toluene in printing plants and styrene in the reinforced plastic industry are typical examples of the two types of industrial occupational exposures. Products containing styrene polymers may release the styrene monomer into indoor air in the nonindustrial environment for a long time. Formaldehyde is another typical indoor pollutant. The source of formaldehyde is the resins used in the production process. During accidents, occupational and environmental exposures may occur simultaneously. Years ago, dioxin was formed as a byproduct of production of phenoxy acid herbicides. An explosion in a factory in... 

Reaction of 1 with 4-fluorobenzoyl chloride yielded the difluoro-containing monomer 2, which is readily polymerized with a bisphenol using potassium carbonate in /V, /V-dimethy 1 acetamide to yield poly(ether ketone)s. The five poly-(ether ketone)s prepared were soluble in polar aprotic solvents and were cast into flexible, creasable films showing good thermal stability. We have demonstrated that 1 -phenoxy-substituted naphthalene moieties undergo a Friedel-Crafts acyla-... 

A series of polymerizations were performed to determine the effect of changing the diphenyl sulfone central group of the bis(phenoxy) and bis(phenylthio) monomers to a pentanedioxy group. The polymers obtained from methyl-substituted 1,5-bis(phenoxy)pentane contained structural units derived from proton transfer reactions [214]. Thus diphenyl methane, 1,2-diphenyl ethane, and benzyl chloride units were detected (Fig. 52). 

Figure 5. Monomers containing the perfluoro-phenoxy group...

Polymerization. Terpolymers of PMVE and TFE with either of the monomers containing a phenoxy group have been prepared in a pressure vessel using an aqueous redox polymerization system. The compositional molar TFE/PMVE ratio in the preferred polymer is about 60/40. The third monomer polymerizes at about the same rate as the PMVE and is fed either neat (as a liquid) or in Freon F-113 solution. Infrared analysis of the band at 10.0/a indicates 75-85% incorporation of the phenoxy compound over the 1-4 mole % monomer change range. One to 2 mole % of the crosslink monomer must be incorporated in the elastomer to ensure good vulcanizate properties. 

If a mesogenic monomer is copolymerized with a nonmesogenic monomer, the mesophase is observed above a minimum concentration of the mesogenic monomer. For example, neither poly (methyl meth-acrylate)-co-[6-[4 -(4"-cyanophenylazo)-phenoxy]hexyl methacrylate]) DP 35, pdi =1.35) nor poly (methyl methacry late)-co-[6-[4 -(4"-n-butoxyphenoxycarbonyl)-phenoxy]hexyl methacrylate] DP 69, pdi =1.12) (Scheme 36) prepared by metal-loporphyrin-initiated copolymerizations and containing 18-20 mol% of the mesogenic monomer exhibit the SmA mesophase of the corresponding SCLCPs [90]. 

In this section we describe some UnPHAs that are built from monomers containing halogen atoms, those bearing methyl, methoxy, ethoxy, hydroxyl, epoxy, acetoxy, carbonyl, cyano, phenyl, nitrophenyl, phenoxy, thiophenoxy or cyanophenoxy groups and PHAs containing aUcyclic monomers. 

Furthermore, PHAs containing monomers with fluorinated phenoxy side groups were produced by P. putida when ll-(2-fluorophenoxy)undecanoicacid, ll-(3-flu-orophenoxy)undecanoic acid, ll-(4-fluorophenoxy)undecanoic acid or 1 l-(2,4-dif-luorophenoxy)undecanoic acid was used as the sole carbon source (Takagi et al. 2004). When ll-(3-fluorophenoxy)undecanoic acid was the precursor of the monomers, a copolymer containing (P)-3-hydroxy-7-(3-fluorophenoxy)heptanoate (10%) and (P)-3-hydroxy-5-(3-fluorophenoxy)valerate (90%) was isolated. When the precursor was ll-(4-fluorophenoxy)undecanoic acid, the monomers present in the copolymer were (P)-3-hydroxy-7-(4-fluorophenoxy)heptanoate and (7 )-3-hydroxy-... 

Condensation of aryl TFVE dimethylchlorosilane via dehydrogenerative hydrolysis/methanolysis yielded a siloxane containing aryl TFVE monomer for the preparation of PFCB aryl ether fluorosilicones [99], Rizzo et al. prepared two disilanol monomers containing perfluorocyclobutane rings, l,2-bis[4-(dimethylhydroxysilyl)phenoxy]-1,2,3,3,4,4-hexalluo-rocyclobutane and l,2-fiw[3-(dimethylhydroxysilyl)... 

The cyclic diether, 1,3-dioxolane, is recommended by Ferro Corporation as a more benign solvent substitute for chlorinated organic solvents, such as methylene chloride, 1,2-dichloroethane, and 1,1,1-trichloroethane, and for ketones, such as methyl ethyl ketone (MEK). This ethylene glycol-based ether is a suitable solvent under neutral and basic conditions in several major-use areas. It is a powerful solvent for softening and dissolving polymers made from polar monomers, for example, polycarbonates, acrylates, cellulosics urethanes, phenoUcs, nitriles, urea-formaldehydes, and alkyds, as well as polyesters, vinyl epoxys, and halogen-containing polymers. As a reaction solvent it is added as a component to a special quaternary ammonium or phosphonium salt solution for preparation of a vesicular phenoxy resin. Other beneficial uses for the solvent dioxolane, include ... 

More examples have been quoted of special growth reactions for molecules having two carbon-carbon double bonds. Cyclopolymerization occurs for diallylaminomethyl phenols, allyl esters of unsaturated acids, 2-(2-vinyl-phenoxy)ethyl methacrylate and acrylate, 2-divinylbenzene and some silicon-containing monomers. - Polymerizations of p-xylylene and its derivatives have been considered further. - The radical polymmzation of some disubstituted vinylcyclopropanes has been represented as shown in equation (2), where X and Y=CN or COjEt. The involvement of the ring must be connected with stabilization by the substituents of the product radical. 

Polyamides with short trimethylene aliphatic flexible sequences were described by Nasr-Isfahani et al. [4]. The poly condensation of the diacid l,3-(4-carboxy phenoxy)propane with various aromatic diamines by direct polycondensation provide PAs with moderate yield. These PAs were found to be soluble in polar aprotic solvents and soluble even in acetone and in THF. Ferreiro et al. [5] described the effect of lateral oxyethylene moieties on the properties of aromatic polyisophthalamides. Several polyisophthalamides containing short sequences of oxyethylene as pendent substituents were synthesized by the reaction of three aromatic diamine monomers and four novel diacid monomers containing pendent oxyethylene units by the phosphorylation method of polycondensation. The polymers were prepared in high yield and high molecular weight. 

Polymerization of DPAs with Other Heteroatoms. Polymerization of other het-eroatom-containing DPAs (3a-3d) was investigated with the motivation of evaluating the effect of polar groups on the polymerization behavior and polymer properties. The monomers employed involve alkoxy-, phenoxy-, and carbazolyl-substituted DPAs as shown in Table IV (31-32),... 

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