With Halogen-Containing Compounds

Reactions of PH3 with halogen-containing alkenes are described in the subsection covering the reactions with alkenes see Table 18, pp. 271/2. 

PH3 and CF4 react in a dc glow discharge to give PF, PF2, and PF3 [24]. The impact of an electron pulse on a mixture of PH3 with CHF3 or CHCI3 induces reactions of CHFJ and CHClJ, respectively, with PH3 [25]. 

The analogous gas-phase reactions of PH3 with CaHsBr (mole ratio 1 1,250 C, r.t. 5 s) [86] and C3H7Br (mole ratio 1 0.7, in the presence of (C3H7)3N, 320 C, r.t. 10 s) [90] yield the corresponding primary phosphanes with 2.8 [86] and 28.5% [90] yield based on PH3 conversion. 

PH3 in the presence of solid KOH reacts with CH3I in dimethyl sulfoxide in the appropriate reactant ratios to give CH3PH2 or (CH3)2PH [94]. 

Aroyl chlorides react with PH3 in pyridine to give the corresponding aroyl phosphanes, (Ar(0)C)3P, where Ar=CeH5, m-CH3CeH4, p-CH3CeH4, a-CioH7, P-C10H7 [177]. 

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Shokol, V.A. and Kozhushko, B.N., Phosphorohalidites and phospho-ropseudohalidites in the Arbuzov reaction with halogen-containing compounds, Russ. Chem. Rev., 54, 98, 1983. 

ESR of, 16 117 IR spectrum of, 16 117 NMR spectrum of, 16 117 peroxide derivatives of, 16 125-127, see also specific compounds preparation of, 16 115-118 properties of, 16 115-118 Raman spectra of, 16 117 reactions of, 16 118-125 with carbonyls and carbonates, 16 124 with complex anions, 16 125 with halogen-containing compounds, 16 121-123... 

Aminopropyl)silatranes (105 and 105a) react with halogen-containing compounds including acyl chlorides (equations 140 and 141)96 99 365 366 and with aldehydes (equation 142)366 367 to give the corresponding derivatives (106-108). 

Studies of reactive scattering have been almost entirely restricted until recently to the reactions of alkali atoms with halogen-containing compounds. 

The relative intensities of the CN bands depend strongly on the nature of the species added to active nitrogen [145, 146], With halogenated hydrocarbons, red emission from the A 2II state predominates this was classified by Bayes [146] as the P2 emission. The v distribution is broad, peaking at v = 7, and the red system is accompanied by bands from B 2S+ v = 0) that is populated via A 2II (y = 10) because of perturbations and collision-induced transitions. The Pa emission from mixtures of active nitrogen with halogen-containing compounds is quite different, and the relative band intensities in the red system show that v = 0 is now the most populated level. 

Only a few metal complexes of Sc, Y, La, and the lanthanides are known for oxidation states O and -f I , and their oxidation chemistry with halogen-containing compounds has not been explored extensively. The zerovalent bisarene complexes M(TTB)2 (M = Sc, Y, Gd, Dy, Ho, Er, Lu TTB = f/ -LS.S-t-BusCeHa) are oxidized by I2 to give MI3 and the free TTB ligand . These reactions have been utilized for calorimetric determination of metal-arene bond enthalpies in these complexes . 

Sodium antimonate must be used with halogen containing compounds for it to act as effective fire retardant. The source of chlorine may come from polymer (e.g., PVC, chlorinated rubber, etc.) or other chlorinated or brominated material. The benefits of using sodium antimonate over antimony oxide include its low tinting strength and the acid scavenging capability. For these reasons, it is used in semi-opaque or dark colored materials and in polymers such as polyesters and polycarbonates which are acid sensitive. 

Antimony pentoxide is an alternative to antimony trioxide. It finds applications in semi-transparent materials and dark colors because of its low tinting strength. As with antimony trioxide, antimony pentoxide must be used together with halogen-containing compounds to function as a flame retardant (sec discussion under antimony trioxide). The other advantages of antimony pentoxide include its refractive index which is closer to most materials, its very small particle size, its high specific surface area, and its substantially lower density. Because of its small particle size, its is frequently used in the textile industry since its addition has only a small effect on color or on mechanical properties. Production of fine-denier fibers requires a stable dispersion and a small particle size filler. The flame retardancy of laminates is also improved with antimony pentoxide because small particles are easier to incorporate in the interfiber spaces. 

Borates Molybdenum compounds Zinc Borate, Barium Metaborates, Ammonium Fluoroborate, Boric Acid Flexible PVC, polyolefins, unsaturated polyesters, thermoplastic polyesters, epoxies, nylons, urethanes, and phenolics Used in comhination with other retardants for flexible PVC and reinforced polyesters. Behave as synergists with halogen containing compounds CSA Chemical Harwich Chemical Corp. US Borax Chemical Corp. Climax Performance Materials CSA Chemical Sherwin WUhams Chemicals... 

Table 3 Performances of flame-retarded PP loaded with halogen-containing compounds...

Other reactions of silicon with halogen-containing compounds are listed below ... 

HALS are used whenever high performance is desired and the chemistry of the plastic allows. HALS cannot be used with halogen containing compounds, such as, PVC or halogenated FR. Based on the success of HALS, other oxime-based AOs are under development. They may be less expensive than HALS in some cases. 

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