Chlorine polyols

The representative raw materials to produce chlorine polyols are epichlorohydrin, chlorendic anhydride and trichlorobutylene oxide (TCBO) (Figure 18.2). 

Figure 18.2 Structures of raw materials to make chlorine polyols...

Uses Reactive flame retardant for rigid urethane foam, PU elastomer wire insulation, adhesives, coatings, and fibers can replace chlorinated polyols intermediate... 

Phosphites. Tertiary phosphites are also commonly used and are particularly effective ia most mixed metal stabilizers at a use level of 0.25—1.0 phr. They can take part ia a number of different reactions duting PVC processing they can react with HCl, displace activated chlorine atoms on the polymer, provide antioxidant functionaHty, and coordinate with the metals to alter the Lewis acidity of the chloride salts. Typical examples of phosphites are triphenyl phosphite [101 -02-0], diphenyl decyl phosphite [3287-06-7], tridecyl phosphite [2929-86-4], and polyphosphites made by reaction of PCl with polyols and capping alcohols. The phosphites are often included in commercial stabilizer packages. 

This reaction is reported to proceed at a rapid rate, with over 25% conversion in less than 0.001 s [3]. It can also proceed at very low temperatures, as in the middle of winter. Most primary substituted urea linkages, referred to as urea bonds, are more thermally stable than urethane bonds, by 20-30°C, but not in all cases. Polyamines based on aromatic amines are normally somewhat slower, especially if there are additional electron withdrawing moieties on the aromatic ring, such as chlorine or ester linkages [4]. Use of aliphatic isocyanates, such as methylene bis-4,4 -(cyclohexylisocyanate) (HnMDI), in place of MDI, has been shown to slow the gelation rate to about 60 s, with an amine chain extender present. Sterically hindered secondary amine-terminated polyols, in conjunction with certain aliphatic isocyanates, are reported to have slower gelation times, in some cases as long as 24 h [4]. 

In summary, we have developed a recyclable heterogeneous catalyst for the bleach oxidation of alcohols and polyols. In contrast to previously reported systems, neither a chlorinated hydrocarbon solvent nor a bromide cocatalyst is necessary to achieve good activity. Besides bleach-oxidation, PIPO is also effective in the CuCl/nitroxyl catalysed aerobic oxidation of benzyl alcohol. A further advantage of our system is that PIPO is readily prepared from inexpensive and commercially available raw materials. We believe that it will find wide application in organic synthesis. 

Applications Disulfur dichloride is utilized in the manufacture of sulfur dichloride, thionyl chloride and sulfur tetrafluoride and with polyols for the production of additives for high pressure lubricating oils and cutting oils. In addition it is used as a catalyst in the chlorination of acetic acid. Solutions of sulfur in disulfur dichloride is utilized in the room temperature vulcanization of rubbers. 

Polyurethanes and Chloralkali MDI, TDI, propylene and ethylene oxide and derivatives, polyols, polyurethane systems, chlorine and derivatives, caustic potash and soda ... 

A special group of polyols for rigid PU foams is the group of reactive flame retardant polyols containing phosphorus, chlorine or bromine, which confer fire resistance to the resulting PU (Chapter 18). 

TCBO is reacted with various polyols (such as carbohydrates), in the presence of cationic catalysts (for example BF3), with the formation of very viscous and high chlorine content polyols (18.3) [14, 22-24]. 

A variant of the Mannich reaction using an equilibration between phosphorus acid and a trialkyl phosphite was developed [36]. The trialkyl phosphite was synthesised in situ by the reaction of phosphorus trichloride with PO, with the formation of tris (2-chloropropyl) phosphite (reaction 18.14). By equilibration of phosphorus acid with tris (2-chloropropyl) phosphite, bis (2-chloropropyl) phosphite (reaction 18.15) is formed which, by reaction with oxazolidine, gives an interesting phosphonate polyol containing phosphorus, chlorine and nitrogen (reaction 18.16) ... 

Very interesting reactive flame retardants were used successfully in the fabrication of flame retardant rigid PU foams by Solvay under the name of Ixol polyols. These polyols are triols based on epichlorohydrin and brominated unsaturated diol. Ixol polyols have chlorine, bromine and phosphorus in each structure [3, 44, 45]. 

The fire resistance of polyurethanes is based on the introduction of flame retardant compounds including polyols, containing chlorine, bromine or phosphorus in their structure. The polyols containing chlorine, bromine or phosphorus are linked chemically in the polyurethane structure and lead to self-extinguishing polyurethanes, with a permanent flame retardancy. 

Colson, P., Slessor, K. N., Jennings, H. J., and Smith, I. . P. (1975). Can. J. Chem. 53, 1030. A Carbon-13 Nuclear Magnetic Resonance Study of Chlorinated and Polyol Analogs of Glucose and Related Oligomers. 

The most important costabilizers in PVC formulations used mainly in combination with mixed metal salts are alkyl-aryl-phosphites to improve early color. Epoxy compounds, for example, epoxidized fatty esters such as epoxidized soy bean oil, react directly with HCl or substitute labile chlorine atoms, for example, in the presence of zinc ions. Furthermore, the epoxidized fatty esters act as plasticizers. Polyols such as pentaerythritol or dipentaerythritol and P-diketones act as complexing agents and deactivate the negative effect of the formed zinc chloride. Hydrotalcites... 

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