Hydroxy-containing polymers

A novel type of grafting process was developed using a new photosensitive polymer containing vanadium (V) chelates. These polymers were generally synthesized by the condensation of a VOQ2OH complex and a hydroxy-containing polymer to produce photoactive polymer (red in color) with pendant vanadium (V) chelate. 

Hydroxy-containing polymers such as poly(methyl-methacrylate-co-hydroxyethyl methacrylate) [65,66] or secondary cellulose acetate [67,68] were used for this purpose. Vanadium (V) 8-hydroxy quinoline-hydroxy-ethyl methacrylate adduct, prepared by condensation of the latter with a VOQ2OH complex, is polymerized to... 

A hydroxy-containing polymer can be coupled with living polytetrahydrofuran carbocation [Cameron and Duncan, 1983] ... 

These methods determine total hydroxy groups and are applicable to many types of hydroxy containing polymers including polyethylene glycol, polypropylene glycol and glycol/alkylene oxide condensates. 

M.B. Frankel et al, Smokeless Composite Propellants Containing Carboxy- or Hydroxy-Terminated Polymers and a Nitroorganic Oxidizer , USP 3853646 (1974) CA 83, 12972 (1975) 37) A. Reichel et al, High Explo-... 

In a similar way, polyester block copolymers were obtained by reacting acid chloride-terminated polyesters with hydroxy-terminated polyethers,401 or by reacting polyester-containing polymer mixtures with coupling agents such as diisocyanates.402... 

Crown-ether network polymers have also been prepared by adding to a slurry of NaH in THF, an equimolar amount of the appropriate hydroxy-containing crown-ethers followed by the addition of chloromethylated cross-linked polystyrene. Binding of Na, K, Cs picrates and of sodium tetraphenyl-borate to the immobilized crown-ether is achieved under simple conditions [74]. 

The synthesis of PU can be carried out by the reaction described in Eq. (2.24). If the functionality of the hydroxy-containing compounds or the isocyanate is increased beyond 2, branched and possibly crosslinked polymers are produced. Because the nature of the polyol (polyether, polyester, polybutadiene, etc.) and isocyanate components can vary widely, PU are among the most versatile polymers, producing a wide variety of materials such as elastomers, foams, coatings, adhesives, or fibers. 

It is known that borane containing polymers were converted to hydroxy-lated polyomers, as mentioned above. From borane-containing PE, PE-g-PCL was also synthesized [51]. 

Cyclic siloxane-containing polymer was synthesized by the reaction of Bu2Sn(OCH3)2 with dimethyl hydroxy-terminated polysiloxane as shown in Fig. 52 [175],... 

Ammonium polyphosphates, on the other hand, are relatively water insoluble, nonmelting solids with very high phosphorus contents (up to about 30%). There are several crystalline forms and the commercial products differ in molecular weights, particle sizes, solubilities, and so on. They are also widely used as components of intumescent paints and mastics where they function as the acid catalyst (i.e., by producing phosphoric acid upon decomposition). They are used in paints with pentaerythritol (or with a derivative of pentaerythritol) as the carbonific component and melamine as the spumific compound.22 In addition, the intumescent formulations typically contain resinous binders, pigments, and other fillers. These systems are highly efficient in flame-retarding hydroxy-lated polymers. 

The phenolic hydroxy-group in THC s is important to their pharmacological activity,357 and analgesic properties may be due to metabolism to 7-hydroxy-derivatives (using normal monoterpenoid numbering).358 l-Nor-lj8-hydroxyhexahydrocannabinol is a potent analgesic.359 Cannabinol is a rapidly formed metabolite of A -THC and A6-THC in rats.360 The activity of A6-THC- and cannabidiol-containing polymers is reported.361... 

The objectives of this study were to extend these synthetic methods to the preparation of low molecular weight, hydroxy-terminated polymers containing acetylenic bonds and evaluating these prepolymers in castable solid propellant formulations. Since 2-butyne-l,4-diol was commercially available, the formation of polyacetals from this glycol seemed to be an attractive route to the desired polymers. It was believed that the rigid triple bond would inhibit the cyclic acetal formation observed by the earlier workers with the lower members of the saturated glycol series. Thus, in an acetal interchange reaction a linear polymer (I) should be favored over the cyclic acetal (II) ... 

At the end of the polymerization process, the polymers are washed free of sodium chloride, excess sodium polysulfide and solubihzed hydroxy-containing terminals. The molecular mass of the resultant polymer is thought to be at least 5 x 10 10 the yield is 80%. The polymer forms as small dispersed spheres approximately 5 15 lm in diameter, which have a higher density than the aqueous phase in which they are produced, and therefore settle to the bottom of the reactor. The polymer is washed with hot water, followed by decantation, coagulation by acidification, and drying with heat, resulting in a sohd, rubbery mass. 

Ferrocene has been reported to be very effective as a soot reducing agent in combustion [42 — 44]. Thus, when ferrocene compounds are incorporated in a fire retardant polymer, such as a phenolphthalein-based polymer and poly(phosphate ester)s, they have shown added advantages in that they promote extinction and reduce smoke formation by accelerated char reduction [45, 46]. The synthesis of such ferrocene-containing poly(phosphate ester)s was achieved by interfacial polycondensation using a phase transfer catalyst [47]. Accordingly, l,l -bis(p-hydroxy-phenylamido)ferrocene and l,l -bis(p-hydroxyphenylcarbonyl)ferrocene underwent condensation with various aryl phosphoroic acid dichlorides to yield two series of ferrocene-containing polymers, i.e., poly (amide-phosphate ester)s 38a and poly(ester-phosphate ester)s 38b respectively, as shown in Scheme 10-17. 

Oxidative studies on resins with different polymer backbones and functionalities have been performed as accelerated tests.The data is shown in Table 17 for polystyrene and polydiallylamine resins. Although the polydiallylamine resins have a higher initial capacity, they are much more susceptible to oxidative degradation. When the polystyrene resin has a mixture of primary and secondary amino groups or when a hydroxy-containing group is attached to the amine of the functional group, the susceptibility to oxidation is enhanced. Thus one can understand the lower thermal limit for Type II anion resins compared to Type I resins. 

The radical containing an hydroxyethyl group which is formed (9.5), initiates the formation of polymeric chains which, by recombination, give hydroxy-telechelic polymers (reactions 9.6 and 9.7). Based on the principles mentioned various hydroxy-telechelic polymers were obtained by radical polymerisation of styrene [9], acrylonitrile [10], butyl acrylate or butadiene [10-14]. Of course, the oligo-polyols derived from styrene and acrylonitrile are solid and difficult to use in PU, but butyl acrylate and butadiene lead to liquid polymers with terminal hydroxyl groups, which are useful in polyurethane manufacture. 

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