Allyl polymers properties

A comparison of grafting results for mono- and di-allyl polymers provides information about the degree to which chains and loops contributed to the observed surface properties. Interestingly, the 250MW di-aUyl polymer grafted sUghtly more efficiently... 

Other types of polycarbonates have also been made using a very different approach from that involving bisphenol A and related compounds. For example, the reaction between phosgene and allyl alcohol (CH2=CHCH2OH) produces a monomer with carbon-carbon double bonds at both ends of the molecule that can be used for polymerization. Interestingly enough, the polycarbonate produced by this process has very different physical properties from the traditional bisphenol A polymer. The allyl polymer is a clear, transparent, flexible plastic whose primary use is in the production of eyeglass lenses. 

In a previous section, the effect of plasma on PVA surface for pervaporation processes was also mentioned. In fact, plasma treatment is a surface-modification method to control the hydrophilicity-hydrophobicity balance of polymer materials in order to optimize their properties in various domains, such as adhesion, biocompatibility and membrane-separation techniques. Non-porous PVA membranes were prepared by the cast-evaporating method and covered with an allyl alcohol or acrylic acid plasma-polymerized layer the effect of plasma treatment on the increase of PVA membrane surface hydrophobicity was checked [37].The allyl alcohol plasma layer was weakly crosslinked, in contrast to the acrylic acid layer. The best results for the dehydration of ethanol were obtained using allyl alcohol treatment. The selectivity of treated membrane (H20 wt% in the pervaporate in the range 83-92 and a water selectivity, aH2o, of 250 at 25 °C) is higher than that of the non-treated one (aH2o = 19) as well as that of the acrylic acid treated membrane (aH2o = 22). 

Use anionic polymers such as polyacrylic acids cross-linked with allyl ethers of pentaerythritol or sucrose as thickeners, if a gel structure and pseudoplastic (shear-thinning) properties are desirable. Consider adding colloidal alumina to further increase the viscosity at pH 13 [ 15]. 

Grafting can also provide the monolithic polymers with rather unexpected properties. For example, the two-step grafting procedure summarized in Fig. 7, which involves the vinylization of the pore surface by reaction of the epoxide moiety with allyl amine, and a subsequent in situ radical polymerization of N-isopropylacrylamide (NIPAAm) initiated by azobisisobutyronitrile within these pores leads to a composite that changes its properties in response to external temperature [76]. 

Polymer molecular properties. Making a polymer of high quality is much more complicated than making butanal, for example, because the material properties of a polymer depend heavily on a number of molecular properties. For example, 1% of mistakes in a propene polymer chain can spoil the properties of a polymer completely (crystallinity for instance), while 10% of a by-product in a butanal synthesis can be removed easily by distillation. PVC contains only 0.1% defects as allylic and tertiary chlorides and this necessitates the use of a large package of stabilisers ... 

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

Conjugated dienes such as 1,3-butadiene very readily polymerize free radically. The important thing to remember here is that there are double bonds still present in the polymer. This is especially important in the case of elastomers (synthetic rubbers) because some cross-linking with disulfide bridges (vulcanization) can occur in the finished polymer at the allylic sites still present to provide elastic properties to the overall polymers. Vulcanization will be discussed in detail in Chapter 18, Section 3. The mechanism shown in Fig. 14.3 demonstrates only the 1,4-addition of butadiene for simplicity. 1,2-Addition also occurs, and the double bonds may be cis or trans in their stereochemistry. Only with the metal complex... 

Polymers of N, N, N, A-diallyldimethylammonium chloride (DADMAC) (and its copolymers with acrylamide) are allyl resins in terms of the monomers used but are very different in properties since they are not crosslinked. Cyclopolymerization is the mode of reaction (Sec. 6-6b) and the polymers are water-soluble. Applications include potable and wastewater treatment (flocculation aid) and paper and textile industries (antistatic coating, reinforcement, color removal). 

Lenses - [ALLYL MONOMERS AND POLYMERS] (Vol 2) -ofcalcium fluorite [FLUORINE COMPOUNDS, INORGANIC - CALCIUM] (Vol 11) -fromCR-39 [ALLYL MONOMERS AND POLYMERS] (Vol 2) -glasses for [CERAMICS - GLASS STRUCTURE AND PROPERTIES] (Vol 5) -refractory coatings for [REFRACTORYCOATINGS] (Vol21) -selenium m infrared [SELENIUM AND SELENIUM COMPOUNDS] (Vol 21) -ofvitreous silica [SILICA - VITREOUS SILICA] (Vol21)... 

Although the crystalline poly(allyl isocyanate) polymers are reported to be stable, many of these polymers depolymerize upon heating to yield monomers and cyclic trimers. The level of temperature sensitivity is a strong function of the length of the side chain. Room temperature depolymerization occurs in polar solvents in the presence of an initiator. Interestingly, the solution properties of poly(alkyl isocyanates) display an unusual degree of chain stiffness which is attributed to their helical configuration (64). 

---