Copolymerization, of epichlorohydrin

Although the copolymerization of propylene oxide with C02 takes place effectively with organozinc additives or the (tetraphenyl) porphyrin-AlCl system [61], the copolymerization of epichlorohydrin with C02 seldom occurs with these catalysts. Shen et al. [62] showed that a rare earth metal catalyst such as the Nd(2-EP)3/AliBu3 (Al/Nd = 8) system was very effective for the copolymerization of epichlorohydrin with C02 (30-40 atm) at 60 °C (Scheme 16). The content of C02 in the copolymer reached 23-24 mol % when 1,4-dioxane was used as solvent. 

Colestipol Colestipol (20.1.1) is a hydrochloride of the product of copolymerization of epichlorohydrine with diethylentriamine that contains varying numbers of quaternary nitrogen atoms. There is no exact formula of the product of copolymerization, but its approximate structure can be expressed as 20.1.1 [1 ]. 

The effect of the anion on the copolymerization rate is controversial. Hilt et al.41 established for different sodium halides the following order of efficiency F < Cl < Br < J . This order was interpreted on the basis of the increase in nucleophilicity or polarizability of the anions. Sfluparek and Mleziva 43) observed that the reaction rate of the benzoate anion was about twice as high as that of the bromide anion in the copolymerization of epichlorohydrine with phthalic anhydride. On the other hand, Luston and Manasek56) did not detect any effect of the anion size on the copolymerization rate initiated by tetramethylammonium and tetrabutylammonium halides. 

Specialty elastomers based on epichlorohydrin have been produced by both Hercules and BF Goodrich. Elastomers have been made by copolymerization of epichlorohydrin with ethylene oxide and by terpolymerization of epichlorohydrin with ethylene... 

The discovery of coordinate polymerization of oxirane led to an enormous expansion in the range of polyether structures that could be synthesized. Some of the remarkable synthesis chemistry is outlined in Section III. Coordinate copolymerization further increased the range of polymer structures that could be synthesized in highly controlled ways. Two examples have already been described copolymers of epichlorohydrin and ethylene oxide (71) and of propylene oxide and allyl glycidyl ether (94, 137). The activation energy for copolymerization of epichlorohydrin and maleic anhydride was found to be 14.5 kcal/mol, and the polymerization rate is dependent on temperature and proportional to catalyst concentration (138-140). 

Pasika, W. M., Cationic Copolymerization of Epichlorohydrin With Styrene Oxide And Cyclohexene Oxide, J. Macromol. Sci-Chem. A, 1991,28, 545. 

Crystallinity is low the pendent allyl group contributes to the amorphous state of these polymers. Propylene oxide homopolymer itself has not been developed commercially because it cannot be cross-baked by current methods (18). The copolymerization of PO with unsaturated epoxide monomers gives vulcanizable products (19,20). In ECH—PO—AGE, poly(ptopylene oxide- o-epichlorohydrin- o-abyl glycidyl ether) [25213-15-4] (5), and PO—AGE, poly(propylene oxide-i o-abyl glycidyl ether) [25104-27-2] (6), the molar composition of PO ranges from approximately 65 to 90%. 

In contrast to the substituted PPO s, It Is theoretically possible to obtain the same substituted PECH s by homopolymerization of the corresponding mesogenic oxirane, or by its copolymerization with epichlorohydrin. We have attempted these polymerizations in order to better interpret the thermal behavior of the more complicated copolymers that we have obtained by polymer analogous reactions. Homopolymerization would be instructive because the incorporation of nonmesogenic units into liquid crystalline homopolymers doesn t as a rule change the type of mesophase obtained (5). 

Acylated starch can be copolymerized to yield materials for films, lacquers, and fibers.2111 Starch acetate copolymerized with epichlorohydrin was extruded to give cold-water swelling products with a high degree of friability.2112 Epichlorohydrin-crosslinked starch has been acylated with 2,3-di-O-benzoyl-L-threaric anhydride.2113 The reaction proceeded either in /V,/V-dimethy 11 ormam ide or in toluene, and the non-crosslinked product has also been reported.2114... 

Entelis et al. have studied the copolymerization of THF with three different oxi-ranes PO, a-epichlorohydrin (ECH) and nitroglicydyl ether (NGE)31) ... 

Polymers bearing CD moieties have been synthesized by cross-linking of CDs using epichlorohydrin [69, 70], by coupling reaction between modified or native CDs and polymers [71-75], and by homo- and copolymerization of monomers bearing CD moieties [76-78]. 

Copolymerization of caprolactone with epoxides opens a wide range of various functionalities that can be accessed. These functional epoxides can be based on substituted epichlorohydrin [63] or on other molecules. In our laboratory, we recently presented an epoxide system based on 2-methyl-4-pentenoic acid, which is esterified in a first step with a desired functional moiety and then epoxidized to obtain a functional epoxide that is compatible with caprolactone copolymerization [44,62], This toolbox approach allows for the functionalization with different functional moieties on demand. One advantage of these statistical copolymers is that the copolymer composition can be controlled by the reactivity of the monomers, and therefore, defined copolymers can be obtained (Figure 9.7). 

In 2006, Week et al. [48,49] succeeded in synthesizing a highly efficient catalyst for the kinetic resolution of epichlorohydrin by radical homo- and copolymerization of an asymmetric monostyryl-substituted salen hgand with styrene. 

The copolymerization of TMO and epichlorohydrin (ECH) with the chelate catalyst and a 50 50 weight ratio charge is more favorable (Run 3, Table II) again, two fractions, both rubbery in nature, were obtained which differed in solubility and composition. Thus, the chelate catalyst again appears to contain at least two different copolymerization sites. It is significant that these two monomers, which probably have similar steric requirements, do copolymerize better, thus adding credence to the earlier proposal that steric restrictions at certain sites affect... 

This complex, which was effective in initiating the homopolymerization of propylene oxide and epichlorohydrin and the copolymerization of these two monomers, was postulated to first form complex monomer with the zinc atom and then cleave by attack of the alkoxide linked to an aluminum atom to yield polymer. 

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