Epichlorohydrin copolymerization

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). 

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 ]. 

Research Focus Method of preparing surface adhesives using phenolic resins either modified with disulfides or free radically copolymerized with ethane-dithol and then postreacted with epichlorohydrin. 

THF copolymerizes readily with other cyclic ethers such as oxides and oxetanes. The comonomers used include ethylene oxide (67), propylene oxide (99,100), epichlorohydrin (ECH) (101,102), phenyl glycidyl ether (102), 3.3-bis(chloromethyl) oxetane (BCMO) (25, 98, 101, 103) and 3-methyl-3-chloromethyl oxetane (103). Just as in THF homo-polymerization, a large variety of catalysts have veen used. In many cases the kinetics of copolymerization have been studied. Table 22 summarizes the monomer reactivity ratios, rx (THF), and r2 (comonomer) which have... 

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. 

XS = sulfonation, M = methylolation, MO = miscellaneous oxidation, G = grafting, P = phenolation, CM = carboxymethylation, MAC = maleic anhydride copolymerization, MCR = miscellaneous carboxyla-tion reactions, E = epichlorohydrin (also in conjunction with pheno-lated lignin), A = alkoxylation (i.e., ethylene, propylene, and butylene oxides), M+EP = modification with compounds containing unsaturated end groups ( divalent hydrocarbons ) followed by epoxidation with peroxide, MA = methacrylic acid. 

Several copolymers and condensates of oxidized starches with polymers have been developed. For example, products of starch dialdehyde condensation with acrylamide were prepared for further copolymerization with various monomers to form resins for coatings, molding powders,585 and materials for immobilization of enzymes, for instance, alpha amylase.586 Hypochlorite-oxidized starches were also reacted with acrylonitrile.507,521 Hypochlorite-oxidized starches were allowed to react with allylated starch dialdehyde,587 polycondensates of ammonia-dimethylamine-epichlorohydrin,588 polycondensates of starch dialdehyde with melamine,589 urea433,541,590 capable of precipitation of tannin591, carboxyamides,411 urea and formaldehyde,592 proteins,524,593,594 polyfyinyl alcohol),595 alkylammonium salts,519,596 alkoxyalkylamines,597... 

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... 

Functional initiators were also used for the synthesis of macromonomers. Initiation of the polymerization of propylene oxide or epichlorohydrin (ECH) with hydroxyethylacrylate (or hydroxymethylmethacrylate) and BF3 OEt2 provided macromonomers with acrylate (or methacrylate) end-groups [183]. Subsequent radical copolymerization with S or MMA produced the graft copolymers PS-g-PPO, PS-g-PECH and PMMA-g-PECH. 

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). 

Epichlorohydrin copolymer mfg., decolorization Epichlorohydrin copolymer mfg., flocculation Epichlorohydrin copolymer mfg., lipsticks Diethylaminoethyl acrylate copolymer, coatings Vinyl isobutyl ether Vinyl methyl ether copolymer, lacquers Vinyl isobutyl ether Vinyl methyl ether copolymer, latex emulsions Polyvinyl chloride copolymerization... 

Although butyl rubber is by far the most important commercial elastomer to be synthesized by cationic polymerization, several heterocyclic monomers provide useful elastomeric materials via this mechanism also. Epichlorohydrin can be polymerized to high molecular weight using a complex catalyst formed from a trialkylaluminum compound and water as shown in Eq. (58) [64, 130-132], For copolymerizations with ethylene oxide, a catalyst formed from a trialkylaluminum compound, water, and acetylacetone is useful [64,130], The mechanism proposed for these polymerizations is... 

We shall continue this study, attempting to Increase the epoxy end group content of the macromer. Capping agents other than ethylene oxide and other terminating agents will be explored. Macromer copolymerizations with propylene oxide or epichlorohydrin will be explored, attempting to prepare polyether type thermoplastic elastomers and hot-melt adhesive. 

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