Cyclic copolymers

Polymers with pendant cyclic carbonate functionality were synthesized via the free radical copolymerization of vinyl ethylene carbonate (4-ethenyl-l,3-dioxolane-2-one, VEC) with other imsaturated monomers. Both solution and emulsion free radical processes were used. In solution copolymerizations, it was found that VEC copolymerizes completely with vinyl ester monomers over a wide compositional range. Conversions of monomer to polymer are quantitative with complete incorporation of VEC into the copolymers. Cyclic carbonate functional latex polymers were prepared by the emulsion copolymerization of VEC with vinyl acetate and butyl acrylate. VEC incorporation was quantitative and did not affect the stability of the latex. When copolymerized with acrylic monomers, however, VEC is not completely incorporated into the copolymer. Sufficient levels can be incorporated to provide adequate cyclic carbonate functionality for subsequent reaction and crosslinking. The unincorporated VEC can be removed using a thin film evaporator. The Tg of VEC copolymers can be modeled over the compositional range studied using either linear or Fox models with extrapolated values of the Tg of VEC homopolymer. 

The copolymerization of cyclic polar monomers can be used for the preparation of various classes of linear, hetero-chain copolymers. Cyclic compotmds of the same chemical type, differing from one another only in the number of units in the ring or the presence of various substituents, can be copol3nnerlzed to form products, some of which find a wide variety of application. The copolymerization of vario oxides to form linear polyethers has been extensively studiedA A number of wstlgatlons been made of the copolymerization of lactones and lactams to form polyesters and polyamides respectively. 

Pike, D.B., Ghandehari, H. HPMA copolymer-cyclic RGD conjugates for tumor targeting. Adv. Drug Deliv. Rev. 62, 67-183 (2010)... 

Cyclic Polyolefins (GPO) and Gycloolefin Copolymers (GOG). Japanese and European companies are developing amorphous cycHc polyolefins as substrate materials for optical data storage (213—217). The materials are based on dicyclopentadiene and/or tetracyclododecene (10), where R = H, alkyl, or COOCH. Products are formed by Ziegler-Natta polymerization with addition of ethylene or propylene (11) or so-called metathesis polymerization and hydrogenation (12), (101,216). These products may stiU contain about 10% of the dicycHc stmcture (216). 

Dialkyl peroxides have the stmctural formula R—OO—R/ where R and R are the same or different primary, secondary, or tertiary alkyl, cycloalkyl, and aralkyl hydrocarbon or hetero-substituted hydrocarbon radicals. Organomineral peroxides have the formulas R Q(OOR) and R QOOQR, where at least one of the peroxygens is bonded directly to the organo-substituted metal or metalloid, Q. Dialkyl peroxides include cyclic and bicycflc peroxides where the R and R groups are linked, eg, endoperoxides and derivatives of 1,2-dioxane. Also included are polymeric peroxides, which usually are called poly(alkylene peroxides) or alkylene—oxygen copolymers, and poly(organomineral peroxides) (44), where Q = As or Sb. 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerisation is usually initiated by alkah hydroxides, especially potassium hydroxide. In the base-catalysed polymerisation of propylene oxide, some rearrangement occurs to give aHyl alcohol. Further reaction of aHyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly diftmctional. By using sine hexacyano cobaltate as catalyst, a more diftmctional polyol is obtained (20). Olin has introduced the diftmctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalysed homopolymerisation of tetrahydrofuran. Copolymers derived from tetrahydrofuran and ethylene oxide are also produced. 

Metallocene catalysis can also make possible the production of copolymers of propylenes with monomers such as long-chain olefins, cyclic olefins and styrene which is not possible with more conventional Ziegler-Natta catalysts. 

Polymers have also been prepared from cyclic amines such as piperazine and bis-(p-aminocyclohexyl)methane. An early copolymer, Igamid 1C, was based on the latter amine. This amine is also condensed with decanedioic acid, HOOC (CH2)iqCOOH, to produce to silk-like fibre Quiana (Du Pont). 

Plastics are susceptible to brittle crack-growth fractures as a result of cyclic stresses in much the same way as metals. In addition, because of their high damping and low thermal conductivity, plastics are prone to thermal softening if the cyclic stress or cyclic rate is high. Examples of the TPs with the best fatigue resistance include PP and ethylene-propylene copolymers. 

A more complicated behaviour was obtained with divinyl ether due to the formation of both cyclic structures and pendent vinyl groups in the chain. The failure of such olefins as styrene and isopropenylbenzene to give copolymers with 2-fural-dehyde, and in fact to homopolymerize in its presence, was blamed on the strength of the complex formed between the initiator and the aldehyde, believed too stable to initiate polymerization. 

Segmented copolymers can also be prepared by polymerization in the presence of appropriate cyclic trithiocarbonates as RAFF agents.661... 

Figure 11. Cyclic votammetry (top) and in situ electronic conductivity from rotating-disk voltammetry [ , Fig. 9(C)] and sandwich electrode voltammetry [ , Fig. 9(B)] for poly(3-methylthiophene) in acetonitrile containing 0.1 M BU4CIO4.60 (Reprinted from J. Ochmanska and P. G. Pickup, In situ conductivity of poly-(3-methylthiophene) and (3-methylthiophene)x,-[Ru(2,2 -bipyridine)2 (3- pyrrol-l-ylmethyl pyridine)2]2+ copolymers, J. Electroanal. Chem. 297, 211-224, 1991, with kind permission from Elsevier Sciences S.A.)...

Polymerization equilibria frequently observed in the polymerization of cyclic monomers may become important in copolymerization systems. The four propagation reactions assumed to be irreversible in the derivation of the Mayo-Lewis equation must be modified to include reversible processes. Lowry114,11S first derived a copolymer composition equation for the case in which some of the propagation reactions are reversible and it was applied to ring-opening copalymerization systems1 16, m. In the case of equilibrium copolymerization with complete reversibility, the following reactions must be considered. 

The propagating species involved in the polymerization of cyclic formal seem to resemble carbocations, and random copolymers are formed in the copolymerization of cyclic formals with styrene. For the copolymerization of DOL with styrene, the DOL-St cross-sequence was estimated, by NMR or by chemical methods, from the decrease of the formal unit in the copolymer and the formation of nearly random copolymer was confirmed132. ... 

Anionic copolymerization of cyclic monomers occurs only between similar monomer pairs. Random copolymers are not formed between vinyl monomers and epoxides or lactones198 because the propagating species are very different. Thus, the success of the copolymerization of cyclic disulfide and nitropropylene was an exceptional case... 

Anionic copolymerization of e-caprolactam and cj-caprylolactam was also reported212,213. Organosiloxane copolymers can be prepared from two different cyclics by using acid or base catalysts214. ... 

Ethylenimine is known to spontaneously form copolymers with /3-propiolactone274) or cyclic imides275). Crystalline copolyamides of alternating structure were obtained with the latter monomer. 

Propanesultone also forms random and alternating copolymers with N-substituted ethylenimines276) and similar mechanisms involving zwitter ions were suggested. The polymerization through zwitter ions was performed with cyclic phosphonite as the Mn monomer and pyruvic acid as the ME monomer250). 

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