Ring-opening polymerizations examples

Ring-Opening Polymerization. Examples of the formation of copolymers by ring-opening reactions are shown in equations 33 and 34... 

Although the method was proposed by Hall as far back as 1958 [60], the ROP of cyclic ureas has attracted only minor interest The five- and seven-membered cyclic ureas (Scheme 5.8), which are referred to as dimethylene urea and tetramethylene urea, can be successfully ring-opening polymerized. Examples of suitable catalysts for dimethylene urea are sodium hydride, sodium hydroxide, sec-butylUthium, dibutylmagnesium and diethylzinc. The ROP of tetramethylene urea is achieved by heating in the melt or in solution in the presence of sodium hydride [60]. 

We conclude this section by citing some examples of ring-opening polymerizations. Table 5.9 lists several examples of ring-opening polymerizations. In addition to the reactions listed, we recall the polymerizations of lactones and lactams exemplified by equations in Table 5.3 and 5.4, respectively. 

The polymerizations of tetrahydrofuran [1693-74-9] (THF) and of oxetane [503-30-0] (OX) are classic examples of cationic ring-opening polymerizations. Under ideal conditions, the polymerization of the five-membered tetrahydrofuran ring is a reversible equiUbtium polymerization, whereas the polymerization of the strained four-membered oxetane ring is irreversible (1,2). 

HO—R—COOH, or an amino acid, H2N—R—COOH. In some cases, such monomers self-condense to a cycHc stmcture, which is what actually polymerizes. For example, S-caprolactam (1) can be thought of as the self-condensation product of an amino acid. Caprolactam undergoes a ring-opening polymerization to form another... 

Even within the small numbers of studies conducted to date, we are already seeing potentially dramatic effects. Free radical polymerization proceeds at a much faster rate and there is already evidence that both the rate of propagation and the rate of termination are effected. Whole polymerization types - such as ring-opening polymerization to esters and amides, and condensation polymerization of any type (polyamides, polyesters, for example) - have yet to be attempted in ionic liquids. This field is in its infancy and we look forward to the coming years with great anticipation. 

Ring opening polymerization may also occur by an addition chain reaction. For example, a ring opening reaction polymerizes trioxane to a polyacetal in the presence of an acid catalyst. Formaldehyde also produces the same polymer ... 

The only known instance of ring-opening polymerization with these compounds is also the only report on the successful polymerization of 2,5-dihydrofuran74 in which this compound was cationically copolymerized with epichlorhydrin (rx 0, r2 0), propylene oxide (r, 0, r2 0) and 3,3-bischloromethyl oxacyclobutane (/ ] 0, r2 = 1.6). It was shown that all the copolymers obtained possessed a certain degree of unsaturation which was attributed to the presence of open units from 2,5-dihydrofuran. Thus, for example the alternating copolymer with epichlorhydrin had the following structure (IR spectra, Cl content. C=C analysis) ... 

Typical Examples of Calalysl Systems for the Homogeneous Ring-Opening Polymerization of Cydopentene and Cyclooctene c-,... 

The ring-opening polymerization of ketene acetals (45, X=0) provides a novel route to polyesters and many examples have now been reported (Scheme 4.27). " "7 A disadvantage of these systems is the marked acid sensitivity of the monomers which makes them relatively difficult to handle and complicates characterization. This area is covered by a series of reviews by Bailey ct a/.177 228 ... 

Thus, confirmation of whether the product obtained in an attempted reaction in a true random copolymer is important to clarify the mechanism of the propagation reaction and to correlate structure and reactivity in ring-opening polymerizations. Considering that apparent copolymers may be formed by reactions other than copdymerization, for example, by ionic grafting or by combination of polymer chains, characterization of cross-sequences appears to be one of the best ways to check the formation of random copolymers. 

Step growth polymerization can also take place without splitting out a small molecule. Ring-opening polymerization, such as caprolactam polymerization to nylon 6, is an example. Polyurethane formation from a diol and a diisocyanate is another step growth polymerization in which no small molecule is eliminated. 

Ring-opening polymerization of 2-methylene-l,3-dioxepane (Fig. 6) represents the single example of a free radical polymerization route to PCL (51). Initiation with AIBN at SO C afforded PCL with a of 42,000 in 59% yield. While this monomer is not commercially available, the advantage of this method is that it may be used to obtain otherwise inaccessible copolymers. As an example, copolymerization with vinyl monomers has afforded copolymers of e-caprolactone with styrene, 4-vinylanisole, methyl methacrylate, and vinyl acetate. 

In another example, a polymer-supported chromium porphyrin complex was supported on ArgoGel Cl and then employed for the ring-opening polymerization of 1,2-cyclohexene oxide and C02 [95], This complex showed higher activity than a C02-soluble equivalent, and the solid nature of the catalyst meant that recycling of the catalyst was much easier. 

The first example of a hybrid polymer that contains both [NS(0)C1] and [NPC12] units, 141a, was obtained as a pale yellow elastomer by ring-opening polymerization (Scheme 10).305 In the presence of GaCl3, this polymerization process proceeds quantitatively at room temperature in CH2Cl2-306... 

As the first, and perhaps the most well-studied form of living polymerizations, anionic procedures have attracted considerable attention both academically and industrially [2, 3], While numerous examples of living procedures have been developed, they can be classified into two main families carbanionic polymerization of vinyl monomers and anionic ring opening polymerizations. 

Although the first examples of hyperbranched polymers proposed by Flory involved condensation-type polymerization strategies, the first well-characterized hyperbranched example involved the ring-opening polymerization of 2-carboxylic-2-oxazoline derivatives. As early as 1988, Odian and Tomalia [2] reported the ring-opening polymerization of these derivatives to form random... 

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