Divinyl adipate

Divinyl esters reported first by us are efficient monomers for polyester production under mild reaction conditions. In the lipase PF-catalyzed polymerization of divinyl adipate and 1,4-butanediol in diisopropyl ether at 45°C, a polyester with molecular weight of 6.7 x 10 was formed, whereas adipic acid and diethyl adipate did not afford the polymeric materials under similar reaction conditions (Scheme 3). 

Two-step synthesis of sugar-containing polyesters by lipase CA catalyst was reported (Scheme 13)." Lipase CA catalyzed the condensation of sucrose with an excess of divinyl adipate to produce sucrose 6,6 -O-divinyl adipate, which was reacted with a,oo-alkylene diols by the same catalyst, yielding polyesters containing a sucrose unit in the main chain. This method conveniently affords... 

If the condensation proceeds far enough, a network structure is easily formed. Similarly, copolymerization of a little divinyl adipate with vinyl acetate yields a nonlinear polymer in which chains of bifunctional vinyl acetate units are bridged, or cross-linked, by the tetrofunctional divinyl adipate units, as indicated on the following page, where the divinyl adipate unit is enclosed between vertical dashed lines ... 

Divinyl monomers such as divinylbenzene, divinyl adipate, and ethylene dimethacrylate, in which the reaction of one double bond does not alter greatly the reactivity of the other, polymerize to highly cross-linked structures. 

Lipase-catalyzed polymerization of divinyl adipate or divinyl sebacate with a, co-glycols with different chain length has been reported [40]. Lipases CA, MM, PC, and PF showed high catalytic activity toward the polymerization. A combination of divinyl adipate, 1,4-butanediol, and lipase PC afforded the polymer with number-average molecular weight (Mn) of 2.1 x 104. The yield of the polymer from divinyl sebacate was higher than that from divinyl adipate, whereas the opposite tendency was observed in the polymer molecular weight. 

Detailed studies on the lipase-catalyzed polymerization of divinyl adipate and 1,4-butanediol were performed [41-44]. Bulk polymerization increased the reaction rate and molecular weight of the polymer however, the hydrolysis of the terminal vinyl ester significantly limited the formation of the polyester with high molecular weight. A mathematical model describing the kinetics of this polymerization was proposed, which effectively predicts the composition (terminal structure) of the polyester. 

The first case is the copolymerization of monomer A with diene BB where all the double bonds (i.e., the A double bond and both B double bonds) have the same reactivity. Methyl methacrylate-ethylene glycol dimethacrylate (EGDM), vinyl acetate-divinyl adipate (DVA), and styrene-p- or m-divinylbenzene (DVB) are examples of this type of copolymerization system [Landin and Macosko, 1988 Li et al., 1989 Storey, 1965 Ulbrich et al., 1977]. Since r = Yi, Fi = f and the extent of reaction p of A double bonds equals that of B double bonds. There are p[A] reacted A double bonds, p[B] reacted B double bonds, and p2[BB] reacted BB monomer units. [A] and [B] are the concentrations of A and B double bonds,... 

Regarding polyesters, Russell and coworkers reported the lipase (Novo-zyme-435)-catalyzed polycondensation of various triols and divinyl adipate for the synthesis of polyesters having pendant hydroxy groups (Scheme 28) [109]. Before this report, the divinyl adipate was reported to be available for enzymatic polyesterification of diols by Kobayashi and coworkers [110,111], in which the equilibrium of esterification is shifted in the forward direction by tautomerization of the eliminated vinyl alcohol to acetaldehyde. The Mw values of the resulting polyesters varied according to the triol used and ranged from 3000 to 14 000. Analysis by MALDI-TOF mass... 

Fig. 3. GPC elution behavior of polyvinyl acetate gels crosslinked with different amounts of divinyl adipate...

Fjg. 10 Elution behavior of gels with a dense shell, PVAc with 10 wt-% divinyl adipate (n-octane)... 

Many chain-growth copolymerizations include dienes such as divinyl benzene or divinyl adipate that act as crosslinking agents and lead to gel formation. Polymerization kinetics in such cases are complex and are beyond the scope of a book on homogeneous reactions. Here, only binary copolymerization of monofunctional monomers will be examined. For an excellent and extensive treatment that includes copolymerization of more than two monomers as well as crosslinking by bifunctional monomers, the reader is refer to Odian s book [123]. 

This reaction gained technical importance for the synthesis of vinyl esters of higher carboxylic acids [69-72]. Thus, divinyl adipate is now produced by Wacker-Chemie from adipic acid and vinyl acetate. 

Fluorinated polyesters were synthesized by the enzymatic polymerization of divinyl adipate with fluorinated diols.221 Using 3,3,4,4,5,5,6,6-octafluo-rooctan-l,8-diol as glycol monomer in the lipase CA-catalyzed polymerization in bulk produced the polymer with the highest molecular weight (Mn 5 x 103). 

Problem 7.23 Predict the extent of reaction at which gelation would occur in (a) vinyl acetate-ethylene glycol dimethacrylate and (b) methyl methaciylate-divinyl adipate systems, both containing 15 mol% of the divinyl compound. Assume that the reaction conditions for the two systems are such as to yield the same DP. of 1000 for the uncrosslinked polymer. Take rj and values from Table 7.1 for the respective analogous vinyl-vinyl copolymerizations. 

For use in plastics, this might require chain extension with diisocyanates, bisoxazolines, carbodiimides, bis(an-hydrides), and such. One use of the oligomers would be to form polyurethanes by reaction with isocyanates. The use of acid chlorides can be avoided if the polymers are made by ester exchange or made enzymatically, with compounds such as divinyl adipate. Poly(butylene sebacate) with a molecular weight of 46,400 has been made has been made from bis(2,2,2-trifluoroethyl)sebacate and 1,4-butane diol.150 One polyester with a molecular weight of 24,000 has been made by ester exchange from isosorbide and a... 

In addition the Novozym 435-catalyzed bulk polymerization of divinyl adipate and 1,4-butanediol was reported [44]. The highest M, =23 236 in 98.3% yield was obtained after 72 h polymerization at 50 °C. It was found that the product molecular weight was decreased when the reaction was conducted without taking proper precautions to exclude water in reactions that can hydrolyze reactive divinyl ester groups. They also found excellent agreement between their experimental data and that predicted by a mathematical model [66]. 

Uyama, H., and Kobayashi, S. (1994) Lipase-catalyzed polymerization of divinyl adipate with glycols to polyesters. Chem. Lett., 23 (9), 1687-1690. 

Mesiano, A.J., Enick, R.M., Beckman, E.J., and Russell, A.J. (2001) The phase behavior of fluorinated diols, divinyl adipate and a fluorinated polyester in supercritical carbon dioxide. Fluid Phase Equilibria, 178 (1-2), 169-177. 

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