Functional polymer laminates from hyperthermal hydrogen induced cross-linking.

The use of a hyperthermal hydrogen induced cross-linking process to prepare laminates comprising polypropylene, poly(isobutylene-co-isoprene), and poly(vinyl acetate) is described. In this new, milder alternative to conventional plasma techniques, neutral molecular hydrogen projectiles were used to create carbon radicals on impacted surfaces by collision-induced dissociation of C-H bonds, and this process was used to cross-link polymers on a polypropylene surface. It was demonstrated that multiple layers of cross-linked materials could be added, creating polymer laminates with each layer introducing new functionalities and properties. In particular, the present work shows that the process is largely nondestructive toward ester functionalities. First, the esters were grafted to become nonleachable. Then, the esters were subsequently hydrolyzed to convert the surface from hydrophobic to hydrophilic. Afterward, the esters could be recovered by simple esterification demonstrating that further chemical transformations were possible.

An investigation of the influence of R on the abilities of the polar monomers CH2=CH(CH2)8OR (R = Me, PhCH2, Ph3C, Me3Si, Ph3Si) to participate in O- rather than eta(2)-coordination to metallocene alkene polymerization catalysts; an unanticipated role for ether oxygen coordination in promoting polymerization.

Copolymerization of ethylene and propylene with polar monomers of the types CH(2)=CH(CH(2))(n)OH (n = 1-12) in order to introduce polar functionality into the resulting polymers is possible in principle if the hydroxyl groups of the polar monomers are masked such that they cannot coordinate to Lewis acidic catalyst sites and prevent eta(2)-alkene coordination. Although the use of hydrolysable ethers of the types CH(2)=CH(CH(2))(n)OR (R = alkyl, silyl; n = 1-12) is a protecting group strategy, which has been investigated somewhat, in fact this approach has not been investigated systematically and little is known of the effectiveness of various R groups in hindering oxygen coordination to e.g. metallocene polymerization catalyst systems. We report here the results (a) of an NMR study of reactions of an archetypal metallocene polymerization catalyst, Cp(2)ZrMe(mu-Me)B(C(6)F(5))(3), with the polar monomers CH(2)=CH(CH(2))(8)OR (R = Me, PhCH(2), Ph(3)C, Me(3)Si, Ph(3)Si), all protected versions of the readily available, long chain polar monomer 9-decen-1-ol, and (b) of an investigation of the copolymerization reactions of these same polar monomers with ethylene and propylene catalyzed by the well known rac-C(2)H(4)(Ind)(2)ZrCl(2)/MAO catalyst system. While increasing the steric requirements of the groups R does decrease the apparent abilities of the ethers to displace [BMe(C(6)F(5))(3)](-) from the [Cp(2)ZrMe](+) cation, there is no correlation of size of R with the degrees of incorporation of the polar monomers into copolymers of ethylene and propylene. Instead, a heretofore unsuspected role for catalyst activation by the ether linkage is suggested.