A number of new polymers have been studied. They include polymers obtained by chain reaction polymerization of olefins and epoxides with functional groups where the polymerizable group was separated from the functional group by an inert spacer group, the preparation of head-to-head polymers, and the preparation of optically active polymers based on the macromolecular asymmetry.

Abstractω‐Alkenoic acids, either commercially available or synthesized, were esterified to their corresponding methyl esters. They were characterized by their infrared, 1H‐, and 13C‐NMR spectra. The ω‐alkenoates prepared were: propenoate (acrylic acid), butenoate, pentenoate, hexenoate, heptenoate, octenoate, nonenoate, and decenoate. These compounds were epoxidized with m‐chloroperoxybenzoic acid to the corresponding methyl ω‐epoxyalkanoates. The rate of epoxidation of the double bond is found to increase as the double bond is separated from the carbomethoxy group by increasing numbers of methylene groups. When at least three methylene groups are inserted, the rate of epoxidation becomes constant and is similar to the epoxidation of ω‐olefins. The methyl ω‐epoxyalkanoates were characterized by their infrared, 1H‐, and 13C‐NMR spectra. Methyl ω‐alkenoates and methyl ω‐epoxyalkanoates were prepared and characterized, and their purification was studied in preparation for their investigation as monomers for olefin or epoxide polymerization using corrdination initiators.

Several aspects of modern design of macromolecular architecture are discussed: the influence and importance of functional groups which often dominate the characteristics of the macromolecular structure; the importance of the spacer groups that provide flexibility and allow the functional group to act independently from the main chain when the functional group is attached to the main chain. Examples are given for the synthesis of reactive, telechelic polymers, for polymerizability of monomers whose polymerizable group is separated from the functional group by a flexible methylene spacer, and the reactivity of functional groups separated from the main chain by a spacer group.

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH2CHCICHCICH2units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.

ω-Alkenonic acids, methyl ω-alkenoates, and methyl ω-epoxyalkanoates of 3 to 11 carbon atoms with –(–CH2–)– spacer groups between the epoxy ring and the carboxyl group have been synthesized and are being characterized. The compounds which have 1, 2, 5 and 8 –(–CH2–)– groups were selected for more extensive studies including polymerization and copolymerization studies. With an aluminumalkyl–water initiator modified with acetylacetone (AlEt3–H2O–AcAc, 1:0.5:1), methyl ω-epoxyalkanoates have been polymerized to polymers of moderate to high molecular weight (for n=8, Mn=2.5×105, and copolymerized with such cyclic ethers as ethylene oxide, propylene oxide, and n-hexene oxide. Investigations of the copolymerizations of ω-epoxyalkanoates with other cyclic ethers and the use of other modified aluminumalkyl–water systems as initiators are now underway. Classical cationic initiators for ω-epoxyalkanoate polymerizations have not resulted in the formation of high polymers although the epoxides were not present after several days of reaction.