Polymerization of β‐pinene with ziegler‐type catalysts

Abstract

The successful homopolymerization of 0-pineiie by the use of Friedel-Crafts type catalysts is quite well established, and the homopolymers are commercially a~a i l a b l e .~ It was the intent of this work to compare the * This is a partial report of work done under contract with thrw Utilixatioii 1tcbc:trrh and Development Divisions, Agricultural 1tesc:trc.h Service, U. S. L)cpartnieri t of hgriculture, and authorized by the Researrh and Marketing Act.

Synthesis and characterization of functional copolymers of citronellol with butylmethacrylate initiated by benzoyl peroxide

“…The synthesis of copolymer(s) of terpenes is one of the connecting links in this series. A search of literature reveals that attempts have been made by chemists to develop a substitute for polyterpenes from petroleum distillates,1 but no such substitute has been developed yet, as most of the terpenes do not undergo homopolymerization because of steric hindrance,2 low stabilization energy between monomers and free radicals in transition state,3 excessive chain transfer,4 and termination of cyclization as in case of 1,2‐disubstituted ethylene,5 except α,λ‐pinene(s), which have been polymerized by Ziegler‐Natta6, 7 as well as Lewis acid catalysts 8. Thus, literature is almost devoid of radical polymerization of terpenes, except few recent contributions from our laboratory, i.e., geraniol‐ co ‐acrylonitrile/benzoyl peroxide (BPO)/70°C,9 limonene‐ co ‐vinylacetate/AIBN/65°C,10 αterpineol‐ co ‐ N ‐vinylpyrrolidone/BPO/80°C,11 linalool‐ co ‐butylmethacrylate/BPO/80°C,12 linalool‐ co ‐acrylamide/BPO/75°C,13 linalool‐ co ‐acrylonitrile/BPO/75°C,14 geraniol‐ co ‐styrene/BPO/80°C,15 limonene‐ co ‐acrylonitrile/BPO/70°C,16 limonene‐ co ‐methyl methacrylate/BPO/80°C,17 limonene‐ co ‐styrene/AIBN/80°C,18 α‐terpineol‐ co ‐butyl methacrylate/BPO/80°C,19 α‐terpineol‐ co ‐methyl methacrylate/AIBN/80°C 20.…”

Synthesis of optically active copolymers of 2,3,4,5,6‐pentafluorostyrene and β‐pinene with low surface energies

“…These polymerizations involve a cationic mechanism in which adventitious moisture initiates polymerization in the presence of a Lewis acid 36. β‐Pinene has since been cationically polymerized37–43 and copolymerized with several monomers as a mixture of terpenes44 and with isobutylene,45–47 styrene,48–50 and p ‐methylstyrene 48, 50…”