Substitution and elimination reactions of poly(epichlorohydrin) and poly(2‐chloroethyl vinyl ether) using phase transfer catalysis

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Abstract
The reactions of poly(epichlorohydrin) (PECH) and poly(2‐chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra‐n‐butylammonium bromide (TBAB), 18‐crown‐6 (CR6), and dicyclohexyl‐18‐crown‐6 (DCHC) is a solid—liquid two‐phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β‐elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.