Ru and Sm catalyzed polyaddition of dialdehydes to give polyesters. Application of Tishchenko type reactions to polymer synthesis
✍ Scribed by Isao Yamaguchi; Takahiro Kimishima; Kohtaro Osakada; Takakazu Yamamoto
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 211 KB
- Volume
- 35
- Category
- Article
- ISSN
- 0887-624X
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✦ Synopsis
RuH 2 (PPh 3 ) 4 catalyzed Tishchenko type polyaddition of terephthalaldehyde gives aromatic polyester (1), which contains three structural units, [OCH 2 {C 6 H 4 {CH 2 O] (1a), [OCH 2 -C 6 H 4 {CO] (1b), and [CO{C 6 H 4 {CO] (1c).
1
H-NMR spectrum shows the presence of the three units in a 1 : 2 : 1 ratio. Isophthalaldehyde also undergoes similar polyaddition to give another aromatic polyester (2), while 1,12-dodecanedial gives an aliphatic polyester (3) containing the following structural units: [OCH 2 {(CH 2 ) 10 {CH 2 O] (3a), [OCH 2 {(CH 2 ) 10 {CO] ( 3b), and [CO{(CH 2 ) 10 {CO] (3c). The above polymers have M n of 2.7 1 10 3 -5.4 1 10 3 and M w of 4.3 1 10 3 -9.7 1 10 3 , respectively. Mixtures of terephthalaldehyde and 1,12dodecanedial produce copolymers, which contain the units 1a-1c and 3a-3c in a random sequence. In the copolymerization, terephthalaldehyde shows a strong tendency to give 1c units, whereas 1,12-dodecanedial predominantly affords 3a units. SmI 2 also catalyzes polyaddition of terephthalaldehyde to give the corresponding polyester with M n of 1.7 1 10 3 and M w of 3.7 1 10 3 , respectively.