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Coordination‐Insertion Copolymerization of Norbornene and p‐Substituted Styrenes Using Anilinonaphthoquinone‐Ligated Nickel Complexes
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-01-30 , DOI: 10.1002/macp.201900494 Samiul Islam Chowdhury 1 , Ryo Tanaka 1 , Yuushou Nakayama 1 , Takeshi Shiono 1
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-01-30 , DOI: 10.1002/macp.201900494 Samiul Islam Chowdhury 1 , Ryo Tanaka 1 , Yuushou Nakayama 1 , Takeshi Shiono 1
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Coordination‐insertion copolymerization of norbornene (N) and p‐substituted styrene (XS) (X = MeO, Me F, Cl, and Br) is carried out using anilinonaphthoquinone‐ligated nickel complexes [Ni(C10H5O2NAr)(Ph)(PPh3): 1a, Ar = C6H3‐2,6‐iPr; 1b, Ar = C6H2‐2,4,6‐Me; 1c, Ar = C6H5] with modified methylaluminoxane (MMAO) as a cocatalyst. The ligand of the nickel complex affects the catalytic activity. The effect of the p‐substituent on the activity is remarkable and the activity decreases in the following order, Br > Cl > F > Me > MeO. The molecular weight of the produced polymer also decreases with the same order. The activity increases with raising the temperature from 0 to 70 °C accompanied by the decrease in the molecular weight of the produced polymers. The incorporation of XS determined by 1H and 13C NMR decreases in the following order, MeO ≥ Me > F > Cl > Br. The glass transition temperatures of the N/XS copolymers determined by differential scanning calorimetry show a broad range from 120 to 365 °C according to the XS content.
中文翻译：
降冰片烯和对位取代苯乙烯的苯胺-萘醌醌连接的镍配合物的配位-插入共聚
降冰片烯（N）和对位取代的苯乙烯（XS）（X = MeO，Me F，Cl和Br）的配位-插入共聚反应是通过苯甲酰萘醌连接的镍络合物[Ni（C 10 H 5 O 2 NAr）进行的（Ph）（PPh 3）：1a，Ar = C 6 H 3 -2,6- i Pr; 1b，Ar = C 6 H 2 -2,4,6-Me; 1c， Ar ＝ C 6 H 5 ]，用改性甲基铝氧烷（MMAO）作为助催化剂。镍配合物的配体影响催化活性。p的作用活性上的取代基显着，并且活性按以下顺序降低：Br> Cl> F> Me> MeO。产生的聚合物的分子量也以相同的顺序降低。活性随温度从0升高到70°C而增加，同时所产生的聚合物分子量降低。由1 H和13 C NMR确定的XS的引入按以下顺序降低，MeO≥Me> F> Cl> Br。通过差示扫描量热法测定的N / XS共聚物的玻璃化转变温度根据XS含量显示在120至365℃的宽范围内。
更新日期：2020-01-30
中文翻译：
降冰片烯和对位取代苯乙烯的苯胺-萘醌醌连接的镍配合物的配位-插入共聚
降冰片烯（N）和对位取代的苯乙烯（XS）（X = MeO，Me F，Cl和Br）的配位-插入共聚反应是通过苯甲酰萘醌连接的镍络合物[Ni（C 10 H 5 O 2 NAr）进行的（Ph）（PPh 3）：1a，Ar = C 6 H 3 -2,6- i Pr; 1b，Ar = C 6 H 2 -2,4,6-Me; 1c， Ar ＝ C 6 H 5 ]，用改性甲基铝氧烷（MMAO）作为助催化剂。镍配合物的配体影响催化活性。p的作用活性上的取代基显着，并且活性按以下顺序降低：Br> Cl> F> Me> MeO。产生的聚合物的分子量也以相同的顺序降低。活性随温度从0升高到70°C而增加，同时所产生的聚合物分子量降低。由1 H和13 C NMR确定的XS的引入按以下顺序降低，MeO≥Me> F> Cl> Br。通过差示扫描量热法测定的N / XS共聚物的玻璃化转变温度根据XS含量显示在120至365℃的宽范围内。
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