Citation: Rui-ning Shang, Huan Gao, Yu-lian Li, Bin Wang, Zhe Ma, Li Pan, Yue-sheng Li. Synthesis and Properties of Carbazole-functionalized Isotactic Polypropylenes[J]. Acta Polymerica Sinica, ;2019, 50(11): 1187-1195. doi: 10.11777/j.issn1000-3304.2019.19081 shu

Synthesis and Properties of Carbazole-functionalized Isotactic Polypropylenes

School of Materials Science and Engineering, Tianjin University, Tianjin 300350

Corresponding author: Li Pan, lilypan@tju.edu.cn
Received Date: 18 April 2019
Revised Date: 6 May 2019
Available Online: 27 May 2019

A series of novel amino-functionalized isotactic polypropylenes with high molecular weight and satisfying functional comonomer incorporation were prepared by direct copolymerization of propylene and α-olefins carrying carbazole functional groups. The homogeneous non-metallocene catalyst system consisting of dimethyl(pyridylamido)Hf(IV) complex, [Ph₃C][B(C₆F₅)₄], and AliBu₃ showed good tolerance to carbazole groups and promoted the copolymerization of propylene with 11-carbazole-1-undecene effectively under mild reaction conditions, in which very high catalytic activity (up to 4.08 × 10⁶ g_polymer mol_Cat.⁻¹ h⁻¹) was achieved. The functional copolymers obtained possessed high molecular weight (up to 7.02 × 10⁵) and tacticity ([mmmm] > 99%), as well as decent incorporation of carbazole functional groups (up to 13.5 mol%). Besides, DSC and TGA results verified the excellent thermostability of most copolymer products by giving decomposition temperatures around 450 °C as well as high melting points. Representative physical properties such as hydrophilicity, mechanical performance, and fluorescent characteristics of these iPPs functionalized by carbazole groups have also been explored. The increased incorporation of 11-carbazole-1-undecene monomer could reduce the water contact angle gradually and thus make significant improvement in surface properties; the copolymers became hydrophilic when comonomer incorporation exceeded 4.1 mol%. In terms of the mechanical properties, elongation at break of the copolymer barely increased at low incorporation (1.2 mol%), and the material still showed typical attributes of rigidity and brittleness. As more 11-carbazole-1-undecene monomer was incorporated (> 6.2 mol%), toughness of the materials was dramatically enhanced yet their stiffness was inevitably sacrificed. In addition, the introduction of carbazole group endowed the copolymers with unique fluorescent characteristics—they could emit purple fluorescence under 365 nm UV light in both solution and film states, thereby making this kind of functional polypropylene materials valuable and promising for the extensive applications in optoelectronic devices.
- Functional polypropylene,
- Fluorescent property,
- Thermostability,
- Hydrophilicity,
- Mechanical property,
- Transition metal catalyst
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