Citation: Wei-qin Xu, Tian Liang, Hong-jun Yang, Xiao-qiang Xue, Wen-yan Huang, Qi-min Jiang, Bi-biao Jiang. One-step Synthesis of Poly(styrene oxide) Macromonomers Catalyzed by Phosphazene Base and Graft Copolymerization[J]. Acta Polymerica Sinica, ;2019, 50(2): 118-123. doi: 10.11777/j.issn1000-3304.2018.18180 shu

One-step Synthesis of Poly(styrene oxide) Macromonomers Catalyzed by Phosphazene Base and Graft Copolymerization

1.
Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials & School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou 213164
2.
Changzhou Uiversity Huaide College, Jingjiang 214500

Corresponding author: Bi-biao Jiang, jiangbibiao@cczu.edu.cn
Received Date: 13 August 2018
Revised Date: 5 September 2018
Available Online: 12 October 2018

Poly(styrene oxide) (PSO) macromonomers were synthesized in one step through the anionic ring-opening polymerization (ROP) of styrene oxide (SO) at room temperature, with 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2Ʌ⁵,4Ʌ⁵-catenadi-(phosphazene) (t-BuP₄) as the catalyst, and 4-vinylbenzyl alcohol (VBA) as the functional initiator. The copolymerization of PSO macromonomers and methyl methacrylate (MMA) was carried out at different temperatures through free radical co-polymerization to prepare graft copolymers. The structures and properties of the functional initiator, the obtained macromonomers and the grafted copolymers were characterized by nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results showed that functional initiator VBA was synthesized successfully. Super base t-BuP₄ displayed high catalytic activity for the ring-opening polymerization of SO, resulting in PSO macromonomers with polymerizable vinyl group, controlled molecular weight (M_n = 2700 – 11300 g/mol), and narrow molecular weight distribution (< 1.19). NMR measurement confirmed that the copolymerization of PSO macromonomers and MMA was carried out successfully to produce grafted copolymers. With the increase of copolymerization temperature, the conversion of MMA increased (> 96%), while the molecular weight of the copolymers decreased and the molecular weight distribution became narrow. The GPC curves of the product for the copolymerization before precipitation were bimodal, the molecular weight of the obtained polymers was low (6200 – 7800 g/mol) and the molecular weight distribution was wide (6.39 – 10.41). After precipitation, the GPC curves showed a unimodal signal, the molecular weight became larger (4.33 × 10 ⁴ – 5.95 × 10 ⁴ g/mol) and the molecular weight distribution became narrower (1.46 – 1.62). Integral calculation of the GPC curves and NMR measurement confirmed that there were about 3.8% – 4.6% inert components in the synthesized macromonomers. For the thermal analysis of PSO, PMMA- g-PSO and PMMA, the glass transition temperature (T_g) measured by DSC showed that the prepared grafted copolymer had only one T_g, which was in good accordance with the theoretical value calculated according to the Fox equation. This result further proved that the graft copolymers were successfully prepared.
- Macromonomer,
- Graft copolymerization,
- Phosphazene base,
- One-step method
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