Citation: Shuang-bin Fu, Yu-sheng Qin, Li-jun Qiao, Xian-hong Wang, Fo-song Wang. Synthesis of High Primary Hydroxyl Content Poly(carbonate-ether) Polyol[J]. Acta Polymerica Sinica, ;2019, 50(4): 338-343. doi: 10.11777/j.issn1000-3304.2018.18274 shu

Synthesis of High Primary Hydroxyl Content Poly(carbonate-ether) Polyol

1.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022
2.
University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Yu-sheng Qin, ysqin@ciac.ac.cn Xian-hong Wang, xhwang@ciac.ac.cn
Received Date: 21 December 2018
Revised Date: 8 January 2019
Available Online: 24 January 2019

During the past decade, poly(carbonate-ether) polyols, also known as CO₂-polyols, have been synthesized by the copolymerization of CO₂ and propylene oxide (PO) with double metal cyanide (DMC) catalyst in the presence of various chain transfer agents. CO₂-polyols show great potential as substitutes for polyols derived from fossil feedstock in the polyurethane industry. However, the ring opening reaction of PO generally occurs at the methylene carbon-oxygen bond due to less steric hindrance producing CO₂-polyol mainly with the second hydroxyl (2° OH) as terminal group, therefore, the terminal primary hydroxyl (1° OH) content is usually lower than 20%, which leads to their much lower reactivity with isocyanate. Three methods were chosen for increasing the primary hydroxyl content of CO₂-polyols, including ethylene oxide (EO) end-capping, copolymerization end-capping of EO and CO₂, and one-pot ternary polymerization (PO, EO and CO₂) end-capping. The primary hydroxyl content of the polyols was analysed based on the difference in ¹⁹F-NMR chemical shifts between the primary and secondary trifluoroacetyl esters of the polyols. ¹⁹F-NMR and ¹H-NMR spectroscopy indicated that EO end-capping could improve the 1° OH content of CO₂ polyols in some extent, while accompanied with obvious loss of the carbonate unit content. Therefore, the EO end-capping method can only provide polyols with low carbonate unit content. Yet CO₂-polyols with 72% of 1° OH content have been synthesized by copolymerization end-capping of EO and CO₂, and the content of carbonate unit decreases little. Finally, taking advantage of the different reactivity of PO and EO with double metal cyanide catalysts (DMC), we synthesized CO₂-polyols with 62% of 1° OH content by one-pot ternary polymerization of PO, EO and CO₂, and the carbonate unit content was almost unaffected. This strategy provides a safe and efficient possibility to synthesize high 1° OH content CO₂-polyols.
- Carbon dioxide,
- CO₂-Polyol,
- End-capping,
- Primary hydroxyl group
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沈阳化工大学材料科学与工程学院沈阳 110142