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

Shuang-bin Fu; Yu-sheng Qin; Li-jun Qiao; Xian-hong Wang; Fo-song Wang

doi:10.11777/j.issn1000-3304.2018.18274

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

Research Article | 更新时间：2021-01-26

- Synthesis of High Primary Hydroxyl Content Poly(carbonate-ether) Polyol
- Acta Polymerica Sinica Vol. 50, Issue 4, Pages: 338-343(2019)
- 作者机构：
  
  1.中国科学院长春应用化学研究所生态环境材料高分子重点实验室　长春 130022
  2.中国科学院大学　北京 100049
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18274
  CLC：
- Published：2019-4，
  
  Published Online：24 January 2019，
  
  Received：21 December 2018，
  
  Revised：8 January 2019，
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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 50(4):338-343(2019)
DOI：

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 50(4):338-343(2019) DOI： 10.11777/j.issn1000-3304.2018.18274.

摘要

聚(碳酸酯-醚)多元醇又称二氧化碳基多元醇，是通过CO

与环氧丙烷(PO)的调聚反应所制备的. 由于环氧丙烷开环反应时优先在空间位阻较低的亚甲基上的碳-氧键断裂，生成端羟基以仲羟基为主的二氧化碳基多元醇，其伯羟基含量通常低于20%，导致其与异氰酸酯反应的活性较低. 本文提出了环氧乙烷(EO)封端、EO和CO

共聚封端、一锅法三元调聚封端(PO、EO与CO

)等3种方法来提高二氧化碳基多元醇中的伯羟基含量. 研究表明，利用EO封端方法会导致多元醇中碳酸酯含量的降低，而采用EO和CO

共聚进行封端可合成出伯羟基含量达72%的二氧化碳基多元醇，且碳酸酯含量下降很少. 最后我们利用双金属催化剂(DMC)对PO和EO的开环反应速度的差异，采用一锅法将PO、EO和CO

进行三元调聚反应，合成了伯羟基含量可达62%的二氧化碳基多元醇，且碳酸酯含量几乎不受影响.

Abstract

During the past decade

poly(carbonate-ether) polyols

also known as CO

-polyols

have been synthesized by the copolymerization of CO

and propylene oxide (PO) with double metal cyanide (DMC) catalyst in the presence of various chain transfer agents. CO

-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 CO

-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 CO

-polyols

including ethylene oxide (EO) end-capping

copolymerization end-capping of EO and CO

and one-pot ternary polymerization (PO

EO and CO

) end-capping. The primary hydroxyl content of the polyols was analysed based on the difference in

F-NMR chemical shifts between the primary and secondary trifluoroacetyl esters of the polyols.

F-NMR and

H-NMR spectroscopy indicated that EO end-capping could improve the 1° OH content of CO

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 CO

-polyols with 72% of 1° OH content have been synthesized by copolymerization end-capping of EO and CO

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 CO

-polyols with 62% of 1° OH content by one-pot ternary polymerization of PO

EO and CO

and the carbonate unit content was almost unaffected. This strategy provides a safe and efficient possibility to synthesize high 1° OH content CO

-polyols.

关键词

二氧化碳二氧化碳基多元醇封端伯羟基

Keywords

Carbon dioxideCO2-PolyolEnd-cappingPrimary hydroxyl group

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School of Applied Chemistry and Engineering, University of Science and Technology of China

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