Ring-opening polymerizaion of 2,2-dimethyltrimethylene carbonate initiated by <Emphasis Type="Italic">in situ</Emphasis> generated,tetrahydrosalen stablized yttrium borohydride complex and random copolymerization with <Emphasis Type="Italic">ɛ</Emphasis>-caprolactone |
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引用本文: | 孙维林.Ring-opening polymerizaion of 2,2-dimethyltrimethylene carbonate initiated by in situ generated,tetrahydrosalen stablized yttrium borohydride complex and random copolymerization with ɛ-caprolactone[J].高分子科学,2011,29(3):390-396. |
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作者姓名: | 孙维林 |
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作者单位: | Key Laboratory of Macromolecule Synthesis and Functionalization,Ministry of EducationDepartment of Polymer Science and Engineering,Zhejiang University |
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基金项目: | supported by the National Natural Science Foundation(Nos.20674071,20774078);the Special Funds for Major State Basic Research Projects(No.2005CB623802) |
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摘 要: | The poly(2,2-dimethyltrimethylene carbonate)(PDTC)with one hydroxyl and one formate terminal functions was synthesized by in situ generated,tetrahydrosalen stabilized yttrium borohydride complex.The influences of monomer/initiator molar ratio,temperature and reaction time on polymerization of DTC were investigated.Under the condition:DTC]/I]=500,55℃,toluene:0.5 mL,DTC:0.6 g,PDTC with Mn=15600 and PDI=2.15 was obtained. Through 1H-NMR and 13C-NMR analyses,the structure of PDTC was characterized and a coordination-insertion mechanism was proposed.In addition,the random copolymerization of DTC and caprolactone(CL)initiated by rare-earth borohydride compound was studied.The microstructure of PDTC-co-PCL includes four diads:DTC-CL,CL-CL,DTC-DTC and CL-DTC, which were determined by the specific signals in 1H-NMR spectra.Based on the typical signals of the formate(δ= 8.08)and hydroxyl(δ=3.34)end groups of PDTC-co-PCL,a mechanism involving DTC monomer inserts before CL during the initiation process was presumed.Furthermore,the thermal properties of amorphous copolymer were characterized by differential scanning calorimetry(DSC).The results support the random structure of PDTC-co-PCL.
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关 键 词: | Ring-opening polymerization 2 2-Dimethyltrimethylene carbonate ε-Caprolactone Rare-earth borohydride complex |
收稿时间: | 14 July 2009 |
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