聚乙醇酸/聚乙二醇/聚乙醇酸三嵌段聚合物的合成

第28卷第3期合成纤维工业Vol 28 No. 32005年6月CHINA SYNTHETIC FIBER INDUSTRYnthesis of polyglycolide- polyethyleneglycol-polyglycolidetriblock copolymerIfang,Zheng Yubin, Chang JunDepartment of Polymer Science, Dalian Uniersity of Technology, Dalian 116012)CLC number: TQ34063 Document code: A Article ID: 1001-0041(2005)03-0035-02A triblock polymer of polyglycolide-polyethyleneglycol- Reagent Factory, Furanidine by Tianjing Tianzheng Reagentpolyglycolide is mostly produced by ring-open polymerization, Factory and trimethylamine by Shenyang Xinxi Reagent Facto-wherein hydrophilic polyethyleneglycol is present in the center ry. Other chemicals were purchased from Dalianand the hydrophobic polyglycolide is located at both endsIR spectra were recorded with a Nicolet-20DXB IR spec-Polymers making hydrophobic polyglycolide hydrophilic can trophotometer as KBr pellets. 'H NMR spectra were run on abe applied widely as bio-materials to be used as a matrix for Varian INOVA 400 MHz spectrometer using CDCl, as a solthe slow release of drugs, in tissue engineering, etc.vent and 1% by volume of tetramethylsilane(TMs)as an in-The ring-open polymerization needs strict reaction condi- temal reference. The glass-transition temperature(T) ofns and high cost. This triblock polymer can be produced by the polymeric products was determined by differential scan-solution polymerization. This technique has simple process ning calorimetry( DSC) with a 910S thermal analyzer at aand provides active groups, chlorine, at both ends of the pol- heating rate of 10 C/min. The crystallinity of the polymerymer which could be further functionalized easily.was measured on an XD3-A Wide-angle X-ray diffraction1 Experimental(WAXD) apparatus.1.2 Preparation of polyglycolide-polyethyleneglycolAll chemicals were in analytical grade. Chloracetic acid polyglycolide triblock polymerwas offered by Tianjing Guangfu Fine Chemistry InstituteThe reaction for the synthesis of the triblock polymer ispolyethyleneglycol( PEG)by Guangzhou Medical Company as followSOCCICH, COOHCICH, COCIH(OCH12CH2O),H+CCH2COCl→→ClCH2C∈OCH2CH2O分,CCH2C1CICH2C∈OCH2CH2O分,CCH2Cl+(m+n)CCH2COOH0CH∈CH2CO)。CH2C←OCH2CH2QO),CCH2∈OCCH2),ClFirst, the hydroxy endgroup of PEG with M, of 2 000 was lecular weight oligomers, and dried under vacuum at ambientreacted with chloracetyl chloride to yield compound 1. After temperature for at least 12 h. The molecular weight of compurification, compound I was dissolved in 20 mL chloroform pound 2 could be obtained from titrating the concentration ofand taken into a 250 mL three-neck flask. The reaction mix- chloride ion.ture was put in an oil bath of 60C. The chloroacetic acid 2 Results and discussionmonomer dissolved in a proper solvent was added dropwise in- 2.1 IR spectrumto the reaction flask while stirring to avoid the byproduct of中国煤化工 peared at1742.33polychloroacetic acid. In the process of polymerization, trime-thylamine was used to remove HCl produced in the reactionCNMHGo-04. 2005Biography: Duan Jiufang (1979-), female, Ph D. Be en-tered to remove the catalyst, unreacted monomer and low-mo-gaged in the field of functional polymer materi合成纤维工业2005年第28卷cm", attributable to the formation of ester bond. The over- crystalline peaks of compound 2 appeared at 20 equal to 29. 61lapping at 2 943 cm was assigneand 23. 07 while two smooth and low amorphous peaks ap-stretching vibration and the absorption band at 1 147. 21- peared at 20 equal to 42. 68 and 55. 75. The crystallinity of1 094. 09 cm"toC--0 stretching vibrationcompound 2 was calculated as 57. 95% according to integralquantity of crystallineand amorphous peaks3000200026/(°)Fig 3 X-ray difFig. I IR spectrum of compound 22. 2 H-NMR spectrum2.4 DSC analysisThe composition and the molecular weight of compoundPolyglycolide is a high-crystallinity polymer whose T, andwere verified by H-NMR spectroscopy. The molecular weight T. are 36.C and 224C, respectively. The properties of polygigher than 4 000 leads to difficulties in dissolving in CDCItherefore, a sample with the molecular weight of 3 200 was eneglycol. It can be seen from Fig. 4 that T, and T. of theused to determine the triblock structure. Fig. 2 showed a typi- triblock polymer synthesized by solution polymerization werecal H-NMR spectrum of compound 2. It can be seen that the 44 55C and 71 30C, respectively.peak at 8 equal to 3. 11 was assigned to methylene protons ofpolyglycolide units and the peaks at 8 equal to 1. 35 and 3. 62to the methylene protons of PEG oxyethylene units. The number-average molecular we3 089. 2 from the unit ratio of PEG and polyglycolide whichwas obtained from the peak intensities of the methylene protongnal of the PEG chain and the methine proton signalpolyglycolide units. The results from H-NMR measurementsTP℃were similar to the titrated molecular weight of copolymersFig 4 DSC curve of compound 2which proved that compound 2 could be synthesized with prop-er solvents by solution polymerizationThe polyglycolide- polyethyleneglycol- polyglycolide triblock polymer was synthesized successfully by solution polyof the triblockwas57.95% when T and T.were4.55℃and71.30℃,聚乙醇酸/聚乙二醇聚乙醇酸三嵌段聚合物的合成段久芳郑玉斌常军(大连理工大学高分子材料4.03.0201.000学院,大连116012)采用溶液聚合法合成了三嵌段聚合物醇/聚醇酸采用红外光谱、核磁Fig2 H-NMR spectrum of compound 2共振中国煤化工进行了表征。聚合2.3 CrystallinityCNMHG别为4.55℃和e crystallinity of compound2 was investigated by wide-71.30℃。关键词:聚乙醇酸聚乙二醇嵌段聚合物溶angle X- ray diffraction(WAXD).AsFg.3 shown, two sharp液聚合