Synthesis and fractionation of poly(phenylene methylene)

被引:15
作者
Braendle, Andreas [1 ]
Schwendimann, Pascal [1 ]
Niederberger, Markus [1 ]
Caseri, Walter R. [1 ]
机构
[1] Swiss Fed Inst Technol, Dept Mat, Multifunct Mat, Zurich, Switzerland
基金
瑞士国家科学基金会;
关键词
fractionation of polymers; molar mass distribution; polymerization; poly(phenylene methylene); step-growth polymerization; thermal properties; BENZYL ALCOHOL; MOLECULAR-WEIGHT; POLYMERIZATION; POLYBENZYLS; POLYMERS; CHLORIDE; HOMOCONJUGATION; SPECTROSCOPY; CHEMISTRY; ACIDS;
D O I
10.1002/pola.28900
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Poly(phenylene methylene) (PPM) was isolated in a broad range of molar masses by optimization of the catalytic polymerization of benzyl chloride with SnCl4 or FeCl3, followed by fractionation by Soxhlet extraction or phase separation in concentrated solutions in poor solvents. Low molar mass products were also obtained by quenching the reaction at moderate monomer conversions. Products with number average molar masses (M-n) ranging from 200 to 61,000 g mol(-1) were isolated, the latter being an order of magnitude above the previously reported values. DSC analysis of polymers of different molar masses revealed that the glass transition temperature follows the Flory-Fox equation reaching a plateau value of 65 degrees C at a molar mass between 10,000 and 20,000 g mol(-1). The onset of decomposition temperature of higher molar mass products proceeds above 450 degrees C (maximum decomposition rate at 515 degrees C), according to TGA. Furthermore, the substitution pattern of PPM was discussed by study of chemical shifts of the methylene group (CH2) by extensive NMR spectroscopy (H-1, C-13, DEPT, and HSQC) and by comparison with two mono-substituted derivatives of PPMpoly(2,4,6-trimethylphenylene methylene) and poly(2,3,5,6-tetramethylphenylene methylene)which were synthesized analogous to PPM. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 309-318
引用
收藏
页码:309 / 318
页数:10
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