A WAXD and solid-state NMR study on cocrystallization in partially cycloaliphatic polyamide 12.6-based copolymers

被引:23
作者
Vanhaecht, B
Willem, R
Biesemans, M
Goderis, B
Basiura, M
Magusin, PCMM
Dolbnya, I
Koning, CE
机构
[1] Free Univ Brussels, Dept Phys & Colloidal Chem, B-1050 Brussels, Belgium
[2] Eindhoven Univ Technol, Polymer Chem Lab, NL-5600 MB Eindhoven, Netherlands
[3] European Synchrotron Radiat Facil, CRG, DUBBLE, F-38043 Grenoble, France
[4] Eindhoven Univ Technol, Inorgan Chem & Catalysis Lab, NL-5600 MB Eindhoven, Netherlands
[5] Catholic Univ Louvain, Dept Chem, B-3001 Heverlee, Belgium
[6] Free Univ Brussels, High Resolut NMR Ctr, B-1050 Brussels, Belgium
关键词
D O I
10.1021/ma035103r
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
To study the influence of the stereochemistry on the possibility of cocrystallization of linear and cyclic aliphatic residues in copolyamides, a series of copolyamides 12.6/12.1,4-cyclohexanedicarboxylic acid with variable compositions were synthesized. From solid-state NMR studies it could be deduced that cis-1,4-CHDA is present in the amorphous regions whereas the trans residues are located in both the crystalline and the amorphous phase. WAXD patterns confirm the presence of trans-1,4-CHDA inside the crystals and reveal that the cycloaliphatic ring is most likely oriented in a direction perpendicular to the crystal sheets that contain the hydrogen bonds. As a result, the intersheet distance is increased compared to that of polyamide 12.6. Furthermore, the rings prevent the genesis of a pseudohexagonal phase above the Brill temperature. Exceptionally, crossing rather than merging of the (100) and the combined (010)-(110) WAXD reflections is observed with increasing temperature, indicating that the intersheet distances increase and become larger than the interchain distances within the hydrogen-bonded sheets before the crystals start to melt. Incorporation of trans-1,4-CHDA residues into polyamide 12.6 leads to higher melting temperatures, pointing at cocrystallization in terms of a solid solution rather than as defects. In contrast, a slight melting point depression is observed for copolymers with predominately cis-1,4-CHDA residues.
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收藏
页码:421 / 428
页数:8
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