Polyimide nanofoams from caprolactone-based copolymers

Macromolecules

Volumn 29, Issue 10, 1996, Pages 3642-3646

  Hedrick, J L ^a   Russell, T P ^a   Sanchez, M ^a   DiPietro, R ^a   Swanson, S ^a   Mecerreyes, D ^b   Jerome, R ^b  

^a IBM ALMADEN RESEARCH CENTER   (United States)

^b UNIVERSITY OF LIÈGE   (Belgium)

Author keywords

[No Author keywords available]

Indexed keywords

BLOCK COPOLYMERS; CATALYSTS; CROSSLINKING; DECOMPOSITION; FOAMED PLASTICS; MOLECULAR WEIGHT; MONOMERS; POLYESTERS; SIZE EXCLUSION CHROMATOGRAPHY; SYNTHESIS (CHEMICAL); THERMODYNAMIC STABILITY; TITRATION;

CAPROLACTONE; DECOMPOSITION TEMPERATURE; MICROPHASE SEPARATED MORPHOLOGY; POLYIMIDE NANOFOAMS;

POLYIMIDES;

EID: 0030572160     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma950903q     Document Type: Article

References (17)

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12. 4 and filtered, and the solvent was rotary evaporated off. The sample dried in a 60 °C vacuum oven to yield 16.8 g of a light brown foamy solid (61% yield). Proton NMR in deuterated chloroform shows two AB quarters at 7.35 (4H) and 6.8 (8H) ppm and broad singlets at 3.76 (4H) and 1.67 (1H) ppm.
13. 3 followed by 2 × 100 mL of water. The organic layer was reduced to ≈65 mL and added slowly to 500 mL of methanol with vigorous stirring. The resulting solid was collected and dried for 48 h at 40 °C under reduced pressure to yield 13.5 g of the desired product as a white powder. Titration of the amine end group yielded a molecular weight of 10 500 g/mol.
14. Volksen, W.; Yoon, D. Y.; Hedrick, J. L.; Hofer, D. Mater. Res. Soc. Symp. Proc. 1991, 227, 23.
15. The amic ester-α-caprolactone triblock copolymers were prepared by the coreaction of the amino-terminated caprolactone oligomers with 3FDA, 3FET, and PMDA diethyl ester diacyl chloride in NMP in the presence of N-methylmorpholine. A detailed procedure designed to prepare an amic ester-α-methylstyrene copolymer, having a caprolactone content of 25 wt %, using a caprolactone olgiomer of 10 000 g/mol molecular weight is provided (copolymer 3, Table 1). A 3-necked flask equipped with an overhead stirrer and addition funnel was charged with caprolactone olgiomer (1.0000 g, 0.000 095 2 mol), 3FDA (0.913 27 g, 0.000 266 7 mol), and 3FET (0.6515 g, 0.001 778 mol) and carefully rinsed in with 15 mL of NMP. The solution was then cooled to -5 °C, and pyridine (0.710 00 g, 0.008 90 mol) was added to the solution. The PMDA diethyl ester diacyl chloride (1.5600 g, 6.004 490 mol) was dissolved in ca. 25 mL of methylene chloride and added in increments over a 2 h period so as to slowly approach the stoichiometric end point. The polymerization was allowed to proceed overnight and the mixture isolated by precipitation in methanol/water, rinsed with water (to remove excess salts) and cyclohexene (to remove possible homopolymer contamination), and dried in a vacuum oven.
16. -1 heating rate) thermal gravimetric analysis (TGA) measurements were performed on a Perkin-Elmer model TGA-7 instrument in a nitrogen atmosphere.
17. Sanchez, M. I.; Hedrick, J. L.; Russell, T. P. J. Polym. Sci., Part B: Polym. Phys. 1995, 33, 253.