2.3 Synthesis of polymers
All the organic and ferrocene-based polymers are synthesized by Scheme 2. The pre-weighed mixture of aromatic and aliphatic diamines with various compositions (net quantity 1.88 mmol) were dissolved in 20 mL of dried THF in a pre-baked, two-necked, 250 mL round bottom flask equipped with a magnetic stirrer and a condenser. The reaction mixture was stirred for 15 minutes and then 10 mL of triethylamine (TEA) was added to the flask at 0o C which was maintained by ice bath. After stirring for 20 minutes, dicarbonyl chloride (1.92 mmol) solution (in dried THF) was added drop wise to the flask with vigorous stirring. Temperature of the reaction mixture was raised slowly to the room temperature. After stirring for 5-6 hours, the reaction mixture was refluxed for 1 hour. The precipitated product was filtered, washed sequentially with THF and methanol to remove unreacted precursors and side products. The finally obtained polymer material was dried in vacuum for 24 hours.
2.3.1 Synthesis of PF series
i. PF0
Aliphatic diamine 0%, Aromatic diamine 100% (1.88 mmol), Color: Brown. Yield: 84%. FT-IR (in cm−1): 3333.9 (N-H), 3157 (Ar-H), 1637.2(C=O), 1601.4 (N-H), 1312.6 (C-N), 1099.5 (C-O-C), 498.2 (Fe-Cp).
ii. PF50
Aliphatic diamine 50% (0.94 mmol), Aromatic 50% (0.94 mmol), Color: Dark brown. Yield: 78%. FT-IR (in cm−1): 3448.4-3284.9 (N-H), 3110-3082 (Ar-H), 2944.9 (CH2), 1634.2 (C=O), 1519.9 (N-H), 1273.3 (C-N), 1065.4 (C-O-C), 492.1 (Fe-Cp).
iii. PF70
Aliphatic diamine 70% (1.316 mmol), Aromatic 30% (0.564 mmol), Color: Dark brown. Yield: 90%. FT-IR (in cm−1): 3273.6 (N-H), 3167.8 (Ar-H), 2930.1 (CH2), 1622.3 (C=O), 1531.6 (N-H), 1341.3 (C-N), 1026.4 (C-O-C), 475 (Fe-Cp).
iv. PF90
Aliphatic diamine 90% (1.692 mmol), Aromatic diamine 10% (0.188 mmol), Color: Dark brown. Yield: 76%. FT-IR (in cm−1): 3410.3 (N-H), 3135 (Ar-H), 2920(CH2), 1652.6 (C=O), 1535(N-H), 1216 (C-N), 511.7 (Fe-Cp).
2.3.2 Synthesis of PA Series
i .PA0
Aliphatic diamine 0%, Aromatic diamine 100% (1.88 mmol), Color: Brown. Yield: 89%. FT-IR (in cm−1): 3370.7 (N-H), 3095 (Ar-H), 1641.4 (C=O), 1531.9 (N-H), 1216.7(C-N), 1035.3 (C-O-C).
ii. PA50
Aliphatic diamine 50% (0.94 mmol), Aromatic 50% (0.94 mmol), Color: dark brown. Yield: 88%. FT-IR (in cm−1): 3270.5 (N-H), 3030 (Ar-H), 2970 (CH2), 1628.1 (C=O), 1530.6 (N-H), 1210.7 (C-N), 1057.4 (C-O-C).
iii. PA70
Aliphatic diamine 70% (1.316 mmol), Aromatic 30% (0.564 mmol), Color: Brown. Yield: 84%. FT-IR (in cm−1): 3432.8-3317.8 (N-H), 3130-3050 (Ar-H), 2977.9 (CH2), 1628.3 (C=O), 1540.6 (N-H), 1264.2 (C-N), 1034.9 (C-O-C).
iv. PA90
Aliphatic diamine 90% (1.692 mmol), Aromatic diamine 10% (0.188 mmol), Color: Dark brown. Yield: 92%. FT-IR (in cm−1): 3399.3 (N-H), 3134.6 (Ar-H), 2969.1 (CH2), 1635.8 (C=O), 1536.7(N-H), 1262.4 (C-N).
2.3.3 Synthesis of PT series
i. PT0
Aliphatic diamine 0%, Aromatic diamine 100% (1.88 mmol), Color: White. Yield: 87%. FT-IR (in cm−1): 3275.3 (N-H), 3115-3048 (Ar-H), 2925-2869 (CH2), 1641.2 (C=O), 1529 (N-H), 1318 (C-N), 1098.9 (C-O-C).
ii. PT50
Aliphatic diamine 50% (0.94 mmol), Aromatic 50% (0.94 mmol), Color: White. Yield: 82%. FT-IR (in cm−1): 3299.4 (N-H), 3115-3052 (Ar-H), 1641.3 (C=O), 1543.3 (N-H), 1217.4 (C-N), 1100.9 (C-O-C).
iii. PT70
Aliphatic diamine 70% (1.316 mmol), Aromatic 30% (0.564 mmol), Color: White. Yield: 87%. FT-IR (in cm−1): 3307 (N-H), 3115-3048 (Ar-H), 2936-2860 (CH2), 1622.1 (C=O), 1538.2 (N-H), 1224 (C-N), 1091.9 (C-O-C).
iv. PT90
Aliphatic diamine 90% (1.692 mmol), Aromatic diamine 10% (0.188 mmol), Color: White. Yield 86%. FT-IR (in cm−1): 3305.7 (N-H), 2969.8 (CH2), 1640.9 (C=O), 1526.8 (N-H), 1217 (C-N).
2.3.4 Synthesis of PI Series
i. PI 0
Aliphatic diamine 0%, Aromatic diamine 100% (1.88 mmol), Color: White. Yield: 92%. FT-IR (in cm−1): 3259 (N-H), 3025 (Ar-H), 1647.7 (C=O), 1525.3 (N-H), 1237.9(C-N), 1063 (C-O-C).
ii. PI 50
Aliphatic diamine 50% (0.94 mmol), Aromatic 50% (0.94 mmol), Color: White. Yield: 81%. FT-IR (in cm−1): 3412.7-3276.3 (N-H), 3130-3052 (Ar-H), 2938.1 (CH2), 1646.3 (C=O), 1525.7(N-H), 1238(C-N), 1102.7 (C-O-C).
iii. PI70
Aliphatic diamine 70% (1.316 mmol), Aromatic 30% (0.564 mmol), Color: White. Yield: 87%. FT-IR (in cm−1): 3269.3 (N-H), 3160(Ar-H), 2968-2838.1 (CH2), 1646.8 (C=O), 1540.6 (N-H), 1324.4 (C-N), 1106.0 (C-O-C).
iv. PI90
Aliphatic diamine 90% (1.692 mmol), Aromatic diamine 10% (0.188 mmol), Color: White. Yield: 89%. FT-IR (in cm−1): 3289.8 (N-H), 3080 (Ar-H), 2943-2856.4 (CH2), 1624.3 (C=O), 1539.0 (N-H), 1286.2 (C-N), 1152.6 (C-O-C).