Synthesis and structure-properties relationship studies of biodegradable hydroxylammonium-based protic ionic liquids

Article abstract of DOI:10.1016/j.molliq.2016.09.086

In this work sixteen hydroxyl ammonium Protic Ionic Liquids derived from a proton transfer reaction between four different substituted amines and four different low molecular weight aliphatic and alicyclic carboxylic acids have been synthesized. The synthesized PILs were structurally characterized by NMR and FT-IR spectroscopy whereas two of their more important physicochemical properties namely viscosity and glass transition temperature (T_g) were evaluated. The effect of alkyl chain length and substitution on the anionic and cationic component of the PILs scaffold has been discussed for the studied properties. It seems that T_g values are mainly affected by the carboxylate anion structure whereas viscosity is controlled mainly by the structural features of the cationic part of the PILs. In order to estimate their environmental impact and reinforce their “green” character, biodegradation studies, as well as toxicity evaluation experiments have also been conducted. The synthesized PILs can be confidently labelled as green considering that they are not toxic or present low toxicity to the nauplii of the brine shrimp A. salina whereas they show biodegradability levels between 41–64%, according to the manometric respirometric method which measures the biological oxygen demand (BOD₅) by microorganisms in order to degrade PILs via bio-oxidation in five days.

Full text of DOI:10.1016/j.molliq.2016.09.086

Synthesis and Structure-Properties Relationship Studies of Biodegradable
Hydroxylammonium-based Protic Ionic Liquids
Andromachi Tzani, Marianthi Elmaloglou, Charαlampos Kyriazis, Dionysia
Aravopoulou, Ioannis Kleidas, Achilleas Papadopoulos, Efstathia Ioannou,
Apostolos Kyritsis, Epaminondas Voutsas, Anastasia Detsi
PII:
DOI:
Reference:
S0167-7322(16)31868-2
doi:10.1016/j.molliq.2016.09.086
MOLLIQ 6364
To appear in:
Journal of Molecular Liquids
Received date:
Accepted date:
11 July 2016
9 September 2016
Please cite this article as: Andromachi Tzani, Marianthi Elmaloglou, Charlampos Kyri-
azis, Dionysia Aravopoulou, Ioannis Kleidas, Achilleas Papadopoulos, Efstathia Ioannou,
Apostolos Kyritsis, Epaminondas Voutsas, Anastasia Detsi, Synthesis and Structure-
Properties Relationship Studies of Biodegradable Hydroxylammonium-based Protic Ionic
Liquids, Journal of Molecular Liquids (2016), doi:10.1016/j.molliq.2016.09.086
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Synthesis and Structure-Properties Relationship Studies of Biodegradable Hydroxylammonium-
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the weakening of the interionic H-bond interaction in D O. If this hypothesis is true, then it means
2
that the H-D exchange process in this case is very slow, a phenomenon that has been recently reported
for imidazolium-based room temperature ionic liquids.[20],[21] In any case, this is an interesting
observation that definitely merits further investigation which is currently in progress by our research
group.

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ILs
T
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n(cp)
(
°C)
2
3
4
5
6
7
8
9
0
0
0
0
0
0
0
0
94,8
68,8
45,7
31,6
22,6
17,1
13,6
10,8
8,79
298,9 101,2 113,7
-
323,0
180,7
110,0
71,0
45,9
32,8
22,9
18,1
14,3
52,5
35,6
22,3
15,6
11,2
9,0
-
-
-
469,3 50,03 2462,0
-
-
300,0 231,3
182,4 135,6
-
178,0
91,0
56,0
35,7
24,5
18,6
13,8
11,0
59,5
37,9
25,0
17,4
12,8
9,57
7,2
70,5
44,5
29,6
20,8
15,1
11,5
9,33
6,84
-
276,3
154,0
91,6
56,4
37,3
25,5
17,2
12,8
32,3
20,4
13,9
9,9
1105,0
556,2
283,5
183,9
108,2
81,2
-
-
3165,0 108,1
75,7
45,3
28,9
20,5
14,4
10,1
7,9
2130,0
1143,0
507,7
279,9
161,5
106,5
67,8
311,0
186,0
116,5
76,5
51,0
36,5
410,6
1530,0
828,0
422,5
245,4
156,5
103,6
61,8
39,4
26,7
17,4
13,1
9,9
256,5
159,0
96,5
7,5
7,5
5,8
6,7
64,8
4,6
44,6
1
00
5,55
6,2
44,9
3,7
29,4

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