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Synthesis and characterization of α-amino-ε … Cel Cel/min min s N2 40 200 5 10 0.5 Gas1: 200...
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Transcript of Synthesis and characterization of α-amino-ε … Cel Cel/min min s N2 40 200 5 10 0.5 Gas1: 200...
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
ELECTRONIC SUUPLEMENTRAY INFORMATION
Synthesis and Application of a Novel Bio-based Polyol for
Preparation of Polyurethane Foams
Xiaolin Li,a Zheng Fang,
a Xin Li,
b Shigui Tang,
b Kai Zhang
c and Kai Guo,*
b
a School of Pharmaceutical Sciences, Nanjing University of Technology, Nanjing 211816, China b College of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 211816,
China c School of Mechanical and Power Engineering of NJUT, Nanjing University of Technology, Nanjing 211816,
China
Contents
1. Synthesis and characterization of α-amino-ε-caprolactam (ACL)
2. Figure SI1. The mass of the structures 1 and 3.
3. Figure SI2. The LC-MS of the ACL-OL at 24 h.
4. Figure SI3. The LC-MS of the ACL-OL at 72 h.
5. Figure SI4. DMTA date of foams.
6. Figure SI5. DSC date of ACL-RF.
7. Figure SI6. DSC date of PB-RF.
Synthesis and characterization of α-amino-ε-caprolactam (ACL)
A stirred mixture of L-lysine hydrochloride (110 g, 600 mmol) and NaOH (24 g,
600 mmol) in hexanol (2.4 L) was heated to reflux with a Dean-Stark trap used to
remove H2O. The suspension was refluxed for 8 hours until all starting material was
consumed (which was determined by TLC). The suspension was then cooled and
filtered to remove byproduct NaCl. The filtrate was concentrated and the resulting
crude α-amino-ε-caprolactam was dissolved in water. After acidification to pH 6 with
addition of concentrated HCl and partial concentration, crystal was formed at room
temperature to afford ACL hydrochloride (74 g) in 75 % yield. The ACL
hydrochloride was dissolved in methanol and NaOH (18 g, 450 mmol) was added.
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
After stir for 2 h, the suspension was then filtered and the filtrate was evaporated
under reduced pressure conditions to afford ACL (57 g) as a white solid. Mp: 97 -
101 °C. Elemental analysis (%) found: C: 56.36, H: 9.50, N: 21.71; C6H12N2O; C:
56.22, H: 9.44, N: 21.86. HRMS: found m/z = 129.1046 ([M + H]+), calculated
129.1028. 1H-NMR (500 MHz, CD3OD): δ (ppm) = 7.19 (br s, 2 H), 5.12 (d, J = 11.1
Hz, 1 H), 3.58 (s, 1 H), 3.15 (m, 2 H), 1.49-1.14 (m, 6 H). 13
C-NMR (125 MHz,
CD3OD): δ (ppm) = 178.26, 52.82, 41.01, 33.72, 28.17, 27.94.
Figure SI1. The mass of the structures 1 and 3.
Compound 1
Compound 3
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
Figure SI2. The LC-MS of the ACL-OL at 22 h.
1
1
1
1
2 2
2 2 3 3 3
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
Figure SI3. The LC-MS of the ACL-OL at 72 h. For the different position of -NH2
attacking the PO, the compounds 1, 2 and 3 have several different configuration. We
do not talk about it in this article.
3 3
1 1
1
2 2
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
Figure SI4. DMTA date of foams showing the thermostability. (Y-1 is storage modulus;
Y-2 is loss modulus; Y-3 is tan δ)
Details about DMTA experiment: sample dimensions, cylinders of Φ15 × 10 mm; frequency,
0.01～200 Hz; force, 0.0001～18 N; compression mode, 103～3×10
12 Pa; temperature, -150～600
˚C. Tg was determined by the maximum peak at Tan δ.
BP-RF
ACL-RF
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
Figure SI5. DSC date of ACL-RF
Tem p C el200.0150.0100.050.00.0
DSC W/g
1.000
0.000
-1.000
-2.000
-3.000
TG %
-1.000
-2.000
-3.000
-4.000
-5.000
-6.000
-7.000
-8.000
-9.000
8.167%
158.2Cel-1.470W/g
Module: TG/DTA Data Name: ACL-RF Measurement Date: 2013-7-3 Sample Name: ACL-RF Sample Weight: 2.031 mg Reference Name: Reference Weight: 0.000 mg
Temperature Program: Cel Cel Cel/min min s N2 40 200 5 10 0.5
Comment: Operator: cf Gas1: 200 Gas2: 200 Pan: ceramics
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2014
.
Figure SI6. DSC date of PB-RF.
Module: TG/DTA Data Name: PB-RF Measurement Date: 2013-7-3 Sample Name: PB-RF Sample Weight: 2.678 mg Reference Name: Reference Weight: 0.000 mg
Temperature Program: Cel Cel Cel/min min s N2 40 150 5 10 0.5
Comment: Operator: cf Gas1: 200 Gas2: 200 Pan: ceramics
Tem p C el140.0120.0100.080.060.040.020.0
DSC W/g
0.500
0.000
-0.500
-1.000
-1.500
-2.000
-2.500
-3.000
-3.500
TG %
-2.00
-4.00
-6.00
-8.00
-10.00
-12.00
-14.00
-16.00
-18.00
109.8Cel-0.677W/g
18.21%
