ꢀꢀꢀꢁ
80ꢀ ꢀW. Zhang et al.: Nitroxyl radical hindered-amine light stabilizers
piperidine 2ꢀ×ꢀCH3), 2.22 (d, J ꢀ=ꢀ 8.8 Hz, 4H, piperidine 2ꢀ×ꢀCH2), 3.79 (d,
J ꢀ=ꢀ 6.8 Hz, 2H, allyl CH2), 5.12–5.41 (m, 1H, piperidine CH), 7.09–7.13
(m, H, ꢀ=ꢀCH-), 7.19 (d, J ꢀ=ꢀ 8.1 Hz, 2H, CH2ꢀ=ꢀ), 7.26–8.40 (m, 7H, Ar-H),
8.63 (br. s, 1H, NH), 9.35 (br. s, 1H, NH); 13C NMR: δ 20.6, 44.5, 49.0,
59.4, 60.1, 104.3, 115.2, 117.1, 117.7, 119.3, 120.5, 123.9, 132.1, 135.2, 140.3
144.6, 147.7, 151.6, 172.7; FT-IR: 698, 754, 1357, 1495, 1570, 1661, 2973,
Preparation of mixtures of polyethylene with photo-
stabilizers
A mixture of polyethylene and photostabilizer (0.5–1.0% w/w) was
heated to 150°C and stirred until a homogeneous solution was
obtained, from which molding samples were obtained for simulated
aging experiments.
+
3350 cm-1; ESI-HRMS. Calcd for (M+Na) : m/z 553.2590. Found: m/z
553.2526. Anal. Calcd for C27H32N9O3: C, 61.12; H, 6.08; N, 23.76. Found:
C, 61.20; H, 6.01; N, 23.88.
Acknowledgments: The authors gratefully acknowl-
edge financial support from the Industrial Research
2-[2-(5-Methyl-2-hydroxyphenyl)benzotriazol-5-amino]-N-
allylamino-6-(2,2,6,6-tetramethylpiperidin-N-oxyl-4-ol)-s- Project of Shaanxi Science and Technology Department
triazine (5b)ꢁYield 48%; mp 168–169°C; 1H NMR: 1.33 (s, 12H,
(2014K08-29) and the Scientific Research Foundation of
Northwestern University.
piperidine 4ꢀ×ꢀCH3), 1.54 (d, J ꢀ=ꢀ 11.2 Hz, 4H, piperidine 2ꢀ×ꢀCH2), 2.87 (s,
3H, CH3), 4.05 (d, J ꢀ=ꢀ 6.8 Hz, 2H, allyl CH2), 5.05–5.16 (m, 1H, piperi-
dine CH), 7.09–7.14 (m, H, ꢀ=ꢀCH-), 7.22 (d, J ꢀ=ꢀ 8.4 Hz, 2H, CH2ꢀ=ꢀ), 7.39–
8.62 (m, 6H, Ar-H), 8.65 (br. s, 1H, NH), 9.54 (br. s, 1H, NH); FT-IR:
661, 751, 1350, 1469, 1577, 1637, 2964, 3227, 3356 cm-1; ESI-HRMS. Calcd
References
[1] Di, Z. C.; Lu, W. Z.; Wang, K. L.; Liang, J. Studies on UV transpar-
ent characteristics of carbon nanotube filled LDPE films. Chem.
J. Chin. Universities 2004, 25, 394–396.
[2] Butola, B. S.; Joshi, M. Photostability of HDPE filaments sta-
bilized with UV absorbers (UVA) and light stabilizers (HALS).
J. Eng. Fiber. Fabr. 2013, 8, 61–68.
[3] Evans, P. D.; Gibsonb, S. K.; Cullis, L.; Liu, L.; Sebe, G. Pho-
tostabilization of wood using low molecular weight phenol
formaldehyde resin and hindered amine light stabilizer. Polym.
Degr. Stability 2013, 98, 158–168.
[4] Chai, R. D.; Chen, S. J.; Zhang, J. Combined effect of hindered
amine light stabilizer and ultraviolet absorbers on photodegrada-
tion of poly(vinyl chloride). J. Vinyl Add. Technol. 2012, 18, 17–25.
[5] Bojinov, V. B. Synthesis of novel bifunctional hindered amine-
UV absorber polymer stabilizers. Polym. Degr. Stability 2006,
91, 128–135.
+
for (M+Na) : m/z 544.2761. Found: m/z 544.2785. Anal. Calcd for
C28H34N9O3: C, 61.75; H, 6.29; N, 23.15. Found: C, 61.69; H, 6.24; N, 23.26.
2-[2-(2-Hydroxy-5-chlorophenyl)benzotriazol-5-amino]-N-
allylamino-6-(2,2,6,6-tetramethylpiperidin-N-oxyl-4-ol)-s-
triazine (5c)ꢁYield 49%; mp 176–177°C; 1H NMR: 1.34 (s, 12H,
piperidine 4ꢀ×ꢀCH3), 1.63 (d, J ꢀ=ꢀ 7.1 Hz, 4H, piperidine 2ꢀ×ꢀCH2), 4.42
(d, J ꢀ=ꢀ 11.8 Hz, 2H, allyl CH2), 5.12–5.24 (m, 1H, piperidine CH), 7.07
(m, H, ꢀ=ꢀCH-), 7.21 (d, J ꢀ=ꢀ 8.8 Hz, 2H, CH2ꢀ=ꢀ), 7.42–8.34 (m, 6H, ArH),
8.42 (br. s, 1H, NH), 9.37 (br. s, 1H, NH); FT-IR: 628, 729, 1350, 1495,
+
1578, 1637, 2966, 3226, 3351 cm-1; ESI-HRMS. Calcd for (M+Na) : m/z
564.2210. Found: m/z 564.2238. Anal. Calcd for C27H31N9O3Cl: C, 57.39;
H, 5.53; N, 22.31. Found: C, 57.52; H, 5.43; N, 22.40.
[2-(2-Hydroxy)benzotriazol-5-amino]-4,6-di(2,2,6,6-tetra-
methylpiperidin-N-oxyl-4-ol)-s-triazine (5d)ꢁYield 52%; mp 155–
1
157°C; H NMR: δ 1.26 (s, 24H, piperidine 8ꢀ×ꢀCH3), 1.72 (d, J ꢀ=ꢀ 8.2 Hz,
8H, piperidine 4ꢀ×ꢀCH2), 2.47 (br. s, 1H, NH), 3.85–4.31 (m, 1H, piperi-
dine CH), 6.88–8.28 (m, 7H, Ar-H); 13C NMR: δ 20.4, 44.5, 57.5, 59.9,
105.3, 115.4, 117.2, 119.4, 120.4, 124.3, 135.5, 146.7, 151.6, 173.3; FT-IR:
628, 754, 1356, 1552, 1577, 1637, 2929, 3238, 3358 cm-1; ESI-HRMS. Calcd
[6] Konstantinova, T.; Lazarova, R.; Bojinov, V. On the photosta-
bility of some naphthalimide dyes and their copolymers with
methyl methacrylate. Polym. Degr. Stability 2003, 82, 115–118.
[7] Yang, Y. C.; Cheng, J.; Cheng, C. M.; He, J.; Guo, B. H.; Zhao, Y. F.
Design, synthesis and anti-oxidative evaluation of novel anti-
oxidant molecules in polyolefin. Chem. J. Chinese Universities
2011, 32, 286–291.
[8] Chen, W.; An, P.; Chen, Y. X.; Li, Y.; Yan, X. L.; Chen, L-G.
Synthesis and light-stabilizing ability of a series of hindered
piperidine derivatives. Synth. Commun. 2012, 42, 1419–1425.
[9] Hodgson, J. L.; Coote, M. L. Clarifying the mechanism of the
Denisov cycle: how do hindered amine light stabilizers protect
polymer coatings from photo-oxidative degradation macromol-
ecules. Macromolecules 2010, 43, 4573–4583.
[10] Gryn’ova, G.; Ingold, K. U.; Coote, M. L. New insights into the
mechanism of amine/nitroxide cycling during the hindered
amine light stabilizer inhibited oxidative degradation of poly-
mers. J. Am. Chem. Soc. 2012, 134, 12979–12988.
[11] Katritzky, A. R.; Zhang, S. M.; Wang, M. Y.; Kolb, H. C.; Steel, P.
J. Novel syntheses of polysubstituted pyrroles and oxazoles by
1,3-dipolar cycloaddition reactions of benzotriazole-stabilized
nitrile ylides. J. Heterocycl. Chem. 2002, 39, 759–765.
[12] Gou, X. F.; Liu, D.; Hua, C. W. Synthesis and properties of
multifunctional hindered amine light stabilizers. Heterocycl.
Commun. 2014, 20, 15–20.
+
for (M+Na) : m/z 668.3280. Found: m/z 668.3285. Anal. Calcd for
C33H43N9O5: C, 61.38; H, 6.71; N, 19.52. Found: C, 61.45; H, 6.62; N, 19.39.
2-[2-(2-Hydroxy-5-methylphenyl)benzotriazol-5-amino]-
4,6-di(2,2,6,6-tetramethylpiperidin-N-oxyl-4-ol)-s-triazine
1
(5e)ꢁYield 49%; mp 157–159°C; H NMR: 1.12 (s, 24H, piperidine
8ꢀ×ꢀCH3), 1.72 (s, 3H, CH3), 1.91 (d, J ꢀ=ꢀ 11.8 Hz, 8H, piperidine 4ꢀ×ꢀCH2),
3.85–4.31 (m, 2H, 2ꢀ×ꢀpiperidine CH), 5.12 (br. s, 1H, NH), 6.78–8.29
(m, 7H, Ar-H); FT-IR: 812, 1354, 1576, 1577, 1637, 2932, 2969, 3345 cm-1;
+
+
ESI-HRMS. (M+Na) : Calcd for (M+Na) : m/z 718.2590. Found: m/z
718.2635. Anal. Calcd for C34H45N9O5: C, 61.89; H, 6.87; N, 19.11. Found:
C, 61.78; H, 7.01; N, 19.18.
2-[2-(2-Hydroxy-5-chlorophenyl)benzotriazol-5-amino]-
4,6-di(2,2,6,6-tetramethylpiperidin-N-oxyl-4-ol)-s-triazine
1
(5f)ꢁYield 48%; mp 166–167°C; H NMR: 1.19 (s, 24H, piperidine
8ꢀ×ꢀCH3), 1.93 (d, J ꢀ=ꢀ 12 Hz, 8H, piperidine 4ꢀ×ꢀCH2), 3.84–4.31 (m, 2H,
2ꢀ×ꢀpiperidine CH), 5.23 (br. s, 1H, NH), 6.77–8.18 (m, 7H, Ar-H); FT-IR:
+
820, 1125, 1354, 1578, 1637, 2970, 3362 cm-1; ESI-HRMS. Calcd for (M+) :
m/z 698.3150. Found: m/z 698.3181. Anal. Calcd for C33H42N9O5Cl: C,
58.27; H, 6.22; N, 18.53. Found: C, 58.12; H, 6.15; N, 18.64.
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