新型紫外线吸收剂1,4-二芳基-1,3-丁二炔类化合物的合成及其性能研究
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摘要
本文以含有端基炔的芳硫醚为原料,碘苯二乙酯为氧化剂,氯化亚铜为催化剂,室温下反应30 min,合成了1, 4-二(2-芳硫基苯基)-1, 3-丁二炔化合物。通过~1HNMR、~(13)CNMR等对其进行了结构表征,并研究了其光学性质,以及作为紫外线吸收剂在紫外光固化涂料中的应用。结果表明:该类化合物能够有效吸收270～360 nm的紫外光,且光降解程度小,并具有与树脂、单体相容性好、无气味等特点。同时,合成的目标化合物在光固化过程中不参与自由基体系的固化,且增强了涂料及固化涂层的光稳定性,有益于紫外光固化涂料的存储,是一类具有发展前景的紫外光吸收剂。
In this paper, aryl sulfide containing terminal alkyne was used as raw material,(diacetoxyiodo)benzene was used as oxidant, cuprous chloride was used as catalyst, and 1,4-bis(2-arylthiophenyl)-1,3-butadiyne was synthesized by reaction at room temperature for 30 minutes. The 1,3-butadiyne compound was characterized by ~1HNMR, ~(13)CNMR, etc., and its optical properties and application as an ultraviolet absorber in UV-curable coatings were investigated. The results show that the compound can effectively absorb ultraviolet light from 270 nm to 360 nm and has strong absorption intensity and low degree of UV degradation. It has good compatibility with resin, monomer and no odor. At the same time, it does not participate in the curing of free radical systems, which enhances the light stability of coatings and cured coatings, and is beneficial to the storage of UV-curable coatings. It is a kind of ultraviolet light absorber with promising prospects.
In this paper, aryl sulfide containing terminal alkyne was used as raw material,(diacetoxyiodo)benzene was used as oxidant, cuprous chloride was used as catalyst, and 1,4-bis(2-arylthiophenyl)-1,3-butadiyne was synthesized by reaction at room temperature for 30 minutes. The 1,3-butadiyne compound was characterized by ~1HNMR, ~(13)CNMR, etc., and its optical properties and application as an ultraviolet absorber in UV-curable coatings were investigated. The results show that the compound can effectively absorb ultraviolet light from 270 nm to 360 nm and has strong absorption intensity and low degree of UV degradation. It has good compatibility with resin, monomer and no odor. At the same time, it does not participate in the curing of free radical systems, which enhances the light stability of coatings and cured coatings, and is beneficial to the storage of UV-curable coatings. It is a kind of ultraviolet light absorber with promising prospects.
引文
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[19] Zhang K, Zhang C, He Z H, Huang J, Du X, Wang L, Wei S P, Pu L, Wang Q. Highly enantioselective synthesis and anticancer activities of chiral conjugated diynols[J]. ChemBioChem, 2018, 19(21): 2293-2299.
[20] Kitamura T, Zhang B X, FuJiwara Y. Novel [4 + 2]-cycloaddition of 1-phenyl-1-benzothiophenium salts with dienes. Experimental evidence for a lack of aromaticity in the thiophene ring[J]. Journal of Organic Chemistry, 2003, 68(3): 731-735.
[2] Diepens M M, GiJsman P P. Photodegradation of bisphenol a polycarbonate[J]. Polymer Degradation & Stability, 2007, 92(3): 397-406.
[3] Calvo M E, Castro Smirnov José R, Míguez Hernán. Novel approaches to flexible visible transparent hybrid films for ultraviolet protection[J]. Journal of Polymer Science Part B: Polymer Physics, 2012, 50(14): 945-956.
[4] 万震, 刘嵩, 李克让. 防紫外线织物的最新研究进展[J].印染, 2001, 27(1): 42-44.Wan Z, Liu S, Li K R. The latest research progress of UV protection fabrics[J]. Dyeing & Finishing, 2001, 27(1): 42-44.
[5] Maria D S, Claramunt R M., Bobosik V, Torralba M C, Torres M R, Alkorta I, Elguero J. Synthesis and structural study of 2-arylbenzotriazoles related to tinuvins [J]. Tetrahedron, 2013, 69(14): 3027-3038.
[6] Matsumoto S, Kumasaka R, Yagi M, Kikuchi A. Triplet-triplet energy transfer between UV absorbers in solutions at room temperature[J]. Journal of Photochemistry & Photobiology A: Chemistry, 2017, 346: 396-400.
[7] Hao J J, Yang Y. Exploring the ESIPT dynamical processes of two novel chromophores: symmetrical structure CHC and asymmetric structure CHN[J]. Organic Chemistry Frontiers, 2018, 5(8): 1330-1341.
[8] Wang X D, Xu Y L, Yang L, Lu X, Zou H, Yang W Q, Zhang Y Y, Li Z C, Ma M L. Synthesis, spectra, and theoretical investigations of 1,3,5-triazines compounds as ultraviolet rays absorber based on time-dependent density functional calculations and three-dimensional quantitative structure-property relationship[J]. Journal of Fluorescence, 2018, 28(2): 707-723.
[9] González M. T, Fumagalli F, Benevenuto C. G, Da Silva Emery F, Gaspar L. R. Novel benzophenone-3 derivatives with promising potential as UV filters: relationship between structure, photoprotective potential and phototoxicity[J]. European Journal of Pharmaceutical Sciences, 2017, 101: 200-210.
[10] Broniowska Zaneta, Pomierny B, Smaga I, Filip M, Budziszewska B. The effect of UV-filters on the viability of neuroblastoma (SH-SY5Y) cell line[J]. Neuro Toxicology, 2016, 54: 44-52.
[11] Wnuk A, Rzemieniec J, Staron J, Litwa E, Lason W, BoJarski A, KaJta M. Prenatal exposure to benzophenone-3 impairs autophagy, disrupts RXRs/PPA rgamma signaling, and alters epigenetic and post-translational statuses in brain neurons[J]. Molecular Neurobiology(In printing).
[12] Nagayoshi H, Kakimoto K, Takagi S, Konishi Y, KaJimura K, Matsuda T. Benzotriazole ultraviolet stabilizers show potent activities as human aryl hydrocarbon receptor ligands[J]. Environmental Science & Technology, 2014, 49(1): 578-587.
[13] Chen Y, Ye J S, Li C S, Zhou P L, Liu J, Ou H S. Degradation of 1H-benzotriazole by UV/H2O2 and UV/TiO2: kinetics, mechanisms, products and toxicology[J]. Environmental Science Water Research & Technology, 2018, 4(9): 1282-1294.
[14] Chai R D, Chen S J, Zhang J. Combined effect of hindered amine light stabilizer and antioxidants on photodegradation of poly (vinyl chloride)[J]. Journal of Thermoplastic Composite Materials, 2012, 25(7): 879-894.
[15] Braveenth R, Ahn D H, Han J H, Moon J S, Kim S W, Lee H, Qiong W, Kwon J H, Chai K Y. Utilizing triazine/pyrimidine acceptor and carbazole-triphenylamine donor based bipolar novel host materials for highly luminescent green phosphorescent OLEDs with lower efficiency roll-off [J]. Dyes and Pigments, 2018, 157: 377-384.
[16] 杨坤, 陈鸣才, 许凯, 徐社阳. 含双硫键结构的苯并三唑紫外吸收剂的合成及应用[J]. 精细化工, 2014, 31(8): 1005-1008.Yang K, Chen M C, Xu K, Xu S Y. Synthesis and application of UV absorber of benzotriazole compound containing a disulfide bond[J]. Fine Chemicals, 2014, 31(8): 1005-1008.
[17] Shun A L K S, Tykwinski R R. Synthesis of naturally occurring polyynes[J]. Angewandte Chemie, 2010, 45(7): 1034-1057.
[18] Feng R K, Ning H Q, Su H, Gao Y, Yin H T, Wang Y D, Yang Z, Qi C Z. Selective synthesis of alkynylated isoquinolines and biisoquinolines via Rh(Ⅲ) catalyzed C-H activation/1,3-diyne strategy[J]. The Journal of Organic Chemistry, 2017, 82(19): 10408-10417.
[19] Zhang K, Zhang C, He Z H, Huang J, Du X, Wang L, Wei S P, Pu L, Wang Q. Highly enantioselective synthesis and anticancer activities of chiral conjugated diynols[J]. ChemBioChem, 2018, 19(21): 2293-2299.
[20] Kitamura T, Zhang B X, FuJiwara Y. Novel [4 + 2]-cycloaddition of 1-phenyl-1-benzothiophenium salts with dienes. Experimental evidence for a lack of aromaticity in the thiophene ring[J]. Journal of Organic Chemistry, 2003, 68(3): 731-735.