两种光稳定剂的合成研究
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摘要
光稳定剂是一类添加于化妆品、纺织物、高分子材料中的用来减免紫外线辐射伤害的物质。紫外光吸收剂是一类广为使用的光稳定剂，其需求量不断增加。但是目前所用的一些紫外吸收剂存在着一些缺点，因此研制结构稳定、性能优良的新型紫外吸收剂具有显著的意义。
本文合成了2，2’-亚甲基-二-[6-(2H-苯并三唑-2-基)-4-(1，1，3，3-叔辛基)酚]与2，2’-亚甲基-二-[(5-甲氧基-6-苯甲酰基)-苯酚]两种高分子量化的紫外吸收剂，并对其结构进行表征。考虑了各种因素对反应的影响。2，2’-亚甲基-二-[6-(2H-苯并三唑-2-基)-4-(1，1，3，3-叔辛基)酚]的优化合成工艺：第一步原料2-苯并三唑-4-叔辛基酚：多聚甲醛：二正丙胺的最佳摩尔比例为1∶0.9∶1.8，反应温度120℃，反应时间为2 h；第二步反应温度为160℃，反应时间为10 h，反应溶剂邻二甲苯适宜用量为35 g，碱催化剂为NaOH，适宜用量为0.4 g；第三步加入7.5 g冰醋酸反应0.5 h后，加入结晶助溶剂甲醇，适宜用量为40 mL，收率可达95％。2，2’-亚甲基-二-[(5-甲氧基-6-苯甲酰基)-苯酚]的优化合成工艺：第一步原料2-甲氧基-6-羟基二苯酮：37％甲醛溶液：二正丙胺的最佳摩尔比例6∶4∶4，溶剂为甲醇，适宜用量为25 mL，反应温度70℃，反应时间为6 h，单体加料方式为两次加入；第二步反应温度为90℃，反应时间为10 h，碱催化剂为甲醇钠甲醇溶液，适宜用量为1 mL(质量分数为28％)，使用溶剂为正丁醇，适宜用量为20 mL：加入的结晶助溶剂甲醇的适宜用量为20 mL，收率可达60％。
Light stabilizer is a kind of substance adding to cosmetics, cloth, polymer materials to reduce damage caused by UV. UV absorber is one kind of light stabilizer used commonly which is in great need. But there are some defects of the UV absorber on sale, so research-hing on new type UV absorber which has stable structure and well property is very important.
The article stated synthesis of two kind of polymer UV absorber, 2,2'-methylene bis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetrarnethylbutyl)phenols)(Ⅰ) and bis(5,5'-benzoyl-4-hydroxy-2-methoxy phenyl) methane(Ⅱ). The structures of the compounds had been identified by ~1HNMR, IR, MS. Considering many parameters, the optimum conditions of (Ⅰ) were obtain as following: at 120℃, the raw materials with ratio of 2- benzotriazol-4-tetramethylbutyl phenol, paraformaldehyde and (C_3H_7)_2NH 1:0.9:1.8 for 2 h;then at 160℃, 35g o-dimethylbenzene as solvent, 0.4g NaOH as catalyst for 10 h; at last 7.5 g acetice acid added to crystal for 0.5 h, 40 mL methanol added to achieve (Ⅰ), with yield 95%. Considering many parameters, the optimum conditions of (Ⅱ) were obtain as following: at 70℃, the raw materials with ratio of 2- methoxy -6-hydroxy diphenyl ketone which was added for twice , 37% formaldehyde solution and (C_3H_7)_2NH 6:4:4 for 6 h, 25 mL methanol as solvent; then at 90℃, 1 mL (28% w/w) sodium methoxide as catalyst, 20 mL n-butanol as solvent for 10 h; at last 20 mLmethanol added to achieve (Ⅱ) with yield 60%.
本文合成了2，2’-亚甲基-二-[6-(2H-苯并三唑-2-基)-4-(1，1，3，3-叔辛基)酚]与2，2’-亚甲基-二-[(5-甲氧基-6-苯甲酰基)-苯酚]两种高分子量化的紫外吸收剂，并对其结构进行表征。考虑了各种因素对反应的影响。2，2’-亚甲基-二-[6-(2H-苯并三唑-2-基)-4-(1，1，3，3-叔辛基)酚]的优化合成工艺：第一步原料2-苯并三唑-4-叔辛基酚：多聚甲醛：二正丙胺的最佳摩尔比例为1∶0.9∶1.8，反应温度120℃，反应时间为2 h；第二步反应温度为160℃，反应时间为10 h，反应溶剂邻二甲苯适宜用量为35 g，碱催化剂为NaOH，适宜用量为0.4 g；第三步加入7.5 g冰醋酸反应0.5 h后，加入结晶助溶剂甲醇，适宜用量为40 mL，收率可达95％。2，2’-亚甲基-二-[(5-甲氧基-6-苯甲酰基)-苯酚]的优化合成工艺：第一步原料2-甲氧基-6-羟基二苯酮：37％甲醛溶液：二正丙胺的最佳摩尔比例6∶4∶4，溶剂为甲醇，适宜用量为25 mL，反应温度70℃，反应时间为6 h，单体加料方式为两次加入；第二步反应温度为90℃，反应时间为10 h，碱催化剂为甲醇钠甲醇溶液，适宜用量为1 mL(质量分数为28％)，使用溶剂为正丁醇，适宜用量为20 mL：加入的结晶助溶剂甲醇的适宜用量为20 mL，收率可达60％。
Light stabilizer is a kind of substance adding to cosmetics, cloth, polymer materials to reduce damage caused by UV. UV absorber is one kind of light stabilizer used commonly which is in great need. But there are some defects of the UV absorber on sale, so research-hing on new type UV absorber which has stable structure and well property is very important.
The article stated synthesis of two kind of polymer UV absorber, 2,2'-methylene bis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetrarnethylbutyl)phenols)(Ⅰ) and bis(5,5'-benzoyl-4-hydroxy-2-methoxy phenyl) methane(Ⅱ). The structures of the compounds had been identified by ~1HNMR, IR, MS. Considering many parameters, the optimum conditions of (Ⅰ) were obtain as following: at 120℃, the raw materials with ratio of 2- benzotriazol-4-tetramethylbutyl phenol, paraformaldehyde and (C_3H_7)_2NH 1:0.9:1.8 for 2 h;then at 160℃, 35g o-dimethylbenzene as solvent, 0.4g NaOH as catalyst for 10 h; at last 7.5 g acetice acid added to crystal for 0.5 h, 40 mL methanol added to achieve (Ⅰ), with yield 95%. Considering many parameters, the optimum conditions of (Ⅱ) were obtain as following: at 70℃, the raw materials with ratio of 2- methoxy -6-hydroxy diphenyl ketone which was added for twice , 37% formaldehyde solution and (C_3H_7)_2NH 6:4:4 for 6 h, 25 mL methanol as solvent; then at 90℃, 1 mL (28% w/w) sodium methoxide as catalyst, 20 mL n-butanol as solvent for 10 h; at last 20 mLmethanol added to achieve (Ⅱ) with yield 60%.
引文
1 陈登龙，章文贡，朱兰瑾．二(邻甲酸甲酯苯酚)乙醇胺铝酸酯紫外线吸收剂的研究．塑料科技，2004(sum．161)：4～6
2 黄翀，欧阳艳东，方奕文．天然紫外吸收剂脱色对光谱特性的影响．汕头大学学报，2003，18(3)：77～79
3 尤向阳．抗A紫外光线吸收剂的合成．河北化工．2000(4)：32～33
4 由宏君，刘聚民．光稳定剂的特点．当代化工，2004，33(5)：266～268
5 舒万艮，申雄军．国内外光稳定剂的发展现状及趋势．精细与专用化学品，2002(5)：3～5
6 李宇，李宗石．苯并三唑类紫外吸收剂的现状及发展趋势．精细与专用化学品，2007，15(5)：5～7
7 罗维巍，宫红，姜恒．2-羟基-4-甲氧基二苯甲酮-β-环糊精包合物的制备与表征．化学研究，2006，17(1)：35～37
8 丁著明，刘丽湘，周淑静．紫外吸收剂的研究进展．精细与专用化学品，2005，13(13)：5～10
9 李华，郑玉斌，王林．聚合型紫外线吸收剂的合成研究．含2-羟基-4-丙烯酸酯基二苯酮的丙烯酸酯类乳液聚合．合成树脂及塑料．2004，21(2)：56～59
10 孔宪明，宫红，姜恒等．2-羟基-4-甲氧基二苯甲酮的合成及工业放大试验．精细化工，2006，23(7)：625～627，663
11 拉沙那．苯并三唑型紫外吸收剂合成工艺研究．精细化工．2000，17(1)：7～9
12 盛学斌，孙岩峰，宫国梁等．含2，4-二羟基苯基三嗪的抗紫外辐射分散染料的合成．染料与染色．2005，42(4)：27～30
13 多英全，陈煜，罗运军等．3，4，5-三甲氧基苯甲酰-3，5-二甲基苯甲酰甲壳素的制备与表征．化工学报，2005，56(10)：2014～2018
14 吕海涛，孙美娟，丁采真．紫外吸收剂UV-9的合成．莱阳农学院学报 2001，18(2)：149～151
15 刘桂阳，张增强。纺织品防紫外整理的开发现状．浙江纺织服装职业技术学院学报．2006(1)：29～33
16 Kazumori M, Ken I. Heat-sensitive recording material comprising a diazonium salt,a coupler and benzotriazole compound. US 5679494,1997-12-21
17 Somorin O, Nishi N, Tokura Set al. Studies on chitin EM DASH 2, preparation of benzyl and benzoul chitin.Polymer Journal, 1979,11 (5) : 391～396
18 Mac Leay Ronald E, Kmiec Jennifer P, Stein Daryl L. Preparation of N-2-hydroxy -3-(2H-benzotriazol-s-yl)benzyl)oxamides as light stabilizers for polymers. CA 2099154
19 Nishida K, Morimoto M, Irie N. Heat-resistant transparent thermoplastic methacrylim ide polymers. Jpn.Kokai. JP 0.22953
20 Kubota N, Nishimura J. Benzotriazolyl bisphenols. Jpn.Kokai. JP 61118373
21 Eguehi H, Nishikawa K. Light-resistant polyester fibers and their manufacture. Jpn. Kokai. JP 03193912
22 Sato M, Takeuchi Y. Heat-sensitive recording material. US 20030141491, 2003-07-31
23 Kazumori M, Masanobu T. Heat-sensitive recording material. US 20030118851, 2003-06-26
24 Kazumori M, Masanobu T.Heat-sensitive recording material. US 2002018417, 2002-12-12
25 Fukuoka S, Shimura K, Tokuyama H. Light fastness treatment agents for hydrophobic fibers. Jpn.Kokai. JP 63203880
26 Nakahara Y, Takahashi M, Suzuki S. Polyester compositions with improved weatherability. Jpn.Kokai. JP 01245046
27 Toray I, Inc. Agricultural cover films. Jpn.Kokai. JP 8206470
28 Aumueller A, Neumann P. Preparation of 2-hydroxy-4- alkoxybenzophenones. US 4980 512, 1990-12-25
29 Notari M, Mizia F, Rivetti F. Process for the synthesis of 2-hydroxy-4-alkyloxy benzophenone. US 5849955, 1998-12-15
30 Lachamann B, Rosenkranz H J.Process for the production of 2, 4-dihydroxy-benzophenone. US 3843729, 1974-10-22
31 Kim S S, Kim S H, Lee Y M. Preparation, characterization, and properties of β-chitin and N-acetylated β-chitin. Journal of Polymer Science , Part B : Polymer Physics,1996,34(14) : 2367～2374
32 Kubota N, Naohiro J. Benzotriazolyl bisphenols. Jpn.Kokai. JP 61118373,1986-06-05
33 Naoyuki S, Toshiyuki Y, Eisuke K et al. Process For Prepareing Bis(2-Hydroxyphenyl-3-Benztriazole)Methanes. US 5808086,1997-07-28
34 William E L, Semyon M, Mahmut L. Process For Prepareing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)MS 5237071, 1993-08-17
35 Kubata, Naohiro, Process For Prepareing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl) -4-hydrocarbyl phenols), EP 0180993, 1986-05-14
36 Yamauchi, Edogawa-ku. Benzotriazolyl-alkylene bisphenol compounds, process for their preparation, and stabilized organic materials containing them. EP 0847997, 1998-06-17
37 Scholl, Thomas, Dipl,Bergisch, Gladbach. Berfahren zur Herstellung von Derivaten des Bis-[2-hydroxy-phenyl-3 (2H)-benztriazil]methans. DP 4118545, 1992,12,10
38 Shigetoshi H, Kiyoshi F, Shoichi H et al. Color Photographic Photosensitice Material Containing Ultraviolet Ray-Absorbing Compound. US 3936305,1974-12-02
39 Fukuoka S, Shimura K, Rokuyama H. Light fastness treatment agents for hydrophobisfibers. Jpn.Kokai. JP 63203880,1988-08-23
40 Kubota N, Shibata T, Sugibuchi K. 5,5'-Methylenebis(2-hydroxy-4-alkoxybenzophenones). Jpn.Kokai. JP 53101346, 1978-09-04
2 黄翀，欧阳艳东，方奕文．天然紫外吸收剂脱色对光谱特性的影响．汕头大学学报，2003，18(3)：77～79
3 尤向阳．抗A紫外光线吸收剂的合成．河北化工．2000(4)：32～33
4 由宏君，刘聚民．光稳定剂的特点．当代化工，2004，33(5)：266～268
5 舒万艮，申雄军．国内外光稳定剂的发展现状及趋势．精细与专用化学品，2002(5)：3～5
6 李宇，李宗石．苯并三唑类紫外吸收剂的现状及发展趋势．精细与专用化学品，2007，15(5)：5～7
7 罗维巍，宫红，姜恒．2-羟基-4-甲氧基二苯甲酮-β-环糊精包合物的制备与表征．化学研究，2006，17(1)：35～37
8 丁著明，刘丽湘，周淑静．紫外吸收剂的研究进展．精细与专用化学品，2005，13(13)：5～10
9 李华，郑玉斌，王林．聚合型紫外线吸收剂的合成研究．含2-羟基-4-丙烯酸酯基二苯酮的丙烯酸酯类乳液聚合．合成树脂及塑料．2004，21(2)：56～59
10 孔宪明，宫红，姜恒等．2-羟基-4-甲氧基二苯甲酮的合成及工业放大试验．精细化工，2006，23(7)：625～627，663
11 拉沙那．苯并三唑型紫外吸收剂合成工艺研究．精细化工．2000，17(1)：7～9
12 盛学斌，孙岩峰，宫国梁等．含2，4-二羟基苯基三嗪的抗紫外辐射分散染料的合成．染料与染色．2005，42(4)：27～30
13 多英全，陈煜，罗运军等．3，4，5-三甲氧基苯甲酰-3，5-二甲基苯甲酰甲壳素的制备与表征．化工学报，2005，56(10)：2014～2018
14 吕海涛，孙美娟，丁采真．紫外吸收剂UV-9的合成．莱阳农学院学报 2001，18(2)：149～151
15 刘桂阳，张增强。纺织品防紫外整理的开发现状．浙江纺织服装职业技术学院学报．2006(1)：29～33
16 Kazumori M, Ken I. Heat-sensitive recording material comprising a diazonium salt,a coupler and benzotriazole compound. US 5679494,1997-12-21
17 Somorin O, Nishi N, Tokura Set al. Studies on chitin EM DASH 2, preparation of benzyl and benzoul chitin.Polymer Journal, 1979,11 (5) : 391～396
18 Mac Leay Ronald E, Kmiec Jennifer P, Stein Daryl L. Preparation of N-2-hydroxy -3-(2H-benzotriazol-s-yl)benzyl)oxamides as light stabilizers for polymers. CA 2099154
19 Nishida K, Morimoto M, Irie N. Heat-resistant transparent thermoplastic methacrylim ide polymers. Jpn.Kokai. JP 0.22953
20 Kubota N, Nishimura J. Benzotriazolyl bisphenols. Jpn.Kokai. JP 61118373
21 Eguehi H, Nishikawa K. Light-resistant polyester fibers and their manufacture. Jpn. Kokai. JP 03193912
22 Sato M, Takeuchi Y. Heat-sensitive recording material. US 20030141491, 2003-07-31
23 Kazumori M, Masanobu T. Heat-sensitive recording material. US 20030118851, 2003-06-26
24 Kazumori M, Masanobu T.Heat-sensitive recording material. US 2002018417, 2002-12-12
25 Fukuoka S, Shimura K, Tokuyama H. Light fastness treatment agents for hydrophobic fibers. Jpn.Kokai. JP 63203880
26 Nakahara Y, Takahashi M, Suzuki S. Polyester compositions with improved weatherability. Jpn.Kokai. JP 01245046
27 Toray I, Inc. Agricultural cover films. Jpn.Kokai. JP 8206470
28 Aumueller A, Neumann P. Preparation of 2-hydroxy-4- alkoxybenzophenones. US 4980 512, 1990-12-25
29 Notari M, Mizia F, Rivetti F. Process for the synthesis of 2-hydroxy-4-alkyloxy benzophenone. US 5849955, 1998-12-15
30 Lachamann B, Rosenkranz H J.Process for the production of 2, 4-dihydroxy-benzophenone. US 3843729, 1974-10-22
31 Kim S S, Kim S H, Lee Y M. Preparation, characterization, and properties of β-chitin and N-acetylated β-chitin. Journal of Polymer Science , Part B : Polymer Physics,1996,34(14) : 2367～2374
32 Kubota N, Naohiro J. Benzotriazolyl bisphenols. Jpn.Kokai. JP 61118373,1986-06-05
33 Naoyuki S, Toshiyuki Y, Eisuke K et al. Process For Prepareing Bis(2-Hydroxyphenyl-3-Benztriazole)Methanes. US 5808086,1997-07-28
34 William E L, Semyon M, Mahmut L. Process For Prepareing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)MS 5237071, 1993-08-17
35 Kubata, Naohiro, Process For Prepareing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl) -4-hydrocarbyl phenols), EP 0180993, 1986-05-14
36 Yamauchi, Edogawa-ku. Benzotriazolyl-alkylene bisphenol compounds, process for their preparation, and stabilized organic materials containing them. EP 0847997, 1998-06-17
37 Scholl, Thomas, Dipl,Bergisch, Gladbach. Berfahren zur Herstellung von Derivaten des Bis-[2-hydroxy-phenyl-3 (2H)-benztriazil]methans. DP 4118545, 1992,12,10
38 Shigetoshi H, Kiyoshi F, Shoichi H et al. Color Photographic Photosensitice Material Containing Ultraviolet Ray-Absorbing Compound. US 3936305,1974-12-02
39 Fukuoka S, Shimura K, Rokuyama H. Light fastness treatment agents for hydrophobisfibers. Jpn.Kokai. JP 63203880,1988-08-23
40 Kubota N, Shibata T, Sugibuchi K. 5,5'-Methylenebis(2-hydroxy-4-alkoxybenzophenones). Jpn.Kokai. JP 53101346, 1978-09-04