新型二苯甲酮类光稳定剂的合成及性能研究
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摘要
二苯甲酮类化合物具有特殊的光化学性质,其在紫外线吸收剂、光引发剂、医药工业与电子工业等领域有广泛应用。
本文拟在通过文献查阅和综合相关资料比较,采用两种方法合成2,4-二硝基二苯甲酮并通过对反应条件的摸索——原料配比、催化剂用量、反应温度、反应时间等因素的比较,设计正交试验对反应条件进行优化和摸索,以便找出最佳的反应条件和分离方法。从而获得纯度和产率较高的产品,然后在此基础上进行还原反应和烃基化反应合成七种在国内尚未见文献报道的新型二苯甲酮类衍生物。本文合成的化合物在240～400nm范围内比紫外线吸收剂UV-9和UV-531有更好的紫外吸收效率,并且热稳定性也有了很大提高。
另外对于产物结构的鉴定,我们采用NMR、ESI-MS、FT-IR等分析手段分别对产物结构进行了归属和验证。最后,将合成产物分别与聚乙烯熔融共混后制成薄膜并测试了紫外吸收性能,发现薄膜制品的紫外吸收性能与目标化合物相比基本无变化,证明目标化合物对聚乙烯制品可以起到光稳定作用,为光稳定剂的设计合成及应用提供了理论的依据及实际的可行性。
Benzophenone derivatives,which have good photoehemistry properties, are commonly applied in the area of Ultra-violet absorbers, photoinitiators, medicinal, electronic industry and so on.
In this paper, two methods of synthesis of 2,4-dinitrobenzophenone were seleiced compared literature with relevant information available, and we designed orthogonal experiment to optimize and explore the reaction conditions in order to identify the best reaction condition and separation methods. Through the exploration of reaction conditions - the ratio of raw materials, the amount of catalyst, reaction temperature, reaction time, etc. Then, we can obtain a higher purity and yield of the product, upon which reduction and alkylation reaction were carried out to synthesize seven new benzophenone derivatives never reported at home.In this paper, the compounds synthesized have better efficiency than UV-9 and UV-531 UV absorbers in the range of 240～400 nm, and their thermal stability has also been greatly improved.
In addition, we used NMR, ESI-MS, FT-IR and other analytical tools to identify structure of attribution and authentication. Finally, we made our products and polyethylene melt to prepare films and tested the ultraviolet receptivity, then discovered that films' UV absorption were almost same with the target compound, which proved the target compound played an important role of the stabilization of polyethylene product and applied the theoretical basis and practical feasibility for designing the light stabilizers.
本文拟在通过文献查阅和综合相关资料比较,采用两种方法合成2,4-二硝基二苯甲酮并通过对反应条件的摸索——原料配比、催化剂用量、反应温度、反应时间等因素的比较,设计正交试验对反应条件进行优化和摸索,以便找出最佳的反应条件和分离方法。从而获得纯度和产率较高的产品,然后在此基础上进行还原反应和烃基化反应合成七种在国内尚未见文献报道的新型二苯甲酮类衍生物。本文合成的化合物在240～400nm范围内比紫外线吸收剂UV-9和UV-531有更好的紫外吸收效率,并且热稳定性也有了很大提高。
另外对于产物结构的鉴定,我们采用NMR、ESI-MS、FT-IR等分析手段分别对产物结构进行了归属和验证。最后,将合成产物分别与聚乙烯熔融共混后制成薄膜并测试了紫外吸收性能,发现薄膜制品的紫外吸收性能与目标化合物相比基本无变化,证明目标化合物对聚乙烯制品可以起到光稳定作用,为光稳定剂的设计合成及应用提供了理论的依据及实际的可行性。
Benzophenone derivatives,which have good photoehemistry properties, are commonly applied in the area of Ultra-violet absorbers, photoinitiators, medicinal, electronic industry and so on.
In this paper, two methods of synthesis of 2,4-dinitrobenzophenone were seleiced compared literature with relevant information available, and we designed orthogonal experiment to optimize and explore the reaction conditions in order to identify the best reaction condition and separation methods. Through the exploration of reaction conditions - the ratio of raw materials, the amount of catalyst, reaction temperature, reaction time, etc. Then, we can obtain a higher purity and yield of the product, upon which reduction and alkylation reaction were carried out to synthesize seven new benzophenone derivatives never reported at home.In this paper, the compounds synthesized have better efficiency than UV-9 and UV-531 UV absorbers in the range of 240～400 nm, and their thermal stability has also been greatly improved.
In addition, we used NMR, ESI-MS, FT-IR and other analytical tools to identify structure of attribution and authentication. Finally, we made our products and polyethylene melt to prepare films and tested the ultraviolet receptivity, then discovered that films' UV absorption were almost same with the target compound, which proved the target compound played an important role of the stabilization of polyethylene product and applied the theoretical basis and practical feasibility for designing the light stabilizers.
引文
[1]宁培森,郭振宇,丁著明.紫外线吸收剂的研究进展[J].聚合物与助剂,2007年第1期
[2]刘忠泽.二苯甲酮系列产品的合成及应用[J].精细化工中间体,2002,32(2):7-9
[3]白福臣,程凤梅,叶永成等.受阻胺类光稳定剂的研究进展[J].塑料科技,2002,(4)pp:20-24
[4]丁学里,方岩雄.塑料助剂生产技术与应用[M].广东科技出版社
[5]吕世光.塑料助剂手册.北京:轻工业出版社,1986,349-358
[6]丁著明.苯并三唑类光稳定剂的合成和应用[J].天津化工,1991(1):34-38
[7]周大纲,谢鸽成.塑料老化与防老化技术[M].中国轻工业出版社,1998:157
[8]何中琴.UVC紫外线屏蔽整理[J].印染译丛,1999,6:42-46
[9]H.S.Freeman,MaryE.Mason,JasonLye.DisperseDyesContaining a Built-in Oxalanilide Stabilizer.Dyes and Pigments,1999,42:53-63
[10]Merritt,C.,Scott,G..W.Transient Absorption Spectra of 2-Hydroxybenzophenone Photostabilizers.Chemical Phys.letter.,1980,69:169
[11]王德平.受阻胺光稳定剂[J].现代塑料加工应用,1999,4(11):41.
[12]Heller H.J.,Blattmann H.R.,Some aspects of stabilization of polymers against light,Pure Appl.Chem.,1973,36(1):141-161
[13]Denisov E.T.,The role and reactions of nitroxyl radicals in hindered piperidine light stabilization,Polym.Degrad.Stab.,1991,34(3):325-332
[14]Klemchuk P.P.,Gande M.E.,Stabilization mechanisms of hindered amines,Polym.Degrad.Stab.,1998,22(3):241-274
[15]Chateauneuf J.,Lusztyk J.,Ingold K.V.,Absolute rate constants for the reactions of some carbon-centered radicals with 2,2,6,6-tetramethyl,J.Org.Chem.,1988,53(8):1629-1632
[16]Brede O.,David F.,and Steenken S.,Photo-and Radiation-induced chemical generation and reactions of styrene radical cations in polar and non-polar solvents,J.Chem.Soc.,Perkin Trans.2,1995,(1):23-32
[17]Gugumus F.,Mechanisms of thermooxodative stabilization with HAS,Polym.Degrad.Stab.,1994,44(3):299-322
[18]Gugumus F.,Current trends in mode of action of hindered amine light stabilizers,Polym.Degrad.Stab.,1993,40(2):167-215
[19]Gugumus F.,Mechanisms and kinetics of photostabilization of polyolefins with HALS,Angew Makromol.Chem.,1990,177:241-289
[20]Step.E.N.,Turro N.J.,Klemchuk P.P.et al.,Model studies on the mechanism of hals stabilization,Angew Makromol.Chem.,1995,232(1):65-83
[21]Zahradnickova.A.,Sedlar J.,Dastych D.,Peroxy acids in photo-oxidized polypropylene,Polym.Degrad.Stab.,1991,32(2):155-176
[22]Klemchuk P.P.,Gande M.E.,Cordola E.,Hindered amine mechanisms:PartⅢ-Investigations using isotopic labelling,Polym.Degrad.Stab.,1990,27(1):65-74
[23]Cogen J.M.,Semiempirical prediction of the thermochemistry of intermediates Involved in the cyclic mechanism of hindered amine stabilizers,Polym.Degrad.Stab.,1994,44(1):49-53
[24]EclderV.B.,Schumacher R.,Untersuchungen uber wirkungsmechanismen von lichtschutzmitteln Ⅰ.Mitteilung,Angew Makromol.Chem.,1973,31(1):35-54
[25]Yip R.W.,Siebrand W.,Hydrogen abstraction by triplet ketones.Applicability of the electronic-vibrational energy transfer model,Chem.Phys.Lett.,1972,13(3):209-212
[26]PadronA.J.C.,Mechanistic aspects of polymer photostabilization,J.Photochem.Photobiol.A:Chem.,1989,49(1):1-39
[27]Carlsson D.J.,Chan K.H.,Durmis J.et al,Decomposition of polypropylene hydroperoxide by hindered amines,J.Polym.Sci.,Polym.Chem.Ed.,1982,20(2):575-582
[28]Carlsson D.J.,Suprunchuk T.,Wiles D.M.,Singlet oxygen attack on model compounds for polyolefins and cellulose,J.Polym.Sci.,Polym.Lett.Ed.,1976,14(8):493-498
[29]Carlsson D.J.,Grattan D.J.,Suprunchuk T.et al,The photodegradation of polypropylene Ⅳ.UV stabilizer decomposition,J.Appli.Polym.Sci.,1978,22(8):2217-2228
[30]Carlsson D.J.,Wiles D.M.,The photodegradation and photostabilization of polymers.A review,J.Radiat.Curing,1975,2(4):2-14
[31]Yang Y.Y.,Lucki J.,Rabek J.F.et al,Photostabilising effect of bis(hindered piperidine) compounds:Part Ⅱ-In singlet-oxygen degradation of cis-1,4-poly (butadiene),Polym.Photochem.,1983,3(2):97-108
[32]张志新.国内外光稳定剂市场现状及预测.塑料助剂.2001,3:11-15
[33]由宏君,姜恒,宫红.相转移法合成2,4-二羟基二苯甲酮.抚顺石油学院学报,2001,21(4):15-17
[34]RiesU J,MihmG,Nar B,et al.6-substituted benzimidazoles as new nonpeptide angiotensin Ⅱ receptor antagonists:synthesis,biological activity and structure-a cture-activity relationship.J Med Chem,1993,36(25):4040-4051
[35]Nouet S,Dodey P R,Bondoux X R,et al.Specific nonpeptide photoprobes as tool for the structure study of the angiotensin Ⅱ AT1 receptor.J Med Chem,1999,42(22):4572-4583
[36]Alexander Aumueller.Preparation of 2-hrdroxy-4-alkoxy-benzophenones.US4980512,1990-08-13
[37]Neumann P,Aumueller A.Process for the preparation of 2,4-dihydroxy-benzo phenone.US4990680,1991-03-24
[38]NishihamaS,Fukui H.Sunscreen formulation and testing.Cosmetics&Toiletries,2001,116(9):49-60
[39]Hodgson P C,UV-stable thermosetting polymer coating compositions containi ng unsatpolyesters and vinylfunctionl monomers and UV stabilizers:WOP,22752,2002-03-21
[40]Reynolds W.Ultra-violent resistand premix compositions and articles using such compositions:USP,6337362,2002-01-08
[41]魏先红,李萍.钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)与2,4-二羟基配合物的合成与表征.精细化工中间体,2006,36(3):70-73
[42]Materzzi A,Vasca E.Thermoanalytical investigation of Ni(Ⅱ),Co(Ⅱ) and Cu(Ⅱ)complexes with imidazale-4-acetic acid.Thermochimica acta,2001,7:373
[43]Materzzi A,Aquili S.Biomimetic complexes:thermal stability,kinetic study and decomposition mechanism of Ni(Ⅱ)-,Co(Ⅱ)-and Cu(Ⅱ)-complexes 4-hydroxymethyl-5-methylimidazole complexes.Thermochimica acta,2004,19:421
[44]Ahmed I S,Mossolamy E H.syhthesis and characterization of oxazolonecomp lexes with Fe(Ⅲ),Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ) and Zn(Ⅱ) in different counterions.J.Anal.Appl.pyrolysis,2003,70:679
[45]何光耀,聚合物光稳定化进展,合成材料老化与应用,1998,(2),36-46
[46]吴婉娥,陈开勋,朱绪恩,华栋,受阻胺光稳定剂开发进展,精细化工,1997,14,6-10
[2]刘忠泽.二苯甲酮系列产品的合成及应用[J].精细化工中间体,2002,32(2):7-9
[3]白福臣,程凤梅,叶永成等.受阻胺类光稳定剂的研究进展[J].塑料科技,2002,(4)pp:20-24
[4]丁学里,方岩雄.塑料助剂生产技术与应用[M].广东科技出版社
[5]吕世光.塑料助剂手册.北京:轻工业出版社,1986,349-358
[6]丁著明.苯并三唑类光稳定剂的合成和应用[J].天津化工,1991(1):34-38
[7]周大纲,谢鸽成.塑料老化与防老化技术[M].中国轻工业出版社,1998:157
[8]何中琴.UVC紫外线屏蔽整理[J].印染译丛,1999,6:42-46
[9]H.S.Freeman,MaryE.Mason,JasonLye.DisperseDyesContaining a Built-in Oxalanilide Stabilizer.Dyes and Pigments,1999,42:53-63
[10]Merritt,C.,Scott,G..W.Transient Absorption Spectra of 2-Hydroxybenzophenone Photostabilizers.Chemical Phys.letter.,1980,69:169
[11]王德平.受阻胺光稳定剂[J].现代塑料加工应用,1999,4(11):41.
[12]Heller H.J.,Blattmann H.R.,Some aspects of stabilization of polymers against light,Pure Appl.Chem.,1973,36(1):141-161
[13]Denisov E.T.,The role and reactions of nitroxyl radicals in hindered piperidine light stabilization,Polym.Degrad.Stab.,1991,34(3):325-332
[14]Klemchuk P.P.,Gande M.E.,Stabilization mechanisms of hindered amines,Polym.Degrad.Stab.,1998,22(3):241-274
[15]Chateauneuf J.,Lusztyk J.,Ingold K.V.,Absolute rate constants for the reactions of some carbon-centered radicals with 2,2,6,6-tetramethyl,J.Org.Chem.,1988,53(8):1629-1632
[16]Brede O.,David F.,and Steenken S.,Photo-and Radiation-induced chemical generation and reactions of styrene radical cations in polar and non-polar solvents,J.Chem.Soc.,Perkin Trans.2,1995,(1):23-32
[17]Gugumus F.,Mechanisms of thermooxodative stabilization with HAS,Polym.Degrad.Stab.,1994,44(3):299-322
[18]Gugumus F.,Current trends in mode of action of hindered amine light stabilizers,Polym.Degrad.Stab.,1993,40(2):167-215
[19]Gugumus F.,Mechanisms and kinetics of photostabilization of polyolefins with HALS,Angew Makromol.Chem.,1990,177:241-289
[20]Step.E.N.,Turro N.J.,Klemchuk P.P.et al.,Model studies on the mechanism of hals stabilization,Angew Makromol.Chem.,1995,232(1):65-83
[21]Zahradnickova.A.,Sedlar J.,Dastych D.,Peroxy acids in photo-oxidized polypropylene,Polym.Degrad.Stab.,1991,32(2):155-176
[22]Klemchuk P.P.,Gande M.E.,Cordola E.,Hindered amine mechanisms:PartⅢ-Investigations using isotopic labelling,Polym.Degrad.Stab.,1990,27(1):65-74
[23]Cogen J.M.,Semiempirical prediction of the thermochemistry of intermediates Involved in the cyclic mechanism of hindered amine stabilizers,Polym.Degrad.Stab.,1994,44(1):49-53
[24]EclderV.B.,Schumacher R.,Untersuchungen uber wirkungsmechanismen von lichtschutzmitteln Ⅰ.Mitteilung,Angew Makromol.Chem.,1973,31(1):35-54
[25]Yip R.W.,Siebrand W.,Hydrogen abstraction by triplet ketones.Applicability of the electronic-vibrational energy transfer model,Chem.Phys.Lett.,1972,13(3):209-212
[26]PadronA.J.C.,Mechanistic aspects of polymer photostabilization,J.Photochem.Photobiol.A:Chem.,1989,49(1):1-39
[27]Carlsson D.J.,Chan K.H.,Durmis J.et al,Decomposition of polypropylene hydroperoxide by hindered amines,J.Polym.Sci.,Polym.Chem.Ed.,1982,20(2):575-582
[28]Carlsson D.J.,Suprunchuk T.,Wiles D.M.,Singlet oxygen attack on model compounds for polyolefins and cellulose,J.Polym.Sci.,Polym.Lett.Ed.,1976,14(8):493-498
[29]Carlsson D.J.,Grattan D.J.,Suprunchuk T.et al,The photodegradation of polypropylene Ⅳ.UV stabilizer decomposition,J.Appli.Polym.Sci.,1978,22(8):2217-2228
[30]Carlsson D.J.,Wiles D.M.,The photodegradation and photostabilization of polymers.A review,J.Radiat.Curing,1975,2(4):2-14
[31]Yang Y.Y.,Lucki J.,Rabek J.F.et al,Photostabilising effect of bis(hindered piperidine) compounds:Part Ⅱ-In singlet-oxygen degradation of cis-1,4-poly (butadiene),Polym.Photochem.,1983,3(2):97-108
[32]张志新.国内外光稳定剂市场现状及预测.塑料助剂.2001,3:11-15
[33]由宏君,姜恒,宫红.相转移法合成2,4-二羟基二苯甲酮.抚顺石油学院学报,2001,21(4):15-17
[34]RiesU J,MihmG,Nar B,et al.6-substituted benzimidazoles as new nonpeptide angiotensin Ⅱ receptor antagonists:synthesis,biological activity and structure-a cture-activity relationship.J Med Chem,1993,36(25):4040-4051
[35]Nouet S,Dodey P R,Bondoux X R,et al.Specific nonpeptide photoprobes as tool for the structure study of the angiotensin Ⅱ AT1 receptor.J Med Chem,1999,42(22):4572-4583
[36]Alexander Aumueller.Preparation of 2-hrdroxy-4-alkoxy-benzophenones.US4980512,1990-08-13
[37]Neumann P,Aumueller A.Process for the preparation of 2,4-dihydroxy-benzo phenone.US4990680,1991-03-24
[38]NishihamaS,Fukui H.Sunscreen formulation and testing.Cosmetics&Toiletries,2001,116(9):49-60
[39]Hodgson P C,UV-stable thermosetting polymer coating compositions containi ng unsatpolyesters and vinylfunctionl monomers and UV stabilizers:WOP,22752,2002-03-21
[40]Reynolds W.Ultra-violent resistand premix compositions and articles using such compositions:USP,6337362,2002-01-08
[41]魏先红,李萍.钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)与2,4-二羟基配合物的合成与表征.精细化工中间体,2006,36(3):70-73
[42]Materzzi A,Vasca E.Thermoanalytical investigation of Ni(Ⅱ),Co(Ⅱ) and Cu(Ⅱ)complexes with imidazale-4-acetic acid.Thermochimica acta,2001,7:373
[43]Materzzi A,Aquili S.Biomimetic complexes:thermal stability,kinetic study and decomposition mechanism of Ni(Ⅱ)-,Co(Ⅱ)-and Cu(Ⅱ)-complexes 4-hydroxymethyl-5-methylimidazole complexes.Thermochimica acta,2004,19:421
[44]Ahmed I S,Mossolamy E H.syhthesis and characterization of oxazolonecomp lexes with Fe(Ⅲ),Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ) and Zn(Ⅱ) in different counterions.J.Anal.Appl.pyrolysis,2003,70:679
[45]何光耀,聚合物光稳定化进展,合成材料老化与应用,1998,(2),36-46
[46]吴婉娥,陈开勋,朱绪恩,华栋,受阻胺光稳定剂开发进展,精细化工,1997,14,6-10