含硫高折光指数光学树脂单体的合成

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,含硫高折光指数光学树脂单体的合成,答辩人： 张云芳,指导老师： 曾兆华 副教授,1,答辩内容,研究背景,创新之处,实验合成及测试表征,机理推测和性能讨论,可固化基团的改性,结论,2,上世纪四十年代，美国,PPG,公司首先用浇铸法制成了塑料透镜，即目前的热固性树脂,CR,39,（二甘醇双烯丙基碳酸酯）眼镜片。,随着丙烯酸树脂研制成功和同轴注射机的问世，光学树脂广泛应用在精密成型的透镜，探照灯、信号灯投影仪，视力矫正接触透镜，衍射光栅等方面。,目前，在三维光子晶体的制备方面也有重要应用。,1.1,光学树脂的发展及应用,3,目前文献报道的高折光树脂多含以下原子离子或基团：,卤族元素(除氟)： 密度大、摩尔体积小,重金属离子： 与稀土元素形成不饱和有机酸盐,苯环,和稠环： 易极化性,硫原子：,二价的硫离子外层剩余的两对孤对,电子容易受到极化,折光指数,的提高程度最大而且,色散,和,密度,的增加相对最小,1.2,含硫高折光指数光学树脂,4,目前，在聚合物里引入硫元素是提高折射率的研究热点。根据单体的结构可将含硫光学树脂分为：,聚氨酯型光学树脂,加成型光学树脂,缩聚型光学树脂,环氧型光学树脂,氢转移型光学树脂,环硫型光学树脂,含有硫代氨基甲酸酯键,力学性能优异,强度高,耐刮擦性能强,5,二.创新之处,采用室温条件合成二硫代氨基甲酸酯的方法，选取合适的,仲胺和卤代物合成了一系列二硫代氨基甲酸酯，并且其中一,些产物折光指数较高，具有光活性。,避开传统的热固化方式，采用光固化方式,6,三.实验合成及测试表征,3.1,合成方法：,脂肪族仲胺,无水磷酸钾,室温搅拌,二硫化碳,卤代烃,二硫代氨基甲酸酯,氮负离子,二硫代氨基,甲酸盐,7,TOPOLENE M,8,9,10,11,12,3.2.1二苄胺类二硫代氨基甲酸酯的表征,Fig 31 FTIR Spectra of dithiocarbamates based on dibenzyl amine,S CN,SCH2,3.2产物结构表征,13,Fig 32 UV absorption Spectra of dithiocarbamates based on dibenzyl amine,SCN,280,nm,SCS,250,nm,苯环,226,nm,14,Fig 33,1,H NMR Spectrum of DPDTEt,DPDTEt结构中各H在谱图中相应的化学位移分别为a7.30，b4.95，5.32，c3.39，d1.37。,Fig 34,1,H NMR Spectrum of DPDTAl,DPDTAl结构中各H在谱图中相应的化学位移分别为a7.30，b4.90，5.32，c4.07，d5.96，e5.34，f5.19。,15,Fig 35,1,H NMR Spectrum of DPDTHE,DPDTHE结构中各H在谱图中相应的化学位移分别为a7.31，b4.97，5.32，c3.66，d3.81，e2.10,Fig 36,1,H NMR Spectrum of DPDTTO,DPDTTO结构中各H在谱图中相应的化学位移分别为a7.32，b4.91，5.31，c3.63，d3.91，e2.16，f4.17，4.28，g1.96，h5.51，i6.13。,16,3.2.2哌嗪类二硫代氨基甲酸酯的表征,Fig 37 FTIR Spectra of Dithiocarbamates,based on piperazine,a：PIDTEt，b：PIDTAl,c：PIDTHE，d：PIDTTO,Fig 38 UV absorption Spectra of dithiocarbamates based on piperazine,17,Fig 39,1,H NMR Spectrum of PIDTEt,PIDTEt结构中各H在谱图中相应的化学位移分别为a1.39,b3.33, ,c,4.26，H1.50附近的峰为氘代氯仿中的水的峰。,18,Fig 310,1,H NMR Spectrum of PIDTAl,PIDTAl结构中各H在谱图中相应的化学位移分别为a5.32，b5.17，c5.95，d3.98，e4.25，H1.22，H2.14可能是杂质峰。,Fig 311,1,H NMR Spectrum of PIDTTO,PIDTTO结构中各H在谱图中相应的化学位移分别为a6.13，b5.62，c1.95，d4.23，e3.88，f2.18，g4.25，h4.21。,19,3.2.3二环己胺类二硫代氨基甲酸酯的表征,Fig 312 FTIR Spectra of dithiocarbamates,based on bicyclohexylamine,a：DCDTEt，b：DCDTHE,c：DCDTTO, d：DCDTTO,Fig 313 UV absorption Spectra of dithiocarbamates based on bicyclohexylamine,20,Fig 314,1,H NMR Spectrum of DCDTHE,DCDTHE结构中各H在谱图,中相应的化学位移分别为,a1.60，b1.30，,c3.50，d5.17，5.25,e1.83，f3.97。,21,3.2.4 N甲基哌嗪类二硫代氨基甲酸酯的表征,Fig 315 FTIR Spectra of dithiocarbamates,based on Nmethyl piperazine,a：MPDTEt，b：MPDTHE,c：MPDTAl，d：MPDTTO,Fig 316 UV absorption,Spectra of dithiocarbamates,based on Nmethyl piperazine,22,Fig 317,1,H NMR Spectrum of MPDTEt,MPDTEt结构中各H在谱图中相应的化学位移分别为a2.27，b2.48，c3.32，d3.92，4.32，e1.34。,Fig 318,1,H NMR Spectrum of MPDTAl,MPDTAl结构中各H在谱图中相应的化学位移分别为a2.32，b2.48，,c没有，d4.01，e5.92，f5.17，g5.32。,23,紫外光谱证明，产物在,250,nm,和,280,nm,有明显的吸收。,红外光谱说明，在体系中,存在未反应完全的胺类,，表现为,3400,cm,-1,-3600,cm,-1,的吸收。,SCN,在,1270,cm,-1,-1280,cm,-1,和,直接与S原子相连的CH,2,键在,12201270,cm,1,有明显吸收峰。,核磁共振的测试表明，,哌嗪类,和,二苄胺类,二硫代氨基甲酸酯的合成效果非常好，各个碳原子上氢的位移和积分基本和理论结构式吻合。,24,3.2.5 部分硫代氨基甲酸酯的元素分析,通过上面的测试表明，,哌嗪类,二硫代氨基甲酸酯与,二苄胺类,硫代氨基甲酸酯的纯度相对较高，因此，从中选取了几个产品进行了元素分析测试。,Table 3-1 Element analysis of some dithiocarbamates,产品,C,H,N,PIDTEt,实验值,40.61,6.378,9.386,理论值,40.78,6.16,9.51,DPDTAl,实验值,69.15,6.111,4.391,理论值,68.97,6.11,4.47,DPDTEt,实验值,68.20,6.356,4.486,理论值,67.73,6.35,4.65,25,四.机理推测和性能讨论,4.1 反应机理推测,4.1.1 无水磷酸钾的作用机理,26,Table41 Refractive index，Abbe number and content of each group,当含苯环，硫的含量相差不大时，折光指数相差不会很大，,只有相差约10以上时，折光指数才会有较明显的差别。,4.2硫、苯环含量对折光指数的影响,27,五.topoleneM的改性,主要改性方法：topoleneM的氯乙酰化,topoleneM的苯甲酰化,28,改性卤代物的二硫代氨基甲酸酯的合成与表征,以二苄胺为原料，分别与上述改性的卤代物反应，合成相应的二硫代氨基甲酸酯 ,产物结构如下：,29,Fig 54FTIR Spectrum of DPDTTC,Fig 55 FTIR Spectrum of DPDTTB,Fig 53 UV absorption Spectra,a: DPDTTC,b: DPDTTB,250,nm,附近是SC = S共轭吸收峰，,280,nm,附近是S = CN共轭吸收峰。,226,nm,附近是苯环的共轭吸收峰。,30,Fig. 5-6,1,H NMR Spectrum of DPDTTC,H在谱图中相应的化学位移分别为a7.32，b5.30，4.90，c4.50，d4.50，e4.20，f4.90，g1.96，h5.61，i6.12。1.50是溶剂中水的峰。,31,Table5-1 The refractive index of topolene M before and after modification,topolene M,benzoyl-topolene M,chloracetyl -topolene M,nd,1.4785,1.5305,1.4769,v,d,39,31.5,40,Table5-2The refractive index of,DPDTTO，DPDTTB, DPDTTC,DPDTTO,DPDTTB,DPDTTC,nd,1.561,1.570,1.610,v,d,32,36,30,苯环对增加折光指数作用很大，并使体系色散增大。,topolene M苯甲酰化后的氯原子上的位阻太大，使反应不完全。,32,Table5-3 Refractive index of dithiocarbamate before and after UV irradiation,样品,光照前n,d,光照后n,d,PIDTTO,1.532,1.570,DPDTTO,1.567,聚合、质脆,DPDTTB,1.575,聚合、质脆,DPDTTC,1.610,聚合、质脆,PIDTTO/ DPDTTC=1：1,1.587,DPDTAl,1.642,不聚合,将PIDTTO/ DPDTTC按照质量比1：1混合光照，薄膜的折光指数,达到了1.587，而阿贝数d43，色散较低。,33,结论,1. 在无水磷酸钾作用下，采用仲胺与二硫化碳、卤代物反应，生成相应的二硫代氨基甲酸酯。通过红外光谱、紫外光谱、核磁共振、元素分析对产品进行了一系列的测试，表明确实生成了该结构。,二环己胺和N甲基哌嗪反应不是很彻底，二苄胺和哌嗪的反应比较完全。,34,3. 含硫密度越高，苯环密度越高，折光指数越高。卤代物结构分子链越长，对折光指数不利。,含有丙烯酸酯类基团的,topolene M,的产物可以在自由基光引发剂引发下固化,。对,topolene M,上的羟基通过酰化进行了改性，将改性后的,topolene M,与二苄胺反应得到了折光指数较高、色散值低的固化膜。,35,致谢,本论文是在导师曾兆华副教授和杨建文副教授的悉心指导下完成的。陈用烈教授对实验工作提出了很多宝贵的意见，在此，谨向三位老师表示衷心的感谢和崇高的敬意。,黄亮博士生和吕学义硕士在实验过程中给予了我 很大的帮助，在此，向他们表示诚挚的谢意。,在实验过程中，实验室所有的师兄师姐都给了我很大的帮助，在此，向他们表示衷心的感谢！,36,Thank 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