【作者】 张良；

【导师】 路建美；

【作者基本信息】 苏州大学 ， 应用化学， 2009， 博士

【摘要】 聚合物荧光和三阶非线性光学材料兼具小分子材料光学品质优良和高分子材料可加工性优越的优点,是荧光材料和三阶非线性光学材料的研究重点之一。苯并噻唑衍生物通常具有光学稳定性和热稳定性,将苯并噻唑结构经过一定的化学修饰,并键合到聚合物中,得到的聚合物材料能够保留发（生）色团的功能,因而,这方面的研究在获得聚合物荧光和三阶非线性光学材料方面具有重要的学术价值。本论文以含苯并噻唑的聚合物为研究对象,以对苯并噻唑结构构成激发态分子内质子转移（ESIPT）、增加共轭程度、引入偶氮结构为修饰方法,研究不同发（生）色团结构对聚合物荧光和三阶非线性光学性能的影响为手段,以获得性能优异的聚合物荧光和三阶非线性光学材料为目的,设计、合成、表征、测试了一系列端基、侧链功能化的聚合物的结构和性能,并进一步进行了荧光光谱调节,还对比研究了不同取代基、共轭性、推拉电子结构对三阶非线性光学性能的影响。论文主要进行了以下几个方面的工作:（1）设计并合成了一个含具有激发态分子内质子转移（ESIPT）发荧光功能的ATRP引发剂2-（2-苯并噻唑）-5-溴甲基苯酚（BYBP）,并以之引发苯乙烯进行原子转移自由基聚合（ATRP）。讨论了反应温度、催化体系相对引发剂的投料比这些因素对ATRP的影响,聚合物的结构由¹HNMR进行了表征,以得到的聚合物为大分子引发剂进行了扩链。得到的聚苯乙烯有很好的荧光性能,发射波长在约530nm处,发草绿色荧光,斯托克斯位移约190 nm。（2）设计并合成了一个含共轭苯并噻唑结构的ATRP引发剂2-溴-2-甲基-丙酸4-（2-苯并噻唑-2-乙烯基）苯基酯（BPBVE）,并以之引发MMA进行ATRP。讨论了反应温度、催化体系相对引发剂的投料比这些因素对ATRP的影响,聚合物功能性端基的存在用UV-vis及¹H NMR作了验证。聚合反应时间与单体转化对数成一阶线性关系,数均分子量随单体转化线性增长,得到的聚合物的分子量分布指数在1.07-1.23之间。得到的聚合物的DMF溶液发蓝色荧光,聚合物溶液对金属离子具有响应,八种金属离子(Zn²⁺,Co²⁺,Ni²⁺,pb²⁺,Mn²⁺,Cu²⁺,Fe³⁺,Ag⁺)会使聚合物溶液荧光有不同程度的淬灭。（3）合成了含共轭苯并噻唑结构的单体甲基丙烯酸4-（2-苯并噻唑-2-乙烯基）苯基酯（BVMA）,单体BVMA的ATRP以上述BPBVE作为引发剂进行,得到的PBVMA结构经¹H NMR表征。以得到的PBVMA为大分子引发剂、4-甲基丙烯酸氧基-己氧基-4’-硝基均二苯乙烯（HNS）为第二单体进行了扩链,均聚物PBVMA的DMF溶液发蓝光,而PBVMA-b-PHNS由于发生分子内能量转移,其DMF溶液荧光发射波长主要在约610 nm处,为橙光。BVMA的ATRP还以2-溴-2-甲基-丙酸4-硝基均二苯乙烯-己氧基酯（BPNHE）为引发剂进行,获得的聚合物结构同样经¹H NMR表征,发现该聚合物的DMF溶液荧光随分子量变化而变化,数均分子量为15900的聚合物的DMF溶液发白色荧光。所有聚合反应时间与单体转化对数成一阶线性关系,数均分子量随单体转化率增加而线性增长,大多数聚合物的分子量分布指数小于1.50。（4）合成了甲基丙烯酸4-（2,5-二苯基-3,4-二酚-2氢-吡唑-3-基）-苯基酯与甲基丙烯酸偶氮苯酯的无规共聚物[PDPMA-co-PMOAB],结构经¹H NMR验证,该聚合物同时具有三苯基吡唑啉的荧光性能和偶氮结构的光化学特性,通过侧链偶氮结构的光致顺反异构可以调节聚合物的荧光强度。（5）合成了2-溴-2-甲基-丙酸4-苯并噻唑-2-偶氮-苯基酯（BPBE）、2-溴-2-甲基-丙酸4-（6-甲氧基苯并噻唑-2-偶氮）-苯基酯（BPMBE）、2-溴-2-甲基-丙酸4-（6-硝基苯并噻唑-2-偶氮）-苯基酯（BPNBE）三个含不同取代基的偶氮苯并噻唑结构的ATRP引发剂,并以之引发MMA进行ATRP,偶氮苯并噻唑结构成功引入PMMA的链端,经测试表明所得聚合物并不具有明显的三阶非线性光学性能。合成了甲基丙烯酸4-苯并噻唑-2-偶氮-苯基酯（BAMA）、甲基丙烯酸4-（6-甲氧基苯并噻唑-2-偶氮）-苯基酯（MBAMA）、甲基丙烯酸4-（6-硝基苯并噻唑-2-偶氮）-苯基酯（NBAMA）三个含不同取代基的偶氮苯并噻唑结构的甲基丙烯酸酯类单体,将三个单体通过自由基聚合得到聚合物,偶氮苯并噻唑结构成功引入聚合物的侧链,发现取代基团为硝基的单体及聚合物三阶非线性光学性能要优于取代基团为氢、甲氧基的单体及聚合物。合成了甲基丙烯酸4-噻唑-2-偶氮-苯基酯（TAMA）、甲基丙烯酸4-苯并噻唑-2-偶氮-苯基酯（BAMA）、2-{4’-[[N-（2-甲基丙烯酰基）乙基]-N-乙基]苯基偶氮}-5-硝基噻唑（MANT）、2-{4’-[(N-（2-甲基丙烯酰基）乙基]-N-乙基]苯基偶氮}-6-硝基苯并噻唑（MANBT）四个含杂环偶氮结构的甲基丙烯酸酯类单体,将四个单体通过自由基聚合得到聚合物,发现生色团通过增加共轭程度和引入推拉电子体系均能有效提高单体及聚合物的三阶非线性光学性能。更多还原

【Abstract】 Polymer materials with fluorescent and third-order nonlinear optical （NLO） properties have received much attention for they remain good optical properties of small molecules and excellent processabilities of polymers. Many benzothiazole derivates can be covalently bounded to polymer chain as a result of their photophysical and thermal stability. Novel benzothiazole-containing initiators and monomers with fluorescent or NLO properties can be synthesized using chemical modification method. By selecting functional ATRP initiators and monomers, functional polymers can be obtained.In this thesis, we focused on the design, synthesis and characterization of novel polymers containing benzothiazole moieties for fluorescent materials and third-order NLO materials. The fluorescent and third-order NLO properties were studied. The work can be summarized as follows:（1） A novel initiator, 2-benzothiazol-2-yl-5-bromomethyl-phenol （BYBP） containing excited state intramolecular proton transfer （ESIPT） fluorophore was synthesized. Atom transfer radical polymerization （ATRP） of styrene was conducted successfully using BYBP as an initiator. Factors such as the reaction temperature and mole ratio of catalyst to initiator, which could affect the ATRP system, were discussed in the paper. Chain extension was conducted using polymer as the macro-initiator which was characterized via H NMR. The optical property of initiator was well preserved in the obtained polystyrene, and the end-functionalized polystyrene exhibited obvious fluorescent emission at about 530 nm. The Stokes shift was about 190 nm.（2） A new initiator, 2-bromo-2-methyl-propionic acid 4- （2-benzot hiazole-2-yl-vinyl）- phenyl ester （BPBVE） was synthesized for the heterogeneous atom transfer radical polymerization of methyl methacrylate. Factors such as the reaction temperature and mole ratio of catalyst to initiator, which could affect the ATRP system, were discussed in the paper. The functional end group was characterized via UV-vis and ¹H NMR spectroscopy. The rates of polymerizations exhibited first-order kinetic with respect to the monomer, and a linear increase in the number-average molecular weight with increasing monomer conversion was observed for these initiation systems. The polydispersity indices of the polymer were relatively low （1.07-1.23） up to high conversions. In DMF solution the end-functionalized PMMA decreased its fluorescence intensity in the presence of metal cations (Zn²⁺, Co²⁺, Ni²⁺, Pb²⁺, Mn²⁺, Cu²⁺,Fe³⁺,Ag⁺).（3） A benzothiazole-containing monomer, 4-（2-benzothiazole-2-yl-vinyl）-phenyl methacrylate （BVMA） was synthesized. Atom transfer radical polymerization （ATRP） of BVMA was conducted using BPBVE as an initiator. The obtained poly（4-（2-benzothiazole-2-yl-vinyl）-phenyl methacrylate） （PBVMA） was characterized via ¹H NMR, and chain extension with 4-methacryloxy-hexyloxy-4’-nitrostilbene （HNS） was conducted using PBVMA as the macroinitiator. The homopolymer PBVMA in DMF solution emitted blue fluorescence, and the copolymer PMABE-b-PHNS emitted relatively strong orange fluorescence at about 610 nm due to the intramolecular energy transfer. ATRP of BVMA was also conducted using 2-bromo-2-methyl-propionic acid 4-nitrostilbene-hexyloxy ester （BPNHE） as an initiator. The obtained polymer was characterized via ¹H NMR and the fluorescence changed with increase of number average molecular weight （M_n）. The polymer with M_n = 15900 emitted white fluorescence in DMF solution. All the rates of polymerizations exhibited the first-order kinetic with respect to the monomer, and a linear increase in the number average molecular weight with monomer conversion increasing was observed. Most of the polydispersity indices （PDIs） of the polymers were below 1.50.（4） A polymethacrylate derivative,poly（4-（2,5-diphenyl-3,4-dihydro-2H-pyrazol -3-yl）-phenylmethacrylate-co-4-methacryloyloxyazobenzene） [PDPMA-co-PMOAB] was synthesized. The structure of the copolymer was characterized by ¹H NMR. The copolymer combined photoluminescence property and photochemical behavior of both triphenyl pyrazoline and azobenzene moieties in the side-chains. The photoluminescence property of the polymer so obtained could be modified through the photochemical isomerization reaction of the photoactive groups.（5） 2-Bromo-2-methyl-propionic acid 4-benzothiazole-2-ylazo-phenyl ester （BPBE）, 2-bromo-2-methyl-propionic acid 4-（6-methoxy-ben zot hiazole-2-ylazo） -phenyl ester （BPMBE）, and 2-bromo-2-methyl-propionic acid 4-（6-nitro-benzothiaz-ole-2-ylazo）-phenyl ester （BPNBE） were synthesized and acted as the initiators for the heterogeneous atom transfer radical polymerization of MMA. No obvious third-order nonlinear optical property was observed for the obtained polymers. 4-benzothiazole -2-ylazo-phenyl-methacrylate （BAMA）,4-（6-methoxy-benzothiazole-2-ylazo）-phenyl-methacrylate （MBAMA）, and 4-（6-nitro-benzothiazole-2-ylazo）-phenyl- methacrylate （NBAMA） were synthesized and acted as monomers for normal radical polymerizatio ns. Third-order nonlinear optical property of the monomers and polymers were studied. 4-thiazole-2-ylazo-phenyl methacrylate （TAMA）, 4-benzothiazole-2-ylazo-phenyl-methacrylate（BAMA）,2-{4’-[[N-（2-methacryloyl）ethyl]-N-ethyl]phenylazo}-5-nitrothi azole （MANT）, and 2-{4’-[[N-（2-methacryloyl）ethyl]-N-ethyl]phenylazo}-6-nitroben zothiazole （MANBT） were synthesized and acted as monomers for normal radical polymerizations. Third-order nonlinear optical property of the monomers and polymers were studied.更多还原