二齿钛配合物催化的降冰片烯均聚合及共聚合研究

发布时间：2018-06-28 16:29

本文选题：降冰片烯 + 席夫碱钛配合物　；参考：《浙江大学》2017年博士论文

【摘要】：降冰片烯(NBE)是一种具有双键的环状单体,能以加成聚合、开环易位聚合以及自由基/阳离子聚合等方式得到聚合物。降冰片烯的加成聚合物具有高透明性、低双折射率、低介电损耗等优异性能,在微电子、电器、光学器件等领域具有广泛应用。为了改善加成型聚降冰片烯的加工性能,常常引入第二单体与降冰片烯进行共聚合。新型催化体系以及共聚合体系的开发是降冰片烯聚合领域的研究热点。本文采用[N,O]和[N,N]二齿鳌合的钛配合物,在不同助催化体系的作用下,分别实现了降冰片烯的均聚合及其与1-辛烯、1,3-丁二烯和异戊二烯的共聚合,探讨了聚合条件对聚合反应及聚合物结构和性能的影响。以3,5-二叔丁基水杨醛缩苯胺氯化钛(SF-Ti)为主催化剂,三异丁基铝(TIBA)或三乙基铝(TEA)和四(五氟苯基)硼酸三苯基甲酯(B)作为助催化剂,实现了降冰片烯的加成均聚合。采用SF-Ti/TIBA/B三元催化体系,[Ti]/[Al]/[B]=1:5:1,[NBE]/[Ti]=200:1,于甲苯中60 ℃下聚合4小时,得到数均分子量为4.2× 1 04 g/mol,分子量分布指数为3.5的聚合物,聚合产率为72.2%,催化活性达3.39×103 gPNBE/(molTi h)。SF-Ti/TEA/B三元催化体系在相同条件下催化NBE均聚合,所得聚合物的数均分子量为3.6×10~4g/mol,分子量分布略窄(MWD=2.3),聚合产率为 59.9%,催化活性为 1.88×103 gPNBE/(molTi h)。高温1HNMR、DSC、TGA 等表征结果表明,两种催化体系得到的聚合物均为降冰片烯的加成聚合物,且均具有优异的热稳定性(Td≈440 ℃)。SF-Ti/T-IBA/B三元催化体系还可催化降冰片烯与1-辛烯(OC)的共聚合,得到重均分子量为1.3-4.5×10~4g/mol,分子量分布指数为1.91-2.45的无规共聚物,该共聚物可溶于常见有机溶剂。测得在共聚合条件下两种单体的竞聚率分别为:rNBE = 3.01,roc = 0.08。改变降冰片烯与1-辛烯两种单体的投料比,可调节共聚物中降冰片烯的含量。DSC、TGA分析显示,共聚物只有一个玻璃化转变温度(87-174 ℃),且具有优良的热稳定性,热分解温度高于300℃ 两者均随降冰片烯的含量增加而提高。研究了 SF-Ti/TIBA二元催化体系催化的降冰片烯与1,3-丁二烯的共聚合。该催化体系对两者的共聚合具有较高的催化活性,所得共聚物的数均分子量为0.2-1.3×10~4g/mol,分子量分布适中(MWD=2～2.2)。设定聚合条件为:[Al]/[Ti]=7:1,[Monomer]/[Ti]=200:1,[NBE]/[BD]=5:5,甲苯中 40℃下聚合 6 小时,共聚物的产率可达91%。改变单体投料比和聚合条件,共聚物中降冰片烯含量始终维持在55%左右,说明该共聚物主链中两种单体单元具有高度的交替倾向。DEPT 13513CNMR和FTIR结果分别显示降冰片烯以加成聚合的方式插入到共聚物主链中;1,3-丁二烯则主要以1,4聚合方式插入共聚物链中。热分析结果表明,共聚物具有较低的玻璃化转变温度(Tg=50-70 ℃)和较高的热分解温度(Td=380 ℃)。共聚物可溶于有机溶剂,用溶液浇筑方法制得的共聚物薄膜在可见光范围内具有很高的透光性(透过率大于80%)。用含硫二胺钛配合物(SNN-Ti)/三异丁基铝(TIBA)二元催化体系实现了降冰片烯的加成均聚合及其与异戊二烯的共聚合。当[Al]/[Ti]=5:1,[NBE]/[Ti]=200:1,100 ℃下于甲苯中聚合6小时,降冰片烯均聚物的产率可达到62.1%。均聚物的重均分子量为4.5-6.8×10~4g/mol,分子量分布指数介于1.39-2.03之间。降冰片烯与异戊二烯共聚合的反应条件更加温和,[AI]/[Ti]=5:1,[Monomer]/[Ti]=400:1,[NBE]/[IP]=5:5,40 ℃下聚合6小时,共聚物产率可达到97.9%。测得两种单体的竞聚率分别为:rNBE = 0.056;rIP = 0.002,且共聚物的组成随单体投料比和聚合条件的变化不大(共聚物中降冰片烯含量为43-63%),交替共聚倾向明显。核磁共振谱表明共聚物中降冰片烯和异戊二烯分别以加成聚合和1,4聚合方式插入。共聚物具有良好的溶解性和优异的热稳定性,玻璃化转变温度为65-82 ℃,热分解温度高于300℃。共聚物薄膜对可见光的透过率高于80%,是一种优秀的透明材料。通过聚合物中的活性双键与巯基小分子的“巯-烯”点击反应,可以得到羟基或者羧基修饰的部分极性聚合物,拓宽了该共聚物的应用范围。
[Abstract]:NBE is a circular monomer with double bonds. It can be polymerized by addition polymerization, open ring translocation polymerization and free radical / cationic polymerization. The adduct polymer of norbornene has excellent properties such as high transparency, low birefringence, low dielectric loss and so on. It is widely used in microelectronics, electrical appliances, optical devices and so on. In order to improve the processing properties of added polynorlene, second monomers and norbornene are often co polymerized. New catalytic systems and copolymerization systems are the hot topics in the field of polyborate polymerization. This paper uses [N, O] and [N, N] two chelating titanium complexes, under the action of different catalytic systems, respectively. The copolymerization of norbornene and Its Copolymerization with 1- octene, 1,3- butadiene and isoprene were realized. The effects of polymerization conditions on the polymerization and the structure and properties of the polymer were discussed. The main catalyst was 3,5- dibutyl salicylaldehyde aniline chloride (SF-Ti), three isobutadiene (TIBA) or triethyl aluminum (TEA) and four (five fluoro phenyl) boron. Acid three phenyl methyl ester (B) was used as a co catalyst to realize the addition polymerization of norbornene. Using a SF-Ti/TIBA/B three element catalytic system, [Ti]/[Al]/[B]=1:5:1, [NBE]/[Ti]=200:1, and polymerization at 60 C in toluene for 4 hours, a polymer with a mean molecular weight of 4.2 x 104 g/mol and a molecular weight distribution index of 3.5 was obtained, and the polymerization yield of 72.2% was catalyzed. The catalytic system of 3.39 * 103 gPNBE/ (molTi h).SF-Ti/TEA/B three element catalyzes the polymerization of NBE under the same condition. The average molecular weight of the polymer is 3.6 x 10~4g/mol, the molecular weight distribution is narrow (MWD=2.3), the polymerization yield is 59.9%, the catalytic activity is 1.88 x 103 gPNBE/ (molTi H). The high-temperature 1HNMR, DSC, and other characterization results show two urges. The polymers obtained by the chemical system are all addition polymers of norbornene, and both have excellent thermal stability (Td 440).SF-Ti/T-IBA/B three catalyst system and also can catalyze the copolymerization of norbornene and 1- octyl (OC). The copolymers with a heavy average molecular weight of 1.3-4.5 * 10~4g/mol and the fraction distribution index of 1.91-2.45 are obtained. The content of the two monomers in the copolymerization condition is rNBE = 3.01 and ROC = 0.08. changes the feeding ratio of the two monomers of norbornene and 1- octadiene, which can adjust the content of norbornene in the copolymer.DSC. The TGA analysis shows that the copolymer has only one glass transition temperature (87-174 degrees C), and it is excellent. Both good thermal stability and thermal decomposition temperature are higher than 300 degrees centigrade. The copolymerization of norbornene and 1,3- Butadiene Catalyzed by SF-Ti/TIBA two element catalytic system has been studied. The catalytic system has a high catalytic activity for the copolymerization of both, and the number average molecular weight of the copolymer is 0.2-1.3 x 10~4g/. Mol, the molecular weight distribution is moderate (MWD=2 ~ 2.2). The polymerization conditions are as follows: [Al]/[Ti]=7:1, [Monomer]/[Ti]=200:1, [NBE]/[BD]=5:5, and polymerization for 6 hours at 40 C in toluene. The yield of the copolymer can be 91%. to change the monomer feeding ratio and polymerization conditions. The content of Borneol in the copolymer is maintained at about 55%, indicating that the main chain of the copolymer is two. The monomer unit has a high degree of alternating tendency.DEPT 13513CNMR and FTIR results to show that norbornene is inserted into the main chain of the copolymer in addition polymerization, and 1,3- butadiene is mainly inserted in the copolymer chain by 1,4 polymerization. The thermal analysis results show that the copolymer has a lower glass transition temperature (Tg=50-70 C) and higher level. The thermal decomposition temperature (Td=380). The copolymer is soluble in organic solvent and the copolymer film obtained by solution pouring method has high transmittance in the visible light range (transmittance greater than 80%). The addition polymerization of norbornene and its isoamyl with SNN-Ti / three isobutyl aluminum (TIBA) two are used. Copolymerization of diene. When [Al]/[Ti]=5:1, [NBE]/[Ti]=200:1100 C is polymerized for 6 hours in toluene, the yield of borneol homopolymer can reach 62.1%. homopolymer 4.5-6.8 x 10~4g/mol, molecular weight distribution index is between 1.39-2.03. The reaction conditions of the copolymerization of norbornene and isopentene two ene are more mild, [AI]/[Ti] At =5:1, [Monomer]/[Ti]=400:1, and [NBE]/[IP]=5:5,40 C for 6 hours, the yield of the copolymer can reach 97.9%. and the yield of the two monomers is rNBE = 0.056, rIP = 0.002, and the composition of the copolymer varies little with the monomer feeding ratio and the polymerization conditions (the content of the borneol in the copolymer is 43-63%), and the alternation copolymerization tends to be obvious. The magnetic resonance spectra show that the copolymer has good solubility and excellent thermal stability, the glass transition temperature is 65-82, and the thermal decomposition temperature is higher than 300. The transmittance of the copolymer film to visible light is higher than 80%, which is an excellent transparent material. Material. By clicking the active double bond in the polymer with the mercapto alkenes of small mercapto molecules, the hydroxyl or carboxyl modified partial polar polymers can be obtained, which widens the application range of the copolymer.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O631.5

【相似文献】