【作者】 邢跃鹏；

【导师】 陈义旺；

【作者基本信息】 南昌大学 ， 高分子科学与工程， 2011， 博士

【摘要】 当前,为了提高降冰片烯类聚合物的可加工性能,利用后过渡金属催化剂制备降冰片烯和功能单体共聚物的研究成为聚烯烃材料领域的一个新热点。本文合成了新型含氟催化剂Ni{CF3C(O)CHC[N(naphthyl)]CH3}2并采用单晶X-射线衍射技术解析了其结构。采用含氟催化体系Ni{CF3C(O)CHC[N(naphthyl)]CH3)2/B(C6F5)3和不含氟催化体系Ni{CH3C(O)CHC[N(naphthyl)]CH3)2/B(C6F5)3催化降冰片烯与甲基丙烯酸正丁酯,长链1-烯烃(1-己烯,1-辛烯,1-癸烯)共聚,采用含氟催化体系Ni{CF3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3催化降冰片烯与苯乙烯,降冰片烯甲酸甲酯共聚,探索了共聚单体结构对共聚物结构、性能和可加工性能的影响。在甲苯中采用双-(β-酮胺)镍(Ⅱ)Ni{RC(O)CHC[N(naphthyl)]CH3}2(R=CH3,CF3)和三五氟苯硼B(C6F5)3体系催化降冰片烯与甲基丙烯酸正丁酯共聚合。对于降冰片烯与甲基丙烯酸正丁酯共聚,这两种催化体系都具有较高的催化活性。探索了共聚单体比例和催化剂结构对产率和聚合活性的影响,推测了双-(β-酮胺)镍(Ⅱ)/三五氟苯硼B(C6F5)3体系催化降冰片烯与甲基丙烯酸正丁酯共聚合过程中可能的含有失活反应的插入机理。通过Kelen-TUdOs法得到的单体竞聚率分别为rn-BMA=0.095,norbornene=12.626。成功制备了共聚物薄膜并且共聚物在可见光范围具有良好的透光性。采用双-(β-酮胺)镍(Ⅱ)Ni{RC(O)CHC[N(naphthyl)]CH3}2(R=CH3,CF3)和三五氟苯硼B(C6F5)3体系催化降冰片烯与1-烯烃(1-己烯,1-辛烯,1-癸烯)共聚合并且这两种催化体系都具有较高的催化活性。探索了催化剂结构和共聚单体比例对聚合活性和单体插入率的影响。对于不含氟催化体系Ni{CH3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3催化降冰片烯与1-辛烯共聚,通过Kelen-TUdos法得到的单体竞聚率分别为r1-octene=0.009,rnorbomene=13.461。通过1H NMR和13C NMR的分析,共聚过程是按照乙烯基加成型聚合方式进行的。TGA分析表明共聚物具有良好的热稳定性(分解温度高于400℃),DSC分析表明共聚物的玻璃化转变温度在215到275℃之间。共聚物在常见有机溶剂中具有良好溶解性并且通过广角X-射线衍射证明共聚物是非晶的。在甲苯中采用含氟催化体系Ni{CF3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3催化降冰片烯与苯乙烯共聚合。催化体系对于降冰片烯与苯乙烯共聚具有较高的催化活性达到1.37×105(gpolymer/molNi·h)。探索了共聚单体比例对聚合活性和单体插入率的影响,当苯乙烯加入摩尔比为10-50%时,苯乙烯在共聚物中比例可控制在1.1-5.6%。通过Kelen-TUdOs法得到的单体竞聚率分别为rSt=0.453,rNB=19.810。所制备的共聚物具有非常高的玻璃化转变温度(Tg>320℃)。采用溶液成膜法制备了共聚物薄膜,共聚物膜在可见光范围具有良好透光性,透光率达到75-80%。在甲苯中采用含氟催化体系Ni{CF3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3催化降冰片烯与降冰片烯甲酸甲酯共聚合。催化体系对于降冰片烯与降冰片烯甲酸甲酯共聚具有较高的催化活性达到2.69×105(gpolynler/molNi·h).通过改变共聚单体比例的共聚反应得知降冰片烯甲酸甲酯在共聚物中具有非常高的插入率,当降冰片烯甲酸甲酯加入摩尔比为10-90%时,降冰片烯甲酸甲酯在共聚物中比例可控制在7.9-77.6%。通过Kelen-TUdOs法得到的单体竞聚率分别为rNB-COOCH3=0.578,rNB=0.859。分别采用溶液成膜,干/湿相转变和静电纺丝技术对共聚物加工,采用溶液成膜法制备的共聚物薄膜在可见光范围具有良好透光性,干/湿相转变法制备的聚合物膜具有微孔结构,静电纺丝技术制备的聚合物纤维直径约3μm。更多还原

【Abstract】 The research of the copolymerization of norbornene and functional monomer catalyzed by late transition metal catalyst is an area of great recent interest in polyolefin material in order to improve the processability of polynorbornenes. Novel fluorinated catalyst Ni{CF3C(O)CHC[N(naphthyl)]CH3}2 was synthesized and the structure was solved by single crystal X-ray refraction technique in this paper, copolymerization of norbornene and n-butyl methacrylate, 1-alkene(1-hexene,1-octene,1-decene) catalyzed by fluorinated catalyst system Ni{CF3C(O)CHC[N(naphthy])]CH3}2 and non-fluorinated catalyst system Ni{CH3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3 and copolymerization of norbomene and styrene, methoxycarbonylnorbornene catalyzed by fluorinated catalyst system Ni{CF3C(O)CHC[N(naphthyl)]CH3}2 were studied to investigate the effect of monomer structures on copolymer structures, properties and processabilities.Copolymerization of norbomene with n-butyl methacrylate were carried out with catalytic systems of bis-(β-ketoamino)nickel(II) complexes Ni{RC(O)CHC[N(naphthyl)]CH3}2 (R=CH3, CF3) and B(C6F5)3 in toluene. Both of the above catalytic systems exhibited higher activity for copolymerization of norbomene and n-butyl methacrylate. Influence of the comonomer feed content and catalyst structure on the yield and polymerization activity were investigated. The insertion mechanism including deactivation reaction on copolymerization of norbornene and n-butyl methacrylate catalyzed by bis-(β-ketoamino)nickel(II)/B(C6F5)3 catalytic systems was proposed. The reactivity ratios were determined by the Kelen-TUdOs method, and rn-BMA=0.095, rnbornene=12.626. Copolymer films were prepared and showed good transparency in the visible region.Copolymerization of norbornene with higher 1-alkene were carried out in toluene with catalytic systems based on nickel(Ⅱ) complexes Ni{RC(O)CHC[N(naphthyl)]CH3}2 (R=CH3, CF3) and B(C6F5)3 and exhibited high activity for both catalytic systems. Influence of the catalyst structure and comonomer feed content on the polymerization activity as well as on the incorporation rates were investigated. The reactivity ratios were determined to be rn-QCtcne=0.009 and rnrborniene=13.461 by the Kelen-TUdOs method for Ni{CH3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3 system. The achieved copolymers were confirmed to be vinyl-addition copolymers through the analysis of 1H NMR and 13C NMR. TGA analysis results showed that the copolymers exhibited good thermal stability (Td> 400℃) and the glass transition temperature of the copolymers were observed between 215 and 275℃. The copolymers are confirmed to be noncrystalline by wide-angle X-ray diffraction (WAXD) analysis results and showed good solubility in common organic solvents.Copolymerization of norbornene (NB) with styrene (St) were carried out with catalytic system of Ni{CF3C(O)CHC[N(naphthyl)]CH3}2 and B(C6F5)3 in toluene. The catalytic system exhibited higher activity 1.37×105 (gpolymer/molNi·h) for copolymerization of norbornene and styrene. Influence of the comonomer feed content on the polymerization activity as well as on the incorporation rates were investigated. The styrene content in copolymers can be controlled to be 1.1-5.6 mol% at content of 10-50 mol% of the styrene in the monomer feeds ratios. The reactivity ratios were determined by the Kelen-TUdOs method, and rSt=0.453,rNB=19.810. The prepared copolymers had very high glass transition temperature (Tg> 320℃). Copolymers were processed by solution casting method and the films showed good transparency in the visible region with 75-80% transmittance.Copolymerization of norbornene (NB) with methoxycarbonylnorbornene (NB-COOCH3) were carried out with catalytic system of Ni{CF3C(O)CHC[N(naphthyl)]CH3}2 and B(C6F5)3 in toluene. The catalytic system exhibited higher activity 2.69×105(gpolymer/molNi·h) for copolymerization of norbornene and methoxycarbonylnorbornene. The influence results of the comonomer feed content on the polymerization showed that the NB-COOCH3 has a very high insertion ratio in all copolymers, and the NB-COOCH3 content in copolymers can be controlled to be 7.9-77.6 mol% at content of 10-90 mol% of the NB-COOCH3 in the monomer feeds ratios. The reactivity ratios were determined by the Kelen-TUdOs method, and rNB-COOCH3=0.578,rNB= 0.859. Copolymers were processed by solution casting method, dry/wet phase inversion technique and electrospinning respectively. The films prepared by solution casting method showed good transparency in the visible region. The membranes processed by dry/wet phase inversion technique were microporous structures. The fibers diameters fabricated by electrospinning were about 3μm.更多还原