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本文设计合成了卟啉的降冰片烯单体,采用Grubbs催化剂与长链烷基的降冰片烯单体开环易位聚合,直接得到了卟啉降冰片烯聚合物,通过紫外-可见吸收光谱、荧光光谱、电化学等手段研究了卟啉降冰片烯聚合物的性质,与小分子单体相比,所得卟啉高分子共聚物相当好地保持了卟啉应有的光物理、电化学等特性. 相似文献
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采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。 考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。 采用1H NMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。 结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。 得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%~90%时,其在共聚物中的插入率为22.1%~76.9%,所得聚合物具有较好的热稳定性(Td>360 ℃),在THF和CHCl3等许多普通溶剂中有很好的溶解性能。 相似文献
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本文合成了两个新的催化剂,苯基-三苯基膦-[N-萘基-3-甲基水杨醛亚胺]合镍(4a)与苯基-三苯基膦-[N-萘基-5-硝基水杨醛亚胺]合镍(4b),并研究了它们催化降冰片烯的聚合。发现两种催化剂在助催化剂甲基铝氧烷(MAO)存在下都具有良好的催化降冰片烯聚合物活性。在50 ℃时,催化剂4b表现出最高催化活性。 相似文献
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以Cs-对称芴基氨基二甲基钛络合物{[t-Bu NSi Me2Flu]Ti Me2}为催化剂,Ph3CB(C6H5)4为助催化剂,实现了降冰片烯与α-烯烃[己烯(2a)、辛烯(2b)、癸烯(2c)、十二烯(2d)和十八烯(2e)]的无规共聚,其中共聚物3e的结构经13C NMR确证。研究了2的侧链长度对3的共聚活性、热性能和光学性能的影响。结果表明,3a~3e均有较高的共聚活性,其值随着α-烯烃侧链长度和浓度的增加而提高,3e的共聚活性最高[63 100kg(polymer)·mol-1(Ti)·h-1];并具有高分子量(1.3×105~1.6×105)和窄分子量分布(1.10~1.48)以及可控的Tg(14℃~175℃)。3a~3e用甲苯通过涂膜法制得的自组装膜(3a'~3e')的透过率在90%左右,其中3e'的透过率高达96%。 相似文献
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合成了两种双吡唑亚胺镍配合物: 双-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.1)和双-4-甲氧基-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.2). 研究了Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯(NBE)单体聚合的催化性能, 考察了各种聚合条件, 如温度、Al/Ni摩尔比及催化剂浓度对降冰片烯的催化效率、单体转化率、聚合物分子量及分子量分布的影响. 研究结果表明, Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯聚合具有较高的催化效率, 可达到105 g PNBE/(mol Ni)数量级, 所得聚降冰片烯(PNBE)的重均分子量在105以上, 分子量分布指数在2左右. 聚合产物的1H NMR和FTIR谱分析结果表明, 该聚合反应是以单体的乙烯基加成聚合机理进行的. 相似文献
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以传统Ziegler-Natta催化体系TiCl4/Al(#em/em#-Bu)3催化降冰片烯(NBE)和异戊二烯(IP)的共聚合, 制得可溶于常规有机溶剂的共聚物, 其数均分子量为2.0 × 104~6.5 × 104, 分子量分布指数为1.5~2.9, 降冰片烯结构摩尔含量为26%~60%. 考察了助催化剂用量、 聚合温度及2种单体投料比对共聚合的影响. 结果表明, 当降冰片烯与异戊二烯的投料摩尔比为4∶6时, 于40 ℃聚合6 h, 得到的共聚物产率为96%, 数均分子量为6.5×104, 降冰片烯结构含量45%. 用 1H NMR, 13CNMR, GPC和DSC等方法表征了共聚产物的微观结构与热性能. 13C NMR DEPT结果表明, 共聚反应中降冰片烯单体以加成方式聚合. DSC结果显示, 共聚物只有一个玻璃化转变温度(Tg=20~40 ℃). 通过Kelen-Tüdös方法得到2种单体的竞聚率分别为rNBE=0.07, rIP=0.44. 相似文献
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A series of palladium complexes ( 2a–2g ) ( 2a : [6‐tBu‐2‐PPh2‐C6H3O]PdMe(Py); 2b : [6‐C6F5–2‐PPh2‐C6H3O]PdMe(Py); 2c : [6‐tBu‐2‐PPhtBu‐C6H3O]PdMe(Py); 2d : [2‐PPhtBu‐C6H4O] PdMe(Py); 2e : [6‐SiMe3–2‐PPh2‐C6H3O]PdMe(Py); 2f : [2‐tBu‐6‐(Ph2P=O)‐C6H3O]PdMe(Py); 2g : [6‐SiMe3–2‐(Ph2P=O)‐C6H3S]PdMe(Py)) bearing phosphine (oxide)‐(thio) phenolate ligand have been efficiently synthesized and characterized. The solid‐state structures of complexes 2d , 2f and 2g have been further confirmed by single‐crystal X‐ray diffraction, which revealed a square‐planar geometry of palladium center. In the presence of B(C6F5)3, these complexes can be used as catalysts to polymerize norbornene (NB) with relatively high yields, producing vinyl‐addition polymers. Interestingly, 2a /B(C6F5)3 system catalyzed the polymerization of NB in living polymerization manner at high temperature (polydispersity index 1.07, Mn up to 1.5 × 104). The co‐polymerization of NB and polar monomers was also studied using catalysts 2a and 2f . All the obtained co‐polymers could dissolve in common solvent. 相似文献
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以均苯三甲酰氯(TMC)和1,3-二氨基-2-丙醇(DAP)为原料,通过酯化、酰胺化和酯胺解反应,合成了树枝状大分子化合物均苯三甲酰胺-胺(TMAAM),并优化了合成工艺.考察了甲醇用量、缚酸剂种类及用量和原料DAP用量等对反应收率的影响,分析了酯胺解反应机理.用红外光谱(IR)、核磁(NMR)和高分辨质谱(HRMS)分析了TMAAM的化学结构.该合成方法反应条件温和,操作简单,后处理方便,并具有较高的反应经济性,产品收率最高可达57%. 相似文献
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Catellani reactions of aryl iodides allow the double functionalization at the ortho and ipso positions in one pot. Catellani reactions involving a nitrene intermediate are not yet known. In this paper, a few palladium amino complexes were prepared from PdCl2, anthranil and iodoarenes, and their structures were determined by X‐ray single‐crystal diffraction. These complexes are supported by a pincer C,N,O tridentate ligand forming fused six‐membered palladacycles. The high stability of the palladium complexes inhibits their reductive elimination. 相似文献
14.
Yu Lu Xianmao Lu Brian T. Mayers Thurston Herricks Younan Xia 《Journal of solid state chemistry》2008,181(7):1530-1538
This paper compares the performance of three long-chain acids—oleic and elaidic (both olefinic) and stearic (aliphatic)—as a capping agent in the synthesis of magnetic Co nanoparticles. The particles were formed through thermal decomposition of dicobalt octacarbonyl in toluene in the presence of the long-chain acid, and characterized by TEM, high-resolution TEM, and SQUID measurements. Infrared spectra revealed that some of the added olefinic acid was transformed from cis- to trans-configuration (for oleic acid) or from trans- to cis- (for elaidic acid) to facilitate the formation of a densely packed monolayer on the surface of Co nanoparticles. As compared to aliphatic acids, olefinic acids are advantageous for dense packing on small particles with high surface curvatures due to a bent shape of the cis-isomer. The presence of an olefinic acid is able to control particle growth, stabilize the colloidal suspension, and prevent the final product from oxidation by air. Our results indicate that oleic acid, elaidic acid, and a mixture of oleic/stearic acids or elaidic/stearic acids have roughly the same performance in serving as a capping agent for the synthesis of Co nanoparticles with a spherical shape and narrow size distribution. 相似文献
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Shakir M Shahid N Sami N Azam M Khan AU 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,82(1):31-36
The mononuclear Schiff base complexes of the type, [ML(CH3OH)2] [M = Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by template condensation of l-leucine and glyoxal. The complexes have been characterized on the basis of the results of the elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz, FT-IR, Mass, 1H NMR and 13C NMR spectra. The UV–vis and magnetic moment data revealed an octahedral geometry around Co(II), Ni(II) ion with distortion around Cu(II) ion complex confirmed by EPR data. The conductivity data show a non-electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that all the complexes exhibit a significant binding to calf thymus DNA. 相似文献
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In recent years certain new technologies demand optically transparent high Tgpolymer materials.Some aliphatic polymers containing cyclic structure are in the marketalready and have been applied to manufacture various devices in optics industry.However,these polymers are usually of nonpolar character and their difficulties inadhesion and solubility in solvents limited their applicability in many technologies[1 ,2 ] .The polymerization of polar group-containing internal cyclic olefins by transit… 相似文献
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The
ring-opening metathesis polymerization (ROMP) kinetics of three different
norbornene-based monomers, ethylidene norbornene (ENB), endo-dicyclopentadiene
(DCPD) and exo-DCPD, in the presence of
Grubbs’ catalyst are examined using differential scanning calorimetry
and rheokinetic viscosity measurements. Several different parameters were
considered, such as, the monomer healing agents (including different monomer
mixtures), the catalyst concentration, and test temperature to determine how
these parameters influence cure development. The polymerization kinetics,
quantified by exothermic peak locations in the case of differential scanning
calorimetry and rheokinetic transition times in the case of viscosity measurements,
are shown to be highly dependent on monomer type and catalyst concentration.
The ENB monomer had the fastest kinetics even at the lowest catalyst concentration
compared to the other diene monomers and mixtures. 相似文献
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A series of salicylaldimine‐based neutral Ni(II) complexes (3a–j) [ArN = CH(C6H4O)]Ni(PPh3)Ph [3a, Ar = C6H5; 3b, Ar = C6H4F(o); 3c, Ar = C6H4F(m); 3d, Ar = C6H4F(p); 3e, Ar = C6H3F2(2,4); 3f, Ar = C6H3F2(2,5); 3g, Ar = C6H3F2(2,6); 3h, Ar = C6H3F2(3,5); 3i, Ar = C6H2F3(3,4,5); 3j, Ar = C6F5] have been synthesized in good yield, and the structures of complexes 3a and 3i have been confirmed by X‐ray crystallographic analysis. Using modified methylaluminoxane as a cocatalyst, these neutral Ni(II) complexes exhibited high catalytic activities for the vinylic polymerization of norbornene. It was observed that the strong electron‐withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalyst activity for vinylic polymerization of norbornenes. In addition, catalyst activity, polymer yield and polymer molecular weight can also be controlled over a wide range by the variation of reaction parameters such as Al:Ni ratio, norbornene:catalyst ratio, monomer concentration, polymerization temperature and time. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
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Mark Lautens Alaa S. Abd-El-Aziz Cathleen M. Crudden 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):569-574
The ring-opening metathesis copolymerizations of deltacyclene, substituted deltacyclene, and norbornene was achieved using RuCl3, ReCl5, and molybdenum alkylidene catalysts. The reaction conditions employed are similar to those used previously in the syntheses of homopolymers. The low conversion copolymerization of deltacyclene and norbornene showed that deltacyclene is more reactive than norbornene by a factor of 2.4. The characterization and physical properties of these copolymers were determined using NMR, GPC, Tg, and viscosity measurements. © 1993 John Wiley & Sons, Inc. 相似文献
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Synthesis and copolymerization of oligo(lactic acid) derived norbornene macromonomers with amino acid derived norbornene monomer: Formation of the 3D macroporous scaffold 下载免费PDF全文
Sutthira Sutthasupa Fumio Sanda Kajornsak Faungnawakij Puttinan Meepowpan 《Journal of polymer science. Part A, Polymer chemistry》2015,53(14):1660-1670
Norbornene macromonomers 2 and 3 bearing 10‐ and 20‐mers of lactide were synthesized by ring‐opening polymerization of lactide using 5‐norbornene‐2, 3‐exo‐exo‐dimethanol as an initiator and DBU as a catalyst. Macromonomers 2 and 3 were copolymerized with amino acid derived norbornene monomer 1 , using the Grubbs 2nd generation ruthenium catalyst. The random and block copolymers with Mn's ranging from 28,000 to 180,000 were obtained almost quantitatively where the Mn's of the block copolymers were higher than those of the random ones. Three‐dimensional macroporous structure polymers with average pore size of 10 µm could be found in poly( 1 ) and the block co‐polymer of 1 and 2 or 1 and 3 at the high ratio of 1 . Meanwhile, poly( 2 ) and poly( 3 ) along with block and random copolymers with low ratio of 1 exhibit much larger pores in the range of 50–300 µm. The porosity increased with increase in the unit ratio of 1 . The compressive strength of the porous structure of poly( 2 ) and poly( 3 ) was improved by the copolymerization with 1 . © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1660–1670 相似文献