3,6-二-(3-(对氯苯)丙烯酰)-9-乙基咔唑的合成及光谱研究

以咔唑为原料,首先与乙酸酐进行酰基化反应得到3,6-二乙酰基咔唑,再通过与溴乙烷反应制得9-乙基-3,6-二乙酰基咔唑,然后与对氯苯甲醛进行缩合反应制得3,6-二-(3-(对氯苯)丙烯酰)-9-乙基咔唑。利用IR、~1HNMR和~(13)CNMR谱对其结构进行了表征,同时进行了紫外-可见和荧光光谱的测定,表明有较好的发光性能。     

3,6-二-(3-(对甲基苯)丙烯酰)-9-乙基咔唑的合成

以咔唑为原料,首先与溴乙烷反应生成9-乙基咔唑,再通过与乙酸酐进行酰基化反应得到9-乙基-3,6-二乙酰基咔唑,然后与对甲基苯甲醛进行羟醛缩合反应制得3,6-二-(3-(对甲基苯)丙烯酰)-9-乙基咔唑。利用1HNMR和13CNMR谱对其结构进行了表征。     

用咔唑单体合成乙烯咔唑工艺的研究

以咔唑和1,2-二氯乙烷为原料,合成氯乙基咔唑,再通过消除反应合成产率较高的乙烯咔唑(NVC),研究合成工艺对产率的影响;并用傅立叶变换红外光谱仪(FT-IR)和熔点测试技术对产物的结构进行表征.研究表明:氯乙基咔唑经沉淀法提纯所得产物的收率最大,为72.85%,且缩短了提纯处理时间;当加入的碱与氯乙基咔唑的摩尔比为1.77∶1时,乙烯咔唑收率最大,为81.05%.     

含咔唑基聚合物的合成、发光性能及应用

采用封管聚合法合成了3种含咔唑基聚合物——聚乙烯基咔唑(PVK)、聚2-(9-咔唑基)乙基甲基丙烯酸酯(PCEM)和聚N-〔3-(9-乙基咔唑基)〕甲基丙烯酰胺(PECMA),考察了其紫外光谱和荧光光谱,探讨了取代基对咔唑基团发光性能的影响。结果表明,单体CEM和ECMA表现出明显的结构自猝灭效应(SSQE),而相应的聚合物未见SSQE。单体乙烯基咔唑(NVK)、CEM的荧光最大发射波长分别为440、435 nm,相对于咔唑(418nm)有明显的红移,ECMA则蓝移(410 nm),而相应的聚合物红移或蓝移都不明显。将聚合物作为空穴传输材料,通过共聚引入8-羟基喹啉铝高分子后,8-羟基喹啉铝高分子发光材料的电致发光起亮电压由14 V下降至9V,发光效率提高了3~4倍。     

9-乙基四氢咔唑的合成工艺研究（文章加急）

该文以苯肼、环己酮为起始原料,经醋酸环化合成四氢咔唑,收率达70.5%,再与溴乙烷经烷基化反应制得9-乙基四氢咔唑。产物的结构经~1HNMR和~(13)CNMR表征。经单因素实验考察,确定合成9-乙基四氢咔唑的最优条件为:n(四氢咔唑)∶n(溴乙烷)∶n(氢氧化钠)=1∶4∶1.5,m(四氢咔唑)∶m(碘化钾)=1∶0.01,c(四氢咔唑)=0.50 mol/L,c(十六烷基三甲基溴化铵)=2.5×10~(-3)mol/L,乙腈为溶剂,回流反应9 h,收率为86.0%。该路线与传统工艺(环己酮先经氯化再与N-乙基苯胺缩合)相比,可避免氯化副产物生成,反应易控制,更适合工业生产。     

N-乙基-3-咔唑丙烯酸的合成及性质研究

用N-乙基咔唑合成N-乙基-3-咔唑甲醛,在吡啶介质中以六氢吡啶为缩合剂,通过N-乙基-3-咔唑甲醛与丙二酸的Knoevenagel缩合反应合成N-乙基-3-咔唑丙烯酸,并对影响产率的因素进行了研究。结果表明,当n(N-乙基-3-咔唑甲醛)∶n(丙二酸)∶n(吡啶)∶n(六氢吡啶)=1.0000∶3.0000∶2.0000∶0.0015时,在105℃下反应2h,N-乙基-3-咔唑丙烯酸的产率为85%,纯度为99.45%。     

掺杂聚乙烯基咔唑的螺噁嗪光致变色的性能

将PVK(聚乙烯基咔唑)以不同的比例掺杂至螺噁嗪光致变色化合物的体系中,通过对螺噁嗪开环体紫外-可见光谱和聚乙基咔唑荧光光谱的分析可以得出,掺杂体系中聚乙烯基咔唑中的电子空穴可容纳螺噁嗪光致变色过程中迁移的电子,从而提高了螺噁嗪开环的效率。     

甲基丙烯酸乙基咔唑酯／N-乙烯基咔唑共聚物的研制

以甲基丙烯酸乙基咔唑酯、N-乙烯基咔唑为原料,以偶氮二异丁腈为引发剂,采用共聚合方法合成甲基丙烯酸乙基咔唑酯／N-乙烯基咔唑共聚物。分别用IR、UV—vis对其结构进行了表征。利用凝胶渗透色谱仪测定了共聚物的相对分子质量,并讨论了影响相对分子质量的因素,提高引发剂浓度、反应温度都使相对分子质量下降,而延长反应时间则有利于增加相对分子质量。     

丙烯基咔唑合成与表征

以咔唑与1,3-二溴丙烷为原料,四丁基溴化铵为相转移催化剂采用微波诱导催化法合成了丙烯基咔唑。通过实验,对比得到了加热时间、加热功率、1,3-二溴丙烷用量、四丁基溴化铵用量以及氢氧化钾溶液对溴丙基咔唑产率的影响。得到了微波催化法的最佳工艺:咔唑2.5 g,1,3-二溴丙烷用量3.05g,四丁基溴化铵用量1.8 g,氢氧化钾溶液用量16.8 g,反应功率700 W,反应40 min,产率达到84.76%。并对产物结构进行了红外光谱表征,产物的红外光谱图中在3420cm~(-1)处咔唑的N-H峰消失,说明H被取代,在1600cm~(-1)处有丙烯基上C=C吸收峰红外光谱表明产物为丙烯基咔唑。     

相转移催化法合成N-乙基咔唑的研究

以咔唑和溴乙烷为原料,在季铵盐相转移催化剂的条件下合成了N-乙基咔唑,考察了温度、催化剂种类、催化剂用量以及投料比等因素对N-乙基咔唑收率的影响,确定了最佳的催化剂及工艺条件。结果表明,四丁基溴化铵具有最佳的催化活性,在适宜反应条件下,N-乙基咔唑的收率可达97%。     

水在凝胶中的存在状态及其对凝胶力学性能的影响

以偶氮二异丁腈为引发剂,通过化学引发聚合合成甲基丙烯酸β-羟乙酯（HEMA）/N-乙烯基吡咯烷酮（NVP）二元共聚物和HEMA /NVP /甲基丙烯酸甲酯（或甲基丙烯酸丁酯）三元共聚物水凝胶,通过示差扫描量热法（DSC）结合热重法（TG）研究了不同单体配比的共聚物水凝胶中水的状态,证明了凝胶中存在3种不同状态的水：非冻结结合水、可冻结结合水和可冻结自由水.结果发现可冻结水的含量主要由NVP含量所决定,NVP单元基本不能键合水,而非冻结水的含量主要受HEMA含量和疏水性单体甲基丙烯酸酯含量影响.疏水性单体的引入使材料的力学强度提高,对凝胶体系具有增塑作用的是非冻结水而不是可冻结的结合水和自由水.     

Transparent organic materials made from copolymerization of styrene with urethane‐methacrylate macromer. II. Macromer mixture system

A urethane‐methacrylate (UM) macromer mixture was prepared by reacting tolylene diisocyanate with a mixture of 1,4‐butylene glycol (as the rigid glycol) and poly(ethylene glycol), followed by end capping with 2‐hydroxyethyl methacrylate. The transparent polymeric material was fabricated by copolymerizing the macromer mixture with styrene. The effects of the styrene content and the composition of the macromer mixture on the properties were studied. The results showed that the material displayed a unique balance of excellent transparency, high heat resistance, good impact strength, and low water absorption, especially when the soft macromer (UM2) content was 20 or 40%. The visible light transmittance was more than 90%, and the refractive index was much higher than that of poly(methyl methacrylate). All properties were extensively regulated according to practical demand. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 674–679, 2001     

甲基丙烯酸缩水甘油酯的合成

甲基丙烯酸甲酯和甲醇反应得到甲基丙烯酸钾,和环氧氯丙烷（ECH）反应,合成了甲基丙烯酸缩水甘油酯。考察了催化剂选择、反应温度、反应时间、物料配比、催化剂用量等因素对反应的影响。结果表明,较佳的反应条件为：十六烷基三甲基溴化铵为催化剂,反应温度1100C,反应时间4h,n（甲基丙烯酸钾）：n（ECH）：1：7,催化剂用量0．2g。在此条件下,产品收率可达79％,含量大于98％。     

制备聚甲基丙烯酸甲酯/多壁碳纳米管的动力学

对原位聚合制备聚甲基丙烯酸甲酯(PMMA)/多壁碳纳米管(MWCNTs)复合材料的动力学进行了研究,并采用三段聚合模型拟合分析了碳纳米管的引入对MMA(甲基丙烯酸甲酯)聚合过程动力学的影响。实验结果表明,碳纳米管的引入减缓聚合速度并推迟凝胶效应阶段的到来;超声波的引入使碳纳米管在MMA体系中分散均匀并使聚合速度加快,导致聚合体系更早进入凝胶效应阶段.     

Synthesis,properties, and morphology based on polyurethane and polymethyl methacrylate AB-crosslinked copolymers

The AB-crosslinked copolymer was prepared as a transparent material from toluene diisocyanate (TDI) or hexamethane diisocyanate (HDI), triethylene glycol (TEG), hydroxyethyl methacrylate (HEMA), and methyl methacrylate (MMA). The optical transmission, impact resistance, thermal mechanical properties, and morphology of the copolymer were studied. The results indicate that this material has a microheterogeneous structure with the dispersed phase size no more than 0.1 μm. © 1994 John Wiley & Sons, Inc.     

Degree of conversion of a copolymer of an experimental monomer and methyl methacrylate for dental applications

The aim of this study was to determine the degree of double bond conversion of the copolymer of an experimental monomer and methyl methacrylate after photopolymerization. A mixture of an experimental monomer with four methacrylate groups and methyl methacrylate monomer (mass ratio 70 : 30) was polymerized by using various concentrations of light initiator system. The degree of conversion was determined with FTIR spectrometry. A photopolymerized 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloxypropoxy)‐ phenyl]propane/triethylene glycol dimethacrylate (mass ratio 40 : 60) copolymer was used as a control material for degree of conversion. The maximum degree of conversion for the experimental monomer/methyl methacrylate copolymer was 62% and was obtained with 2 wt % initiator concentration. It was comparable to that of the control polymer (64%). The results of this study suggest that the experimental monomer/methyl methacrylate system can be polymerized by light initiator system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1908–1912, 2004     

All-organic Poly(butyl methacrylate)/Poly(vinylidenefluoride-trifluoroethylene) Dielectric Composites with Higher Permittivity and Low Dielectric Loss for Energy Storage Application

With the rapid development of electronic industry and technology, there are increasingly stringent requirements on dielectric materials with higher permittivity, lower loss, and enhanced breakdown field. Since single dielectric material cannot meet the demands of industrialization, polymer-based dielectric materials with better quality have been widely applied. This study focused on a poly(butyl methacrylate/poly(vinylidene fluoride-trifluoroethylene) dielectric composite thin film, which were prepared by solution casting method. X-ray diffraction and differential scanning calorimetry data indicated that introducing poly(butyl methacrylate) led to increase in the crystallinity. The result of scanning electron microscopy showed the good compatibility between poly(vinylidene fluoride-trifluoroethylene) and poly(butyl methacrylate). Besides, the dielectric film remained good mechanical property. The dielectric properties were studied as a function of filler content and frequency. The results showed that the permittivity was as high as 13.3, while the breakdown field was 322?MV m^?1 when the fraction of poly(butyl methacrylate) was 10%. Blending poly(butyl methacrylate) improved the dielectric performance of the poly(vinylidene fluoride-trifluoroethylene).     

共聚改性含铅有机玻璃板材的研制与性能研究

采用甲基丙烯酸甲酯、甲基丙烯酸正丁酯与甲基丙烯酸铅进行三元共聚的方法,制备了含铅聚甲基丙烯酸甲酯(俗称有机玻璃)板材,并且讨论了各种组成对板材冲击强度、维卡软化点、表面硬度、透光率、耐溶剂性的影响。     

Preparation and properties of [poly(methyl methacrylate)/imogolite] hybrid via surface modification using phosphoric acid ester

Novel polymer nanohybrid was prepared by free radical polymerization of methyl methacrylate in the presence of inorganic nanofiber ‘imogolite’ as reinforcing nanofiller. Imogolite is a hydrous aluminosilicate with a unique nanofiber structure. The surface of imogolite was modified with 2-acidphosphoxyethyl methacrylate, which has a polymerizable methacrylate group and a phosphoric acid moiety, before preparation of polymer hybrid. The polymer nanohybrid was prepared by free radical polymerization in the presence of surface modified imogolite. The mechanical properties of (PMMA/modified imogolite) hybrid with the modified imogolite were improved in comparison with those of PMMA and (PMMA/unmodified imogolite) blend. Furthermore, the hybrid film prepared from the surface modified imogolite kept the transparency similar to PMMA film. These results indicate the usefulness of the surface modification method with phosphoric acid groups and imogolite nanofibers as a reinforcing material.     

Synthesis and characterization of in situ polymerized poly(methyl methacrylate)–cerium molybdate nanocomposite for electroanalytical application

In the present study, a new technique to synthesize composites of poly(methyl methacrylate) cerium molybdate (PMMA–CeMoO4) is reported. The study concerns the characterization of poly(methyl methacrylate; PMMA) and PMMA–CeMoO₄ nanocomposites are also discussed. The physical properties of the material were described using TGA–DTA, FTIR, X‐ray, TEM, and SEM studies. The adsorption efficiency towards heavy metal ions was determined by distribution studies and material was found to be highly selective for lead, a heavy toxic metal ion, indicating the utility of the synthesized material for the removal of this ion from the waste stream. The material was used as electroactive component for the construction of an ion‐selective membrane electrode. The membrane electrode was mechanically stable, having wide dynamic range, with quick response time and could be operated for at least 5 months without any considerable divergence in the potential response characteristics. The electrode was successfully used as indicator electrode in complexation titrations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013