3-甲基邻苯二酚/糠胺型聚苯并噁嗪的制备与性能

通过分子设计合成了含有酚羟基的3-甲基邻苯二酚/糠胺型苯并噁嗪(M-f). 通过差示扫描量热法(DSC)测得M-f的放热峰值温度(T_p)为172 ℃, 而间甲酚/糠胺型苯并噁嗪(MC-f)的T_p为244 ℃, 表明酚羟基的引入有利于降低苯并噁嗪的开环固化温度. 通过非等温DSC法研究2种苯并噁嗪单体的固化动力学, Kissinger法和Ozawa法的计算结果均表明M-f的表观活化能低于MC-f. 此外, 通过拉伸剪切强度测试考察了聚苯并噁嗪对于金属基材的黏附性能, M-f聚合物对于铝和低碳钢基材的拉伸剪切强度分别为2.53 MPa和3.09 MPa, 均高于MC-f聚合物.     

对炔丙氧基苯基噁唑啉的合成及改性苯并噁嗪树脂的研究

通过四步法合成了对炔丙氧基苯基噁唑啉(p-propynyloxyphenyl-2-oxazoline简称POPO),采用核磁共振氢谱(1H-NMR)、傅立叶红外光谱(FTIR)、气相色谱质谱联用仪(GC-MS)和元素分析证实了其分子结构,以示差扫描量热仪(DSC)和热重分析(TGA)揭示了其固化行为和热分解性质,该化合物熔点为120℃,起始固化温度为200℃,固化峰值温度为280℃,自固化产物5 wt%热失重温度为321℃.在此基础上,通过溶液共混法制备了双酚A型苯并噁嗪(BZ)/对炔丙氧基苯基噁唑啉(POPO)共聚树脂,且对其固化机理、固化产物的热分解性质和动态力学性能进行考察.结果表明,该噁唑啉作为交联剂,与苯并噁嗪发生开环聚合和自身炔基发生三聚成环反应,使固化产物的交联密度增加,DSC、TG和动态热机械分析(DMA)表明噁唑啉的引入提高了固化树脂的热性能和动态力学性能.且在噁唑啉含量为10 wt%时,固化树脂的综合性能较优,较之纯的双酚A型苯并噁嗪树脂,起始固化温度从215℃降低至180℃,残碳率从28%提高至44%,玻璃化转变温度从166℃提高至186℃.     

新型阻燃剂1 ,3 ,5-三(5 ,5-二甲基-1 ,3-二氧杂己内磷酸酯基)苯的合成及表征

以1,3,5-三羟基苯、新戊二醇、三氯氧磷等为原料,采用简洁、高效的合成路线,通过两步反应合成了新型阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂己内磷酸酯基)苯.通过红外光谱、核磁共振氢谱、质谱、元素分析以及热失重分析等对产物结构和热性能进行了表征和研究.热失重分析表明:该阻燃剂起始分解温度为295.26℃ ,在295.26℃ ~343.38℃和350.40℃ ~578.04℃温区迅速炭化;当阻燃剂被加热到681.03℃时,炭残余量高达43.33 %.     

液体聚硫橡胶增韧双酚A-苯胺型聚苯并噁嗪的研究

以液体聚硫橡胶(LP-3)为增韧剂,对双酚A-苯胺型苯并噁嗪(B-a)树脂进行了改性,通过核磁共振氢谱(1H-NMR)、红外光谱(FTIR)、示差扫描量热仪(DSC)对B-a与LP-3的共混和固化过程进行了研究,通过动态热机械分析仪(DMA)、弯曲和冲击实验、热失重分析仪(TGA)对固化物的机械性能和热性能进行了表征.结果表明,在共混过程中,B-a与LP-3发生了开环加成反应,加成产物的酚羟基对苯并噁嗪的开环聚合具有一定的促进作用,共混物较B-a具有更快的固化速率.当LP-3的加入量为5 wt%时,固化物的韧性就可以得到明显改善,冲击强度相比B-a固化物提高了3.4倍,而且此时的固化物具有高的储能模量(30℃时E'=3.9 GPa)、高的玻璃化转变温度(T_g=206℃)和良好的热稳定性(T_(5%)=322℃,T_(10%)=342℃),表现出最佳的综合性能.     

芴基苯并噁嗪单体的合成、固化动力学及热性能

以芴、苯酚、对甲氧基苯酚和多聚甲醛为原料,采用溶液法合成了直接在芴的苯环结构上进行修饰的2个新型芴基苯并噁嗪单体3-芴基-3,4-二氢-1,3-苯并噁嗪(FBZ-1)和3-芴基-6-甲氧基-3,4-二氢-1,3-苯并噁嗪(FBZ-2)。利用FT-IR,~1H NMR和~(13)C NMR对其结构进行了表征。采用示差扫描量热法(DSC)研究了2个单体的固化动力学,计算了固化反应活化能,确定了最佳固化温度。通过DSC和热重(TGA)分析了单体及其聚合物的热性能。结果表明,FBZ-1和FBZ-2呈现出典型的热开环固化特征,放热峰顶温度(5℃·min~(-1)的升温速率)分别为231.2℃,228.7℃,其聚合物初始热分解温度(热失重5%时)达290℃、299℃;850℃时的残炭率(Yc)达到40.9%和36.9%,极限氧指数(LOI)分别是33.86、32.26。     

基于乙炔基-苯并噁嗪单元双重交联反应的聚酰亚胺树脂的制备与性能

为开发可低温固化的聚酰亚胺树脂, 通过分子结构设计将苯并噁嗪单元引入聚酰亚胺树脂中, 合成了含苯并噁嗪单元及乙炔基封端的双官能化新型聚酰亚胺预聚体(PIBzA). 经高温处理, 苯并噁嗪单元发生开环交联, 同时, 乙炔基端基发生三聚成环反应, 从而在固化树脂中形成双重交联网络结构. 苯并噁嗪单元的引入使聚酰亚胺树脂最快固化反应温度降低约32 ℃, 有效降低了固化温度. 同时, 苯并噁嗪单元的引入未大幅度降低树脂的耐热稳定性, 其玻璃化转变温度(T_g)介于266~290 ℃之间, 5%热失重温度(T_d,5%)接近500 ℃, 依然可以满足耐高温复合材料的应用需求. 此外, PIBzA固化树脂具有低介电特性, 其介电常数k介于2.3~3.0, 介电损耗介于0.002~0.008, 可满足透波复合材料及先进微电子封装材料的应用需求.     

一种不含β-氢的苯并噁嗪的表征分析及催化固化研究

以邻烯丙基双酚A、多聚甲醛和烯丙基胺为原料，采用无溶剂的方法合成了一种不含β-氢的苯并噁嗪(2，2-二(3，8-二烯丙基-3，4-二氢-2H-1，3-苯并噁嗪)-丙烷(B—dbo)．GPC和元素分析结果表明，此噁嗪中间体主要是单量体和二聚体．用FTIR和^1H NMR对中间体结构进行了表征．结果表明，此苯并噁嗪的分子结构中存在三种反应官能团：噁嗪环、N-烯丙基、Ar-烯丙基．用DSC和FTIR研究三种反应基团在固化时的反应情况．将双酚A、邻烯丙基双酚A、TiCl4和PCl5作为催化剂按适量的比例加入B—dbo中，用DSC研究其固化行为，并对TiCl4催化试样在不同的固化温度下进行FTIR测试分析，提出在TiCl4催化下苯并噁嗪环副反应及开环固化机理．     

含双螺环三聚磷腈单元的苯并噁嗪树脂的结构和热稳定性

以双螺环取代三聚磷腈基双苯甲酰氯和4-氨基(N-苯基)苯并噁嗪单体为原料合成了一种含双螺环取代三聚磷腈结构单元的苯并噁嗪树脂单体(HCP-5);采用傅立叶变换红外光谱仪(FT-IR)和核磁共振谱仪(1 H NMR,13 C NMR,31P NMR)表征了苯并噁嗪树脂单体的结构,基于FT-IR和示差扫描量热法研究了其固化行为,并利用热重分析和示差热重分析研究了HCP-5树脂单体、均聚物及其与双酚A型苯并噁嗪树脂(Bz)共聚物的热稳定性.结果表明,HCP-5均聚物具有很好的热稳定性和成炭性,其在317℃下的热失重为5%,在800℃下的残炭率为50%,可用于普通苯并噁嗪树脂改性.此外,HCP-5/Bz(1∶1;质量分数)共聚物在332℃下的热失重为5%,在800℃下的残炭率为48%.     

含硅芳炔树脂/苯并噁嗪/氰酸酯三元聚合体系研究

以双酚A型氰酸酯(BADCy)和含炔丙氧基苯并噁嗪(P-appe)为改性剂,通过与含硅芳炔树脂(PSA)的溶液混合与浓缩制备了含硅芳炔树脂/氰酸酯/苯并噁嗪三元共混体系(PPB),研究了该共混体系的热固化过程、共混树脂的热稳定性和动态力学性能、弯曲性能和冲击性能.结果表明,开环后的苯并噁嗪能催化氰酸酯的环三聚反应,可降低氰酸酯的固化温度;PPB热固化中三嗪环可与噁嗪环反应形成氰酸酯与苯并噁嗪共聚;当PPB树脂中PSA树脂的质量分数为70%时,三元共混树脂浇铸体在氮气中质量损失5%的温度(Td5)高于500oC,玻璃化转变温度高于450oC;BADCy/P-appe改性PSA树脂的三元共混体系相容性好,共混树脂浇铸体PPB-5的弯曲强度较PSA树脂提高了115%,冲击强度提升了104%,断裂面出现明显的韧性断裂特征.     

6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪及其共聚物的合成

以6-甲基-3-羟乙基-3,4-2H-1,3-苯并噁嗪(MB-OH)和甲基丙烯酰氯为原料, 通过酯化反应合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪(MBEM). 采用自由基溶液聚合法, 以偶氮二异丁腈(AIBN)为引发剂, 以甲苯为溶剂, 以MBEM与N-苯基马来酰亚胺(NPMI)为单体, 合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪-co-N-苯基马来酰亚胺共聚物[P(MBEM-co-NPMI)]. 分别对MB-OH, MBEM, P(MBEM-co-NPMI)进行加热固化, 得到相应的交联聚合物PMB-OH, PMBEM和P[P(MBEM-co-NPMI)]. 对其结构、分子量和热性能进行了表征. 结果表明, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]的最大损耗因子tanδ_max对应的玻璃化转变温度(T_g)分别为92, 129和181℃, 最大损耗模量G"_max对应的T_g分别为56, 91和156℃. 在N₂气氛围下, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]失重5%的温度分别为257, 244和260℃; 失重10%的温度分别为280, 266和284℃; 800℃的残炭率分别为23.2%, 17.8%和14.0%. 表明P[P(MBEM-co-NPMI)]具有优异的耐热性能.     

A study of magnetic,antibacterial and antifungal behaviour of a novel gold anchor of polyaniline/itaconic acid/Fe3O4 hybrid nanocomposite: Synthesis and characterization

The objective of the present investigation is to fabricate the gold anchor polyaniline (PANI) based nanocomposites which is prepared using itaconic acid (IA) with Fe₃O₄ by the simple polymerization reaction. The developed multi responsive antibacterial magnetic polymeric composite is represented as Au@PANI–IA–Fe₃O₄. Further, the chemical structure, thermal and magnetic properties such as FT-IR, TGA/DTA, and VSM analysis are studied. The TEM and SEM/EDX are used to find the shape and composition of gold nanoparticles. The enhanced magnetic properties of ferrite composite are exhibited and the antibacterial properties are determined using E. coli (gram -ve) and S. aureus (gram +ve) bacteria’s. The results of biological properties such as antifungal and antimicrobial are also studied critically conferred. Based on the experimental results, the fabrication method of Au@/PANI/IA/Fe₃O₄ magnetic nanocomposites, and the relationship between the structure and biological properties are discussed in detail.     

核壳型纳米粒子合成方法及其性能的研究进展

核壳纳米粒子作为复合纳米粒子一个重要的分支,由于其光、磁和催化等方面的优异性能,近年来引起了人们广泛的关注.本文主要介绍了核壳纳米粒子的制备方法及诸多性能,并对核壳纳米粒子的发展进行了展望.     

系列磺丁基甜菜碱的表征及表面活性

用FT-IR、1H NMR和元素分析对自制的3种磺丁基甜菜碱(SBm-4)的结构进行了表征,研究了它们的表面性能、泡沫性能和乳化性能。 获得SB12-4的cmc为2.20×10-3 mol/L,γcmc为31.48 mN/m;SB14-4的cmc为2.80×10-4 mol/L,γcmc为29.68 mN/m;SB16-4的cmc为2.30×10-5 mol/L,γcmc为32.06 mN/m。 3种磺丁基甜菜碱的cmc值随着烷基链长增加逐渐减小,γcmc先减小后增加,三者的起泡性随浓度增加而增加,到一定值后保持不变;泡沫稳定性随浓度增加逐渐增强,起泡性随着温度的增加有缓慢增加趋势,泡沫稳定性随温度增加逐渐降低。 3种表面活性剂的乳化能力随浓度增加先增加后降低。     

Effect of Cadmium Substitution on Structural and Magnetic Properties of Nano Sized Nickel Ferrite

The structure and crystal phase of the nanocrystalline powders of Ni_1-xCd_xFe₂O₄ (0≤x≤0.5) mixed ferrite, synthesized by wet chemical co-precipitation method, were characterized by X-ray diffraction. Results showed that the lattice parameter increased with increasing Cd concentration. Microstructure was studied by scanning electron microscopy. TG/DTA stud-ies were carried out on co-precipitated sulphate complexes. These studies revealed the low ferritization temperature (650 oC) of the ferrite system synthesized by presently adopted route of synthesis and occurrence of simultaneous decomposition and ferritization processes.Further studies by infrared spectroscopy were also conducted. Moreover, magnetic properties of the prepared nanoparticles were studied by magnetization and a.c. susceptibility mea-surements. The response of prepared Ni_1-xCd_xFe₂O₄ mixed ferrites to magnetic field was investigated. Results show that, magnetic susceptibility, Curie temperature, and effective magnetic moment decreased as the Cd content increases.     

羟基卟啉化合物的电化学、顺磁共振及时间分辨光电压性质

通过循环伏安法、电子顺磁共振谱和时间分辨电压光谱研究了羟基取代基数目和位置的不同对羟基苯基卟啉化合物的电化学、电子顺磁共振和时间分辨光电压性质的影响. 研究结果表明, 所有氧化还原反应都是在卟啉环上进行的. 卟啉周边取代基数目的增加使得卟啉共轭体系平均电子云密度增大, 导致体系易氧化而难以还原. 对称性增强可能使卟啉化合物的半波电位值向正方向移动, 羟基取代基的给电子效应对于卟啉化合物电化学性质的影响起主导作用. 常态下卟啉分子没有EPR信号, 在光的激发下, 卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子, 这种激发三重态分子在分子轨道上具有两个未成对电子, 这两个电子相距很近, 彼此之间发生很强的相互作用而产生电子, 它的g值随卟啉共轭体系平均电子云密度增大而变大. 时间分辨光电压是由分子中的自由光声载流子的存在而产生的, 光电压的衰减与分子结构密切相关, 它们的电荷分离速度基本上随卟啉周边羟基取代基数目的增加而减慢.     

Structural,Electronic and Optical Properties of the Monoclinic α-CoV_2O_6

First-principles calculations based on density functional theory are performed to investigate the structural,electronic and optical properties of monoclinic α-Co V2O6.Firstly,the geometry structures obtained by geometry optimization are consistent with the experimental values.Then,the energy band structure is studied using both GGA and GGA+U methods.It is found that the on-site Coulomb repulsion of the Co 3d orbital plays a key role in describing the electronic properties of α-Co V2O6,and is necessary to open the energy band gap.According to the partial density of states(PDOS),significant Co–O and V–O hybridizations are observed in the valence and conduction bands,respectively.Furthermore,the Co–O and V–O bonds are found to have significant covalent characters.Below the absorption threshold ~1.9 e V,no absorption can be detected.However,there exists a strong and wide absorption band in the energy range from 1.9 to 11 e V.Such novel optical properties imply that the α-Co V2O6 may have some potential optical applications.     

Synthesis and characterization of new aromatic poly(ether imide)s and their gas transport properties

A series of processable fluorinated poly(ether imide)s (PIs) were synthesized by reacting a diamine monomer, 1,4-bis-[{2′-trifluromethyl 4′-(4″-aminophenyl)phenoxy}] benzene (HQA) with six different aromatic dianhydrides e.g., BPADA, 6FDA, ODPA, BPDA, BTDA and PMDA. The polyimides showed reasonably high glass-transition temperature (T_g up to 280 °C) and high thermal stability (T_d,10 up to 558 °C). The membranes of these polymers showed tensile strength up to 107 MPa with elongation at break up to 15%, low water absorption (0.61–1.29%), low dielectric constant (2.10–3.13 at 1 MHz) and high optical transparency (λ_cut-off up to 466 nm). The PI membrane prepared from 6FDA exhibited high permeability and permselectivity for O₂/N₂ (P_O2 = 11.8 and P_O2/P_N2 = 9.44) gas pair which eventually surpassed the present upper boundary limit drawn by L.M. Robeson.     

Synthesis, Mesogenic and Spectroscopic Properties of 2,5-Disubstituted Thiophene Derivatives

Two series of 2,5-disubstituted thiophene derivatives （series 1： 2,5-bis（p-alkoxyphenylethynyl）thiophene and series 2： 2,5-bis[p-（p-alkoxyphenylethynyl）（phenylethynyl）]thiophene） were synthesized and characterized by ^1H NMR, ^13C NMR, HRMS and elemental analysis. The relationship between the structure and the mesogenic and spectroscopic properties has been discussed. The results show that compounds 1a-1f all exhibited an enantiotropic nematic mesophase, which was confirmed by the polarized optical microscopy （POM）, differential scanning calorimeter （DSC） and variable temperature powder X-ray diffraction （PXRD）. In contrast, the extended conjugated analogues 2a-2b had no liquid crystal properties. As for the spectroscopic properties, incorporating more phenylethynyl units results in red-shifted absorption and emission spectra, greatly enhanced quantum efficiency.     

分子基磁体Cr[N(CN)2]2电子结构和半金属性的第一性原理研究

The electronic structure and half-metallicity of molecule-based ferromagnet Cr[N(CN)₂]₂ have been investigated using first-principles with generalized gradient approximation. The total energy, spin-polarized electronic band structure, density of states (DOSs) and spin mag-netic moments were all calculated. The calculations reveal that the compound Cr[N(CN)₂]₂ is a really half-metallic ferromagnet with a integral magnetic moment of 2.0000 μB per molecule in the optimized lattice constant. Based on the spin distribution and the DOS, it is found that the total magnetic moment is mainly from the Cr²⁺ with relative small contribution from C and N atoms. The sensitivity of the half-metallicity to small change in lattice constant is also discussed.     

Influence of Backbone Structure on Properties of Directly Polymerized Phenoxy Resins from Epichlorohydrin and Various Aromatic Dihydric Phenols Monomers

A series of phenoxy resins was directly prepared through the polymerization of each of the various aromatic dihydric phenols and epichlorohydrin.FTIR and 1H NMR spectra were recorded to characterize the structures of the re-sins.The GPC curves were used to determine the molecular weight distribution.In addition,the thermal properties of the resins were studied with differential scanning calorimetry(DSC)and thermal gravimetric analysis(TGA).The thermal stabilities of the polymers increased with the content of the benzene ring,pendant group increasing or biphenyl groups emerging.The adhesive properties of the polymers were evaluated in terms of the lap shear strength with Fe-Fe adherends.The fracture mechanisms were determined by SEM observation and it was found that there was an important participation of cohesive fracture mechanisms.Also,it has been demonstrated that the extension of these micro-cohesive mechanisms is directly correlated with the adhesive strength.According to these results,the phenoxy resin containing biphenyl groups presented a higher adhesive strength and could improve the adhesive property of the epoxy/phenoxy system to a certain extent.