咪唑类二阶非线性光学活性分子的设计、合成及性能

设计、合成了两个新的咪唑类二阶非线性光学生色团，对其热性能、透明性和 二阶非线性光学性能进行了测定和研究，实验表明生色团为非线性光学性能-透明 性-热稳定性能综合优化的有机二阶非线性光学生色团。     

2,5-二辛氧基聚对苯的合成及表征

蓝色电致发光;2;5-二辛氧基聚对苯的合成及表征     

聚2，2’－二硫代二苯胺的化学合成与表征

从2-氨基苯硫酚出发制备二硫代二苯胺，以此为原料与重铬酸钠在低温溶液中合成聚二硫代二苯胺，并对产物进行了红外光谱、热重、X射线、光电子能谱和扫描电镜分析表征。     

含二呋喃基苯并噻二唑的聚芳炔类衍生物的合成与性能

以四(三苯基磷)钯(Pd(PPh3)4)和CuI为催化剂,在二异丙胺和四氢呋喃溶液中,采用宽能带的1,4-二乙炔基-2,5-二(十二烷氧基)苯(PE)和窄能带的4,7-双(5′-溴-2′-呋喃)-2,1,3-苯并噻二唑(FBT)合成了一系列新型聚芳炔。长链烷氧基的存在使得此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性。通过对上述聚合物的紫外-可见吸收、荧光发射及循环伏安等基本性能进行探讨可知,随着共聚物中FBT含量的增加,共聚物薄膜的吸收起始波长及荧光发射波长均有明显的红移。聚合物薄膜的最大发射峰位于600～650 nm,聚合物中的能量能有效地由PE单元转移到FBT单元上。     

Synthesis and Characterization of Poly(Aryl Ether Ketone)Containing Phthalazinone and Naphthalene Moieties

Poly (aryl ether ketone)s (PAEKs) are one of the most important high performanceengineering thermoplastics, widely used in electronic, electric, aircraft and aerospaceindustries. ICI' PEEK has enjoyed much commercial success due to its high operatingtemperatUre and superior strength. It has a Tg of 143oC, a Tin of 334'C and it is quitesolvent resistant. There is a growing demand for new materials to meet increasedperformance requirementS in many areas. Thus there has been considerable r…     

聚对二氧环己酮的合成及其结晶性能

以对二氧环己酮为原料,经开环聚合反应合成了聚对二氧环己酮（PPDO）。用DSC曲线研究了PPDO的非等温结晶以及非等温冷结晶性能。采用Ozawa方程拟合了PPDO的非等温结晶曲线。采用莫志深方程拟合了PPDO非等温冷结晶曲线。     

含氟聚醚醚酮酮的制备及其性能

以邻氟对苯二酚和4,4′-二氟三苯二甲酮为原料通过亲核缩聚反应,合成含氟聚醚醚酮酮(FPEEKK)材料。 用FTIR、1H NMR和WAXD进行了结构表征,用DSC、TGA测试了热性能,并研究了聚合物的溶解性、吸水性、介电性能及光学性能。 结果表明,含氟聚醚醚酮酮具有较好的热性能（N2气气氛中,5%热分解温度为505 ℃）;能溶于氯仿、四氢呋喃和N,N-二甲基甲酰胺等有机溶剂;具有较低的吸水率(0.24%)和介电常数（ε=3.0）;在近红外区1300和1550 nm处吸收非常弱。     

One-pot Synthesis and Characterization of Poly(meta-aryl sulfide sulfone imide imide)

Poly(meta-aryl sulfide sulfone imide imide) (m-PASSII) was synthesized by one-pot process using 4-chlorophthalic anhydride, 3,3′-diamino diphenyl sulfone and sodium sulfide (Na₂S· xH₂O) as starting materials in N-methyl-2-pyrrolidone at atmospheric pressure. The intrinsic viscosity of m-PASSII was obtained with optimum synthesis conditions is 0.21-0.27 dl/g. The polymer and the separated intermediates which generated during the synthesis process were characterized by elemental analysis, FT-IR spectrum, ¹H-NMR spectrum, X-ray diffraction, DSC, TGA and dissolvability experiment. The polymer is found to have excellent thermal performance with glass transition temperature (T _g ) of 224°C and initial degradation temperature (T _d ) of 441°C. Moreover, the polymer is dissolvable in strong polar solvents.     

Synthesis and Characterization of Poly(p-phenylene benzobisoxazole)/Poly(pyridobisimidazole) Block Copolymers

Poly(p-phenylene benzobisoxazole)/poly(pyridobisimidazole) block copolymers (PBO-b-PIPD) were prepared by introducing poly(pyridobisimidazole) (PIPD) moieties into the main chains of poly(p-phenylene benzobisoxazole) (PBO) in order to enhance its photostability. PBO and copolymer fibers were directly prepared from the polymerization solutions by dry-jet wet-spinning. Chemical structures and molecular chains arrangement of the block copolymers were characterized by Fourier transform infrared (FTIR) spectroscopy, solid-state ¹³C-NMR and wide angle X-ray diffraction (WAXD). Thermal stability of the copolymers was investigated by thermogravimetric analysis (TGA) in nitrogen. Thin films of PBO and copolymers were cast from methanesulfonic acid (MSA) solutions. Both the films and fibers were exposed to UV light to determine their photostability. Changes in the chemical structures and surface morphologies of the films were characterized by FTIR spectra and scanning electronic microscopy (SEM), respectively. After UV light exposure, the retention of strength for copolymer fibers is improved compared to PBO fibers. The results revealed that copolymers suffered less photodegradation in comparison with homopolymer. The mechanism for the improved photostability of the copolymers was discussed.     

高分子量DL-丙交酯的合成及热降解

研究了聚ＤＬ－丙交酯（ＰＤＬＬＡ）的合成及热降解性能。发现影响聚合物分子量的关键因素是单体的重结晶、引发剂的浓度以及安瓿瓶在封管时的干燥和真空度。采用ＤＳＣ、ＴＧＡ分析了ＰＤＬＬＡ的玻璃化转变和热分解。ＰＤＬＬＡ是热不稳定聚合物,影响其热稳定性的主要因素是残留单体、催化剂和低聚物的含量,将聚合物溶解沉淀处理可以延缓其热解速度,提高它的热稳定性。     

3种新型聚苯基醚喹噁啉的合成

用4,4′-二氟代二苯甲酰与双酚A的溶液缩聚制得聚醚苯偶酰(PEB),经邻苯二胺改性后,通过两步法得到聚苯基醚喹噁啉（PEQ-1）。 在PEB的改性反应中加入质量分数分别为1.0%和1.3%的3,3′,4,4′-四胺基二苯醚,可有效增加聚苯基醚喹噁啉的相对分子质量,得到PEQ-2和PEQ-3（总收率≥90%）,其质均相对分子质量分别为7.492×104和1.486×105。 并用IR、 NMR等对这些聚合物进行了表征。 该法操作简便,具有潜在的应用价值。     

Synthesis and Characterization of Reactive Poly(Aryl Ether Ketone Ketone) Containing Cyclohexene Ring

Poly(aryletherketone)sareoneofthemostimportanthighperformanceengineeringthermoplastics,widelyusedinelectronic,electric,aircraft,andaerospaceindustries.Initially,considerableeffortwasmadetomodifytheirchemicalstructure,essentiallytoimprovetheirthermalproperties'.Inthelastfewyears,moreattentionwaspaidtotheirfunctionalization2.Thiscanbeachievedeitherbychemicalmodificationofthepolymerorbydirectsynthesisusingfunctionalizedmonomers.Inthisletter,wesynthesizedanovelmonomer4byintroducingcyclohexeneringa…     

Synthesis and Characterization of New Functional Poly(ester-anhydride)s Based on Succinic and Sebacic Acids

Summary: New functional poly(ester-anhydride)s with allyl pendant groups in the side chains were obtained by polycondensation of sebacic acid (SBA) and poly(3-allyloxy-1,2-propylene succinate) (OSAGE) terminated with carboxyl groups. The carboxyl groups in OSAGE and in SBA were converted to mixed anhydride groups by acetylation with acetic anhydride. After that, prepolymers obtained were condensed in vacuum to yield higher molecular weight poly(ester-anhydride)s. The influence of SBA and OSAGE content in poly(ester-anhydride)s on their selected properties e.g. molecular weight, thermal and solubility characteristics as well as degradation rate and mode, were examined. Poly(ester-anhydride)s were degraded in aqueous buffer of pH 7.4 at 37 °C. The hydrolytic degradation was monitored by determination of weight loss of samples and by determination of ester to anhydride groups ratio.     

聚对甲基苯胺的合成及其晶体结构

在水相中,FeCl3催化对甲基苯胺聚合合成了对甲基苯胺三分子聚合物——(N,N′E,N,N′E)-N,N′-(2-氨基-5-甲基-2,5-环己二烯-1,4-二亚基)二(4-甲基苯胺)(1),其结构经X-射线单晶衍射仪表征。1属六方晶系,R3空间群,晶胞参数:a=21.116(2),b=21.116(2),c=10.364(2),α=90°,β=90°,γ=120°,Mr=315.41,Z=9,V=4002.1(10)3,Dc=1.178 g.cm-3,μ=0.070 mm-1,λ=0.710 73,F(000)=1 512,R=0.067 8,wR=0.112 6。     

Synthesis and Characterization of Poly(N-isopropylacrylamide) and Poly(vinyl acetate) Diblock Copolymers via MADIX Process

The synthesis of diblock copolymers of poly(N-isopropylacrylamide) (PNIPAM) and poly(vinyl acetate) (PVAc) was performed by macromolecular design via interchange of xanthates (MADIX) process. Following the preparation of methyl (isopropoxycarbonothioyl) sulfanyl acetate (MIPCTSA) as chain transfer agent, it was reacted with vinyl acetate to obtain PVAc macro-chain transfer agent. Then, block copolymerization was completed by successive addition of N-isopropylacrylamide (NIPAM). ¹H NMR spectroscopy confirmed the presence of both blocks in the copolymer structure, with the expected composition based on the feed ratio. Size Exclusion Chromatography (SEC) was used to investigate the relative values of molecular characteristics. Only 20% of PVAc was converted to block copolymer. The resultant block copolymer structures were further examined in terms of their morphologies as well as critical micelle concentration (CMC) by using ESEM and Fluorescence Excitation Spectroscopic techniques, respectively. Morphological characterization confirmed amphiphilic block copolymer formation with the existence of mainly ca. 100 nm well distributed micelles. The thermo responsive amphiphilic behavior of the block copolymer solutions were followed by Dynamic Light Scattering (DLS) technique.     

新型手性聚酰胺酰亚胺的合成及其热稳定性

L-异亮氨酸与3,3’,4,4’-联苯四甲酸二酐在乙酸中回流反应制得具有联苯酰亚胺结构的手性N,N’-(4,4’-二邻苯二甲酰基)-二[(S)-(+)-异亮氨酸](3);以3和二苯基甲烷二异氰酸酯为单体,通过缩聚反应合成了新型手性聚酰胺酰亚胺(5),其结构经1H NMR和IR表征。DSC测试结果表明,5在氮气氛中5%失重温度超过370℃;600℃时残余质量为60%,显示出良好的热稳定性。     

Synthesis and Nonlinear Optical Properties of Chromophores with 1,8-Dimethoxy-9,10-dihydroanthracene and Ring-locked Triene

The new chromophore molecules with nonlinear optical （NLO） properties were prepared by Knoevenagel condensation from 1,8-dimethoxy-4,5-diformyl-9,10-dihydroanthracene and isophorone derivative in the presence of piperidine and acetic acid. In these chromophore, the ring-locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The key intermediate dialdehyde was conveniently prepared via a three step reaction, in which 1,8-dimethoxyanthraquinone was reduced with zinc/acetic acid and sodium/ethanol successively, followed by formylation with 1,1-dichlorodimethyl ether in the presence of TiCI4. The solvatochromism and UV spectra indicate that they have higher second-order nonlinear hyperpolarizability μβ values than the corresponding reference compound, without red shift of the charge transfer band.     

含萘结构聚芳醚砜的合成与表征

聚芳醚砜;亚萘基;耐热性;溶解度;含萘结构聚芳醚砜的合成与表征     

Synthesis and Characterization of a Novel Poly(aryl ether) Containing 4-Chloro-2,5-diphenyloxazole

4-Chloro-2,5-bis(4-fluorophenyl)oxazole monomer has successfully been synthesized using cyclization reaction of 4-fluorobenzoyl cyanide with 4-fluorobenzaldehyde. This monomer was converted to poly(aryl ether)s by nucleophilic substitution of the fluorine atoms on the benzene rings of oxazole monomer with bisphenol A. The influence of the reaction time on the molecular weight had been investigated. The polymers were identified by FT-IR,¹H-NMR and TGA. The products exhibited weight-average molar masses up to 2.81 x 10⁴g mol⁻¹ in GPC. These poly(aryl ether)s showed very high thermal stability up to 363 °C for 5 % weight loss in TGA under N₂.     

聚DL-乳酸的合成及其热性能研究

以辛酸亚锡为催化剂催化丙交酯开环聚合DL-乳酸(PDLLA)。研究了影响PDLLA分子量的因素包括丙交酯单体的纯度、催化剂的浓度、反应温度、反应时间及真空度等。用DSC,TGA分析了不同分子量PDLLA的警警化转变和热失重。结果表明,PDLLA是热不稳定聚合物,残留的单体、催化剂及低聚物是影响PDLLA热稳定性的因素,除去其中残留的单体、催化剂及低聚物可以提高PDLLA的热稳定性。