New Heat-Resistant Polyimidates Derived from Bisphenols and Mono- and Dicarboxylic Acid Imidoyl Chlorides

New polyimidates were prepared from bisphenols and mono- and dicarboxylic acid imidoyl chlorides. The structures of the polymers were determined, and their physicochemical, chemical, and thermal properties were studied. The possibility of preparing film and compression materials with good mechanical characteristics from these polymers was examined.     

磺化聚酰胺的合成及性能

以对苯二酚及对氟苯甲腈为原料, 合成了芳香二羧酸单体1,4-二(4-羧基苯氧基)苯(BCPOB-COOH), 再经磺化反应合成了磺化芳香二羧酸单体1,4-二(4-羧基苯氧基)苯-2-磺酸钠(BCPOBS-Na). 另外, 以芳香二胺单体4,4'-二氨基二苯醚(ODA)为原料, 合成了磺化芳香二胺单体4,4'-二氨基二苯醚-2,2'-二磺酸(ODADS). 以N-甲基-2-吡咯烷酮(NMP)为溶剂、 亚磷酸三苯酯(TPP)与吡啶(Py)为缩合剂, 氯化钙或氯化锂或二者的组合为催化剂, 通过Yamazaki-Higashi直接缩聚, 使芳香二羧酸和芳香二胺中的磺化单体与非磺化单体反应, 制得了两种磺化芳香聚酰胺(Sulfonated polyamide, SPA). 通过红外光谱、 核磁共振波谱及热重分析等手段对聚合物的结构及性能进行了表征与分析, 并研究了聚合物的特性黏度、 溶解性、 成膜性及聚合物薄膜的力学性能等. 结果表明, 通过Yamazaki-Higashi直接缩聚制备的2种磺化芳香聚酰胺在极性非质子性溶剂中具有优良的溶解性能、 较高的耐热性能及优异的力学性能.     

新型超支化聚芳酰胺的合成及表征

以3，5—二硝基苯甲酰氯和对氨基苯甲酸为原料，经两步反应合成了新型AB2型单体4—(3，5-二氨基苯甲酰氨基)苯甲酸。在溶液中通过自缩聚反应合成了新型超支化聚芳酰胺，将其活性端氨基与酰氯反应，经原位改性合成了五种封端的超支化聚芳酰胺，并利用IR、^1HNMR、DSC及TG等方法对所合成的六种新型超支化聚合物的结构和性能进行了表征与测试。     

三苄基锡二元羧酸衍生物的合成

以双(三苄基锡)氧化物和相应的二元羧酸反应,合成了14种新的三苄基锡二元羧酸衍生物.利用元素分析、IR和1HNMR表征了这些化合物的结构.生物活性测试表明该类化合物具有较好的杀菌活性.     

Polyanthranilides. I. Synthesis and Characterization of Polyamides from Isatoic Anhydrides

Ring-scission polymerization of simple and bz-nitro and bz-chlorosubstituted isatoic anhydrides is studied in the presence of reagents like aqueous HCl, anthranilamide, N-methyl aniline, o-chloroaniline, and acid amides under various reaction conditions. Only simple isatoic anhydride is found to undergo ring-scission polymerization affording polyanthranilides in the presence of the first four reagents under appropriate conditions. These samples are insoluble in all organic solvents including formic acid. They are characterized by IR spectral study and thermogravimetric and differential thermal analysis.     

旋光性聚酰胺的合成,表征及其手性识别能力

用天然酒石酸与不同芳香二胺成盐后,经高温缩聚反应,合成了五种新的旋光性聚酰胺,讨论了聚合条件对聚合物的[α]_D~(20)值的影响以及聚合物的旋光稳定性、热稳定性。~1H-NMR及园二色(CD)谱显示聚合物的分子链存在某种有序构象。手性拆分实验初步显示所合成的聚酰胺对苯丙氨酸有手性识别能力。     

Stereocomplex Formation from Enantiomeric Polyamides Derived from Tartaric Acid

Summary: The formation of stereocomplexes from the pair of enantiomorphs of the chiral polyamide poly(hexamethylene di‐O‐methyl tartaramide) was investigated for a variety of experimental conditions. DSC and X‐ray diffraction data evidenced that efficiency in enantiomeric association is highly sensitive to the procedure used for preparing the complex. A comparative isothermal crystallization study revealed that the stereocomplex crystallized from the melt at a rate lower than the enantiomerically pure components. The radial growth of individual spherulites was also delayed in the crystallization of the complex. No evidence of stereocoupling was detected for other poly(alkylene di‐O‐methyl tartaramide)s with the alkylene unit length different from six. It was concluded that molecular interlocking of hydrogen bonds in the enantiomeric pair is highly selective in this family of polymers.

Spherulitic growth at 200 °C from the melt.     

Synthesis and Characterization of Complex Mixtures Consisting of Cyclic and Linear Polyamides from Ethyl Bis-Ketal Galactarates

Bis-ketal-protected diethyl galactarate was condensed with different diamines to prepare sugar-based polyamides. Ketal-protected polyamides, which are soluble in organic solvents, were deprotected with 90% trifluoroacetic acid to yield water insoluble materials. FTIR, NMR, GPC, MALDI-TOF, ESI and TGA techniques were used to characterize the structure and the properties of these biodegradable materials.

D-galactaric acid-based polyamides are complex mixtures of cyclic and linear structures. High molecular weight linear polymer formation was limited by competitive cyclization reactions. The percentage of cyclization was highly dependent on the nature of the diamine used. Polycondensation with linear aliphatic diamines favored the formation of macrocycles, identified by MALDI-TOF and ESI.     

吡啶二羧酸修饰的稀土嵌入碲钨酸盐的合成及电化学生物识别性质

在乙酸钠水溶液中, 采用微波加热一步自组装策略合成了一系列罕见的2,6-吡啶二羧酸修饰的稀土嵌入Keggin型碲钨酸盐(PTEA)₇H₃K[RE₂(B-α-TeW₉O₃₃)₃W₃O₅(H₂O)₃(HDPA)]·22H₂O[RE=Ce³⁺(1), Pr³⁺(2), Nd³⁺(3), Sm³⁺(4); H₂DPA=2,6-吡啶二羧酸; PTEA=质子化的三乙醇胺]. 化合物1~4的聚阴离子由3个三缺位Keggin型 [B-α-TeW₉O₃₃]^8-构筑块通过1个{RE₂W₃O₅(H₂O)₃(HDPA)}¹³⁺异金属簇连接而成. 该异金属簇中, 2,6-吡啶二羧酸作为四齿配体与2个稀土离子(RE1和RE2)配位形成平面三杂环结构, 且RE1和RE2所在平面与W2, W2A, W16形成的平面互相垂直. 此外, 化合物1可与羧基化多壁碳纳米管(CMWCNT)复合形成1-CMWCNT复合材料. 该复合材料可以作为电极材料构建电化学生物传感器, 用于检测特定的DNA序列.     

二羧酸基取代三环氮杂冠醚的合成及其晶体结构

合成了一种新型的三环氮杂冠醚4,13-二氧-1,7,10,16-四氮-1,16：7, 10-双亚乙基-9,18-二乙酸环十八烷-8,17-二酮（C_(20)H_(32)H_4O_8）,在无 水乙醇-氯仿混合溶剂中培养出单晶,用X射线衍射法测定了晶体结构。该晶体属单 斜晶系,空间群P2_1/c,晶胞参数a = 0.87474(17) nm,b = 1.3967(3) nm,c = 0.94309(19) nm;β = 111.18(3)°;Z = 4,V = 1.0744(4) nm~3,D_c = 1. 411 g/cm~3,μ = 0.110 mm~(-1),F(000) = 488,R_1 = 0.0678,wR_2 = 0. 1850。     

新型含吡啶基团二羧酸配体的合成及单晶培养

以1,4-二溴-2,5-二甲基苯和4-吡啶硼酸为原料,经两步合成了一种新颖的含吡啶基团的二羧酸配体。通过核磁共振氢谱及傅里叶变换红外光谱对配体结构进行表征,通过热重分析对配体的热稳定性进行了测试;通过溶剂热法对配体的单晶进行培养,并考察反应温度、时间、pH和溶剂等条件对单晶培养的影响。结果表明：在反应温度为80 ℃,反应时间为12 h、溶剂为蒸馏水、溶液pH=5的条件下可获得高质量单晶。该配体为单斜晶系,属于C2/c空间群,结构中含有4个氧原子和2个氮原子,可为金属离子的配位提供足够的位点,有望应用于配合物的设计或催化、吸附和医药载体等行业。     

1,1,3,3-四甲基胍基衍生物的合成及其与二酸的分子识别性能研究

四甲基胍分别与间苯二甲酰氯和间苯二磺酰氯反应合成了间苯二甲酰四甲基胍和间苯二磺酰四甲基胍,其结构经元素分析,IR,1H NMR和EI-MS表征.核磁滴定研究表明,上述化合物可与二酸形成1 ∶1化学计量络合物,其络合常数在5.33×105～3.68×105.     

Aromatic Polyamides of 2,6-Naphthalenedicarboxylic Acid

Wholly aromatic polyamides have been prepared by the interfacial polycondensation of 2,6-naphthalenedicarboxylic acid chloride with m-phenylenediamine. Also, copolyamides with isophthaloyl or terephthaloyl chlorides and the naphthalene diacid chloride were synthesized. The resultant polyamides were amorphous or slightly crystalline as determined by x-ray diffraction, had tensile properties characteristic of hard, strong materials, and were more thermally stable than aromatic polyamides prepared solely from benzene diacid chlorides.     

含呋喃环生物基聚酰胺的合成

随着环境保护和化石资源问题的日益严峻,开发基于可再生生物质资源的生物基高分子材料,成为未来的发展趋势。作为最具有价值的生物基平台化合物之一,呋喃二甲酸及其衍生物可用于制造精细化学品和高分子材料。近年来,通过熔融聚合、溶液聚合、界面缩聚和固相缩聚等方法,将呋喃二甲酸及其衍生物与二元胺反应,制备出不同结构的生物基聚酰胺的均聚物和共聚物。本文从单体、聚合方法、聚合物结构和性能等方面,对含呋喃环生物基聚酰胺的合成作一总结,同时对这一领域的前景和挑战进行了探讨。     

钯催化的乙炔双羰化-高效合成丁烯二酸二甲酯

报道了无酸和重金属盐的催化乙炔双羰化反应的钯催化体系(催化剂组成为PdCl2/KI).正交实验表明空气的初始分压和助剂KI的用量在乙炔双羰化反应中起着重要的作用.在相同的实验条件下,发现催化体系为PdCl2/HCl/CuCl2和PdCl2/H2SO4/FeCl3时,顺、反丁烯二酸二甲酯的总收率分别为15.3％和21.8％,而用PdCl/KI时总收率达到了81.9％.在最优反应条件下,即PdCl2 0.056 mmol,KI 0.677 mmol,总压5.3 MPa,70℃反应3h,顺、反丁烯二酸二甲酯的总收率为91.0％.     

Synthesis of Some Novel Polyamides

Among various high-temperature organic polymers, the aromatic polyamides have shown excellent thermal stability due to the stiffness of the polymer chain and hydrogen bonding of the amide groups, but had limited solubility in most organic solvents [1-3].     

NaHSO_4·SiO_2催化合成二元脂肪酸酯

用NaHSO_4·SiO_2作催化剂,用二元脂肪酸和不同的醇(甲醇、乙醇、丁醇、苄醇)反应合成了一系列二元脂肪酸酯,该法产率高,操作简单,后处理方便,催化剂能回收再利用.并用X射线衍射法测定了化合物3k的晶体结构.化合物3k属正交晶系,Pbca空间群,晶胞参数:a=1.0216(10)nm,b=0.82794(10)nm,c=1.7996(2)nm,α=90°,V=1.5221(3)nm3,Dc=1.302Mg/m3,Z=4,F(000)=632,μ=0.092mm-1,R=0.0518,wR=0.1475.     

超支化聚芳酰胺的合成

由3,5-二硝基苯甲酰氯和邻氨基苯甲酸合成了AB2型单体2-(3,5-二氨基苯甲酰氨基)苯甲酸。该单体进行自缩聚反应,合成了新型超支化聚酰胺(a),将其与酰氯反应,得到了7种封端的超支化聚合物(b~h)。用FT-IR1、H NMR、GPC、DSC测试技术对超支化聚合物进行了表征。封端改性后,聚酰胺的溶解性均得到了提高,聚合物的重均分子量(Mw)为3.36~3.96 kg/mol,特性粘度(ηinh)为0.061~0.078 dL/g,聚合物玻璃化转变温度(Tg)为56~185℃,随封端剂脂肪链增长而降低,随封端剂极性增加而升高。     

新型两亲性聚酰胺的合成及性质

为了设计天然气水合物抑制剂和了解作用机理提供依据,分析两亲性聚酰胺与水相互作用的特征与本质,本文合成了新型水溶性高分子聚柠檬酰丙二胺,在此基础上合成了一种含环己基基团的两亲性聚柠檬酰丙二胺。通过核磁共振波谱、凝胶渗透色谱和示差扫描量热法对产物的结构和性能进行了表征。研究表明,改性的聚柠檬酰胺能形成不可冰冻束缚水,而且比传统的天然气水合物抑制剂聚(N-乙烯基己内酰胺)和聚维酮形成的不可冰冻束缚水多1倍。改性后聚合物中水的比热容增加约36%。聚合物和水之间产生的疏水相互作用,可将水分子更紧密地束缚在聚合物中。改性后的聚合物的疏水性强,造成了水分子彼此紧密束缚程度提高,为不可冰冻束缚水含量的增加提供了必要的环境。