聚苯基磷酸间苯二酚酯的合成、表征及热性能

采用熔融聚合法, 以间苯二酚、 三氯氧磷和苯酚为原料, 通过两步合成, 制备了阻燃剂聚苯基磷酸间苯二酚酯(PRPP). 用红外光谱(FTIR)、 ¹H, ¹³C和³¹P核磁共振(NMR)、 凝胶色谱(GPC)及热重分析(TGA)等对聚合物的结构、 分子量、 热性能进行了表征. 结果表明, PRPP具有与液态商品间苯二酚双(二苯基)磷酸酯(RDP)相同的组成单元, 其数均分子量为3227, 分子量分布系数M_w/M_n=1.31, 聚合度n≈12; PRPP的起始分解温度与液态RDP相同, 但在高温下PRPP的热稳定性优于RDP, 其分解50%质量的温度提高了235 ℃, 在高温阶段表现出优良的成炭性能.     

2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯的分子构型和取代基电子效应对13C NMR谱的影响

测定了meso-和dl-2,3-二氰基-2,3-二(p-X苯基)丁二酸二乙酯(X=OCH₃,CH₃,H,Cl,NO₂)的¹³CNMR谱。结果表明,中心碳-碳键两端相连基团的各碳原子的化学位移值相同,与dl-异构体相比,所有相应meso-异构体的乙氧羰基¹³CNMR吸收峰均处于高场。苯环对位取代基的Hammett基团常数σ与氰基碳原子和乙氧羰基中的羰基碳及次甲基碳的化学位移间线性相关,而且meso-异构体比dl-异构体有更好的线性关系。     

含硅香原料研究(Ⅵ)——顺(反)-1-取代-3-三甲硅基环己醇的合成、13CNMR谱及其香气评定

合成并分离得到7对1-取代-3-三甲硅基环己醇的顺、反异构体,它们的结构通过¹HNMR、¹³CNMR、MS谱及GC(测其纯度)测定,利用¹³CNMR确定了各对顺、反异构体的构型.评定了各化合物的香气,大部分化合物具有甜香或甜香与木香香气,其中(反)-1-正丁基-3-三甲硅基环己醇具有甜香和木香香气,香气透发,留香持久,质量上乘.     

由4-甲氧基-2-溴代丁烯内酯合成螺环-环丙烷类化合物的研究

以4-甲氧基-2-溴代丁烯内酯为合成子,在温和条件下与不同的亲核试剂通过串联的双Michael加成及分子内的亲核取代反应,得到螺环-环丙烷类化合物8a～8d.通过元素分析,IR,¹HNMR,¹³CNMR和MS对化合物进行了结构表征,其中化合物8d经单晶X射线衍射测定,确定了其立体化学结构.     

新的醚链双生物碱尖叶唐松草阿原碱的结构测定

从尖叶唐松草〔Thalictrumacutifolium(Hand.Mazz.)Boivin〕根分离得到一种新生物碱(尖叶唐松草阿原碱).通过IR,MS,¹HNMR,¹³CNMR,2DNMR(包括¹H-¹HCOSY,¹³C-¹HCOSY,NOESY和HMBC)测定了其化学结构,发现由阿朴菲和原小蘖碱通过醚链连接.对多种肿瘤细胞的生长有抑制作用,并有凋亡现象出现,而且对正常细胞的毒性较小     

具有螺旋结构的金属镍有机-无机配位聚合物的合成及表征

在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni₂L₂(bib)₂·2H₂O]·5H₂O}_n(1), [Ni₂L₂(bpy)]_n(2)和{[Ni₂L₂(bibpip)₂·2H₂O]·6H₂O}_n(3)[H₂L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{4²·6⁵·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{4⁸·5⁴·6³}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P\begin{array}{c}\bar{1}\end{array}空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{4⁴·6²}拓扑结构.     

一个基于[Cu4(μ2-OH)2N12]的10-连接3D配合物的合成、结构和光催化性质

通过扩散法合成了一个新的配位聚合物{[Cu₂（OH）（btre）_1.5（1,2,4-btc）]·13H₂O}_n（1·13H₂O）（btre=1,2-二（4H-1,2,4-三唑）乙烷,1,2,4-btc=1,2,4-苯三甲酸根）。测试了1·13H₂O的晶体结构,并用红外光谱、元素分析、粉末X射线衍射对其进行表征。单晶X射线衍射表明1是基于四核铜簇[Cu₄（μ₂-OH）₂N₁₂]构筑的10-连接的3D框架,其拓扑符号为3¹²·4²⁸·5⁵。研究了1·13H₂O的热稳定性以及对甲基橙的催化降解作用。     

等规聚苯乙烯与聚(乙烯/丙烯)嵌段共聚物的研究(Ⅱ)──嵌段共聚物的分离与表征

将配位聚合法合成的等规聚苯乙烯与聚(乙烯/丙烯)嵌段共聚反应产物进行溶剂车取分离,得到嵌段共聚物[iPS-b-Poly(E-co-P)]的含量约为总重量的20％～30％,并用¹³CNMR、FTIR、WAXD、DSC和电子显微镜进行表征．该共聚物是具有等规聚苯乙烯(iPS)与乙丙无规共聚链段结构的三元两嵌段共聚物,且iPS链段有一定的结晶度．由透射电镜可以看出,嵌段共聚物存在微相分离结构,相区尺寸在100nm数量级．     

苯乙烯-甲基丙烯酸甲酯嵌段共聚物的合成与表征

采用阴离子聚合技术合成了一系列苯乙烯-甲基丙烯酸甲酯的两嵌段共聚物(PS－b－PMMA)．采用GPC、FTIR、NMR(¹HNMR、¹³CNMR和固体NMR)和DMA等手段进行了表征．结果表明,所得产物为高分子量、窄分布、具有微相分离结构的两嵌段共聚物．     

新型查尔酮哌嗪衍生物的合成

以4-二甲氨基苯甲醛和2-溴-4′-氟苯乙酮为原料,经缩合和取代反应制得4-二甲氨基-4′-(1-哌嗪基)查尔酮(2); 2与卤代烃反应合成了6个新型的查尔酮哌嗪衍生物,收率71%~88%,其结构经¹H NMR,¹³C NMR和HR-MS表征。     

主链含羟基的芳杂环液晶共聚物聚对苯撑苯并二噁唑的 合成及性能研究

通过在聚合过程中添加少量2,5-二羟基对苯二甲酸(DHTA)部分替代对苯二甲酸(TPA)与4,6-二氨基间苯二酚(DAR)盐酸盐进行共聚, 合成了一系列大分子链上含有羟基基团的DHPBO共聚物, 并制得其初生纤维. 利用FTIR、接触角等分析手段对其化学结构和纤维表面性能进行了表征, 通过单丝拔出实验和SEM考察了DHPBO纤维与环氧树脂基体的界面剪切强度, 并采用轴向压缩弯曲实验和紫外光加速老化实验评价了羟基基团的引入对提高纤维压缩性能和抗紫外性能的影响. 结果表明, 羟基基团的引入使得DHPBO纤维的表面亲水性、与环氧树脂的界面剪切强度以及纤维的压缩性能和抗紫外性能都有了显著提高.     

Poly(terephthalic acid anhydride) as a latent monomer in polybenzoxazole synthesis

High molecular weight poly(p-phenylenebenzobisoxazole) (PBO) was prepared from poly(terephthalic acid anhydride) (PTAA) and 1,3-diamino-4,6-dihydroxybenzene dihydrogenchloride in polyphosphoric acid (PPA). PTAA may react directly with the o-aminophenol groups to form benzoxazoles or react with PPA to generate terephthalic acid (TA) of very small particle size, which dissolves readily in PPA. PTAA provides the advantages of bypassing the requirement of small particle size TA, reducing the amount of water liberated by half, and possibly providing faster kinetics in PBO synthesis. © 1994 John Wiley & Sons, Inc.     

Synthesis of 4,6-dimethyl-tetrahydro- and hexahydro-dibenzothiophene

2-Bromo-3-methylcyclohexanone was synthesized by conjugate addition of trimethylaluminium to 2-bromo-2-cyclohexen-1-one with copper bromide as catalyst, coupled with 2-methylthiophenol and annulated with the aid of polyphosphoric acid to 4,6-dimethyl-1,2,3,4-tetrahydrodibenzothiophene. The latter was hydrogenated to 4,6-dimethyl-1,2,3,4,4a,9b-hexahydrodibenzothiophene, another intermediate in the hydrodesulfurization of 4,6-dimethyldibenzothiophene, by zinc and trifluoroacetic acid, and dehydrogenated to 4,6-dimethyldibenzothiophene.     

Synthesis of 4,6‐Dimethyldibenzothiophene and 1,2,3,4‐Tetrahydro‐4,6‐dimethyldibenzothiophene via Tilak Annulation

1,2,3,4‐Tetrahydro‐4,6‐dimethyldibenzothiophene was prepared by coupling 2‐bromo‐3‐methylcyclohexanone with 2‐methylbenzenethiol and annulating the product with the aid of polyphosphoric acid. A mixture of 1,2,3,4‐tetrahydro‐4,6‐dimethyldibenzothiophene and 4,6‐dimethyldibenzothiophene was prepared by coupling 2‐bromo‐3‐methylcyclohex‐2‐en‐1‐one with 2‐methylbenzenethiol and annulating the product with the aid of polyphosphoric acid. 2‐Bromo‐3‐methylcyclohexanone was synthesized by conjugate addition of Me₃Al to 2‐bromocyclohex‐2‐en‐1‐one with CuBr as catalyst and 2‐bromo‐3‐methylcyclohex‐2‐en‐1‐one by bromination? elimination of 3‐methylcyclohex‐2‐en‐1‐one. 1,2,3,4,4a,9b‐Hexahydro‐4,6‐dimethyldibenzothiophene was prepared by reduction of 1,2,3,4‐tetrahydro‐4,6‐dimethyldibenzothiophene with Zn and CF₃COOH.     

An efficient solid-phase synthesis of 2-alkyl-4,6-diaminopyrimidines and 2,4,6-triaminopyrimidines

An efficient and simple approach for the solid-phase synthesis of 2,4,6-triaminopyrimidines and 2-alkyl-4,6-diaminopyrimidines is described. Primary amines were immobilized on 2-(4-formyl-3-methoxyphenoxy)ethyl polystyrene resin via reductive amination. Attachment of two different 4,6-dichloropyrimidines led to the corresponding 4-chloro-6-aminopyrimidine intermediates. Aromatic nucleophilic substitution with various aliphatic amines or the corresponding lithium amides afforded the desired aminopyrimidines in high yield and excellent purity after acidic cleavage from the resin. The products were characterized by LC-MS, ¹H and ¹³C NMR spectroscopy. Deuterium exchange experiments revealed that the investigated aminopyrimidines have a general tendency toward C-5 protonation.     

Polybenzoxazole from 1,4-bis(trichloromethyl)benzene

High molecular weight poly(phenylenebenzobisoxazole) (PBO) was synthesized from 1,3-diamino-4,6-dihydroxybenzene dihydrochloride (1) and 1,4-bis(trichloromethyl)benzene (3) in polyphosphoric acid (PPA) or a mixture of PPA and methanesulfonic acid. When PPA was used as the solvent, 3 was first converted in situ to terephthalic acid before 1 was added to minimize degradation of 1. Compound 3 did not need to be sealed from atmospheric moisture because the trichloromethyl groups were not moisture sensitive. It was not necessary to use micronized 3. Adjustment of P₂O₅ content was optional for this reaction because no water was liberated from the condensation of 1 and 3. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2143–2145, 1997     

The synthesis,characterization, and crystal structures of poly(2,6‐naphthalenebenzobisoxazole) and poly(1,5‐naphthalenebenzobisoxazole)

The rigid‐rod polymers, poly(2,6‐naphthalenebenzobisoxazole) (Naph‐2,6‐PBO) and poly(1,5‐naphthalenebenzobisoxazole) (Naph‐1,5‐PBO) were synthesized by high temperature polycondensation of isomeric naphthalene dicarboxylic acids with 4,6‐diaminoresorcinol dihydrochloride in polyphosphoric acid. Expectedly, these polymers were found to have high thermal as well as thermooxidative stabilities, similar to what has been reported for other polymers of this class. The chain conformations of Naph‐2,6‐PBO and Naph‐1,5‐PBO were trans and the crystal structures of Naph‐2,6‐PBO and Naph‐1,5‐PBO had the three‐dimensional order, although the axial disorder existed for both Naph‐2,6‐PBO and Naph‐1,5‐PBO. Naph‐2,6‐PBO exhibited a more pronounced axial disorder than Naph‐1,5‐PBO because of its more linear shape. The repeat unit distance for Naph‐2,6‐PBO (14.15 Å) was found to be larger compared with that of Naph‐1,5‐PBO (12.45 Å) because of the more kinked structure of the latter. The extents of staggering between the adjacent chains in the ac projection of the crystal structure were 0.25c and 0.23c for Naph‐2,6‐PBO and Naph‐1,5‐PBO, respectively. Naph‐1,5‐PBO has a more kinked and twisted chain structure relative to Naph‐2,6‐PBO. The kinked and twisted chain structure of Naph‐1,5‐PBO in the crystal seems to prevent slippage between adjacent chains in the crystal structure. The more perfect crystal structure of Naph‐1,5‐PBO may be due to this difficulty in the occurrence of the slippage. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1948–1957, 2006     

A novel intumescent flame-retardant system containing metal chelates for polyvinyl alcohol

A novel flame retardant containing phosphorous-nitrogen structure, the ammonium salt of 2-hydroxyl-5,5-dimethyl-2,2-oxo-1,3,2-dioxapho sphorinane (PNOH), was synthesized and its structure was characterized by ¹H NMR and FTIR spectra. PNOH was used together with ammonium polyphosphate (APP) to prepare a novel intumescent flame retardant (IFR) for polyvinyl alcohol (PVA). When a few amounts (0.5%) of metal chelates were added, the flame retardancy of the IFR-PVA systems was significantly improved, having a high LOI value of 34.2 in a total IFR loading of 15 wt.%. In order to have an understanding of the resulting flame retardant effects, the thermal degradation behaviors of IFR-PVA systems were investigated by thermogravimetric analysis (TGA), and the morphology and structures of residues generated in different conditions were investigated by scanning electronic microscopy (SEM) and FTIR spectra. The results show that NiSAO can promote the thermal stability of the IFR-PVA; the residual char containing polyphosphoric or phosphoric acid is formed during the combustion; the formation of a continuous and dense char layer could inhibit the transmission of heat during contacting with flame and shows good flame retardancy.     

4,6-二硝基-5,7-二氨基苯并氧化呋咱(CL-14)的合成与表征

以2,4,6-三硝基氯苯为原料, 经过叠氮化、脱氮环化和异常亲核取代氢(VNS)反应合成了4,6-二硝基-5,7-二氨基苯并氧化呋咱(CL-14), 三步总收率达到50.3%, 并采用红外光谱、核磁共振光谱、元素分析等进行了结构表征|确定了合成CL-14的最佳VNS反应条件: 以盐酸羟氨作为VNS试剂, 20～40 ℃下反应6 h, 收率达到60%(文献值53%). 研究结果表明, CL-14具有良好的感度特性和热安定性, 其撞击感度与中间产物4,6-二硝基苯并氧化呋咱(DNBF)基本相当, 而其摩擦感度远低于其DNBF|DSC和TG-DTG实验发现, CL-14仅有一个分解过程, 其分解峰温为308.52 ℃.     

Metal-free and metallo-porphyrazines with eight [5-thiopentyl 2-methoxy-4,6-bis (trifluoromethyl) benzoate] substituent

The reaction of (5-hydroxypentylthio magnesium porphyrazine) with 2-methoxy-4,6-bis(trifluoromethyl)benzoic acid in DCCI and PTSA, esterified MgPz having [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl)benzoate] substituent was obtained. Further reactions of the metal-free porphyrazine with M²⁺(Mg, Co, Cu, Zn, Fe) acetates have produced the metallo-porphyrazines. Finally, by the reaction of FePzCl with pyridine or pyrazine compounds, [FePz(py)₂] and [FePz(pyz)]_n complexes were prepared as the novel stable complexes, respectively. The target compounds have been characterized by using different spectroscopic methods such as FT-IR, UV-Vis, mass, ¹H, ¹³C, and ¹⁹F NMR together with elemental analysis. The aggregation and the solubility features were indicated in various concentrations and solvents.