2,2 bis (4-ethynylphenyl) hexafluoropropane

Summary The 2,2 bis(4-ethynylphenyl)hexafluoropropane is prepared via an original synthesis's process using a substitution of 2,2 bis(4-triflatephenyl) hexafluoropropane by trimethylsilyl acetylene. In this process ZnO is used to remove the triflate anion formed during the reaction.This diacetylenic compound melts at 37–38°C, exhibits an onset of polymerization at 120°C. After thermal treatment at 250°C, the obtained network shows a softening point at 300°C. This network remains stable in air up to 435°C.     

Synthesis and characterization of bis (a-methyl-4-nitrobenzyl) peroxide and bis ( a-methyl-4-nitrobenzyl ) ether

以对硝基乙苯为原料,研究了合成标题化合物的方法,并对其进行了结构表征.在合成双-(α-甲基-4-硝基苄基)过氧化物的方法中,使用优选的T(p-OCH3) PPZn作为催化剂,原料的转化率可达16.2％,产物的选择性为44.0％,相应地收率达7.1％.其中以氧气作为氧化剂,使用金属卟啉为催化剂合成对硝基乙苯一步得到双-(α-甲基-4-硝基苄基)过氧化物的方法尚未见文献报道.     

Synthesis and characterization of new poly(amide)s derived from bis(4-(4-aminophenoxy)phenyl)methylphenylsilane and bis(4-carboxyphenyl)R1R2 silane acids

This study describes the synthesis and characterization of a new diamine; bis(4-(4-aminophenoxy)phenyl)methylphenylsilane, which by reaction with bis(4-carboxyphenyl)R₁R₂ silane derivatives, and following the methodology of the direct polycondensation, allowed the preparation of three new poly(amide)s (PAs). These polymers contain two diphenylsilane (Ph–Si–Ph) and oxyether moieties in their repetitive unit. The reaction to obtain the diamine starting from the respective diphenol was developed in two steps. The first step consisted on obtaining the dinitro derivative, bis(4-(4-nitrophenoxy)phenyl)methylphenylsilane, with a yield of 83 %. Then, this compound was reduced by reaction with hydrazine and Pd-activated carbon, with a yield of 67 % in the diamine. Both compounds were characterized by spectroscopic techniques (FT-IR, ¹H, ¹³C and ²⁹Si NMR). The synthesis of the PAs (PA-I, PA-II and PA-III) presented a yield of 35–79 %, glass transition temperature between 136 and 149 °C and inherent viscosities in the range 0.08–0.16 g/dL. PA-I and PA-III presented a transmittance value (at 400 nm) of 91 and 87 %, respectively, while PA-II only reached a value of 70 %. All these results were analysed in accordance with structural details of each repetitive unit and were also compared with those obtained from poly(amides) series not containing flexible elements in their chains. The TGA analyses demonstrated that the new polymers still maintain a high thermal resistance, despite the incorporation of the flexible units.     

碳酸二（4-氨基苯基）酯的合成与表征

以Pd／C为催化剂,甲酸铵为氢给予体,75％（质量分数）甲醇为溶剂,碳酸二（4-硝基苯基）酯为原料,在常压下转移氢化合成了碳酸二（4-氨基苯基）酯。氢化条件温和,后处理简单,没有污染。并用红外、氢核磁谱图表征了该化合物。     

Kinetics of copolycondensation of bis(4-hydroxybutyl) terephthalate and bis(2-hydroxyethyl) terephthalate by ester-interchange reaction

The kinetics of polycondensation and copolycondensation reactions were investigated using bis(4-hydroxybutyl) terephthalate (BHBT) and bis (2-hydroxyethyl) terephthalate (BHET) as monomers. BHBT was prepared by ester interchange reaction of dimethyl terephthalate and 1,4-butanediol. BHBT and BHET were polymerized at 270°C in the presence of titanium tetrabutoxide (TBT) as a catalyst. Applying second-order kinetics for polycondensation, the rate constants of polycondensation of BHBT and BHET, k₁₁ and k₂₂, were calculated as 3.872 min⁻¹ and 2.238 min⁻¹, respectively. BHBT and BHET were also copolymerized at 270°C using TBT. The rate constants of crossreactions in the copolycondensation of BHBT and BHET, k₁₂ and k₂₁, were obtained by using the results obtained from a proton nuclear magnetic resonance (¹H-NMR) spectroscopy and a high-performance liquid chromatography (HPLC). It was found that the rate constants during the copolycondensation of BHBT and BHET at 270°C decreased in the order k₂₁ > k₁₁> k₂₂ > k₁₂ and the monomer reactivity ratio of BHBT was four or five times larger than that of BHET. In calculating the crossreactions, the method by the ¹H-NMR spectroscopy gave more accurate results than that by the HPLC. © 1996 John Wiley & Sons, Inc.     

Thioetherglycidyl resins. III. Products of condensation of bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl)methane with epichlorohydrin

Thioetherglycidyl resins produced by condensation of bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl) methane with epichlorohydrin were obtained by heterophase alkaline condensation. To define the optimal conditions of condensation, the following factors that influence the process were studied: the kind of organic phase and the mole ratios of epichlorohydrin:mercaptan, alcohol:mercaptan, and alkaline hydroxide:mercaptan. For all syntheses yield and the epoxide content were found. The structure of thioetherglycidyl resins with the highest epoxide content was determined by elementary analysis, infrared IR, and NMR spectra. The physical and chemical properties were also defined. The investigations covered the determination of some properties of resins, cured chemically or thermally with different curatives and thermal and mechanical properties of the cured compounds.     

Thioether glycidyl resins. VII. Products of condensation of bis(4-mercaptophenyl)sulfide and bis(4-mercaptophenyl)sulfone with epichlorohydrin

New thioether glycidyl resins by condensation of bis(4-mercaptophenyl)sulfide or bis(4-mercaptophenyl)sulfone with epichlorohydrin were obtained by heterophase alkaline condensation in aqueous and isopropanol medium using sodium hydroxide. The detailed studies on their structures from elemental analysis and IR and ¹H-NMR spectra, physical and chemical properties, and curing conditions are presented. Thioether glycidyl resins compositions were also prepared using curatives typical for epoxy resins and after curing they were characterized from derivatographic, thermomechanical, and mechanical studies.     

Thioether glycidyl resins. II. Products of condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin

New thioether glycidyl resins produced by condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin were obtained by heterophase alkaline condensation in water and isopropyl alcohol solution. To define the optimal conditions of condensation, the following factors that influence the process were studied: the mole ratios of epichlorohydrin–mercaptan, alcohol–mercaptan, alkaline hydroxide–mercaptan. For all reaction products, yield, epoxide content, and chlorine content were determined. The structure of thioether glycidyl resins with the highest epoxide content was determined by elemental analysis and infrared and NMR spectra. The physical and chemical properties were defined. Some properties of the resins, cured chemically or thermally with different curatives, and thermal and mechanical properties of the cured compounds were determined.     

Ethynyl terminated ethers. Synthesis and thermal characterization of 2,2 bis (ethynyl-4-phenylcarbonyl-4-phenoxy-4-phenyl) propane and 2,2 bis (ethynyl-4-phenylsulfonyl-4-phenoxy-4-phenyl) propane

Summary Two ethynyl end-capped ethers 2,2 Bis [ethynyl-4-phenylsulfonyl-4-phenoxy-4-phenyl] propane and 2,2 Bis [ethynyl-4-phenylcarbonyl-4-phenoxy-4-phenyl] propane have been prepared by a three steps synthesis each. They exhibit melting point followed by the thermal polymerisation of the ethynyl groups in the 200–250°C range. Curing lead to thermoset materials where Tg are respectively of 240°C and not detectable.     

Copolymerization of methyl methacrylate with bis(4-methacryloylmethylphenyl)-sulphone

Bis(4-methacryloylmethylphenyl)-sulphone (BMMPhSu), the monomer containing sulphur in the form of sulphone group and two unsaturated bonds C\hbox{=}C in its structure, was applied for obtaining copolymers with methyl methacrylate (MM). 15% solution of BMMPhSu in MM was polymerized in the presence of three curing systems. The curing systems were combinations of benzoyl peroxide (BP), methylethyl ketone peroxide (L), N,N-dimethylaniline (DMA) and cobalt naphthenate (Co). Influence of curing systems on gelation times of the solutions of BMMPhSu in MM at room temperature was determined. The peaks exotherm temperatures were measured. For four polymers containing 15% of BMMPhSu polymerized in the presence of BP and DMA of different concentrations as curing systems. Besides, 8 films of the copolymers BMMPhSu and MM were obtained. The films were obtained by polymerization of 15, 10 and 5% solutions of BMMPhSu using the curing system BP+DMA, and 15% solution of BMMPhSu using the curing systems (BP+L)+DMA+Co and L+DMA+ Co. Some of the films (5) were heated for 4 h at 80°C but the others were not. All obtained films were tested for mechanical properties such as Young's modulus, tensile strength, elongation at break, hardness by the Shore's and Brinnell's methods. Thermal resistance and glass transition temperatures of the obtained copolymers were also determined.     

Effect of copolycondensation temperature on the reactivity ratios of bis(4-hydroxybutyl) terephthalate and bis(2-hydroxyethyl) terephthalate

Summary The effect of copolycondensation temperature on the monomer reactivity ratios of bis(4-hydroxybutyl) terephthalate (BHBT) and bis(2-hydroxyethyl) terephthalate (BHET) was investigated at 260, 270, and 280 °C, in the presence of titanium tetrabutoxide as a catalyst. Adopting 2nd order kinetics to polycondensation, the rate constants of polycondensation of BHBT and BHET, k ₁₁ and k ₂₂, were calculated to be 2.58, 1.30; 3.87, 2.24; and 5.29, 4.06 min⁻¹. In addition, the rate constants k ₁₂ and k ₂₁ of cross reactions could be determined as 0.91, 3.00; 1.49, 4.42; and 2.13, 5.85 min⁻¹ from a proton nuclear magnetic resonance spectroscopic analysis. The monomer reactivity ratios of BHBT were much larger than those of BHET, indicating the block nature of the copolycondensation, but the differences between monomer reactivity ratios were decreased with increasing polycondensation temperature, indicating that a probability of randomization was increased. Received: 15 October 1998/Revised version: 3 December 1998/Accepted: 8 December 1998     

Synthesis and characterization of a novel chloro-bridged bis cadmium(II) complex with bis(2-pyridylmethyl)amino-4-butyric acid

The reaction of CdCl₂ with bis(2-pyridylmethyl)amino-4-butyric acid (Hpmab) leads to the formation of binuclear complex [(Hpmab)(Cl)Cd^II(μ-Cl)₂Cd^II(Cl)(Hpmab)] (1). Complex 1 can be regarded as two distorted octahedrons sharing the basal edge that contain the bridging chloro ligands, in each of which resides at a center of inversion. Cyclic voltammetry of 1 gives one oxidation and two reduced processes.     

Synthesis and characterisation of polyamideimides from bis(4-trimellitimidophenyl)sulfone

Several polyamideimides have been synthesised by the interaction of a number of aromatic diamines with an imidedicarboxylic acid. Since these polymers incorporated a preformed imide group, they did not pose the common problems encountered in imidisation of polyamic acids. They were synthesised by low temperature (<5°C) polycondensation, in 75–92% yields and had viscosities in the range 0.18–0.39 dl/g. They were characterised by IR spectra, elemental analysis, X-ray and thermal methods, and possessed very high solubility in polar aprotic solvents.     

二(4-甲氧基苯基)-羟乙酸甲酯的合成及其晶体结构

提出了一种合成标题化合物的新方法,用IR、1HNMR及X-ray单晶衍射方法对其结构进行了表征。晶体结构分析表明,化合物为正交晶系,空间群P212121,晶胞参数a=0.7749(4)nm,b=1.2680(6)nm,c=1.5462(7)nm,β=90°,V=1.5193(13)nm3,Z=4,Dc=1.322g/cm3,F(000)=640,μ=0.097mm-1,R1=0.0531,wR2=0.1129。     

阻燃剂双(对羧苯基)苯基氧化膦的合成

以苯、三氯化磷、甲苯等为原料，通过改进氧化条件和纯化方法，合成了阻燃剂双（对羧苯基）苯基氧化膦，并用红外、核磁共振和差示热量热分析确定了产品的结构。     

Layered zinc 4-phosphonoisophthalates pillared by flexible bis(imidazole) Co-ligands

This paper reports two zinc phosphonates based on 4-phosphonoisophthalic acid (4-piH₄) and bis(imidazole) co-ligands, namely, [Zn₂(4-pi)(1,2-bix)] (1) and [Zn₂(4-pi)(1,3-bix)] (2) (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene). Both show layer structures in which the inorganic tetranuclear cores of Zn₄P₂O₆ are connected by 4-pi⁴⁻ligands. The 1,2-bix or 1,3-bix ligand binds to the Zn atoms within the tetranuclear unit or between the neighboring tetranuclear units in a cis-coordination mode, and fill in the interlayer spaces in both cases. The luminescent properties are investigated.     

含呋喃基双酚-双(4-羟基-3,5-二甲基苯基)呋喃甲烷的合成与表征

以2,6-二甲基苯酚和糠醛为原料,氢氧化钠为催化剂,经缩合反应合成了双（4羟基-3,5-二甲基苯基）呋喃甲烷。研究了各因素对反应收率的影响规律,选择反应温度、催化剂用量和反应时间为主要影响因素进行了正交实验。实验得出优化后反应条件为：n(2,6-二甲基苯酚)∶n(糠醛)=2.2∶1,n(2,6-二甲基苯酚)∶n(氢氧化钠)= 1∶0.11,反应温度为65?℃,反应时间为5?h。在较优条件下进行实验,所得产物收率为61.7%。采用FTIR、¹HNMR和MS表征确定了产物结构,并测得其熔点为151.1?℃,纯度为99.52%。     

4-(4-甲基-3-戊烯基)-4-环己烯-1,2-酸异辛酯的合成及其增塑性能研究

以β-月桂烯为原料,经Diels-Alder反应和酯化反应,合成了化合物4-(4-甲基-3-戊烯基)-4-环己烯-1,2-酸异辛酯.对酯化反应条件进行了优化,优化后条件为:在回流温度下,以B酸性离子液体[ HSO3-bmim]+[HSO4] -做催化剂,催化剂的质量分数为0.7％,反应时间为80 min,n(酸酐)∶n(异辛醇)为1∶4.0,带水剂甲苯的质量分数为15％.该化合物可作为PVC塑料的主增塑剂使用,具有比邻苯二甲酸二(2-乙基己基)酯(DOP)更加优异的增塑性能.     

双（4-甲苯基）苯基硫化膦定量分析研究

以自制双(4-甲苯基)苯基硫化膦(BMPPS)粗品为原料.经多次重结晶提纯后,用薄层色谱(TLC)、高效液相色谱(HPLC)进行分析,纯品BMPPS的纯度为99.2%,可用作定量分析对照品.对纯品UV扫描发现,BMPPS的吡啶溶液在303nm处有稳定吸收,在浓度为8×10-4～4×10-3mol/L范围内吸光度与浓度呈良好的线性关系,回归方程为:y=190.6x 0.377,r=0.997 8.加标回收率为98.5%～103.8%,方法重现性良好,可用作合成BMPPS粗品的定量分析.