2,2-二(4-羟基-3,5-二硝基苯基)丙烷和2,2-二(4-羟基-3-硝基苯基)丙烷热分解动力学研究

用热分析方法(TG,DTA)、热分解气相色谱和红外光谱等联合手段,对双酚A的二硝基取代产物和四硝基取代产物[2,2-二(4-羟基-3,5-二硝基苯基)丙烷和2,2-二(4-羟基-3-硝基苯基)丙烷]的热稳定性和热分解反应动力学进行了研究,发现它们的稳定性与硝基取代的数目有关,热分解具有失去一端并带走一个甲基的共同机理,然而热分解动力学方程形式不同分别是:dα/dt=50.90e(-E/RT)(1-α)和dα/dt=59.06 e(-E/RT)(1-α)3,从电荷分布均衡点出发对上述现象进行理论探讨。     

2,2-二(4-羟基-3-硝基苯基)丙烷的合成

双酚A经硝化可制得合成阻燃剂的中间体 2 ,2 二 (4 羟基 3 硝基苯基 )丙烷。最佳硝化条件为 :w(HNO3 ) =2 2 % ,反应温度 30℃ ,反应时间 3h ,目标产物的产率最高达到 87 5 %。产物经柱色谱纯化后 ,其元素分析、红外光谱、核磁共振和质谱数据与结构相符     

Refractometric and calorimetric studies of the van der Waals interactions between the molecules of polycarbonate and of the additives acting as plasticizers or antiplasticizers

Considerable deviations of molar refraction from the additivity in the solutions containing polycarbonate and its antiplasticizers symmetrical trinitrotoluene and 1,1-bis(4-hydroxy-3, 5-dichlorophenyl)2,2,2-trichloroethane diacetate are reported. In contrast to this, the solutions of polycarbonate with plasticizer di-n-butyl phthalate and the solutions of antiplasticizers in pure solvent show only insignificant deviation from the additivity. The calorimetric studies showed the differences in the heats of solution of the used antiplasticizers in pure solvent and in the solvent containing a constant amount of polymer, whereas there was no noticeable difference in the polycarbonate–plasticizer (di-n-butyl phthalate) system. Both deviations of the molar refraction from the additivity and differences of the heats of solution prove the existence of strong interactions between the molecules of polycarbonate and the antiplasticizer.     

新型酯基咪唑类表面活性剂的合成与性能

以月桂酸、二溴新戊二醇和N-甲基咪唑为主要原料,经酯化、季铵化反应合成了一种新型双酯双咪唑类表面活性剂二溴-1,3-双(3-甲基咪唑)-2,2-双(十二酸酯甲基)-丙烷(EminC12)。实验得到酯化反应条件:n(月桂酸)∶n(二溴新戊二醇)=2.2∶1,反应温度为115℃,反应时间7 h,对甲苯磺酸为催化剂,甲苯为带水剂,得到中间体1,3-二溴-2,2-双(十二酸酯甲基)-丙烷(DEC12),产率为87%;季铵化反应条件:反应温度150℃,反应时间5 h,目标产物产率可达80%;产物结构通过元素分析、IR、1HNMR得到证实。25℃时其水溶液的临界胶束浓度为0.3 mmol/L,表面张力为39 mN/m,具有较好的起泡性和稳泡性。     

Synthesis and Structure-Property Study of Polyarylates Derived from Bisphenols with Different Connector Groups

Several polyarylates were synthesized from the interfacial or high-temperature solution polycondensation reactions of four bisphenols including 2,2-bis(4-hydroxyphenyl)propane (BPA), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP), and 1,1-bis(4-hydroxyphenyl)-1-phenyl-2,2,2-trifluoroethane (BPAPF) with various aromatic diacyl chlorides. The basic properties such as inherent viscosity, film-forming capability, crystallinity, and mechanical and thermal properties and the “structure-property” relationships of these polyarylates were investigated. The polyarylates derived from asymmetric BPAP and BPAPF had lower crystallinity and higher solubility and glass-transition temperature (T_g) than the corresponding counterparts based on symmetric BPA and BPAPF. The fluorinated polyarylates revealed higher T_g values and decomposition temperatures than the corresponding nonfluorinated polyarylates.     

Radiation yield of hydrogen chloride in gamma-irradiated poly(vinyl chloride) stabilized by epoxy compounds

The G_HCI values of γ-irradiated PVC mixtures were studied after addition of various amounts of three epoxy stabilizers: diglycidyl ether of 2,2-bis(4-hydroxy-3-methylphenyl)propane (I); diglycidyl ether of 1,1-bis(4-hydroxyphenyl)cyclohexane (II), and butyl-cis-9,10-epoxystearate (III). The results indicated that two processes are essential for the stabilization: HCI capture by the epoxy groups, and an external protective effect, due to the remaining part of the stabilizer molecule. The role of the benzene rings in stabilizers I and II, as compared with the protective effect due to the long chains of stabilizer III, is not as dominant as one would expect.     

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s have been prepared by solution polycondensation reaction of different aromatic diamines having preformed 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2,5-bis[p-(3-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole and 2-(4-fluorophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole, with an aromatic dianhydride incorporating ether linkages and hexafluoroisopropylidene group, namely 1,1,1,3,3,3-hexafluoro-2,2-bis-[(3,4-dicarboxyphenoxy)phenyl]-propane dianhydride. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidinone, N,N-dimethylformamide, and pyridine, as well as in certain low boiling-point organic solvents, such as tetrahydrofuran and chloroform. Very thin coatings deposited onto silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy. The polymers showed high thermal stability with decomposition temperature being above 410 °C. They exhibited a glass transition in the temperature range of 183-217 °C, with reasonable interval between glass transition and decomposition temperature. Solutions of some polymers in N,N-dimethylformamide exhibited blue fluorescence, having maximum emission wavelength in the range of 411-424 nm.     

Conformational studies of polycyanurates: a study of internal stress versus molecular structure

A new parameter set (RDA-DR2.21_Inv) is shown to reproduce both the geometries and the physical and mechanical properties of three polycyanurates based on 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)ethane and 1,3-bis(4-cyanatophenyl-1-(1-methylethylidene))benzene. The results show a trend of internal stress within the molecule caused by varying backbone structure. The simulated Young's modulus of elasticity decreases in the order: 1,1-bis(4-cyanatophenyl)ethane>2,2-bis(4-cyanatophenyl)propane>1,3-bis(4-cyanatophenyl-1-(1-methylethylidene))benzene (from 31.11 to 14.33 GPa). Molecular dynamics simulations, carried out on 1,1-bis(4-cyanatophenyl)ethane and 1,3-bis(4-cyanatophenyl-1-(1-methylethylidene))benzene, reproduce the empirical glass transition temperatures (T_g) of the polycyanurates well, although the calculated T_g values are slightly overestimated when compared with the empirical data, presumably due to the ‘perfect’ nature of the simulated network.     

Synthesis and memory characteristics of polyimides containing noncoplanar aryl pendant groups

A series of soluble aromatic polyimides were prepared from 2,2′-diphenyl-4,4′-biphenyl diamine (DPBD), 2,2′-bis(biphenyl)-4,4′-biphenyl diamine (BBPBD), 2,2′-bis[4-(naphthalen-1-yl)phenyl]-4,4′-biphenyl diamine (BNPBD) and 2,2′-bis(3,5-dimethoxyphenyl)-4,4′-biphenyl diamine (BMPBD) by polycondensation with 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyl tetracarboxylic dianhydride via a two-step procedure. The resulting polymers were fully characterized and they exhibited excellent organosolubility, high thermal and dimensional stability. Resistive switching devices with the configuration of Al/polymer/ITO were constructed from these polyimides by using conventional solution coating process. Devices with the active layer based on DPBD, BBPBD and BNPBD exhibited nonvolatile and rewritable flash type memory characteristics with the turn-on voltage at ?2.0 to ?3.0 V and the turn-off voltage at 2.0–3.0 V. Whereas, device based on BMPBD demonstrated a bipolar write-once read-many times (WORM) memory capability with the writing voltage around ±3.0 V. The ON/OFF current ratio of these devices was of about 10⁶ and the retention times can be as long as 10⁴ s.     

吸热型碳氢燃料中氢过氧化物的抑制

在饱和溶解氧加速热氧化条件下,采用碘量比色法跟踪测定了吸热型碳氢燃料ZH-100中氢过氧化物浓度随时间的变化,评价了2,2'-硫代二乙基-3-(3,5-二异丁基-4-羟基苯基)丙酸酯,3,5-二叔丁基-4-羟基苯甲基二乙基磷酸酯,4,4'-二(苯基异丙基)二苯胺,三(2,4-二叔丁基)亚磷酸苯酯,双十八烷基季戊四醇双亚磷酸酯等5种不同类型抗氧剂的抗氧化效果.结果表明,5种抗氧剂不同程度地抑制了燃料中氢过氧化物的生成,加入量100 μg·g-1时可使燃料120℃的氧化诱导期分别延长80、58、10、32和58 h,有效地提高了燃料的热氧化安定性.其中,以含硫双酚类复合型抗氧剂2,2'-硫代二乙基-3-(3,5-二异丁基-4-羟基苯基)丙酸酯的抗氧化效果最佳,在燃料ZH-100中加入50、100和500μg·g-1该抗氧剂,可使燃料140℃的氧化诱导期分别延长4,6和24 h.     

Effects of composition and extrusion parameters on the morphological development and rheological properties of PP/PC blends. Co-continuity investigation

In this work, a new dimethacrylate monomer named ??,????-Bis(4-(2??-hydroxy- 3??methacryloyloxy-propoxy)-3,5-dimethylphenyl)-1,4-diisopropyl-benzene (??,????-BHMPDDB) was synthesized to replace 2,2-bis[4-(2??-hydroxy-3??-methacryloyloxy-propoxy)-phenyl]propane (Bis-GMA) as one component of dental composite materials. The structures of ??,????-BHMPDDB and its intermediate product ??,????-Bis(4-oxiranylmethoxy-3,5-dimethylphenyl)-1,4-diisopropylbenzene (??,????-BODDB) were confirmed by FT-IR, ¹H-NMR, and elemental analysis. ??,????-BHMPDDB was mixed with TEGDMA to form a new dental resin, and double bond conversion, polymerization shrinkage, contact angle, water sorption and solubility, flexural strength and modulus before and after water immersion of this new dental resin were studied. Compared with the commonly used Bis-GMA/TEGDMA dental resin, ??,????-BHMPDDB/TEGDMA had higher double bond conversion (60.5?±?0.3?%), lower polymerization shrinkage (5.6?%), and comparable flexural strength before water immersion (94.1?±?3.9?MPa), which made ??,????-BHMPDDB/TEGDMA having potential to replace Bis-GMA/TEGDMA as matrix phase of dental composites materials. However, ??,????-BHMPDDB/TEGDMA also had drawbacks, such as higher water sorption (5.06?±?0.17?%), water solubility (2.37?±?0.1?%), and lower flexural strength after water immersion (71.4?±?14.6?MPa).     

含氰基二元芳胺固化的酞菁预聚物的合成及表征

以亲核取代反应合成了3种酞菁单体(2,2′-二[4-(3,4-二氰基苯氧基)]丙烷(BAPh)、4,4′-二(3,4-二氰基苯氧基)联苯(BPh)、4,4′-二(3,4-二氰基苯氧基)甲烷(BFPh))和1种含有氰基的高熔点二元芳胺2,6-二(4-氨基苯氧基)苯甲腈(APBN)。通过核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱(FT-IR)、示差扫描量热仪(DSC)和热重分析(TGA)对合成的化合物的化学结构,芳胺和酞菁单体的热聚合行为,不同固化时间预聚物的热性能进行了研究。结果表明,BAPh/APBN和BFPh/APBN体系分别具有宽达101℃与107℃的加工窗口。BFPh型预聚物(固化1 h)比其他2种预聚物具有更高的初始分解温度(390℃下失重5%)、高温残炭率(800℃下61.7%)和固化效率。     

2,2-二(3,5-二氨基- 4-羟基苯基)丙烷的合成

2,2-二(3,5-二氨基-4-羟基苯基)丙烷是一种新型膨胀型阻燃剂和合成N-P系膨胀型阻燃剂的中间体。研究了Fe-A l/C催化水合肼还原2,2-二(4-羟基-3,5-二硝基苯基)丙烷合成2,2-二(3,5-二氨基-4-羟基苯基)丙烷的反应条件。结果表明:对20 mmol的反应物,Fe-A l/C催化剂的用量为0.6 g,反应温度为75℃,反应时间为5 h,物料比n〔2,2-二(4-羟基-3,5-二硝基苯基)丙烷〕∶n(水合肼)=1∶12时,还原产率为93.75%,w〔2,2-二(3,5-二氨基-4-羟基苯基)丙烷〕=96.5%(HPLC),Fe-A l/C催化剂可以重复使用7次。产物经元素分析、红外光谱、核磁共振和质谱分析确证。     

Ring transformation and cyclization reactions of 1,1-dioxo-1,2-thiazines – syntheses of pyridines and benzo[c]thiazines with new substitution pattern

In presence of ammonia/ammonium acetate the 3,5-dimethyl-2-phenyl-1,1-dioxo-1,2-thiazine-4-carbaldehyde ( 1 ) reacts with ethyl cyanoacetate to the ethyl 2-cyano-4-[1-methyl-2-methylthio-2-(N-phenylsulfamoyl)vinyl)-hexa-2,4-dienoate] ( 3 ) and the Knoevenagel condensation product 4-(2-ethoxycarbonyl-2-cyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2 a). The 4-(2,2-dicyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2b ) is obtained from 1 and malononitril. The masked 1,5-dicarbonyl compound 2a undergoes ring transformation to the 3-cyano-1,6-dimethyl-5-[1-methylthio-2-(N-phenylsulfamoyl)vinyl]pyridin-2-one ( 5 ) with methylamine. With ethanolic ethoxide the condensation products 2a,b afford the 7-amino-6-ethoxycarbonyl-4-methylthio-2,2-dioxo-1-phenyl-benzo[c]1,2-thiazine ( 6a ), respectively the corresponding 6-cyano derivative 6b , while 3 cyclizises to furnish ethyl 2-amino-6-methyl-5-[1-methyl-2-methylthio-2-(N-phenyl-sulfamoyl)vinyl]nicotinate ( 4 ).     

4-苄基-2-[(R)-1-[3,5-二(三氟甲基)苯基]乙氧基]吗啉-3-酮的不对称转化的动态动力学拆分

以4-苄基-2-羟基吗啉-3-酮为原料,经两步反应制备得到一对非对映异构体4-苄基-2-[(R)-1-[3,5-二(三氟甲基)苯基]乙氧基]吗啉-3-酮,然后以叔丁醇钾为碱环境,利用不对称转化的动态动力学拆分,转化为手性纯(R)-4-苄基-2-[(R)-1-[3,5-二(三氟甲基)苯基]乙氧基]吗啉-3-酮。转化后手性产物与非对映异构体的比例为96∶4,在工业化制备神经激肽-1(NK-1)受体阻滞剂阿瑞吡坦过程中有较好的应用价值。     

Über die eigenschaften von selbstverlöschenden polyarylestern aus aromatischen dicarbonsäuren und 2,2-bis(4-hydroxyphenyl)-1,1-dichloräthylen

The mechanical, thermomechanical, electrical and some other properties of polyarylates derived from chloro-bisphenol derivates of chloral and phenol, especially from 2,2-bis(4-hydroxyphenyl)-1,1-dichloroethylene and a mixture of tere- and isophthalic acid dichloride (2:1), were examined.     

Kinetic studies on copolycondensation processes. III. Kinetic studies on copolycondensation of terephthaloyl chloride with bisphenols in solution

Kinetics of copolycondensation of terephthaloyl chloride with 2,2-bis(4-hydroxyphenyl) propane and 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane in α-chloronaphthalene solution was examined. The extent of the reaction data obtained experimentally was compared with theoretical values, calculated on the basis of the theoretical dependence derived previously. A satisfactory agreement of experimental results with theory was observed.     

Acetals and Ethers. XVIII. Reaction products of prop-2-enal and but-2-enal with mixture: n-Aliphatic alcohol and ethylene glycol

The direct condensation reaction of prop-2-enal or but-2-enal with mixture of n-aliphatic alcohol and ethylene glycol, in the presence of p-toluenesulphonic acid as catalyst, leads to a complex mixture of saturated, unsaturated, cyclic and linear acetals, moreover, 2-(2-alkoxy-alkyl)-1,3-dioxolanes are the main reaction products. The detailed investigations for n-butanol showed that unsaturated cyclic acetals: 2-vinyl-1,2-dioxolane 1a or 2-(1-propenyl)-1,3-dioxolane 1b , as well as unsaturated linear acetals: 1,1-dibutoxy-prop-2-en 2a or 1,1-dibutoxy-but-2-en 2b are intermediate reaction products. Additionally, it was found in final products presence of eight by-products: 5-butoxy- 4a or 5-butoxy-7-methyl-1,4-dioxepane 4b , 1,1,3-tributoxypropane 5a or 1,1,3-tributoxybutane 5b , 2-[2-(2-hydroxyethoxy)ethyl]- 6a or 2-[2-(2-hydroxyethoxy)propyl]-1,3-dioxolane 6b , 5-(2-hydroxyethoxy)-7-methyl-1,4-dioxepane 7b , 1,3-dibutoxy-1-(2-hydroxyethoxy)-propane 8a or 1,3-dibutoxy-1-(2-hydroxyethoxy)-butane 8b , 1,1-dibutoxy-3-(2-hydroxyethoxy)-propane 9a or 1,1-dibutoxy-3-(2-hydroxyethoxy)-butane 9b , 3-butoxy-1,1-bis-(2-hydroxyethoxy)-propane 10a or 3-butoxy-1,1-bis-(2-hydroxyethoxy)-butane 10b , and 1-butoxy-1,3-bis-(2-hydroxyethoxy)-propane 11a or 1-butoxy-1,3-bis-(2-hydroxyethoxy)-butane 11b , respectively.     

2,2-二(3-氨基-4-羟基)苯基丙烷的合成与结构表征

分别在Pd/C、FeOOH和FeCl3·6H2O/C三种不同催化剂存在下,由水合肼还原2,2 二(4 羟基 3 硝基)苯基丙烷(1)合成了2,2 二(3 氨基 4 羟基)苯基丙烷,筛选出成本低、收率高的理想催化剂为FeCl3·6H2O/C。当物料配比n(水合肼):n(1)=5:1,反应起始温度为70℃,反应时间为80min时,收率为93 0%。产物经重结晶纯化后,由元素分析、红外光谱、核磁共振谱和质谱对其结构进行了表征,确证了产物的结构。     

Synthesis and evaluation of some functionalized difuran diesters as plasticizers for PVC

Butyl, hexyl, and 2-ethylhexyl diesters of 1,1-bis(5-carboxyl-2-furyl)-2,2-dichloroethene, hexyl and 2-ethylhexyl diesters of 1,1-bis(5-carboxyl-2-furyl) ketone, and the hexyl diester of 1,1-bis(5-carboxyl-2-furyl)methane were synthesized from furfural and evaluated for their plasticizing abilities toward PVC, by the application of dynamic mechanical thermal analysis and [di(2-ethylhexyl) phthalate] as a standard of reference. © 1995 John Wiley & Sons, Inc.