N,N-二甲基-γ-氨丙基-γ-氨丙基聚二甲基硅氧烷ASO-121的合成、表征与膜形态

用八甲基环四硅氧烷（D4）与N，N-二甲基-γ-氨丙基-γ-氨丙基二甲氧基硅烷等进行聚合反应，合成了一种N，N-二甲基-γ-氨丙基-γ-氨丙基聚二甲基硅氧烷（ASO-121）柔软剂，用红外光谱、核磁共振氢谱、原子力显微镜等仪器对其结构和成膜形态进行了研究。结果表明，ASO-121能在棉纤维织物和单晶硅表面形成疏水膜，该膜表面略显粗糙，在2μm^2扫描范围内其均方根粗糙度达到了0．226nm。     

有机硅聚合物负载硫、硫、氮三齿配体铂配合物的合成与催化性能

N,N-双(β-甲硫乙基)γ-(三乙氧硅基)丙胺用气相法二氧化硅固载,再与氯亚铂酸钾作用,合成了三齿型铂配合物-聚γ-[N,N-双(β-甲硫乙基)胺基]丙基倍半硅氧烷铂配合物.研究了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性.     

γ-氨丙基硅氧烷与八甲基环四硅氧烷乳液共聚合的研究

合成了γ-氨丙基七甲基环四硅型氧烷和γ-氨丙基甲基二乙氧基硅烷。研究了它们与八甲基环四硅氧烷在阳离子乳化剂及阴离子型乳化剂存在下的乳液共聚合反应。探讨了催化剂量、单体浓度、氨丙基含量及温度等对聚合的影响。     

脂肪醇对聚硅氧烷乳液稳定性的影响

以八甲基环四硅氧烷、N-β-氨乙基-γ-氨丙基二甲氧基基硅烷等为原料，在氢氧化钾催化作用下，通过开环共聚合成了聚硅氧烷乳液，并就稳定剂长链脂肪醇对乳液稳定性的影响进行了较详细的研究，得到了较佳的合成工艺。     

1,1-二苯基(或4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲的合成

以三乙胺为缚酸剂,二苯胺和4,4'-二溴二苯胺分别与三光气反应制得N,N-二苯基氨基甲酰氯(2a)和N,N-(4,4'-二溴二苯基)氨基甲酰氯(2b);2a和2b分别与3-氨丙基三乙氧基硅烷反应合成了两个新型的含非对称取代脲的功能性有机硅氧烷——1,1-二苯基-3-(3-三乙氧基硅基)丙基脲和1,1-(4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲,其结构经1H NMR,13C NMR和IR表征。     

有机硅聚合物负载硫、硫、氮三齿配体铂配合物的合成与催化性能

 N,N-双(β-甲硫乙基)γ-(三乙氧硅基)丙胺用气相法二氧化硅固载,再与氯亚铂酸钾作用,合成了三齿型铂配合物-聚γ-[N,N-双(β-甲硫乙基)胺基]丙基倍半硅氧烷铂配合物.研究了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性.     

乳化剂对聚硅氧烷乳液稳定性的影响

研究了乳化剂烷基酚聚氧乙烯醚(OP)、烷基聚氧乙烯醚和烷基季铵盐对聚硅氧烷乳液聚合的影响。采用复合乳化剂可以提高乳液稳定性。结果表明：①在以D4、N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷为原料的乳液聚合中。当非离子型乳化剂烷基聚氧乙烯醚和离子型乳化剂烷基季铵盐复合使用时,二者性能互补,产生协同效应,可使聚合物乳液具有很大的稳定性。②在实验选定的乳化剂中,非离子型烷基聚氧乙烯醚乳化剂用量为80mL(含量为0．05g／mL)、离子型烷基季铵盐乳化剂为60mL(浓度为0．05g／mL)时。其乳液的电解质稳定性、pH稳定性、冻融高温稳定性和离心稳定性等较好。     

含胺基聚硅氧烷树脂的合成及吸附性能的研究

通过烯丙基溴的硅氢化反应,合成了γ-溴丙基甲基二氯硅烷单体(A);将(A)与β-(乙酰氧基)乙基甲基二氯硅烷单体(B)共水解,得到含溴丙基的线型聚硅氧烷(C);(C)与二甲胺反应,制得含胺基的聚硅氧烷(D);(D)在氢氧化钠的催化下,使(B)链节发生β-消除同时引起交联而莸得多孔性的含二甲胺基的聚硅氧烷树脂(SAR)。测定了(SAR)一些物性及对金属离子的吸附性能。     

灯盏乙素苷元4’-N-取代氨甲基苯甲酸酯的合成及体外抗氧化活性研究

为合成具有较强神经细胞氧化损伤保护作用的灯盏乙素苷元衍生物.以灯盏乙素苷元与N-取代氨甲基苯甲酸为原料,在偶联剂N,N＇-二环己基碳酰亚胺(DCC)/4-N,N-二甲基吡啶(DMAP)的作用下制备了6种灯盏乙素苷元4′-N-取代氨甲基苯甲酸酯衍生物6a～6f,所合成的化合物均经过1H NMR,ESI-MS以及HRMS分...     

聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物的合成与催化性能

γ-氨丙基三乙氧基硅烷与丙烯腈反应，得到γ-(β-氰乙基)胺丙基三乙氧基硅烷。后者用气相法二氧化硅固载，再与氯亚铂酸钾反应，合成了聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物。研究了它对不饱和烃与三乙氧基硅烷的硅氢加成反应的催化特性。     

Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

Cross-coupling reactions of alkenylsilanolates. Investigation of the mechanism and identification of key intermediates through kinetic analysis

The mechanism of the fluoride-free, palladium-catalyzed cross-coupling reaction of potassium (E)-heptenyldimethylsilanolate, K(+)(E)-1(-), with 2-iodothiophene has been investigated through kinetic analysis. The order of each component was determined by plotting the initial rates of the reaction against concentration. These data provided a mechanistic picture which involves a fast and irreversible oxidative insertion of palladium into the aryl iodide and a subsequent intramolecular transmetalation step from a complex containing a silicon-oxygen-palladium linkage. First-order behavior at low concentrations of silanolate with excess palladium(0) complex supports the formation of this complex as the turnover-limiting step. The change to zeroth-order dependence on silanolate at high concentrations is consistent with the intramolecular transmetalation becoming the turnover-limiting step.     

D_4/N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷本体共聚反应聚合度变化的Monte Carlo模拟

用MonteCarlo方法模拟八甲基环四硅氧烷 (D4 )与N β 氨乙基 γ 氨丙基甲基二甲氧基硅烷(APAEDMS)的本体开环共聚动力学 .模拟过程采用自由体积理论简化处理扩散效应并与本征反应动力学耦合 .本征动力学常数通过模拟主要共聚基元反应得到 ,基于优化的动力学常数通过模拟从分子水平揭示D4 APAEDMS本体开环共聚反应过程主要表现为活性阴离子聚合行为 ,同时又伴有部分逐步聚合特征 .     

高分子钯络合物催化的亚胺化合物的加氢反应

制备了一系列以二氧化硅为载体的侧链上含有各种氮配位基团的聚硅氧烷-钯络合物,这些高分子钯络合物能够在常温常压下催化亚胺化合物的加氢反应并表现出不同程度的催化活性.对其中聚-(N,N-二乙酰基)-γ-氨丙基硅氧烷-钯络合物催化的亚苄基苯胺的加氢反应做了比较深入的研究,发现该催化剂在反应中是稳定的并给出唯一的加氢产物,络合物中的N/Pd原子比、反应温度以及不同底物对反应速度的影响也被报道.     

Synthesis and characterization of a series of zinc bis[(alkyl)(trimethylsilyl)amide] compounds

A series of 21 secondary (alkyl)(trimethylsilyl)amines HNR(TMS) [R = n-propyl (1), i-propyl (2), n-butyl (3), i-butyl (4), s-butyl (5), tert-butyl (6), c-pentyl (7), n-pentyl (8), i-pentyl (9), l-methylbutyl (10), 2-methylbutyl (11), 1-ethylpropyl (12), 1,2-dimethylpropyl (13), tert-pentyl (14), phenyl (15), c-hexyl (16), n-hexyl (17), N,N-dimethyl-3-aminopropyl (18), benzyl (19), n-heptyl (20), 1,1,3,3-tert-butyl (21); TMS = Si(CH3)3] has been prepared and fully characterized by elemental analyses, multinuclear (1H, 13C, 29Si, 14N) NMR, IR, UV/vis, MS, and boiling point. A new method for determination of boiling points of milligram-size samples, based on DSC (differential scanning calorimetry), is described. Each amine has been converted to the corresponding zinc bis(amide) compound Zn[N(TMS)(R)]2 [R = n-propyl (22), i-propyl (23), n-butyl (24), i-butyl (25), s-butyl (26), tert-butyl (27), c-pentyl (28), n-pentyl (29), i-pentyl (30), 1-methylbutyl (31), 2-methylbutyl (32), 1-ethylpropyl (33), 1,2-dimethylpropyl (34), tert-pentyl (35), phenyl (36), c-hexyl (37), n-hexyl (38), N,N-dimethyl-3-aminopropyl (39), benzyl (40), n-heptyl (41), 1,1,3,3-tert-butyl (42); TMS = Si(CH3)3] and subsequently fully characterized by elemental analyses, multinuclear (1H, 13C, 29Si, 14N) NMR, IR, UV/vis, MS, and TGA. The experimental IR has been compared to the computationally calculated one for compound 27. Observed trends in volatility of the compounds are discussed in the context of the dominant intermolecular forces present in the condensed phase.     

Self-catalytic cross-linking reaction and reactive mechanism studies of α-aminomethyl triethoxysilanes for α,ω-dihydroxy poly(dimethylsiloxane)

Some kinds of aminomethyl triethoxysilanes, cross-linkers of α,ω-dihydroxy poly(dimethylsiloxane) (PDMS), can act as catalyst to self-catalyze the cross-linking reaction with PDMS, as found in our studies. Three kinds of α-aminomethylsilanes, [(diethyl)aminomethyl triethoxysilane (DMTS), anilinomethyl triethoxysilane (AMTS) and cyclohexylaminomethyl triethoxysilane (CMTS)], and two kinds of γ-aminopropyl silanes, [(γ-aminopropyl triethoxysilane (APTS) and (N-β-aminoethyl)-γ-aminopropyl triethoxysilane (AATS)] were selected to study the self-catalytic cross-linking reaction and its mechanism. The reactivity of the cross-linkers determined by n-hexane extraction experiments, was found to be DMTS > CMTS ? AMTS, but APTS and AATS could not react with PDMS without catalysis. The cross-linking degree was increased with the reactivity. The results of extraction experiments and Fourier transform infra-red (FT-IR) spectra indicated that the cross-linking reaction was an equimolar reaction between the Si-OH groups and Si-OC₂H₅ groups. Formation of electron conjugation of N and Si in α-aminomethyl triethoxysilane molecules has been proposed to elucidate the mechanism of the self-catalytic cross-linking reaction. The Modulated Differential Scanning Calorimeter (MDSC) results showed that the increase of the glass-transition temperature (T_g) of the cross-linked products was dependent on the reactivity of the cross-linkers. The thermo-gravimetric analysis (TGA) results demonstrated that the thermal stabilities of the cross-linked products were also related to the reactivity and the structures of the cross-linkers.     

γ-核酸碱基取代丙基甲基二乙氧基硅烷的合成及其聚合反应研究

本文以Υ-溴丙基甲基二乙氧基硅烷分别与尿嘧啶、胸腺嘧啶、腺嘌呤和5-氟尿嘧啶进行烷基化反应,制得了四种含有核酸碱基或5-氟尿嘧啶的新型有机硅单体。通过它们的缩聚反应,合成了六种侧基含核酸碱基或5-氟尿嘧啶的聚硅氧烷。     

可聚合1,8-萘酰亚胺衍生物掺杂聚硅氧烷复合材料的合成及荧光特性

合成了3种可聚合的1,8-萘酰亚胺衍生物, 并研究了其在二甲基亚砜(DMSO)溶液中的光物理性质. 这些化合物表现出的光物理性质与其电子环境有关. 通过溶胶-凝胶法制备了可聚合1,8-萘酰亚胺衍生物与硅氧烷的共聚物. 尽管3种萘酰亚胺衍生物C-4位的取代基不同, 但在3-氨丙基三乙氧基硅烷(APTES)固凝胶中摩尔分数为0.06%时荧光强度均最大. 利用 ²⁹Si MAS NMR对合成材料进行了表征, 结果表明, 硅氧烷的缩聚程度影响材料的荧光强度, 说明材料中荧光单元的分子运动对材料的荧光性能有重要影响.     

Promotion of base-catalyzed siloxane rearrangements by dimethyl sulfoxide

The effect of small amounts (0.01%–1%) of dimethyl sulfoxide on base-catalyzed polymerization and equilibration of methylsiloxanes has been examined. The addition of 0.5% of the sulfoxide increases the rate of potassium hydroxide-catalyzed polymerization of octamethylcyclotetrasiloxane by factors of 100–1000 and amounts as low as 0.01% have a large effect when low (12 ppm) catalyst concentrations are used. The rate of basecatalyzed equilibration of hexamethyl disiloxane with octamethylcyclotetrasiloxane is similarly enhanced by dimethyl sulfoxide. The equilibration occurs rapidly at 80°C. with 0.01% of potassium hydroxide and 1% of dimethyl sulfoxide, but does not proceed at a measurable rate with potassium hydroxide alone. The combination of 0.01% potassium hydroxide and 1% dimethyl sulfoxide is more effective than 0.1% of tetramethylammonium hydroxide. The large accelerating effect of the sulfoxide is believed to be due to solvation of the cation, which promotes ionization of the metal silanolate, increasing the concentration of silanolate anions.     

Synthesis, characterization and properties of the polysiloxane-based episulfide resin

The polysiloxane episulfide resin (PSER) was synthesized through replacement of the oxygen atoms in 1,3,5,7-tetra-(3-glycidoxypropyl) tetramethylcyclotetrasiloxane (TGCS) with sulfur atoms using potassium thiocyanate (KSCN). It was characterized by FT-IR, ¹H NMR, MS and elemental analysis. The PSER resin was a low viscosity liquid, stable at room temperature. The polysiloxane episulfide resin was very reactive: a mixture of PSER and isophorondiamine gelated in a few seconds at room temperature. When m-phenylenediamine (m-PDA) or 2-ethyl-4-methylimidazole (2E4MZ) was used as curing agent, PSER exhibited higher reactivity compared with the parent polysiloxane epoxy resin. The reaction heat of the PSER resin was much lower in comparison with TGCS. The cured polysiloxane episulfide resin showed higher glass transition temperature and much lower water absorption, while the thermal stability was lower. It was found that methylhexahydrophthalic anhydride (MeHHPA) is not effective for curing the episulfide resin, although it is commonly used for curing epoxy resins.