一种新型阳离子三硅氧烷表面活性剂的合成及其表面性能

以1,2-环氧-9癸烯(ED)和1,1,1,3,5,5,5-七甲基三硅氧烷(MDHM)为原料,在氯铂酸催化下,经硅氢加成反应先制得烷基环氧基三硅氧烷(AETS),再将AETS与二乙醇胺(DEA)进行开环反应合成了一种新型阳离子三硅氧烷表面活性剂(CTSS)。 通过IR和1H NMR对CTSS的结构进行了表征,测定了CTSS的表面张力、润湿性和对pH值的稳定性。 同时对AETS及CTSS的合成条件进行了优化,优化后的工艺条件为:合成AETS的最佳条件为n(ED)∶n(MDHM)(n为物质的量)为1.1∶1,催化剂用量为n(MDHM)的0.075%,反应时间为5 h,反应温度为80 ℃;合成CTSS的最佳条件为n(AETS)∶n(DEA)=1∶1.05,反应时间3 h,反应温度80 ℃。 性能测试结果表明,CTSS在临界胶束浓度(CMC)为1.3×10-3 mol/L时,可以将水的表面张力降低至20.0 mN/m,同时具有良好的润湿性,另外,CTSS在pH值为6.5~8.0时稳定存在。     

新型三嗪类氮-硅成炭剂的合成及其热稳定性

以三聚氯氰(1)和γ-氨丙基三乙氧基硅烷(2)为原料,经亲核取代反应合成了一种新型三嗪类氮-硅成炭剂——2-氯-4,6-二(3-三乙氧基硅烷基-1-氨丙基)-1,3,5-三嗪(3),其结构和热性能经1H NMR,IR和TGA表征。考察了溶剂、缚酸剂、原料比和反应温度对3产率的影响。合成3的最佳反应条件为:以丙酮为溶剂,Na2CO3为缚酸剂,1 10 mmol,n(2)∶n(1)=2.4,于50℃反应6 h,产率98.1%。3的初始分解温度为292℃,700℃时成炭率34.5%。     

一种季铵盐双子表面活性剂的微波合成及性能研究

以四甲基丙二胺和溴代十二烷为原料,以异丙醇为溶剂,用微波辐射的方法反应合成一种季铵盐双子表面活性剂:二溴化-N,N′-二(二甲基十二烷基)丙二铵.研究了合成反应的最佳工艺条件:四甲基丙二胺与溴代十二烷的摩尔比为1.0∶ 2.2,反应时间为15分钟,反应温度为85℃,微波功率300W时,产率为70.55%.测定了不同浓度表面活性剂水溶液的表面张力,对产品的杀菌性能进行评价.结果表明:合成产品的临界胶束浓度为1.00mmol/L,杀菌率达100%时的药剂用量为40mg/L.     

新型含双长链和苄基的有机硅季铵盐的合成

以双十二胺(1)为原料,与氯化苄经取代反应制得中间体苄基双十二胺(2);2与γ-氯丙基三甲氧基硅烷(3)经季铵化反应合成了一种新型的含双长链和苄基的有机硅季铵盐(4),其结构经UV-Vis和FT-IR表征。通过正交实验L9(34)优化了2和4的反应条件。合成2的最佳工艺条件为:以乙腈为溶剂,1 5 mmol,n(1)∶n(Bn Cl)=1.0∶1.2,回流反应20 h,收率80.4%。合成4的最佳工艺条件为:以乙二醇为溶剂,2 5mmol,n(2)∶n(3)=1.0∶1.6,于110℃密闭反应80 h,收率57.8%。     

聚醚改性硅氧烷的合成

利用低含氢硅油与端烯丙基聚氧烯醚进行硅氢加成反应合成了不含活泼氢的聚醚改性硅氧烷(1),羟值52.5 mgKOH·g-1,其结构经IR表征.由正交试验得到合成1的较佳反应条件为:n(Si-H):n(C=C)=1.0:1.1,催化剂H2PtCl6 20 mg·kg-1,于110℃反应3,5 h.     

H_2SO_4/AC无溶剂催化合成香豆素衍生物

以浓硫酸改性活性炭[H2SO4/AC(Cat)]为催化剂,在无溶剂条件下,取代酚和乙酰乙酸甲酯(2)经Pechmann缩合反应合成了5个香豆素衍生物,其结构经1H NMR,13C NMR和IR确证。以间甲酚(1a)和2合成4,7-二甲基香豆素(3a)为例,考察原料配比[r=n(1a)∶n(2)]、反应温度、Cat用量及反应时间对Pechmann反应的影响。在最佳反应条件[1a 5 mmol,r=1.0∶2.0,Cat 18%,于120℃反应3 h]下,3a收率80%。     

由聚乙烯醇醇解液合成苄氧胺盐酸盐

首次采用聚乙烯醇醇解废液(Ⅰ,其中乙酸甲酯含量71%,甲醇含量28%)、盐酸羟胺(2)和氯化苄(4)为原料,经酰胺化、醚化和水解反应合成了苄氧胺盐酸盐,纯度99.3%,总收率90.2%,其结构经IR确证。分别采用L9(33)和L9(43)正交实验对酰胺化反应和醚化反应条件进行优化。最佳酰胺化反应条件为:2 70 mmol,n(2)∶n(Ⅰ)∶n(NaOH)=1.00∶2.03∶2.00,于40℃反应3 h,收率95.3%。最佳醚化条件为:乙酰氧肟酸(3)70 mmol,n(3)∶n(4)=1.00∶1.05,DMF 30 mL,于90℃反应5 h,收率92.0%。     

季铵盐阳离子双酯表面活性剂CDESA的合成研究

以三甲胺、环氧氯丙烷、硬脂酸和硬脂酰氯为原料,在超声条件下反应合成了季铵盐阳离子双酯表面活性剂N,N,N-三甲基-2,3-硬脂酰氧基丙基氯化铵(CDESA)。采用控制单一变量法对CDESA的最佳合成条件进行了探究,实验得出CDESA的最佳合成条件为:超声水浴振动下,n(CMESA)∶n(硬脂酰氯)=1.5∶1.0,反应溶剂为1,4-二氧六环,p H=8,反应时间为3.0 h,反应温度85℃,CDESA的产率达94.39%,熔点为152.2~153.2℃。通过红外光谱和元素分析对CDESA进行了结构表征。     

壬基酚甜菜碱两性表面活性剂的合成和抗温耐盐性能

以壬基酚、环氧氯丙烷、二甲胺和3-氯-2-羟基丙磺酸钠为原料, 在催化剂的作用下经醚化、叔胺化、季铵化, 合成了壬基酚甜菜碱两性表面活性剂(NSZ), 并确定了最佳的反应条件。 壬基酚氯醇醚的最佳合成条件:物料比n(壬基酚):n(环氧氯丙烷)=1:4, 催化剂四丁基溴化铵用量为壬基酚用量的4%(摩尔比), 反应时间为4 h, 反应温度为95 ℃。 壬基酚叔胺的最佳合成条件:物料比为n(壬基酚氯醇醚):n(二甲胺):n(氢氧化钠)=1:2.5:1.1, 反应时间为4 h, 反应温度为60 ℃。 NSZ的最佳合成条件:以异丙醇/水为溶剂且其体积比为2:1, 反应温度为85 ℃, 反应时间24 h, n(3-氯-2羟基丙磺酸钠):n(壬基酚叔胺)=1.2:1, 反应体系的pH值为8~9。 通过测定NSZ在高温高矿化度条件下的界面性能、乳化性能和热稳定性, 证明了NSZ具有良好的耐温抗盐性能。     

壬基酚聚氧乙烯醚型Gemini季铵盐表面活性剂的合成 及其表面性质的研究

合成了系列壬基酚聚氧乙烯醚型Gemini季铵盐表面活性剂(GNPQA), 用核磁、红外和元素分析对它们的结构进行了表征, 考察了反应条件对转化率的影响, 并用表面张力法和稳态荧光探针法对GNPQA的表面性能及胶束聚集数(N)进行了研究. 结果表明, 较优的反应条件: 反应时间为12 h, 反应温度为70 ℃, 反应原料摩尔比为n(双聚壬基酚聚氧乙烯醚)∶n(三乙胺)∶n(环氧氯丙烷)＝1∶1∶1; GNPQA的临界胶束浓度(CMC)值较相应的单体壬基酚聚氧乙烯醚型季铵盐表面活性剂(NPQA)降低了1～2个数量级, 显示了较高的表面活性; 当GNPQA溶液浓度为5～9倍CMC时, N值随浓度增大而线性增大; 随着氧乙烯(EO)单元数的增长, GNPQA的CMC和N值均逐渐减小; 结合GNPQA的表面性能参数和N值的变化规律, 探讨了这类表面活性剂表面及胶束聚集体的结构形态.     

Synthesis and characterization of new cationic hexacoordinate silanes

The reaction of N,N,N',N"-pentamethyldiethylenetriamine (pmdeta) with HSiCl3 and H2SiCl2 in dry CH2Cl2 affords the novel cationic intermolecular hexacoordinate silanes [pmdeta.HSiCl2]+Cl- (1) and [pmdeta.H2SiCl]+Cl(2), respectively. The addition of N,N,N',N',N"-pentaethyldiethylenetriamine (pedeta) to a solution of HSiCl3 in dry CH2Cl2 gives the redistribution product formulated as the salt [pedeta.H2SiCl]+Cl- (3) and SiC4. Treatment of H2SiCl2 with pedeta and N,N,N',N',N",N"'-hexamethyltriethylenetetramine (hmteta) produces [pedeta.H2SiCl]+Cl(3) and [hmteta.H2SiCl]+C1- (HCl) (4). In 4, the fourth amine is not bonded to silicon. Reactions of 2, 3, and 4 with NaBPh4 give the ion exchange products [pmdeta.H2SiC1]+BPh4- (5), [pedeta.H2SiCl]+BPh4- (6), and [hmteta.H2SiCl]+BPh4- (HCl) (7), respectively. The salts 1, 5, 6, and 7 were characterized by single-crystal X-ray diffraction analysis. Most notable is that the cations in 1, 5, 6, and 7 are slightly distorted octahedra in which two hydrogen atoms are at the trans positions. The reactions of 3 with tmeda and pmdeta afford the intermolecular ligand exchange products tmeda.H2SiCl2 and 2, respectively.     

Synthesis of Novel Carbosilane Dendrimers Based on Pentaerythritol

Novel pentaerythritol-based carbosilane dendrimers centered at carbon have been synthesised. Starting from tetraallyl ether based upon pentaerythritol as the core molecule, a succession of alternate Pt-catalyzed hydrosilylation of allyl groups with HSiC13 and allylations of SiC1 groups thus introduced with CH2=CHCH2MgBr in THF provided a divergent synthesis of three generations of carbosilane dendrimers in which the Si atoms are linked by CH2CH2CH2 groups. The reaction conditions for hydrosilylation must be well controlled. After purification by chromatography on silica gel pure products for each generation were obtained. The IR, ^1H and ^13C NMR spectra and elemental analysis data are consistent with the proposed structures. The molecular weights of the resulting carbosilne dendrimers have been determined by vapor pressure osmometry.     

聚甲基硅烷的合成与封端

利用Wurtz反应合成聚甲基硅烷 ,研究两类溶剂对其组成、分子结构和分子量的影响 .FT IR和1 H NMR及2 9Si NMR分析表明 ,以甲苯为溶剂 ,可以避免在溶剂化过程中Kumada重排的发生 ;而以THF 正己烷 (1∶6 ,V V)为溶剂 ,聚甲基硅烷容易支化和形成Si—CH2 —Si结构 .研究发现 ,聚甲基硅烷具有复杂的端基结构 ,封端剂的加入量影响着最终合成聚甲基硅烷的质量 .     

介孔分子筛Al-MCM-41接枝三甲基氯化锡的合成、表征及催化性能

将三甲基氯化锡与Al-MCM-41介孔分子筛在N2气气氛中135 ℃回流4.5 h,得到表面键合有机锡的分子筛(CH3)3Sn-O-MCM-41[(CH3)3SnM]。 采用电感耦合等离子体质谱（ICP-MS）、有机元素分析、红外光谱、N2吸附-脱附、热重分析（TG）、NH3程序升温脱附（NH3-TPD）、X射线多晶衍射（XRD）和透射电子显微镜等测试技术对样品的组成、结构和表面物理化学性质进行表征。 结果表明,有机锡接枝率可达14.44%;接枝前后分子筛的NH3-TPD表面酸量(NH3)由0.652 6 mmol/g增加至1.294 4 mmol/g。 接枝后分子筛的比表面积减小,孔容变大,孔径变小,仍保持六方介孔结构;接枝分子筛(CH3)3SnM用于催化合成乙酸异戊酯,当n(异戊醇)∶n（冰乙酸）=1.0∶1.0,w（催化剂）=5%,138 ℃,回流5 h,反应转化率为96%;催化剂重复使用5次,酯化转化率仍可达到86%。     

多肽在金纳米粒子表面偶联反应效率研究

通过1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)与N-羟基琥珀酰亚胺(NHS)活化反应将多肽偶联到金纳米粒子表面,采用荧光光谱研究其形成的酰胺键的反应偶联效率.考察了实验条件,包括缓冲液的种类(HEPES、Tris-HCl、硼酸、PBS缓冲液)、pH值(pH 6.5~9.0)、缓冲液浓度(10, 25, 40和50 mmol/L)、NHS和EDC的浓度(NHS 0.2~1.0 mol/L,EDC 0.01~0.5 mol/L)及二者比例(0,0.5,1.0,2.0和2.5)、偶联反应时间(4, 8, 12, 24和36 h)等对偶联效率的影响,筛选出最佳实验条件.实验结果表明, 25 mmol/L 4-羟乙基哌嗪乙磺酸(HEPES)缓冲液(pH 7.0), NHS/EDC浓度为0.4 mol/L/0.2 mol/L和24 h的反应时间为EDC-NHS活化反应将多肽偶联到金纳米粒子上的最佳实验条件.本研究结果可为相关研究提供技术参考.     

Theoretical investigation of the mechanisms and stereoselectivities of reductions of acyclic phosphine oxides and sulfides by chlorosilanes

Computational studies were performed to explain the highly varied stereoselectivities obtained in the reductions of acyclic phosphine oxides and sulfides by different chlorosilanes. The reductions of phosphine oxides by HSiCl(3), HSiCl(3)/Et(3)N, and Si(2)Cl(6) and the reductions of phosphine sulfides by Si(2)Cl(6) (all in benzene) were explored by means of B3LYP, B3LYP-D, and SCS-MP2 calculations. For the reductions of phosphine oxides by HSiCl(3), the calculations support the mechanism proposed by Horner in which a hydride is transferred from silicon to phosphorus through a four-centered, frontside transition state. This mechanism leads to retention of stereochemistry at phosphorus. For the other three reductions, two classes of mechanisms were explored. Phosphorane-based mechanisms that were previously proposed by Mislow and involve SiCl(3)(-) were compared with novel alternative mechanisms that involve nonionic rearrangement processes. In one of these, donor-stabilized SiCl(2) is formed as an intermediate. The calculations support a phosphorane-based mechanism for the reductions of phosphine oxides by HSiCl(3)/Et(3)N and Si(2)Cl(6) (which proceed with inversion) but favor the rearrangement pathways for the reductions of phosphine sulfides by Si(2)Cl(6) (which proceed with retention).     

4，5-环氧-α-紫罗兰酮的合成研究

研究以H2O2为氧化剂,钨酸钠／磷酸／十六烷基氯化毗啶原位合成的过氧钨配合物催化α-紫罗兰酮合成4,5-环氧-α-紫罗兰酮的反应,考察了催化剂用量、反应温度、反应时间、pH值、溶剂及季铵盐等因素对反应的影响。结果表明,以1,2-二氯乙烷作溶剂,nα-紫罗兰酮：n钨酸钠：n磷酸：n十六烷基氯化吡啶：n过氧化氢=100：0.3：0．1：0．2：120,pH值为4．0,65℃的条件下反应6h,收率可达85％,其结构通过MS、^1H-NMR、IR、EA等检测技术进行表征。     

Strong intramolecular Si-N interactions in the chlorosilanes Cl3-nHnSiOCH2CH2NMe2 (n = 1-3)

The compounds Cl 3SiOCH 2CH 2NMe 2 ( 1) and Cl 2HSiOCH 2CH 2NMe 2 ( 2) were prepared by reactions of lithium 2-(dimethylamino)ethanolate with SiCl 4 and HSiCl 3. The analogous reaction with H 2SiCl 2 gave ClH 2SiOCH 2CH 2NMe 2 ( 3), but only in a mixture with Cl 2HSiOCH 2CH 2NMe 2 ( 2), from which it could not be separated. All compounds were characterized by IR and NMR ( (1)H, (13)C, (29)Si) spectroscopy, 1 and 2 by elemental analyses and by determination of their crystal structures. Cl 3SiOCH 2CH 2NMe 2 ( 1) and Cl 2HSiOCH 2CH 2NMe 2 ( 2) crystallize as monomeric ring compounds with pentacoordinate silicon atoms participating in intramolecular Si-N bonds [2.060(2) A ( 1), 2.037(2) A ( 2)]. The dative bonds in 1 and 2 between the silicon and nitrogen atoms could also be proven to exist at low temperatures in solution in (1)H, (29)Si-HMBC-NMR experiments by detection of the scalar coupling between the (29)Si and the protons of the NCH 2 and NCH 3 groups. A function describing the chemical shift delta exp (29)Si dependent on the chemical shifts of the individual equilibrium components, the temperature, and the free enthalpy of reaction was worked out and fitted to the experimental VT-NMR data of 1 and 2. This provided values of the free reaction enthalpies of Delta G = -28.8 +/- 3.9 kJ x mol (-1) for 1 and Delta G = -22.3 +/- 0.4 kJ x mol (-1) for 2 and estimates for the chemical shifts of open-chain (index o) and ring conformers (index r) for 1 of delta r = -94 +/- 2 ppm and delta o = -36 +/- 5 ppm and for 2 of delta r = -82 +/- 1 ppm and delta o = -33 +/- 4 ppm. The value of delta r for 1 is very close to that obtained from a solid-state (29)Si MAS NMR spectrum. Quantumchemical calculations (up to MP2/TZVPP) gave largely differing geometries for 1 (with a Si...N distance of 3.072 A), but well reproduced the geometry of 2. These differences are due to Cl...H and Cl...C repulsions and solid state effects, which can be modeled by conductor-like screening model calculations and also rationalized in terms of the topology of the electron density, which was analyzed in terms of the quantum theory of atoms in molecules.     

Cr2O3催化剂上甲烷部分氧化制备合成气

分别采用柠檬酸络合法和直接分解法制备了Cr2O3催化剂, 采用XRD, BET, TPR, XPS, TEM和TGA表征了催化剂的物理化学性质, 在常压固定床石英管(内径5 mm)反应器中考察了Cr2O3催化剂对甲烷部分氧化反应的催化性能. 在500~750 ℃, V(CH4)∶V(O2)=2, 空速12×104 h-1的条件下, O2几乎完全转化, CH4转化率及H2和CO选择性随着温度的升高而增加. 700 ℃下CH4转化率及H2, CO选择性随着空速(6.0×104~24×104 h-1)的升高而增加. 在500 h稳定性实验中, 随着反应时间的延长, CH4转化率及H2, CO选择性缓慢下降, XRD, TEM和BET结果表明, 催化剂的活性下降与烧结和团聚有关, TGA分析表明催化剂具有良好的抗积炭性. 通过CH4脉冲反应, 推测在反应过程中CO, H2, CO2和H2O是直接生成的.