γ-取代丙基环四硅氧烷的合成及其与D_4的乳液共聚反应

本文合成了四种γ-取代丙基环四硅氧烷。通过阳离子型和阴离子型乳液共聚的方法,分别使其与八甲基环四硅氧烷共聚,合成了含有γ-羟丙基、γ-氯丙基和γ-乙酰氧丙基等活性碳官能团有机硅聚合物的稳定乳液;研究了乳液共聚反应过程中的单体转化率、聚合物分子量的变化以及温度、催化剂、乳化剂、取代基团等因素的影响。     

有机硅微乳液的研究进展

近年来大量研究表明,有机硅微乳液与有机硅乳液相比,具有许多优异的性能,如优异的热稳定性、渗透性等。本文主要阐述了有机硅微乳液的形成原理、制备方法及制备过程中的影响因素。在有机硅微乳液的形成原理里,详细介绍了增溶理论和界面张力理论;在有机硅微乳液的制备中,着重讨论了表面活性剂、助表面活性剂、催化剂等对有机硅微乳液形成的影响。     

硅氧烷乳液聚合过程中大颗粒形成机理的研究Ⅱ．聚硅氧烷乳液的耐酸碱稳定性

研究了阴离子型与阳离子型聚硅氧烷乳液的耐酸碱稳定性。发现阴离子型乳液对酸碱都相当稳定，在乳液制备过程中，酸性催化剂不会引起乳液颗粒的凝聚；而阳离子型乳液的耐酸碱稳定性较差，尤其是引起乳液颗粒慢速凝聚的碱浓度下限值很低，碱是制备阳离子型乳液的催化剂，碱引起乳液颗粒的慢速凝聚是阳离子型乳液中大颗粒形成的主要原因。在乳液聚合过程中所发生的相当部分的乳化剂从水相向有机硅相的转移也是影响阳离子型乳液稳定性的一个重要因素。     

硅氧烷乳液聚合过程中大颗粒形成机理的研究：Ⅱ.聚硅氧烷乳液的耐酸碱…

研究了阴离子型与阳离子型聚硅氧烷乳液的耐酸碱稳定性，发现阴离子型乳液对酸碱都相当稳定，在乳液制备过程中，酸性催化剂不会引起乳液颗粒的凝聚；而阳离子型乳液的耐酸三稳定性性差，尤其是引起乳液颗粒慢速凝聚的碱浓度下限值很低，碱是制备阳离子型乳液的化剂，碱引起乳液颗粒的慢速凝聚是阳离子型乳液中大颗粒形成的主要原因，在乳液聚合过程中所发生的相当部分的乳化剂从水相向有机硅相的转移也是影响阳离子型乳液稳定性的一     

八甲基环四硅氧烷阴离子乳液聚合反应的研究

有机硅高分子乳液在工业上有很广泛的应用,例如用作织物处理剂、润滑剂、涂层等。经有机硅高分子乳液处理后的纺织品,可以提高柔软、防皱、防缩、手感等诸方面性能。用机械设备乳化本体聚合的有机硅高聚物制得的乳液往往不够理想;而用乳液聚合方法制备的有机硅乳液,其颗粒小而均匀, 稳定性好, 有利于提高乳液的应用效果     

有机硅改性丙烯酸酯乳液的流变性

聚合物乳液;流变性能;反应性乳液;有机硅改性丙烯酸酯乳液的流变性     

有机硅核-壳型聚丙烯酸酯乳液的合成及油田固砂性能研究

有机硅核-壳型聚丙烯酸酯乳液的合成及油田固砂性能研究;聚丙烯酸酯乳液;有机硅改性;固砂;渗透率     

反应性乳化剂对有机硅-丙烯酸酯乳液共聚合的影响

有机硅改性丙烯酸酯;乳液聚合;反应性乳化剂对有机硅-丙烯酸酯乳液共聚合的影响     

有机硅改性聚氨酯丙烯酸酯细乳液的制备及性能

将自制的聚氨酯大单体与含乙烯基有机硅单体、丙烯酸酯进行共聚反应,通过合适的工艺条件,制备了一系列性能稳定的细乳液。研究了聚合方法、有机硅含量对共聚细乳液及胶膜性能的影响。结果表明,种子细乳液法制得的聚合物结构明确,细乳液粒径均在150 nm左右,分布指数约为0.07,有机硅的引入使乳液胶膜耐水性及耐高温性得到了明显提高。     

有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究

用一次投料法、单体乳液滴加法和引发剂滴加法有机硅改性丙烯酸酯共聚乳液，聚合过程、胶粒形态及乳液稳定性的观测结果表明：单体乳液滴加法是合成该类乳液的最佳方法，研究了单体乳液滴加法中有机硅含量与聚合反及胶膜性能的关系，结果表明：有机硅含量在１５％以下时，聚合反应可以顺利进行，胶膜性能不仅依赖于聚合时有机硅单体的总量，而且还依赖于有机硅单体中活性硅氧烷所占的比例。     

八甲基环四硅氧烷阴离子乳液聚合反应的研究

研究了八甲基环四硅氧烷(D_4)在十二烷基本磺酸(DBSA)及其钠盐(Na-DBSA)作用下的阴离子乳液聚合反应,讨论了温度、乳化剂和催化剂用量对反应速度及聚合物分子量的影响。认为该聚合反应包括D_4的水解开环、D_4和羟基硅氧烷的加成及羟基硅氧烷之间的缩合三类基本反应,乳液颗粒表面是主要反应区。     

硅氧烷乳液聚合的研究Ⅲ.八甲基环四硅氧烷在阳离子乳液聚合过程中乳液颗粒的形成

八甲基环四硅氧烷(D_4)在阳离子乳液聚合过程中,首先被乳化成颗粒较大的“过渡粒子”,在这里以D_4的水解开环和加聚反应为主,然后转变为颗粒较小的稳定乳液粒子。聚合物端基≡SiOH的缩合反应主要在乳液粒子中进行。     

POLYMERIZATION OF OCTAMETHYLCYCLOTETRASILOXANE WITH HEXAMETHYLDISILAZYL-LITHIUM AS INITIATOR*

 This work focused on the anionic polymerization of octamethylcyclotetrasiloxane (D₄, D = Me₂SiO_2/2) initiated by a new kind of initiator hexamethyldisilazyl-lithium (MM^NLi). ²⁹Si-NMR spectroscopy and gas chromatography (GC) were used to characterize the polymerization products. The process was accelerated by adding a small amount of high activity monomer D₃ and by raising the polymerization temperature. At the end of polymerization more than 95% of the monomer was converted to polymer and only a very small amount ofD₄ and D₅ remained in the polymers.     

硅氧烷乳液聚合的研究——Ⅱ.八甲基环四硅氧烷阳离子乳液聚合机理

根据八甲基环四硅氧烷(D_4)在阳离子乳液聚合过程中,聚合物的分子量及数目的变化等特点,提出并证明了D_4在乳液粒子表面进行聚合的机理的假设。     

四氢呋喃开环聚合的研究——Ⅲ.本体聚合的总生长反应速度常数

用溴丙烯-高氯酸银或癸二酰氯-高氯酸银引发四氢呋喃在0℃进行本体聚合,测得总生长反应速度常数(k_p)分别为0.32×10~(-3)及0.38×10~(-3)升·克分子~(-1)·秒~(-1)。这样低的k_p值认为是由于ClO_4~-抗衡负离子具有强的亲核性所致。在溴丙烯-高氯酸银催化体系配此中加大银盐用量(到过量51％),引发诱导时间缩短,聚合速度加快,而k_p值的增大不明显。     

己内酰胺与环硅氧烷阴离子开环共聚合——Ⅱ.聚合反应过程研究

 研究探讨了己内酰胺和八甲基环四硅氧烷两种完全不同的环单体的共聚过程。在反应初期,环硅氧烷快于己内酰胺而先聚合,随后己内酰胺很快达高转化率。随聚合反应时间延长和环硅氧烷单体配比的增加,共聚体中的硅氧烷含量都相应增加。研究提出并证实了聚合过程中的一些主要反应,并由此推断了共聚产物的结构表达式。     

STEREOELECTRONIC PROPERTIES OF PHOTOSYNTHETIC AND RELATED SYSTEMS—VIII. AB INITIO QUANTUM MECHANICAL CHARACTERIZATION OF THE ELECTRONIC STRUCTURE AND SPECTRUM OF THE BACTERIOPHEOPHORBIDE a ANION RADICAL

Ab initio configuration interaction wavefunctions and energies are reported for 16 doublet states of the anion radical of ethyl bacteriopheophorbide a (Et-BPheo a^-˙), and are employed in an analysis of the electronic absorption spectrum. The lowest excited doublet state D₁ is predicted to lie 8601 cm^-1 above the ground state D₀; the D₁← D₀ transition is nearly forbidden, with a computed oscillator strength f= 0.002. The visible absorption spectrum is shown to consist of transitions to three ²(π, π*) states, D₂, D₃, and D₄. The D₄← D₀ transition (y-polarized, f= 0.91) appears to account for observed intense absorption at 15 800 cm^-1. The Soret band of Et-BPheo a^-˙ is shown to consist of transitions to several ²(π,π*) states, D₇-D₁₅. Transitions of particularly high intensity include D₇← D₀ (y-polarized, f= 0.72), D₁₀← D₀ (y-polarized, f= 1.1), D₁₂← D₀ (xy-polarized, f= 0.86) and D₁₅← D₀ (y-polarized, f= 0.83). Spin density data and plots are used to describe and compare the general features of the unpaired spin distributions in D₀ and D₁, which are in reasonable agreement with other reported calculated values and available experimental data for D₀.     

HIGHLY ACTIVE CATALYTIC STEREOSPECIFIC POLYMERIZATION OF STYRENE

A novel highly active catalyst of TiCl_4/MgCl_2--Al(C_2H_5), system (called SN-1 catalyst, in whichrare earth compound NdCl_3, is included) was used for studying stereospecific polymerization of styrenein benzene solution. Highly isotactic polystyrene was prepared with far better yield and higher cataly-tic efficiency than the results ever reported in literatures. The influences of concentration of mono-mer, catalyst, triethyaluminum as well as polymerization temperature on the catalytic efficiency, yield,tacticity and molecular weight of polystytene have been investigated.     

UV LASER INITIATED STEREOSELECTIVE HOMOGENEOUS CATALYSIS POLYMERIZATION OF PHENYLACETYLENE

In this paper, the stereoselective homogeneous catalysis polymerization of phenylacetylene by using two kinds of catalysts W(CO)_5CH_3I and W(CO)_4I_2 produced from UV laser photolysis of W (CO)_6 in CH_3I, I_2—C_6H_6 and CHI_3—C_6H_6 respectively was studied. The effects of laser energy, laser irradiation time and lifetime of catalyst on the polymerization of phenylacetylene were discussed. The photoproducts of W (CO)_6 in CH_3I, I2—C_6H_6 and CHI_3—C_6I_6 were determined by IR spectra. The structures of polyphenylacetylene obtained by W (CO)_5CH_3I and W (CO)_4I_2 catalysts were characterized by IR spectra and ~1H NMR spectra.     

"CAGE" VANADYL POLYCARBOXYLATE-THIOUREA COMPLEX FOR THE POLYMERIZATION OF ACRYLONITRILE

The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by " cage " vanadyl polycarboxylate (P=VO)-thiourea (TU) complex was investigated. The overall rate ofpolymerization isThe relationship between the induction period (τ) and the temperature of polymerization as well as the concentrations of reactants can be expressed as follows :The molecular weight of polyacrylonitrile increases with increasing monomer concentration and decreases with increasing temperature of polymerization and concentrations of vanadyl polycarboxylate and thioureaThe polymerization mechanism was proposed and discussed.