EFFECT OF POLYMERIZATION CONDITIONS ON THE LADDERLIKE STRUCTURE OF POLYPHENYLSILSESQUIOXANE

The ladderlike structure of PPSQ synthesized by using four kinds of catalysts (MgF_2,LiF, KOH and DCC) at different polymerization conditions has been investigated by IRand NMR. In the system using MgF_2 as the main catalyst, the most important factorwhich affects the ladderlike structure of PPSQ is the composition of the dual catalysts,MgF_2 and DCC. PPSQ prepared by using KOH as the catalyst has the highest regularityof ladderlike structure among all samples. PPSQ with different degree of ladder regularitycan be obtained by choice of polymerization conditions.     

Epoxy resin containing polyphenylsilsesquioxane: Preparation,morphology, and thermomechanical properties

Polyphenylsilsesquioxane (PPSQ) was incorporated into an epoxy resin to prepare organic–inorganic composites, and two strategies were adopted to afford composites with different morphologies. Phase separation induced by polymerization occurred in the physical blending system. However, nanostructured composites were obtained when a catalytic amount of aluminum triacetylacetonate was added to mediate the reaction between PPSQ and diglycidyl ether of bisphenol A (DGEBA). The intercomponent reaction significantly suppressed the phase separation on the micrometer scale. Organic–inorganic composites with different morphologies displayed quite different thermomechanical properties. Both differential scanning calorimetry and dynamic mechanical analysis showed that the nanostructured composites possessed higher glass‐transition temperatures than the phase‐separated composites with the same loading of PPSQ, although the intercomponent reaction between PPSQ and DGEBA reduced the crosslinking density of the epoxy matrix. This result was ascribed to the presence of nanosized PPSQ domains in the nanostructured composites, which acted as physical crosslinking sites and thus reinforced the epoxy networks. The nanoreinforcement of the PPSQ domains afforded the enhanced dynamic storage modulus for the nanostructured composites in comparison with the phase‐separated composites with a PPSQ concentration less than 15 wt %. In terms of thermogravimetric analysis, the organic–inorganic composites displayed improved thermal stability and flame retardancy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1093–1105, 2006     

PHASE STRUCTURE AND COMPATIBILITY OF LADDERLIKE POLYPHENYLSILSESQUIOXANE (PPSQ)/POLYCARBONATE (PC) BLENDS PREPARED BY SOLUTION CASTING*

Blends of PC and PPSQ (A) with high M_w and good ladderlike regularity or PPSQ(B) withlow M_w and more defective Si-atoms in its structure have been prepared by solution casting. Thedispersed spheres (PPSQ(A)-rich) are unevenly dispersed in the continuous PC-rich phase and there isno phase-inversion as PPSQ(A) content increases when the percentage of PPSQ(A) is not more than70%. PPSQ(B)-rich spheres are evenly dispersed in the continuous phase (PC-rich) and phase-inversion occurs when PPSQ(B) percentage is up to 70%. T_g of PPSQ(A)/PC or PPSQ(B)/PC at somecompositions are lower than that of pure PC due to the enlarged free-volume of PC-rich phase becausesome spheres of rigid PPSQ chains are included in the PC-rich phase. PC and PPSQ(A) or PPSQ(B)are partially compatible. The compatibility of PC and PPSQ(B) is better than that of PC and PPSQ(A)with high M_w and good ladderlike regularity. Heat history has some influence on the T_gs andcompatibility of PPSQ(A)/PC and PPSQ(B)/PC blends.     

STUDY ON PYROLYSIS OF POLYPHENYLSILSESQUIOXANE

X-ray photoelectron spectroscopy and Raman spectroscopy were used to determine the chemical change ofpolyphenylsilsesquioxane (PPSQ) during pyrolysis in flowing nitrogen. Two temperature ranges were found for pyrolysedPPSQ below and above 600℃, respectively. The former is related to the rearrangement of PPSQ backbone and the latterreflects that most of backbone structure of PPSQ might be broken down and unorganized. Carbon formed in carbonization ofPPSQ sample pyrolysed at 900℃ should be sp~3 bonded carbon with crystallite size effects or defects.     

镍基气凝胶催化CH4-CO2重整制取合成气反应的研究 Ⅲ.影响催化剂积碳性能因素的探讨

考察了823K焙烧的干凝胶xNCA550、气凝胶aNCA550及浸渍型催化剂iNCA550在923K、1073K、1173K反应温度下的积碳行为，对催化剂表面碳的活性及类型进行了分析，并探讨了影响催化剂积碳的因素。实验结果表明，随反应温度的提高，催化剂的积碳能力减弱，尤以气凝胶催化剂aNCA550明显。催化剂的积碳主要发生在反应的初期，反应温度越高，到达积碳量相对稳定期所需要的时间越短；随着反应时间的延续，催化剂积碳量缓慢增长，并且表面碳的活性降低。催化剂的酸性和镍晶粒大小是影响其积碳性能的主要内在因素，而它们对积碳的影响程度受反应温度的影响，反应温度越高，催化剂表达酸性中心利于积碳的作用越小，小晶粒镍抑制催化剂积碳的能力越强。     

镧配位催化N-十八烷基马来酰亚胺均聚合

N-取代马来酰亚胺聚合物中的酰亚胺环为平面五元环结构,阻碍了酰亚胺单元绕聚合物主链的旋转,限制了聚合物主链的运动,使聚合物的热性能和化学稳定性得到了很大的提高．近些年来,有关N-取代马来酰亚胺均聚合研究的报道已经有很多,但大多采用自由基聚合方法和负离子聚合方法,采用配位催化聚合方法很少．     

RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS*

Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry.     

甲基丙烯酸甲酯 - 甲基丙烯酸共聚物/梯形聚苯基硅倍半氧烷原位共混体系的性能研究

甲基丙烯酸甲酯 甲基丙烯酸共聚物（Ｐ（ＭＭＡ ＭＡＡ））与低分子量或高分子量梯形聚苯基硅倍半氧烷（ＰＰＳＱ）的共混物经原位聚合法制成．用光学透明法、荧光光谱、ＤＳＣ等技术研究了该共混体系的相容性及组分间的相互作用及结构转变．结果表明，当ＰＰＳＱ含量较小时，由于ＰＰＳＱ与Ｐ（ＭＭＡ ＭＡＡ）间存在着较强的氢键作用，该共混体系在一定配比下相容，且低分子量ＰＰＳＱ与Ｐ（ＭＭＡ ＭＡＡ）间的相容性较好．当ＰＰＳＱ的含量≤１％时，ＰＰＳＱ的加入对该共混物的Ｔｇ影响不大，但其Ｔｆ随ＰＰＳＱ含量增加而增大．此外，还测试了Ｐ（ＭＭＡ ＭＡＡ）／ＰＰＳＱ原位共混物的硬度及冲击强度．     

Schiff碱镧配合物的合成及其催化烷基异氰酸酯聚合

通过氯化镧与Schiff碱钠盐(NaSalen)的交换反应制备了4种镧的Schiff碱配合物La(HSalen1-4)3,对其中以3,5-二叔丁基水杨醛缩苯胺为配体的配合物La(HSalen2)3进行了X-射线单晶衍射分析,测定其单晶结构为五角双锥构型,七配位的镧金属中心与氮和氧原子相连.将所得的La(HSalen)3...     

硅倍半氧烷改性聚酰亚胺(PI/Si)复合膜性能简

通过在聚酰亚胺(PI)中分别添加笼型八氨基苯基硅倍半氧烷(OAPS)、笼型八苯基硅倍半氧烷(OPS)、梯形聚苯基硅倍半氧烷(PPSQ)和无机纳米SiO2,制备了4种含硅聚酰亚胺(PI/Si)复合膜. 对PI/Si复合膜的相容性、力学性能、热性能和阻燃性能进行了研究. 结果表明,OAPS与PI间展现出较好的相容性,PPSQ次之,而OPS,SiO2与PI的相容性较差;但相容性与复合膜的力学和热性能无明显的对应关系. SiO2可提高PI的力学性能;PI/OAPS复合膜的Tg最高;OAPS,PPSQ或SiO2的加入使PI复合膜的热稳定性稍有提高,而少量OPS的加入大大降低PI膜的热稳定性. 这类PI/Si复合膜的显著特点是能够大幅提高PI膜的极限氧指数,含硅化合物能够增加PI燃烧后残炭量,使残炭的形貌得到显著改善. PI/Si复合膜在燃烧过程中在表面形成一层白色含硅包裹层,起到隔热隔氧及保护内层有机物不被燃烧的作用. 硅倍半氧烷对炭层形貌的改善显著,展现出比SiO2更好的阻燃性能.     

Low molecular weight by-products in the Ziegler polymerization of higher terminal olefins

For the polymerization of n-octadecene-1 with catalysts derived from titanium tetrachloride and triethylaluminum, it has been shown that, in addition to polymerization of the olefin, the formation of isomerized olefin occurs. The latter is predominantly trans-n-octadecene-2 and its formation is favored by increase in Al:Ti mole ratio, in catalyst concentration, and in reaction temperature. It has also been shown that 1,1-disubstituted ethylene is present in the nonpolymeric reaction products. The influence of added trans-n-octadecene-2 or trans-n-octadecene-7 on the polymerization of n-octadecene-1 has been studied, and it is shown that the 2-isomer has the more pronounced effect on polymer yield and intrinsic viscosity. It has also been shown that no significant copolymerization of terminal with nonterminal octenes or octadecenes occurs under these conditions. Results indicate that, in polymerizations of this kind, the interaction of catalyst with isomerized monomer is probably an important factor in determining polymer yield and molecular weight. The isomerization reaction is also of interest as a general preparative method for trans-2-olefins.     

配位催化苯乙烯乳液聚合的动力学研究

以Ni(COD)2和含磷、氧配体为催化剂,利用乳液聚合法合成了间规聚苯乙烯.对产物进行了13C-NMR、1H-NMR、GPC、TEM、DSC、TG等表征.在此反应体系下,最佳聚合条件为:乳化剂用量为1.50 g,[St]0=1.79 mol·L-1,T=60℃,t=2h,[Ni(COD)2]=1.102 mmol·L-...     

Preparation and Properties of Polyallenes. I. Polymerization of Allene by Ziegler-Type Catalysts

The polymerization of allene induced by organoaluminum-vanadium oxytrichloride catalysts has been investigated in aliphatic hydrocarbons and at normal pressure. For the catalysts investigated, the polymerization activity decreases at decreasing order of alkylation of the aluminum alkyl: AIR₃ > AIR₂X > AIRX₂ (R is Et or i-Bu; X is halogen). Compared with other aluminum trialkyls, trimethylaluminum shows a low activity. For the Al-i-Bu₃-VOCl₃ system, the effects of catalyst ratio, reaction time, and temperature have been studied.     

合成气制乙醇Rh-Nb2O5/SiO2催化剂中的SMPI和助催剂作用本质的研究

使用负载型催化剂由合成气制乙醇是一碳化学研究的一个重要发展。本实验室前已报道用化学反应法检验出Rh-Nb_2O_5/SiO_2表面上除了铑位外同时还存在氧化铌位。本文为兰部分工作所组成: (1)进一步用氢还原过的Nb_2O_5/SiO_2催化乙炔聚合成聚乙炔的化学方法推断Rh-Nb_2O_5/SiO_2上可能存在着Nb—H键。(2)用FTIR法检测上述催化剂的红外光谱吸收带, 1740(w) cm~(-1)为V_(Rh-H), 1560 cm~(-1)(broad, m)、1269 cm~(-1)(s)为与Nb—H有关的吸收, 后者可能属于桥式Rh—H—Nb的吸收。(3)XPS检测出合成气处理的Rh-Nb_2O_5/SiO_2表面上存在Rh~0、Rh~Ⅰ、Nb~Ⅴ、Nb~Ⅳ和两种不同的沉积碳。根据这些结果, 提出活性中心可能为A(参见正文图3)简写为B(见图3), CO转化的主要途径是而后C—O还原断裂生成=CH_2***, 再与CO偶联为CH_2=C=O, 最后还原为乙醇或乙醛。根据实验结果对本体系催化剂中SMPI和助催剂作用的实质作了讨论。     

利用光学显微镜研究溶剂诱导的梯形苯基聚倍半硅氧烷结晶

通过溶剂诱导结晶的方法研究了梯形苯基聚倍半硅氧烷(PPSQ)的球晶结构. 采用光学显微镜研究了溶液的浓度、溶剂的挥发时间以及温度等影响因素对梯形苯基聚倍半硅氧烷的球晶结构形貌的影响. 实验结果表明:稀释溶液浓度与提高结晶温度在改变球晶的形态方面具有相同的效果. 球晶的尺寸会随着溶液浓度的降低或者结晶温度的升高而增加. 这都归因于梯形苯基聚倍半硅氧烷在二甲苯中的溶解度的增加. 在不改变其它结晶条件的情况下,延长溶剂的挥发时间也会形成更大的球晶. 当在光学显微镜下旋转样品时球晶的结构不会发生改变,这表明球晶具有均一的晶体学取向结构. 负性球晶的特征也表明梯形苯基聚倍半硅氧烷的分子链是沿着球晶的切线方向排列. 考虑到梯形苯基聚倍半硅氧烷具有刚性的分子链,还提出了梯形苯基聚倍半硅氧烷可能的球晶结构模型.     

基团转移聚合中分子量和分子量分布的研究

<正> 基团转移聚合的主要优点是能在室温下进行甲基丙烯酸酯、丙烯酸酯和丙烯腈等极性单体的控制聚合,得到实测分子量和理论分子量相近的、多分散指数较小的聚合物。对于每一种新发现的引发剂和催化剂组成的引发-催化体系,亦是在高转化率的前提下,视其实测分子量和理论分子量的相符程度和多分散指数的大小而评判其优劣。目前已报道的有关控制分子量及多分散指数的工作,大多限于研究催化剂含量的影响。而反应条     

新型Ti-Co复合负载化催化剂制备支化聚乙烯

以反应法制备了TiCl4、乙酰丙酮改性的TiCl4和Co(acac) 2 为主催化剂 ,SiO2 MgCl2 为载体的复合负载型催化剂 (TiCl4 CH3COCH2 COCH3 Co(acac) 2 SiO2 MgCl2 ) ,以烷基铝作为助催化剂 ,以单一乙烯单体制备了支化聚乙烯 .研究了复合催化剂的组成、烷基铝种类和聚合反应温度等对聚合反应和产物结构性能的影响 .探讨了聚合反应机理 .聚合产物经IR、1 3 C NMR谱分析 ,结果表明Ti Co复合催化剂具有低聚原位共聚功能 ,可制得含有丁基、戊基、己基等各类支链结构的支化聚乙烯 .     

Effect of polyphenylsilsesquioxane on the ablative and flame-retardation properties of ethylene propylene diene monomer (EPDM) composite

Polyphenylsilsesquioxane (PPSQ) microspheres with ladder structure synthesized in the laboratory have been incorporated into ethylene propylene diene monomer (EPDM) composite in order to study the effect of PPSQ on the ablative and flame-retardation properties of EPDM composites. The results showed that PPSQ microspheres serve as an effective ablative additive and flame retardant for EPDM composites. Thus, PPSQ greatly improved the ablative properties of EPDM composites, with a 4.8 wt% loading leading to a remarkable reduction in the linear ablation rate of EPDM by about 50%. Moreover, this loading of PPSQ improved the flame retardancy and smoke suppression, and significantly reduced the PHRR of EPDM composite from 504 kW/m² to 278 kW/m². Moderate tensile strength could be obtained and the breaking elongation was improved for the EPDM/PPSQ composites. TGA results showed that PPSQ had little influence on the thermal decomposition of EPDM. SEM, CONE, and TG-FTIR tests showed that the char structure of EPDM composites was the primary factor through which PPSQ affected the ablative and flame-retardation properties of EPDM. The chars formed during the ablation of EPDM composites containing PPSQ had better structural stability and thermal stability, owing to the fact that they were denser, remained intact, and had an ordered arrangement of holes.     

程序升温表面炭气化反应动力学研究

本文用程序升温表面反应(TPSR)方法,研究了甲烷裂解沉积在不同催化剂上的炭与水蒸汽反应的动力学。结果表明,炭与水蒸汽反应属一级反应,活化能在212.0—256.7KJ/mol之间。该法简便、迅速。所获得的动力学参数对研究在不同催化剂上的炭与水蒸汽反应性能差异具有实际意义。     

以固体光气为原料合成氯代甲酸(2-乙基)己酯

氯代甲酸(2-乙基)己酯是一种化工中间体,主要用来制备过氧化二碳酸二(2-乙基)己酯(简称EHP),EHP是一种高活性聚合引发剂。由固体光气和2-乙基己醇为原料合成氯代甲酸(2-乙基)己酯的研究未见报道。本文以固体光气和2-乙基己醇为原料合成了氯代甲酸(2-乙基)己酯,研究了反应物加入顺序、反应时间、反应温度、催化剂种类及用量对氯代甲酸(2-乙基)己酯收率和纯度的影响,得到了优化的合成工艺,对产物结构进行了分析,进一步用其合成了常用的高活性聚合引发剂过氧化二碳酸二(2-乙基)己酯(EHP)。