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1.
分别在亚乙基双(茚基)二胺化铪茂(简称1)和异亚丙基(环戊二烯基)(1-芴基)二甲基锆茂(简称2)催化作用下,对乙烯(E)与1-己烯(H)无规共聚合进行了研究.结果表明,在单体浓度比[H]/[E]较小时共聚合速率随单体浓度比增加而增加,进一步增加单体浓度比则导致共聚合速率降低.催化体系1/Al(1Bu)2H/[Ph3C][B(C6F5)4](3)催化共聚活性比2/MAO高得多.两单体竞聚率乘积(rE×rH)小于1,表明聚合物为无规共聚物.两催化体系共聚合能力相当.DSC分析显示,共聚物具有较宽的熔融峰,甚至出现双熔点.与催化体系2/MAO相比,1/Al(iBu)2H/3催化共聚物具有更高的分子量和更宽的密度变化范围.  相似文献   

2.
研究了两个新茂钛催化剂茂基三呋喃甲氧基钛 [OCp Ti(OCH2 ) 3 — cat- 1]和茂基三苄氧基钛 [Cp Ti(OCH2 Ph) 3— cat- 2 ]与甲基铝氧烷 (MAO)组成的催化体系对苯乙烯的间规均聚合。考察了聚合温度对催化效率、间规指数、粘均分子量的影响 ,也研究了铝 /钛摩尔比与聚合结果的关系以及聚合动力学行为。发现 cat- 1/MAO和cat- 2 /MAO两催化体系都是在较高温度 (6 0℃或 6 5℃ )才有最大催化效率 ,但 cat- 1中因有杂环氧对单体苯乙烯向活性中心配位的排斥 ,使得 cat- 1的催化效率不如 cat- 2强。对于两体系 ,都有间规指数随温度升高而明显增大 ,间规聚苯乙烯 (s PS)分子量随温度升高而下降。 cat- 1/MAO催化体系最大催化效率时的 Al/Ti摩尔比为 40 0 ,对于cat- 2 /MAO体系则为 80 0  相似文献   

3.
研究了一种钕催化体系——以乙醇为配体的三氟甲磺酸钕/三异丁基铝催化体系[Nd(CF3SO3)3.3H2O.C2H5OH-Al(-i Bu)3]催化苯乙烯(St)与异戊二烯(Ip)的共聚合行为。讨论了n(St)/n(Ip)、n(Al)/n(Nd)、聚合时间等的影响。研究结果表明,该催化体系不能引发St均聚,但可实现St与Ip的共聚,共聚活性低于Ip均聚活性,且强烈依赖于单体组成。共聚物的分子量达到2.9×106。St以单个分子或/和短嵌段的形式嵌入Ip长链段中。其中Ip单元以cis-1,4结构为主,cis-1,4的物质的量分数达91%。随着n(St)/n(Ip)增大,共聚物中St含量明显增加,但St含量的增加对Ip单元的cis-1,4含量没有影响。  相似文献   

4.
以N,N-二(2,6-二异丙基苯基)苊二亚胺氯化镍(NiLCl2)为主催化剂,AlEt2Cl为助催化剂,催化乙烯与4-乙烯基吡啶(4-VP)共聚合。研究结果表明,在一定条件下,该催化体系可以催化乙烯与4-乙烯基吡啶共聚合。极性单体的浓度对共聚合反应活性、共聚物的组成等有很大的影响,随着4-乙烯基吡啶浓度的增加,参与共聚的乙烯迅速减少,4-乙烯基吡啶均聚增加。最佳反应条件是单体浓度为0.46mol/L、n(Al)/n(Ni)为600、温度为30℃,这时共聚合催化活性达到19.7 kg/mol Ni.h,共聚物中4-乙烯基吡啶的摩尔百分数可达4.2%。  相似文献   

5.
用限制几何构型茂金属催化体系[2-Me4Cp-4,6-tBu2-PhO]TiCl2/Al(iBu)3/Ph3C+B(C6F5)4-(CGC)研究了乙烯/降冰片烯的共聚。考察了降冰片烯单体浓度对聚合反应活性和聚合物性能、结构的影响。用核磁共振(13C-NMR)、扫描电镜(SEM)、差热分析(DSC)和X射线衍射(X-ray)方法对共聚物进行了表征。结果表明,所得产物(降冰片烯含量(2.5~9.4)NB%)的形貌是交联网状的,主要是含有等规和间规交替序列的无规共聚物;在0.4 mol/L浓度下可得到有双熔点(92℃,112℃)分布的共聚物。  相似文献   

6.
长乙烯序列无规乙丙共聚物的合成与表征   总被引:1,自引:0,他引:1  
用δ-Ticl_8-Et_2AlCl作催化剂,合成了含长乙烯序列的无规乙丙共聚物。影响乙烯丙烯共聚合产率的主要聚合参数是[Ti]、[Al]/[Ti]比和聚合温度,在55℃左右聚合产率呈现极大值;影响共聚物组成的主要参数是乙丙混合气中单体C_2的含量,当其在60克分子%以上,有利于生成长乙烯序列无规乙丙共聚物;[Ti]、单体C_2含量和聚合温度对共聚物的分子量有显著影响。用沉淀分级方法证明了共聚物组成的不均一性;用DSC,扭摆和TEM等方法对共聚物和与其组成相同的共混物进行对比,发现共聚物的T_m,T_c和X_c%均小于共混物;共聚物的T_g随C_2含量的增加向低温方向迁移,而共混物的T_g则随C_2含量增加移向高温;共聚物与共混物的形态结构均呈两相体系,前者PE片晶堆砌疏松,后者堆砌紧密;共聚物的常温断裂强度高达140公斤/厘米~2,与钒催化剂制备的序列型AP447的强度(135公斤/厘米~2)相近。  相似文献   

7.
淀粉接枝共聚物是一种新型功能性材料。以机械活化淀粉(mSt)为接枝母体,丙烯酰胺(AM)和丙烯酸(AA)为接枝单体,研究了在淀粉/单体/乳化剂/油/水反相乳液体系中引发机械活化淀粉与丙烯酰胺/丙烯酸接枝共聚反应的动力学,考察了引发剂浓度[I]、单体浓度[M]、淀粉乳浓度[mSt]和乳化剂浓度[E]等因素对表观聚合速率Rp的影响。结果表明,在本文考察范围内动力学关系式为Rp∝[mSt]1.5[M]1.7[I]0.9[E]0.92,单体浓度和淀粉乳液浓度对聚合反应速率影响显著,聚合反应速率随体系温度升高而加快,在45~60℃范围内,聚合反应的表观活化能为89.5kJ/mol,聚合过程中单基终止与双基终止反应同时存在。  相似文献   

8.
研究了茂金属催化体系[2-C5Me4-6-tBuC6H3O]TiCl2/Al(iBu)3/Ph3CB(C6F5)4催化5-亚乙烯基-2-降冰片烯(ENB)与乙烯(E)的共聚反应。考察了聚合条件对催化活性、共聚物中ENB的含量和共聚物分子量的影响。利用氢核磁共振谱(1H-NMR)、差示扫描量热仪(DSC)和凝胶渗透色谱仪(GPC)对合成的共聚物进行表征。结果表明,在ENB/E共聚反应中,ENB环内双键参与聚合,ENB环外双键(亚乙烯基)保留。合成了ENB物质的量分数高达50.1%和玻璃化转变温度高达170.5℃的共聚物。合成的共聚物分子量分布较窄(PDI=1.93~2.11),最高分子量达到193 kg/mol。  相似文献   

9.
辛酸亚锡催化下开环聚合制备不同物质的量比L-丙交酯/ε-己内酯(LLA/CL)共聚物。核磁共振(1H和13C-NMR)结果表明,共聚物组成与投料比基本一致,聚合过程中酯交换反应导致序列结构重新分布,二级酯交换系数(TII[CLC])随CL用量增加而增大。共聚物组成明显影响单元序列长度,各序列长度随相应单体投料量增加而增大,CL投料比≤50%的平均序列长度(LLL和LC)与相应的无规序列长度(LRC和LRLL)较接近,共聚物趋于无规分布。差示扫描量热(DSC)和广角X射线衍射(WAXD)表明共聚物是结晶态聚合物,结晶性与单元序列长度密切相关。共聚物组成显著影响其力学性能,随CL物质的量分数增加,且≤35%时表现出屈服形变的特点,具有热塑性弹性体的特征。  相似文献   

10.
以AIBN为引发剂在氯仿溶剂中成功地合成了耐热型苯乙烯-苯乙烯/N-(α-甲基-丁酯基)-马来酰亚胺共聚物(St-co-BAM)。通过IR、TG、DTA对共聚物的表征,研究了其耐热性能;讨论了单体全程配比、温度、引发剂浓度对共聚合初始速率的影响,测得共聚合总活化能Ea=76.2kJ/mol,共聚合增长活化能Ep=13.4kJ/mol,比一般的正常乙烯基单体Ep值小。  相似文献   

11.
In this paper, we present a new method for inserting several triangulated surfaces into an existing tetrahedral mesh generated by the meccano method. The result is a conformal mesh where each inserted surface is approximated by a set of faces of the final tetrahedral mesh. First, the tetrahedral mesh is refined around the inserted surfaces to capture their geometric features. Second, each immersed surface is approximated by a set of faces from the tetrahedral mesh. Third, following a novel approach, the nodes of the approximated surfaces are mapped to the corresponding immersed surface. Fourth, we untangle and smooth the mesh by optimizing a regularized shape distortion measure for tetrahedral elements in which we move all the nodes of the mesh, restricting the movement of the edge and surface nodes along the corresponding entity they belong to. The refining process allows approximating the immersed surface for any initial meccano tetrahedral mesh. Moreover, the proposed projection method avoids computational expensive geometric projections. Finally, the applied simultaneous untangling and smoothing process delivers a high‐quality mesh and ensures that the immersed surfaces are interpolated. Several examples are presented to assess the properties of the proposed method.  相似文献   

12.
Standards are the basis for production enterprises to organize production, ex-factory inspection, trade (delivery) and technical exchanges, product certification, quality arbitration and supervision.……  相似文献   

13.
14.
A flow calorimeter for enthalpy increment measurements on condensed gases is presented. A better knowledge of the properties of the liquefied natural gas is needed, and therefore a liquid loop has been designed for our flow calorimeter. The fluid loop in the calorimeter is designed in order to avoid the two-phase region, since two phases would give compositional disturbances in the measurements. The avoidance of the two-phase region is made possible by increasing the pressure of the test fluid after the measurement section, then heating the fluid at super-critical pressure past the critical point. Finally, the fluid is throttled to the low-pressure gas state at the inlet condition of the compressor that circulates the fluid. To perform the pressure increase, a new cryogenic pump has been designed. To evaluate the new equipment, measurements were taken on liquid ethane over the temperature range 146–256 K at pressure between 0.9 and 5.1 MPa.  相似文献   

15.
On November 30, 2007, the China Association for Standardization (CAS) held a press conference at Beijing Diaoyutai State Guest House. Leaders from the China Household Electric Appliance Research Institute, the China Household Electric Appliance Association, and the China Consumers' Association attended and made speeches.……  相似文献   

16.
Zusammenfassung Bei der Gestaltung von Ernteprozessen — beispielsweise des Prozesses Mähdrusch, Körnertransport und -abnahme — als transportverbundene Fließarbeitsverfahren mit mindestens zwei verschiedenen Arbeitsmitteln gibt es einen großen Optimierungsspielraum. Solche Prozesse sind mehrstufige Bedienungsprozesse mit gemischter Anordnung der Bedienungseinrichtungen. Außerdem besitzen sie stark ausgeprägte räumliche Aspekte. Es wird vor allem gezeigt, welche Merkmale solcher Prozesse in Simulationsmodellen abgebildet sein müssen, welche Zielgrößen in Abhängigkeit von welchen Einflußgrößen unter Berücksichtigung welcher Prozeßbedingungen ermittelt werden sollten und wie der Bewertungsprozeß zur Ermittlung der gewünschten Informationen gestaltet werden muß.  相似文献   

17.
In the present study a high‐boron high speed steel (HSS) roll material was designed. Many expensive alloy elements have been substituted by cheap boron alloy, and high‐boron high speed steel roll has been manufactured by centrifugal casting method. The microstructures, mechanical properties and wear resistance of centrifugal casting high‐boron high speed steel roll have been investigated by optical microscopy (OM), scanning electron microscopy (SEM), and X‐ray diffraction (XRD) analysis, hardness test, impact test and wear test. The results indicated that the solidification microstructures of high‐boron high speed steel roll consisted of M2(B,C), (W,Mo)2(B,C), M3(B,C), M23(B,C)6 type borocarbides and martensite, a small amount of retained austenite. Borocarbides were continuously distributed over the grain boundary. After quenching from 1050 °C, local broken network appeared in partial borocarbides, and fine secondary borocarbide precipitated from the matrix. After tempering from 525 °C, the amount of precipitated borocarbide increased significantly. After heat treatment, the hardness of high‐boron high speed steel roll excelled 60 HRC, and its impact toughness excelled 8.0 J/cm2. The single groove steel rolling amount of high‐boron high speed steel rolls increases by 500% than that of bainite cast iron roll, when the rolls are used in K1 mill housing of bar mill.  相似文献   

18.
The definition of the thixotropy is a decrease in viscosity with time in shear and a subsequent recovery of viscosity after the shear deformation is removed.We ...  相似文献   

19.
正Responding to ISO’s appeal for survey for the to-be-developed ISO Strategy Plan for 2016-2020,SAC hosted a special workshop over the needs and comments of various fi elds on June 8 in Beijing.The workshop was attended by ISO President-elect and Ansteel General Manager Zhang Xiaogang,SAC Vice-Administrator Yu Xinli,and 30 experts from  相似文献   

20.
正The review group of Asia Pacific Laboratory Accreditation Cooperation(APLAC)carried out a 4-day peer review of the proficiency testing provider(PTP)for China National Accreditation Service for Conformity Assessment(CNAS)from July 28 to 31,2014.CNAS passed the PTP review with excellent performance.Two senior peer reviewers of APLAC made a comprehensive,rigorous and detailed review of CNAS’s PTP accreditation activities,and made the on-spot inspection of the review groups in Shanghai and Shenzhen respectively.  相似文献   

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