CMMS和DCPMS在丙烯聚合中的应用

将CMMS(环己基甲基二甲氧基硅烷)和DCPMS（二环戊基二甲氧基硅烷）外给电子体分别与CS-1型和CS-2型聚丙烯主催化剂进行丙烯聚合评价，结果表明CMMS和DCPMS是高效催化剂的有效助催化剂，它们能够提高聚丙烯的真实等规度。它们提高聚丙烯真实等规度的能力为DCPMS>CMMS>DDS。     

聚丙烯专用料在纺丝工业生产的技术研究与应用

本文章是作者在中原油田石油化工总厂气聚车间工作期间,针对气聚车间聚丙烯反应催化剂应用上的不同,以及对不同高效催化剂的氢调性能进行了认真仔细的研究。CS-Ⅰ型催化剂无第一放热高峰,氢调敏感。该催化剂活性和等规度受氢调影响较小,PP产品的等规度较高,灰份较低。CS-Ⅰ型催化剂更适用于在间歇本体聚丙烯装置上生产高熔体指数聚丙烯。     

纺丝用聚丙烯专用料的工业生产试验

对不同聚丙烯催化剂的氢调性能进行了考察。CSI型催化剂无第一放热高峰,氢调敏感。该催化剂的活性和产品的等规度受氢调影响较小,聚丙烯产品的等规度较高,灰分较低。CSI型催化剂适用于在间歇本体聚丙烯装置上生产高熔体指数聚丙烯。     

CS－1型催化剂在聚丙烯树脂生产中的应用

中科院化学所研制成功ＣＳ－１型高效催化剂，通过营口市向阳化工厂转化为生产力，产品达到了国际第三代高效催化剂水平。在小本体聚丙烯树脂生产装置上应用获得成功；应用于大型连续性装置试生产ＰＰＨ－Ｔ－０２２牌号聚丙烯，预聚合后钛活性略高于ＴＫ催化剂，平均７９万ｇｐｐ／ｇＴｉ，单耗略低于ＴＫ催化剂，产品聚丙烯等规度在９７％以上，物理机械性能达到国家标准，是络合Ⅱ型催化剂理想的更新换代产品。     

CS—1型催化剂在聚丙烯树脂生产中的应用

中科院化学所研制成功ＣＳ－１型高效催化剂，通过营口市向阳化工厂转化为生产力，产品达到了国际第三代高效催化剂水平。在小本体聚丙烯树脂生产装置上应用获得成功；应用于大型连续性装置试生产ＰＰＨ－Ｔ－０２２牌号聚丙烯，预聚合后钛活性略高于ＴＫ催化剂，平均７９万ｇｐｐ／ｇＴｉ，单耗略低于ＴＫ催化剂，产品聚丙烯等规度在９７％以上，物理机械性能达到国家标准，是络合Ⅱ型催化剂理想的更新换代产品。     

高效催化剂本体法聚丙烯纺丝研究

通过对本体法聚丙烯的纺丝研究，找到了较合适的纺丝工艺，实验证明，利用高效催化剂生产的本体法聚丙烯，灰份少、氯含量低、熔融指数高、等规度高，能生产出性能优良的聚丙烯纤维。     

外给电子体CMMS、DCPMS制备高结晶度聚丙烯的研究

CMMS、DCPMS外给电子体分别与CS 1型、CS 2型聚丙烯主催化剂进行丙烯聚合评价,结果表明DCPMS是高效催化剂的有效助催化剂,能够有效提高聚丙烯的真实等规度、结晶度,DCPMS更适宜制备相对高结晶性聚丙烯。     

CP型高效催化剂用于生产聚丙烯的研究

本文介绍了CP型高效催化剂用于液相本体法聚丙烯的工业生产。该催化剂生产聚丙烯聚合速率较平稳,催化效率达12.7～18万克PP/克Ti,产品全等规度为89～93%,易用氢调节PP分子量。产品含钛和氯离子低,可免除脱氯的后处理,是国内首先开发用于生产聚丙烯的高效催化剂。文中对聚合反应聚丙烯分子量的控制,影响催化效率等因素作了研究,给出产品的结构和性能数据,以及制品的加工使用结果。     

高效聚丙烯催化剂研制成功

对我国聚丙烯产业的发展至关重要的CS-1型高效催化剂研制及工业化试生产在1992年2月通过中科院主持的鉴定。目前,我国以炼厂气为原料的中小型间歇式液相本体法聚丙烯生产使用的催化剂,活性和定向能力较低,生产出的聚丙烯产品含氯量高,等规度较差,加工应用受到很大限制,通常应用于塑料编织袋等低档产品。而国际上和     

新型二醚类聚丙烯催化剂技术开发与应用

我国现有聚丙烯装置主要采用传统丙烯聚合非均相催化剂，生产的聚丙烯产品中析出邻苯二甲酸酯干扰人体内分泌系统，对人体健康有严重的危害。经过多年研发，在新型二醚类聚丙烯催化剂方面取得突破性进展，开发新型二醚类聚丙烯催化剂，与邻苯类催化剂相比催化活性有近一倍的提高，聚丙烯的等规度大于95%,在催化活性、原料单耗、氢调性、产品等规度等方面优于进口催化剂；形成了具有自主知识产权的二醚类催化剂新技术，打破了国外垄断，且成功实现了量产和工业化应用，采用新型催化剂生产的聚丙烯指标明显优于国内外同类产品，降低了生产成本，具有显著的经济效益和社会效益。     

异丁基三乙氧基硅烷作为外给电子体生产高熔融指数聚丙烯

利用异丁基三乙氧基硅烷作为外给电子体与N-Ⅲ催化剂组成高活性及高氢调敏感性催化体系,在间歇式液相本体法聚丙烯生产工艺中,通过控制每釜氢气加入量为氢气钢瓶压降23~25 MPa,单釜主催化剂加入量65 g,生产熔融指数在30~35 g/10 min之间的高熔指聚丙烯,产品等规度97.0%,灰分1.3×10-4。实验证明,异丁基三乙氧基硅烷作为外给电子体的N-Ⅲ催化体系反应初期活性适中,活性衰减慢,无明显放热高峰。     

几种齐格勒一纳塔聚丙烯催化剂的中试评价研究

应用75kg／h聚丙烯中试装置评价了A、B、C、D4种聚丙烯催化剂的性能，考察了催化剂的活性、氢调敏感性、等规度、聚合物细粉等性能。结果表明，B、C、D3种国产催化剂活性高于进口催化剂A，且3种国产催化剂的氢调敏感性好、等规指数可调，能够适应聚丙烯中试装置生产的需要，但D催化剂聚合物细粉较多。B、C、D国产催化刹生产的T30S产品，其质量能够达到标准要求。     

聚丙烯及其催化剂的表征方法

介绍了聚丙烯(PP)及其催化剂的表征方法.对等规度、分子结构、相对分子量分布、酯含量、表观密度、热性能、晶体结构、元素分析、催化剂活性、孔结构以及粒径分布的测定作了详细研究.通过以上分析方法的总结,有助于聚丙烯的制备工艺和性能研究.     

聚丙烯等规指数调节研究

在Ｎ催化体系的基础上,研究了不同种类和不同用量内、外给电子体以及不同催化剂合成条件对聚丙烯（ＰＰ）等规系数的影响;经过大量的催化剂合成和小聚合研究,找到了１种调节ＰＰ等规指数的有效方法。在ＰＰ工业装置上的应用试验进一步验证了小试的结论。     

Microstructure of two polypropylene homopolymers with improved impact properties

Two polypropylene homopolymers, samples A and B, synthesized with heterogeneous Ziegler-Natta catalysts, are studied in this work. Both samples show improved impact properties at low temperature than isotactic PP. Particularly, sample B exhibits better toughness, higher molecular weight and slight lower flexural properties than sample A. Then, these two samples were fractionated into six fractions via temperature rising dissolution fractionation, respectively. Both samples are mainly composed of fractions 4, 5 and 6, which were collected above 100 °C and have high isotacticity. On the one hand, the fractions of sample B have higher molecular weight than the corresponding fractions of sample A collected at the same temperatures. On the other hand, ¹³C NMR and DSC analyses of the fractions indicate clearly that fractions of sample B have lower isotacticity and crystallinity than the corresponding fractions of sample A. The above difference in microstructure between samples A and B should be the key factors resulting in their difference in mechanical properties finally. Both polypropylene homopolymers possibly become new type of impact PP.     

Tacticity distribution of isotactic polypropylene prepared with heterogeneous Ziegler-Natta catalyst. 2. Application and analysis of SSA data for polypropylene

Accurate characterisation of the tacticity distribution in isotactic polypropylene is important for obtaining better structure property correlations and for the indirect investigation of the active sites in heterogeneous Ziegler-Natta catalysts. In this work, successive self-nucleation and annealing (SSA) DSC measurement is applied for the study of tacticity distribution in polypropylene fractions with varying isotacticity. The results are compared with ¹³C NMR and temperature rising elution fractionation (TREF). Analysis of the lamellar thicknesses and average meso sequence lengths (MSL) revealed that the fractions could be classified into three main groups according to the lamellar structure generated in SSA. The fractions with relatively low isotacticity crystallise mainly by the longest crystallisable sequence of the chain. In more isotactic fractions, the lamellar thicknesses are close to the average crystallisable sequence lengths of the chains. For the highest isotacticity fractions correlation was not found. Because of these differences the correlation between the melting temperature and isotacticity (meso diad-%) was non-linear. Good correspondence between the SSA melting curves and the TREF fractograms was observed.     

Tacticity distribution of isotactic polypropylene prepared with heterogeneous Ziegler-Natta catalyst. 1. Fractionation of polypropylene

Two polypropylene samples, one with relatively low isotacticity and the other with high isotacticity were fractionated using a series of solvents and temperatures. For both samples 4-9 fractions were collected and characterised with differential calorimetry, size exclusion chromatography and ¹³C NMR spectroscopy. The collected fractions showed typical characteristics of a fractionation based on isotacticity, but also similarities to results from temperature rising elution fractionation (TREF), even though a separate controlled crystallisation step was not used. The melting temperatures of the fractions were found to increase linearly as a function of the meso diad fraction. A calibration, which can be used to convert DSC melting curves to wt% curves of isotacticity, was constructed for the temperature range 108-165 °C. The calibration enables quick analysis of samples in polypropylene manufacturing processes.     

聚丙烯催化剂性能评价

通过熔体流动速率和等规指数测试、扫描电子显微镜观察评价了国内外几种聚丙烯(PP)催化剂,考察了催化剂的活性、流动性、氢调敏感性等.结果表明:1#催化剂具有较高的活性,可达38.92 kg/g,且氢调敏感性和抗杂质能力较强,但用其生产的PP粉料中存在粒子开裂和大量粉末;2#和3#催化剂活性较低,但工艺可操作性好.PP粉料的粒子大小均匀、致密、粉末少;5#催化剂活性最高,但PP灰分高、细粉较多;6#催化剂聚合活性较高,但PP灰分最高、细粉含量大.     

Polypropylene with high melt flow rate and high isotacticity prepared by phosphate‐mixed external donors

High melt flow rate (MFR) of polypropylene can improve its processability and its high isotacticity is favor of keeping good mechanical properties of polypropylene. In this study, as a convenient and effective method, the mixture of phosphate and alkoxysilane as mixed external donors for Ziegler‐Natta catalyst is used to improve MFR of polypropylene. The MFR of polypropylenes prepared by mixed external donors is three to five time higher than that prepared by dicyclopentyl dimethoxysilane (Donor‐D) alone, which is attributed to broad molecular weight distribution and low molecular weight of polypropylene prepared by mixed external donors. In addition, isotacticity and lamella thickness of polypropylene prepared by mixed external donors containing triisopropyl phosphate or phenyl‐phosphonic acid dipentyl ester are very close to that prepared by Donor‐D, which lead to keep high thermal properties and good mechanical properties for the polypropylenes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44704.