降冰片烯与丙烯共聚合的研究进展

继高活性茂金属催化体系成功开发以降冰片烯和乙烯共聚物为代表的高性能环烯烃共聚物以来, 降冰片烯与其他α-烯烃如丙烯的共聚物研究也备受学术界和工业界的重视。本文介绍了降冰片烯与丙烯共聚合的催化剂和聚合机理等方面的最新研究进展, 包括各种不同结构的茂金属催化剂催化降冰片烯与丙烯共聚合的特点及其共聚物的结构分析。C₂-对称和C_s-对称的茂金属催化剂催化降冰片烯与丙烯共聚合时链转移反应较多, 以致催化活性较低, 所得的聚合产物分子量偏低。采用限定几何构型茂金属柄型-二甲基亚甲硅基(芴基)(氨基)二甲基钛催化剂进行降冰片烯与丙烯共聚合时, 催化活性可高达10⁷ g polymer·(mol cat·h)^-1, 所得共聚物的相对分子质量超过20万, 降冰片烯含量可达70%(mol)且玻璃化转变温度高。     

单环戊二烯基钛类茂金属催化剂的应用

综述了限制几何构型茂金属(单环戊二烯基钛类茂金属)催化剂在烯烃聚合方面的应用,包括乙烯/链烯烃共聚合,长链α-烯烃和降冰片烯的共聚,含乙烯端基大分子单体的共聚,乙烯和苯乙烯的聚合以及高分子量的无规聚丙烯的合成。研究表明,单环戊二烯基允许各种单体的插入,环戊二烯上的取代基团及配体基团的引入,影响催化烯烃聚合活性,控制聚合物的分子量和聚合分散度。     

茂金属催化剂使α-高碳烯和环烯成为新聚烯烃的共聚单体

90年代聚烯烃技术的最大突破是茂金属催化剂的开发和利用。人们使用茂金属催化剂开发了从前不能合成的新的烯烃共聚物,它使α-高碳烯(HAO)和环烯与乙烯和丙烯的有效共聚成为可能,在其活性反应中心和共聚单体几乎能百分之百地聚合,这是传统齐格勒催化剂做不到的,因为后者只能使乙烯或丙烯比其它较重的共聚单体聚合速度更快。     

复合型催化剂催化乙烯-降冰片烯共聚性能研究

为深入了解不同种类催化剂对乙烯-降冰片烯(COG)共聚产物性能的影响,以期获得综合性能优良的新型COC共聚物,分别采用非茂金属ST1、茂金属M1及两者复合型STM三种催化剂,研究了常压溶液聚合条件下乙烯与降冰片烯的共聚性能,通过差示扫描量热仪、凝胶渗透色谱仪以及核磁共振仪等表征分析了三类COC共聚物的热稳定性、玻璃化温...     

环状聚烯烃列入国家重点研发计划

正日前,在科技部发布的《"十四五"国家重点研发计划"高端功能与智能材料"重点专项2021年度项目申报指南征求意见的通知》中,环状聚烯烃列入国家关键医用与防疫材料方向重点研发计划。环状聚烯烃,即环烯烃共聚物(COC/COP),是一种具有环状结构的非晶性透明高分子材料,具有环内碳碳双键的环状烃。目前应用最多的是COC是使用茂金属催化剂将乙烯和降冰片烯(双环庚烯)共聚而得,     

新型乙烯－环烯烃共聚物

新型乙烯－环烯烃共聚物日本出光公司已开发出弹性乙烯－环烯烃共聚物，它有较高含量的环烯烃降冰片烯，具有类似于橡胶的性质。另外，三井和赫斯特正在联合开发这类共聚物，使用赫斯特公司的金属茂催化剂技术，但该材料不同于出光公司的乙烯－环烯烃共聚物，它具有工程塑...     

N-酰化咪唑啉-2-亚胺镍催化剂制备环烯烃共聚物

在助催化剂二氯乙基铝(EtAlCl_2)活化作用下,以N-酰化咪唑啉-2-亚胺镍配合物有效催化了降冰片烯/1-己烯共聚,制备出含1-己烯柔性支链的聚(降冰片烯/1-己烯)环烯烃共聚物,研究了助催化剂用量、反应温度及1-己烯反应单体用量对催化剂催化活性及所得聚合物结构和性质的影响。结果表明,N-酰化咪唑啉-2-亚胺镍配合物不仅可高活性催化降冰片烯/1-己烯共聚[催化活性最高达3.88×10~5 g/(mol·h)],且即使在120℃下仍可有效催化合成出高1-己烯含量的环烯烃共聚物,热稳定性良好;同时,随着EtAlCl_2用量和1-己烯反应单体用量增加,聚合物中1-己烯单体插入率逐渐增大,最高可达7.11% (物质的量分数),但配合物催化活性、聚合物数均分子量及玻璃化转变温度呈下降趋势;另外,升高聚合温度有助于提高催化活性及1-己烯单体插入率,但易导致聚合物分子量减小。由此可见,在该催化体系下通过调整EtAlCl_2用量,反应温度及1-己烯反应单体用量,即可实现对环烯烃共聚物的结构性能进行有效调控。     

FI催化剂在制备乙烯基共聚物中的应用

综述了带有芳氧基亚胺配体的ⅣB族金属络合物(FI催化剂)催化的乙烯类共聚合。Ti-FI催化剂可用于乙烯与α-烯烃、乙烯与环烯烃的共聚合。相比传统的茂金属催化剂,FI催化剂可以制备共聚单体含量更高的共聚物。FI催化剂对极性基团具有良好的耐受性,将其用于乙烯与极性单体的共聚合,可取得理想的效果。与亚胺N原子相连的芳香环上的邻位H原子被F原子所取代的Ti-FI催化剂催化乙烯类聚合时,表现出活性聚合的特征。因此可通过控制单体加入顺序制备嵌段共聚物。用两种不同的FI催化剂,且以二乙基锌为链穿梭剂,可制备多嵌段共聚物。优化配体结构可制备高效的乙烯类共聚合催化剂。这些将有利于实现聚烯烃的功能化和高性能化。     

咪唑烷-2-亚胺为配体的镍配合物催化的降冰片烯与苯乙烯共聚

为了研究[P, N]型镍催化剂的双重强供电子效应对烯烃与极性单体共聚性能的影响，本文设计合成了两种咪唑烷-2-亚胺为配体的镍配合物Ni1和Ni2,并通过核磁对其表征，研究了该类镍配合物在二氯乙基铝(EtClAl₂)助催化剂的活化下催化降冰片烯均聚及其与苯乙烯的共聚行为。结果表明，以EtClAl₂为助催化剂时，配合物Ni1催化降冰片烯均聚活性高达1.92×10⁷ g/(mol·h)。该体系配合物同样有效催化降冰片烯与苯乙烯共聚，Ni1的聚合活性高达2.14×10⁶ g/(mol·h)。该体系催化剂对降冰片烯与苯乙烯共聚表现出良好的聚合性能，从而为高效镍金属催化剂的开发提供理论依据。     

苯胺基肟类钯催化剂的合成及其催化烯烃聚合的研究

本文通过一步法制备了新型的苯胺基肟类中性钯催化剂,并通过核磁氢谱、核磁碳谱、元素分析对相应的配体和催化剂结构进行了测试表征,结果表明,成功制备了所设计的配体以及相应催化剂。进一步研究了钯催化剂对催化降冰片烯单体的均聚合行为,结果表明,钯催化剂在助催化剂dMMAO作用下,可高活性催化降冰片烯单体的均聚合,活性高达540 kg/(mol Pd·h);同时发现,该催化剂的热稳定性好,可以在80℃以较高活性催化降冰片烯单体均聚合。     

New polymers by copolymerization of olefins with bio oil components

Oleic acid methyl ester can be converted by metathesis reaction in the presence of ethene into 1‐decene and 9‐decenoic acid methyl ester. Both components are suitable comonomers for the synthesis of polyolefin specialties by copolymerization with ethene or propene. For this copolymerization, metallocene/methylaluminoxane catalyst or other single‐site catalysts are more active than classical Ziegler‐Natta catalysts because they insert higher amounts of longer‐chain α‐olefins or olefins with polar groups. The microstructure of these copolymers can be tailored in a great variety using metallocene complexes with different symmetries.     

Synthesis and properties of ethylene/styrene copolymers produced by metallocene catalysts

Ethylene/styrene copolymers were synthesized under constant polymerization conditions using six different metallocene catalysts activated with methylaluminoxane. For all the catalysts used, the activity and molecular weight of the copolymers produced decreased with the amount of styrene in the reactor feed, but the styrene content of the copolymers increased. Catalysts with carbon bridges and bulky ligands gave rise to copolymers with higher styrene content. As a result of the increased styrene content of the copolymer, the melting temperature decreased. This effect was ascribed to a decrease in the crystallinity of the copolymers. It was also found that lamellar thickness could be significantly diminished by the incorporation of comonomers. The copolymers showed a broad spectrum of mechanical properties as a function of the comonomer ratio. At low styrene contents, they behaved like typical semicrystalline thermoplastics, and at higher styrene contents, they exhibited the properties typical of elastomers. Of the catalysts tested, [rac‐ethylenebis(4,5,6,7‐tetrahydro‐1‐indenyl)]zirconium dichloride emerged as the most promising for the production of ethylene/styrene copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3420–3429, 2006     

聚烯烃弹性体技术进展

聚烯烃弹性体为一类新型乙烯与高级α-烯烃共聚物，由于应用茂金属催化技术且分子结构中引入大量高级α-烯烃共聚单体并保留一定聚乙烯结晶相而兼备可塑性和弹性，具有良好的机械性能、加工性能和热性能。聚烯烃弹性体主要生产商有Exxon公司、Dow化学公司、Mitsui公司和LG公司，均采用溶液法聚合工艺及茂金属催化技术，其中,以Dow化学公司的Insite聚合工艺与CGC茂金属催化技术为代表，限定几何构型（CGC）催化剂为桥联单茂结构催化剂，其自身结构变化对催化性能影响较大，改变桥基团、Cp环上的烷基取代基和配位基团均可得到不同结构和性能的催化剂。Exxon公司采用Exxpol茂金属催化剂开发Exact塑性体［密度(0.860~0.915) g·cm^-3］，包括乙烯-辛烯共聚物、乙烯-己烯共聚物和乙烯-丁烯共聚物;采用同种催化技术，溶液法生产丙烯基弹性体，商品名为Vitamaxx。2003年，日本Mitsui公司-三井弹性体新加坡公司100 kt·a-1的乙丙橡胶弹性体装置投产，装置采用茂金属催化技术和独有的溶液法聚合工艺，商品名为Tafmer［密度(0.862~0.905) g·cm^-3］。韩国LG公司将独特的茂金属催化剂与溶液法聚合工艺相结合，生产聚烯烃弹性体［密度(0.865~0.903) g·cm^-3］，商品名为LUCENE。我国目前没有聚烯烃弹性体生产企业，开展过一些高共聚性能茂金属催化剂的研发，应用于聚烯烃弹性体技术开发。     

Influence of the catalyst matrix structure of the supported Ziegler-Natta catalysts on the homo- and copolymerization of olefins

The vanadium catalytic complexes immobilized on the same support (aluminium hydroxide, AH) and distinguished by structure and composition have been compared for ethylene and propylene homo- and copolymerization to find relationship between the polymerization activity, copolymerization relative reactivity of comonomers and the supported catalyst structure. The catalytic complexes of vanadium with supported aluminoxanes (II) and catalysts with dispersed solid phase of vanadium compounds on the support surface (III) are more active than catalyst (I) in which vanadium has the covalent bond with surface of support. The relative reactivity of comonomers in copolymerization also depends on type of supported catalyst. The catalysts III unlike I and II can produce the ethylene and propylene copolymers with high content of propylene. The promoting effect of propylene on ethylene polymerization rate takes place only in the presence of catalysts III. Received: 2 October 1996/Revised: 17 January 1997/Accepted: 23 January 1997     

Progress in the catalyst for ethylene/α-olefin copolymerization at high temperature

Ethylene/α-olefin copolymers are one of the most widely-used polyolefin materials. With the continuous improvement of polyolefin catalysts, high-performance polyolefin materials were synthesized by adjusting the chain microstructure, changing the comonomer type and comonomer insertion amount, among which the ethylene/α-olefin random copolymer elastomer (POE) and olefin block copolymer elastomer (OBC) are the most famous and well accepted by the market. The excellent properties of POE and OBC first depend on their polymer chain microstructure. The chain microstructure of polyolefins is fundamentally determined by the catalysts, polymerization conditions, comonomer feed policies, and reaction engineering. High-performance ethylene/α-olefin copolymer elastomers are currently prepared by high-temperature solution polymerization process, which needs to be carried out at a temperature above the melting point of the polymer and is beneficial to speed up the polymerization reaction rate and control the polyolefin chain microstructure. However, the high-temperature solution polymerization process launched more stringent requirements for the olefin coordination polymerization catalyst. Systematic reports on catalysts for high-temperature solution copolymerization of ethylene and α-olefins are lacking. In this review, we screened some catalysts suitable for the controllable copolymerization and high-temperature solution copolymerization of ethylene/α-olefin based on the catalyst's heat resistance, copolymerization activity, comonomer insertion ability, molecular weight, and distribution of the copolymer, including traditional Z–N catalysts, metallocene catalysts, and post-metallocene catalysts. And the future development of catalysts for high-temperature solution copolymerization of olefins, catalysts for precise control of polyolefin chain microstructures, and catalysts for olefin copolymerization with polar monomers at high temperature are envisaged.     

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

The behaviors of three different catalyst systems, TiCl₄/MgCl₂, Cp₂ZrCl₂ and Cp₂HfCl₂, were investigated in ethylene/1,5‐hexadiene copolymerization. In the Fourier transform infrared spectra of the copolymers, cyclization and branching were detected for 1,5‐hexadiene insertion in the metallocene and Ziegler–Natta systems, respectively. DSC and viscometry analyses results revealed that copolymers with lower T_m and crystallinity and higher molecular weight were obtained with metallocene catalysts. The sequence length distribution of the copolymers was investigated by using the successive self‐nucleation and annealing thermal fractionation technique. The continuous melting endotherms obtained from successive self‐nucleation and annealing analysis were employed to get information about short‐chain branching, the branching dispersity index, comonomer content and lamella thickness in the synthesized copolymers. The results established that metallocene catalysts were much more effective than Ziegler–Natta catalysts in the incorporation of 1,5‐hexadiene in the polyethylene structure. Metallocene‐based copolymers had higher short‐chain branching and comonomer content, narrower branching dispersity index and thinner lamellae. Finally, the tendency of the employed catalysts in the 1,5‐hexadiene incorporation and cyclization reaction was explored via molecular simulation. The energy results demonstrated that, in comparison to Ziegler–Natta, metallocene catalysts have a much higher tendency to 1,5‐hexadiene incorporation and cyclization. © 2018 Society of Chemical Industry     

Chain transfer reaction in metallocene catalyzed ethylene copolymerization with allyltrimethylsilane

Summary In order to investigate the polymerization behavior of allytrimethylsilane as a comonomer, ethylene was copolymerized with allyltrimethylsilane at 80°C in toluene using methylaluminoxane (MAO) activated metallocene catalysts. The catalytic activity of the polymerization strongly depended on both the type of the catalysts and the concentration of allyltrimethylsilane. End group analysis of the copolymers by means of ¹H and ¹³C NMR spectroscopy revealed that allyltrimethylsilane rather act as a chain transfer agent in the copolymerization, even though considerable amount of allyltrimethylsilane was incorporated in the polymer chain with rac-Et(Ind)₂ZrCl₂ catalysts. The chain transfer reaction influence strongly the molecular weight and comonomer content of the copolymers. Received: 22 June 1999/Revised version: 9 September 1999/Accepted: 30 September 1999     

Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004     

不同形貌介孔材料催化剂的制备及在乙烯聚合中的应用

利用面包圈状、棒状、高比表面积球状和空心球状4种不同形貌的介孔材料作为载体负载甲基铝氧烷和茂金属双（正丁基环戊二烯基）二氯化锆（BuCp）制备负载型茂金属催化剂,并在2 L不锈钢高压聚合釜进行高压乙烯聚合小试试验。文中研究了4种反应器的组成、结构和微观形貌。扫描电镜、小角X光粉晶衍射、氮气吸附-脱附测试结果表明,4种不同形貌介孔材料在负载茂金属后仍然保持较好微观形貌及其特有的介孔材料孔道结构,负载茂金属后反应器的孔结构参数较负载前有所减小,孔壁厚度有所增强,表明茂金属成功进入介孔材料孔道中。元素分析结果表明,所得催化剂表面的Al元素质量分数范围为16%～22%,Zr元素质量分数范围为0.4%～0.7%。聚合试验结果表明,催化剂对乙烯均聚和共聚的活性均优于当前工业用载体955硅胶负载同样茂金属后的乙烯均聚和乙烯和己烯共聚的活性,其中空心球状介孔材料反应器为最适合乙烯聚合的催化剂。