功能化聚烯烃合成:从催化剂到极性单体设计

由于极性基团的存在,烯烃与极性单体配位共聚反应受限于低聚合活性与低聚合物分子量.因此,解决极性单体中极性基团问题是功能化聚烯烃高性能合成的关键.本文旨在重点评述近年来后过渡金属催化烯烃与极性单体共聚制备功能化聚烯烃方面的研究进展.首先简要概括了功能化聚烯烃合成用催化剂的里程碑式发展,然后详细论述了近年来我们在功能化聚烯烃合成用极性单体设计上的系列研究发现,重点突出了设计极性二乙烯基单体克服极性单体问题(快的链转移反应与极性基团对中心金属的螯合)的概念与设计含次级配位作用的乙烯基呋喃单体合成新型功能化聚烯烃的策略;最后展望了烯烃与极性单体共聚制备功能化聚烯烃的未来重点发展方向与挑战.     

膦酚中性镍催化烯烃聚合及烯烃与极性单体共聚研究进展

烯烃与极性单体共聚制备功能化聚烯烃最为直接,但存在诸多挑战,是聚烯烃领域近20年的研究热点与难点。后过渡金属催化剂在功能化聚烯烃合成上具有优势,已经涌现出了二亚胺、水杨醛亚胺、膦磺酸镍钯经典催化体系;相比之下,膦酚镍催化体系早期关注较少。然而,近期对于膦酚镍催化体系的研究已经揭示,膦酚镍催化体系将是一个极具基础与应用前景的体系。本文总结近5年膦酚镍催化剂的结构特点,综述其在乙烯聚合、乙烯与极性单体共聚合、丙烯与极性单体共聚合方面的重要进展,并总结出膦酚镍催化剂的优势,对极性单体种类、催化剂结构设计、丙烯与极性单体立构规整共聚、聚合反应机理、功能化聚烯烃综合性能进行了展望。     

稀土金属配合物催化芳香型乙烯基极性单体立构选择性聚合

鉴于聚合物的立构规整度对其性能起着重要的作用,如何提高聚合物的立构规整度一直以来都是配位聚合领域的重要研究课题。经过几十年的发展,配位聚合已经在 α-烯烃、苯乙烯、共轭二烯烃等非极性烯烃单体的立构选择性聚合方面取得了巨大的成就。但非极性聚烯烃材料表面性能差,而化学性质稳定,难以被后功能化。因此通过极性单体的立构选择性聚合将极性基团引入聚烯烃大分子链中对于提高其性能具有非常重要的意义。然而,在传统的配位聚合中,单体上的极性原子(基团)易于向金属中心配位,导致催化体系失去立构选择性,甚至失去活性。因此选择合适的配体、金属种类与极性单体组合的策略对实现立构选择性聚合至关重要。近年来,针对2-乙烯基吡啶、含杂原子苯乙烯衍生物以及硼氮杂芳香型乙烯基单体的定向聚合,开发了大量的稀土金属配合物催化体系,聚合物的立构规整度取得了较大的突破,同时对单体上极性原子在聚合中的作用也有了新的认识。本综述以单体种类为主线,详细讨论了配体的结构、取代基的电子效应、空间位阻效应、中心稀土金属种类和聚合溶剂等对催化剂聚合活性、立构选择性的影响,并探讨可能的聚合反应机理。     

极性乙烯基单体立体选择性聚合催化剂

极性单体是指带有极性基团的烯烃类单体,主要包括含卤素类极性单体、含氧类极性单体、含氮类极性单体和含磷类极性单体。其中带有乙烯基且与所带极性基团相共轭的极性单体称为极性乙烯基单体,如甲基丙烯酸甲酯、2-乙烯基吡啶和乙烯基磷酸酯等。这类单体所形成的极性乙烯基聚合物是极性基团作为侧链的烯烃聚合物,该类化合物在黏性、韧性、界面性质(染色性和印刷性)、与溶剂或其他聚合物的相容性方面较传统非极性聚烯烃材料有明显的优势。为了使聚合物具有好的物理性能,获得具有一定规整度的聚合物是近年来研究的热点。聚合物的立体结构对其本身的物理性能有着显著的影响,如熔点、玻璃化转变温度和机械性能等。获取立构规整性聚合物的最有效方式是发展催化聚合反应的立体选择性催化剂。本文综述了近几年极性乙烯基单体立体选择性聚合催化剂的研究进展,这里所涉及的极性乙烯基单体包括:丙烯酸酯类、丙烯酸酰胺、乙烯基磷酸酯、乙烯基吡啶和杂原子取代苯乙烯单体。所涉及的聚合体系是配位聚合、路易斯酸碱对和阴离子聚合体系。     

边臂策略在聚烯烃催化剂设计中的应用

提出用"边臂"策略设计和改造烯烃聚合催化剂,以钛、镍等配合物为模型,系统研究了边臂基团对配合物的配位模式、配合物的稳定性,对乙烯均聚活性以及乙烯与α-烯烃、环烯烃以及极性单体共聚合的活性和对聚烯烃的结构与性能的影响.研究结果表明通过边臂基团可以调节催化中心的空间形状和电子特性,实现对催化物种性质的控制与调节,调控烯烃聚合活性和聚烯烃的结构与性能.     

功能化聚烯烃材料的制备与性质研究

聚烯烃年产量巨大、用途广泛,但是其最大的缺点之一是其非极性.向非极性聚烯烃中引入少量的极性官能团可以极大地改善其性质、拓宽其用途、提高其商业价值.因此,功能化聚烯烃材料受到了学术界和工业界一致的关注.本文将主要基于作者课题组的相关工作,介绍其在催化剂结构创新、极性单体的选择、聚合新技术等方面的研究进展.在此基础之上,制...     

聚烯烃-极性聚合物嵌段共聚物最新研究进展

聚烯烃-极性聚合物嵌段共聚物(polyolefin-b-polar polymer block copolymer,POBP)包含非极性/非功能化聚烯烃和极性/功能化聚合物嵌段,由于其独特的结构和性能特点,引起了人们的广泛关注。POBP的传统用途是作为聚烯烃和其它材料(如极性聚合物)的增容剂,近年来在诸多新兴的研究领域也取得了一定应用,包括多孔渗透膜、功能性杂化纳米材料、固体聚合物电解质等。POBP的制备方法主要两种:(1)配位聚合向其它聚合方式的聚合机理转变,即首先由配位聚合制备出聚烯烃大分子引发剂,随后引发极性单体聚合得到POBP;(2)聚烯烃反应性功能化端基与极性聚合物反应性端基之间的偶联反应。本文综述了POBP的最新研究进展,重点评述了新颖的合成路径和POBP在制备新型功能材料方面的应用进展。     

后过渡金属配合物催化烯烃-极性单体共聚

在非极性聚烯烃链中引入少量极性基团可明显改善聚烯烃材料性能.依据配合物种类全面综述了2010年以来后过渡金属配合物催化烯烃-极性单体共聚研究进展.从α-二亚胺、膦酚和水杨醛亚胺型配合物到酮胺、膦磺酸、膦-氧化膦和N-杂环卡宾型等多种新型骨架结构配合物,总结了这些催化剂对催化活性、共聚物分子量、极性基团插入率、共聚物微观结构和材料性能的有效调控.尽管取得了许多重要进展,这一领域产业化和商业化应用依然面临诸多限制和挑战.展望了应对这些挑战需要关注的问题.     

膦基苯磺酸(PO)金属配合物催化乙烯与极性单体的共聚反应及其机理研究进展

含有膦基苯磺酸(PO)配体的烷基金属配合物表现出罕见的烯烃聚合催化性质,其不但可以催化乙烯均聚形成线性聚乙烯,而且可以催化乙烯与众多的极性单体如CH2=CHX、CO等共聚产生功能化线性聚烯烃.总结了PO配体的结构特点和(PO)Pd(Ⅱ)配合物引发的新型聚合反应,综述了(PO)Ni(Ⅱ)催化剂在催化乙烯和极性单体共聚方面的应用,以及含有膦基二磺酸配体OPO的Pd(Ⅱ)、Ru(Ⅳ)催化剂的特殊催化性质.另外,从配体的对称性、柔性和轴向官能团位阻以及纯电子效应等方面对PO金属催化剂的构效关系和共聚催化反应机理进行了探讨.     

非茂钯催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合的研究

本文探索了乙烯/丙烯/极性单体三元共聚物的合成方法.乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚物由于分子中引入了ω-Cl-α-乙烯基极性单体,改变了乙烯丙烯共聚物的化学惰性.我们采用催化剂Cat.L-Pd配位催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,合成了极性三元无规共聚物.探讨了催化剂结构、聚合条件对三元共聚合行为的影响,并优化了聚合条件.采用红外光谱(FTIR)、核磁共振碳谱(氢谱)(~(13)C(~1H)NMR)、示差扫描量热(DSC)和高温凝胶渗透色谱(GPC)等方法研究了共聚物的结构与性能.FTIR与~(13)C(~1H)NMR结果表明,催化剂Cat.L-Pd能够有效催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,共聚物中ω-氯代极性单体的插入量达3.6 mol%.极性单体不发生均聚合反应,但能够有效参与乙烯和丙烯的共聚合反应,形成三元无规共聚物.丙烯能够发生均聚合反应,但是不能形成聚丙烯长链段,主要发生乙烯与丙烯共聚合反应.乙烯最易发生聚合反应,并能够形成较长链段的聚乙烯.共聚物的Mw高于2×10~5g/mol.分子量分布在1.6～3.0,说明该类催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合行为遵循单中心聚合机理.     

The World of Synthetic Polymers.An Industrial Perspective

Synthetic polymers have become the building block in almost every aspects of our daily life. Billions of pounds of polymers are produced each year and the demand is continuously growing both in terms of volume and advanced performance. The general property of a class of polymers is often bounded by the synthetic process that produces the polymer. For example,polyolefins, are non-polar polymers due to the poor tolerance of transition metal catalysts toward polar monomers. Conversely, latices are polar polymers, since the emulsion polymerization process limits the use of non-polar monomers which have low solubility in water. It is highly desirable to be able to design polymer systems with optimum polarity balance to meet the application demand while staying within the industrial manufacturing constraints.An overview of industrial polymerization methods will be followed by a presentation on the recent development of a new emulsion polymerization technology. The technology involves the use of Cyclodextrin, acting as "Phase Transport Catalyst", facilitating the diffusion of very hydrophobic and water insoluble monomers through the aqueous medium. A new class of latex polymers and their attributes will be discussed.     

Asymmetric Cationic [P,O] Type Palladium Complexes in Olefin Homopolymerization and Copolymerization

Metal‐catalyzed ethylene homopolymerization and ethylene‐polar monomer copolymerization to produce new kinds of polyolefins with novel microstructures are of great interest. So far, there are some disadvantages for traditional transition metal catalyst systems. Therefore, it is critical to develop new catalysts or alternative strategies. In recent years, some cationic [P, O] palladium complexes have been demonstrated with the abilities to obtain oligomers and the high molecular weight polymers. Most importantly, these complexes showed high activity and generated polymers with specific microstructures when used for copolymerization of ethylene with industrially relevant polar monomers. This review summarizes several types of high performance cationic [P, O] palladium catalysts in ethylene oligomerization, ethylene homopolymerization and the copolymerization of ethylene with polar monomers. Specially, the regulation of steric and electronic effects at specific sites of the metal complexes was focused.     

直接共聚法制备功能化聚烯烃研究进展

从催化剂研究发展的角度概述了直接配位共聚法制备功能化聚烯烃的研究现状 ,重点讨论了催化剂的结构 ,主催化剂和助催化剂以及催化剂和极性基团之间的相互作用对直接功能化聚合反应的影响。     

Recent Advances in Transition Metal-Based Catalysts for Ethylene Copolymerization with Polar Comonomer

The synthesis of polar functionalized polyolefin (PFP) offers improvement in mixing properties, polymer surface, and rheological properties with the potential of upgraded polyolefins for modern and ingenious applications. The synthesis of PFP from metal-based catalyzed olefin (non-polar in nature) copolymerization with polar comonomers embodies energy-efficient, atom-efficient, and apparently an upfront methodology. Despite their outstanding success during conventional polymerization of olefin, 3^rd and 4^th group (early transition metal)-based catalysts, owing to their electrophilic nature, face challenges mainly due to Lewis basic sites of the polar monomers. On the contrary, late transition metal-based catalysts have also made progress, in recent years, for PFP synthesis. The recent past has also witnessed several advancements in the development of dominating palladium-based catalysts while their lower resistance towards ligand functional groups has limited the practical application of abundant and cheaper nickel-based catalysts. However, the relentless efforts of the scientific community, during the past half-decade, have indicated rigorous progress in the development of nickel-based catalysts for PFP synthesis. In this review, we have abridged the recent research trends in both early as well as late transition metal-based catalyst development. Furthermore, we have highlighted the role of transition metal-based catalysts in influencing the polymer properties.     

Novel polyolefin materials via catalysis and reactive processing

Recent advances in transition metal catalyzed olefin polymerization and melt processing stimulate the production of new polymers derived from old monomers. Modern polyolefin processes do not require polymer purification and give excellent control of molecular and supermolecular polyolefin architectures. Progress in catalyst design and preparation of tailor-made homo-and copolymers is highlighted for isotactic, syndiotactic, atactic and stereo-block polypropylene (PP), novel 1-olefin copolymers, and ethylene copolymers with polar monomers, e.g., CO and acrylics. Today polyethylene short-and long-chain-branching is controlled either by uniform ethylene copolymerization with 1-olefins using single-site” metallocene catalysts, or by migratory polyinsertion of ethylene, respectively. Stiff cycloaliphatic polymers expand the frontiers of polyolefins into engineering applications. New families of polyethylenes and EPM with pendent polypropylene chains are obtained via copolymerization of PP macromonomers or polymer-analoguous coupling of functionalized PP during melt processing.     

Synthesis of functional polyolefins using cationic bisphosphine monoxide-palladium complexes

The copolymerization of ethylene with polar vinyl monomers, such as vinyl acetate, acrylonitrile, vinyl ethers, and allyl monomers, was accomplished using cationic palladium complexes ligated by a bisphosphine monoxide (BPMO). The copolymers formed by these catalysts have highly linear microstructures and a random distribution of polar functional groups throughout the polymer chain. Our data demonstrate that cationic palladium complexes can exhibit good activity for polymerizations of polar monomers, in contrast to cationic α-diimine palladium complexes (Brookhart-type) that are not applicable to industrially relevant polar monomers beyond acrylates. Additionally, the studies reported here point out that phosphine-sulfonate ligated palladium complexes are no longer the singular family of catalysts that can promote the reaction of ethylene with many polar vinyl monomers to form linear functional polyolefins.     

Polymerization in non-aqueous lyotropic liquid crystals: Influence of the unsaturation site

Two surfactants, bis[2-(dodecyloxycarbonyl)ethyl](p-vinylbenzoyl)methylammonium chloride (SI) and bis[2-(10-undecenoyloxycarbonyl)ethyl](p-methylbenzoyl)methylammonium chloride (SII) were synthesized and copolymerized with polar and non-polar monomers to form regularly layered structures.The results showed a pronounced difference between the two surfactants. SI with the double bond close to the polar group accepted a large number of monomers, in contrast to the behavior of SII. For SI the polymerization changed the conformation of the p-vinylbenzoyl group depending on the location of the added monomer while copolymerization of the monomers with SII gave no significant change.A comparison with earlier results from bis[2-(10-undecenoyloxycarbonyl)ethyl](p-vinylbenzoyl)methylammonium chloride provided proof of copolymerization of all the groups.     

Polymerization of Polar Monomers Using Cyclopentadienyl Complexes of the Alkaline Earth Metals

Tetramethylcyclopentadienyl complexes of magnesium, calcium and strontium are efficient catalysts at −78 °C for the solution polymerization of polar monomers such as alkyl methacrylates in the presence of only small amounts of triethylaluminium as cocatalyst. The molecular mass of the resulting polymers is predictable on the monomer/catalyst ratio. The polymerization reaction follows a first order kinetics with respect to the initial catalyst concentration. Block-copolymers are easily available by sequential dosage of the monomer. A living polymerization mechanism is proposed involving activation of the catalyst by alkylation and subsequent insertion of coordinated monomers.     

Influence of Polyethylene Glycol Unit on Palladium‐ and Nickel‐Catalyzed Ethylene Polymerization and Copolymerization

The transition‐metal‐catalyzed copolymerization of olefins with polar functionalized co‐monomers represents a major challenge in the field of olefin polymerization. It is extremely difficult to simultaneously achieve improvements in catalytic activity, polar monomer incorporation, and copolymer molecular weight through ligand modifications. Herein we introduce a polyethylene glycol unit to some phosphine‐sulfonate palladium and nickel catalysts, and its influence on ethylene polymerization and copolymerization is investigated. In ethylene polymerization, this strategy leads to enhanced activity, catalyst stability, and increased polyethylene molecular weight. In ethylene copolymerization with polar monomers, improvements in all copolymerization parameters are realized. This effect is most significant for polar monomers with hydrogen‐bond‐donating abilities.     

Computational insights on the challenges for polymerizing polar monomers

Taking Pd di-imine catalysts as an example, we use first principles density functional theory (B3LYP/6-31G) to investigate the chain propagation steps for polymerization of polar monomers. We start with the complex formed from insertion of ethylene into the polymer chain and consider insertion into the Pd-C bond for each of four polar monomers: methyl acrylate, vinyl acetate, vinyl chloride, and acrylonitrile. We find 2,1-insertion is favored in each case (by 3 to 5 kcal/mol), resulting in a product with a strong interaction of the polar group for the growing polymer chain with the metal. Next, we insert another unit of the same polar monomer or an ethylene unit (except for acrylonitrile). We optimize the structures for all important intermediates and transition states using a continuum dielectric to account for solvation effects. These studies pinpoint the critical difficulties in designing catalysts to polymerize polar monomers.