On the Development of Titanium κ¹‐Amidinate Complexes, Commercialized as Keltan ACE™ Technology, Enabling the Production of an Unprecedented Large Variety of EPDM Polymer Structures

Abstract

ARLANXEO Elastomers has developed and commercialized Keltan ACE TM technology, a class of half-sandwich cyclopentadienyl j 1 -amidinate metal complexes, which are extremely active for the production of first-class ethylene/propylene/diene copolymers (EPDM). In this review, the development and some of the key features of the Keltan ACE TM catalyst system are presented. Many different ACE catalysts have been synthesized over the past years, including bridged and bimetallic catalysts. With Keltan ACE TM , a complete range of EPDM products with similar polymer characteristics as their Ziegler-Natta (ZN) counterparts can be produced, including variations containing very high 5-ethylidene-2-norbornene (ENB) contents, controlled long chain branching, very high molecular weight, as well as oil-extended products. Moreover, other EPDM structures can be polymerized. The Keltan ACE TM catalyst technology also allows the production of EPDMs with very high amounts of dicyclopentadiene (DCPD) or 5-vinyl 2-norbornene (VNB) without excessive gelation and reactor fouling, that is, products that cannot or are extremely difficult to obtain via classical ZN catalysis. In a next step, high-VNB-EPDM can be postreactor modified, for example, via metathesis chemistry. In addition, EPDM polymers with a very broad or even bimodal molecular weight distribution can be obtained in a single reactor with certain ACE catalyst structures at particular activator/precatalyst ratios. V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2877-2891 KEYWORDS: catalysts; EPDM; Keltan ACE Technology; polyolefins; post metallocene; product diversification; rubber INTRODUCTION The early 1950s can be considered as the start of the polyolefin age. Since then, the production and consumption of olefin-based polymeric materials have been steadily increasing to high volumes. Intense catalyst and product development has resulted in a wide range of different types of polyolefins each with designed properties and applications.

Controlled polymerization of olefin and its macromolecular engineering

“…目前, Z-N钒系催化剂是工业生产乙丙橡胶广泛采用的催化 剂, 产能占乙丙橡胶总产能的70%以上, 所制备的乙丙 橡胶具有分子量高、共聚物链段无规度高、不易结 晶、共聚物易加工等特点, 同时催化剂成本低且易溶 于烃类溶剂、工艺成熟, 但钒系催化剂的催化活性低, 工业生产中需要水洗工艺脱除聚合产物中的催化剂残 留物 [3] . 近年来, 茂金属催化剂在乙丙橡胶生产中所占 [9,10] .…”

Progress in advanced catalyst and their use in ethylene/propylene copolymerization

“…DSM公 司在Nova公司技术的基础上开发了一系列含单阴离 子配体的单茂钛催化剂. 含脒基配体的单茂钛化合 物22(图8)催化乙烯/丙烯/非共轭二烯三元共聚时具 有高催化活性(~4.7×10 7 g mol −1 h −1 bar −1 ) [62,63] . Lanx-ess公司采用此类催化剂开发的先进催化弹性体技术 (advanced catalysis elastomers, ACE)已成功应用于高 品质乙丙橡胶的工业化生产 [60,64] .…”

Polar‐Functionalized, Crosslinkable, Self‐Healing, and Photoresponsive Polyolefins

“…Thef ully saturated hydrocarbon backbone results in good stability towards oxidative and thermal degradation as well as high resistance against aqueous media and polar solvents. [33,34] In EPDM synthesis,t he ethylidene norbornene (ENB) comonomer is widely used owing to its high copolymerization activity as well as its ability to maintain high polymer molecular weights even at high comonomer incorporations.…”