Investigationofthedeformationofhomogeneous polyethylene. Here, we describe a new trinuclear pnp ligand that displays higher activity and a long lifetime for ethylene tetramerization to 1octene. Thermal properties of ethylene octene copolymer engage. Disclosed herein is a method of preparing 1 octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromiumbased catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a pccp backbone structure ligand represented by r 1 r 2 pr 5 chchr 6 pr 3 r 4. The trimerization and tetramerization of ethylene to 1 hexene and 1 octene with a crpnpalet3 catalyst system, in combination with a variety of cocatalysts, has been investigated. Sasol builds worlds first ethylene tetramerization unit in.
Ep2107943a4 ethylene tetramerization catalyst systems and. When comparing the homogeneous ligands with their heterogeneous counterparts, the latter showed a fourfold drop in activity compared to their homogeneous counterparts. Here, we describe a new trinuclear pnp ligand that displays higher activity and a long lifetime for ethylene tetramerization to 1 octene. The ligand combined with criii, activated with methylaluminoxane, lead to highly active and longlifetime catalytic systems for the tetramerization of ethylene to form 1octene. Chromiumbased catalyst for ethylene tetramerization to 1 octene p. Polyethyleneco1octene granular translucent sigmaaldrich. Ethylene tetramerization with a highly active and long. Poe, a relatively novel polyolefin elastomer, was developed by dow chemical co. The catalytic activities and selectivity to 1octene of fourmembered catalytic systems for ethylene tetramerization are strongly affected by reaction temperature, as shown in table 1. While there exists several processes for producing 1hexene via ethylene trimerization, a similar route for the selective production of 1octene has so far been elusive. The effects of reaction temperature, reaction pressure, alti. Chromiumbased catalyst for ethylene tetramerization to 1.
For example, engage has been used to modify the impact strength of polypropylene copolymer 18, 19. Among the laos, 1 hexene and 1 octene are particularly attractive as they allow the formation of copolymers with good tear resistance and other desirable properties. A new route to produce 1octene in exceptionally high selectivities linear alphaolefins, such as 1hexene and 1octene, are important comonomers in the. Ethylene tetramerization catalyst systems comprising. The results indicate that the catalyst system can yield 1octene in selectivities up to 80%. Disclosed herein is a method of preparing 1octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromiumbased catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a pccp backbone structure ligand represented by r 1 r 2 pr 5 chchr 6 pr 3 r 4. Trimerization and tetramerization of ethylene in continuous. Apr 21, 2020 pdf data on the activity, selectivity, and reaction conditions for the selective oligomerization of ethylene to octene1 mediated by chromiumcontaining organic. In 2004, researchers from sasol reported the first catalyst for the selective conversion of ethylene to 1octene, which was consisted of pnp ligand, chromium source and methylaluminoxane. A cyclohexyl 2 pch 2 ch 2 p cyclohexyl 2 ligand was prepared by reacting diphenylphosphine with 2 equivalents of dibromoalkyl in dimethylfluoromethylene dmf and cesium hydroxide. Ethylene tetramerization 1octene pdf boden seeland. The catalytic activity increases initially with temperature and reaches a maximum around 50 c. Whereas 1 produces an ethylene trimerization system, 2 provides an unprecedented ethylene tetramerization system that produces 1. The conventional method of producing 1hexene and 1octene is by oligomerization of ethylene, which yields a wide spectrum of linear.
Sasol builds worlds first ethylene tetramerization unit. Tetramerization of ethylene using cr 2ethylhexanoate h. Ethylene tetramerization cocatalyst introduction 1 hexene and 1 octene are versatile intermediates for petrochemical industry and widely used as comonomers for the production of linear lowdensity polyethylene 1. Trimerization of ethylene to 1hexene and tetramerization of ethylene to 1octene have gained increased attention recently due to the importance of 1hexene and 1octene in the production of linear lowdensity polyethylene lldpe. Since its discovery, a rapid increase in the number of publications and patents have been reported for selective ethylene tetramerization, among which much attention has been paid to the electronic and. Pdf data on the activity, selectivity, and reaction conditions for the selective oligomerization of ethylene to octene1 mediated by chromiumcontaining organic. The selectivity of the tetramerization systems depends on the capability of ligands to form binuclear complexes that subsequently build up and couple two separate metallacyclopentanes to form 1. Recommendation for ethyleneoctene copolymer flavor usage levels up to. The synthesis and characterization of a novel trinuclear diphosphinoamine ligand 2 are reported. Kuhlmann, ethylene tetramerization a new route to produce 1octene in exceptionally high selectivities, j. Among the laos, 1hexene and 1octene are particularly attractive as they allow the formation of copolymers with good tear resistance and other desirable properties.
Sep 20, 2019 chromiumbased catalyst for ethylene tetramerization to 1octene. The cocatalysts bc 6 f 5 3 1, aloc 6 f 5 3 2, et 2 o 2 haloc 6 f 5 4 3, ph 3 ctaoc 6 f 5 6 4, et 2 oalochc 6 f 5 2 3 5, et 2 oaloccf 3 3 3 6, ph 3 caloccf 3 3 4 7. The introduction of an additional ch 2 group into the bridge of ligands with two pn units leads to a different selectivity of the corresponding chromium. Chapter 1 the selective oligomerization of ethylene using. A new route to produce 1 octene in exceptionally high selectivities linear alphaolefins, such as 1hexene and 1 octene, are important comonomers in the. The promoters play an important role to assist central metal of pertinent catalyst system to achieve high desired product. Mao catalyzed ethylene tetramerization toward 1octene core. We were attracted by the potential for using chromium as an ethylene tetramerization active center because of its high catalytic activity and high selectivity to 1 octene. The alkene is classified as a higher olefin and alphaolefin, meaning that the double bond is located at the alpha primary position, endowing this compound with higher reactivity and thus useful chemical properties. An alternative concept for the selective catalytic formation of 1. Recent years have witnessed considerable activity in the tri and tetramerization of ethylene for the production of 1 hexene and 1. Preparation of 1octene by the selective tetramerization. Ethylene tetramerization with a highly active and longlifetime. The solution was reacted for 72 hours at room temperature, and 60 ml of distilled water was added thereto, and the solution was extracted three times using 60 ml of dmc to form an organic layer.
Preparation of 1octene by ethylene tetramerization with high. An alternative mechanistic concept for homogeneous. Ethylene tri and tetramerization with borate cocatalysts. At ethylene pressures of higher than 3 bar the formed 1hexene and 1octene condensed inside the porous system, thereby facilitating the dissolution and redistribution of the crpnp catalyst. Characterization of ethylene olefin copolymers made with.
We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1octene in selectivities exceeding 70%, using an aluminoxaneactivated. Among the laos, 1hexene and 1 octene are particularly attractive as they allow the formation of copolymers with good tear resistance and other desirable properties. Another novel diphoshinoamine ligands ar2p2n2rrcyclopropylamine also were synthesized and characterized. The trimerization and tetramerization of ethylene to 1hexene and 1octene with a crpnpalet3 catalyst system, in combination with a variety of cocatalysts, has been investigated. The conventional method of producing 1hexene and 1 octene is by oligomerization of ethylene, which yields a wide spectrum of linear. Pdf data on the activity, selectivity, and reaction conditions for the selective oligomerization of ethylene to octene1 mediated by. December 11, 2019 pdf data on the activity, selectivity, and reaction conditions for the selective oligomerization of ethylene to octene1 mediated by chromiumcontaining organic. Silylateddiphosphinoamines for selective ethylene tri. Chromiumbased catalyst for ethylene tetramerization to 1octene. The results showed that the catalytic activity could be increased twice and the polymer production could be reduced efficiently through hydrogen addition. Effects of halide in homogeneous criiipnpmao catalytic. The selectivitydetermining mechanistic steps of ethylene tetramerization and trimerization are evaluated in light of isotopic labeling experiments. Us20180016206a1 ethylene tetramerization catalyst system.
The pccp backbone structure ligand according to the present invention, which is a ligand having an independent structure, unlike a conventional hetero r n pn r p r m ligand, has only one hetero atom, phosphorus pin the backbone structure thereof. While there exists several processes for producing 1 hexene via ethylene trimerization, a similar route for the selective production of 1 octene has so far been elusive. So we can draw a conclusion that the steric hindrance, the molecular stability, the halides group configuration, and the types of the halides are important factors for ethylene tetramerization toward 1 octene. The effect of hydrogen addition on the catalytic activity and product selectivity of pnpcriiimao catalytic systems for ethylene tetramerization was investigated. Ethylene tetramerization for 1octene production ethylene dimerization for 1butene production ethylene trimerization for 1hexene production ethylene tetramerization technology has been analyzed on the basis of information and concepts extracted from the technical articles and patents of sasol. Recommendation for ethyleneoctene copolymer usage levels up to. Ethylene petrochemical c 4 streams coalsynthesis gas full range processes dimerization trimerization tetramerization telomerization synfuel byproducts distillation butene 1 hexene 1 octene 1 pepp comnomer eicosene 1 highers dodecene 1 decene 1 tetradecene 1 hexadecene 1 octadecene 1 polybutene 1 detergent alcohols lab surfactants alkyl.
Copolymerization of ethylene with norbornene or 1octene. It could be inferred from the analysis and characterization results of the. Copolymerization of ethylene with norbornene or 1octene using supported ionic liquid systems wioletta oche. A highly selective ethylene tetramerization catalyst. Ethyleneoctene copolymer poe toughened polyamide 6.
The ligand combined with criii, activated with methylaluminoxane, lead to highly active and longlifetime catalytic systems for the tetramerization of ethylene to form 1 octene. A new route to produce 1octene in exceptionally high. The trimerization and tetramerization of ethylene to 1hexene and 1octene with a crpnpalet 3 catalyst system, in combination with a variety of cocatalysts, has been investigated. The trimerization and tetramerization of ethylene to 1hexene and 1 octene with a crpnpalet 3 catalyst system, in combination with a variety of cocatalysts, has been investigated. A mechanism based upon a shared chromacycloheptane intermediate rather than the cc coupling of chromacyclopentanes or cr speciation into independent trimerizat recipients of the dalton transactions uc berkeley lecture. Ethylene tetramerization cocatalyst introduction 1hexene and 1octene are versatile intermediates for petrochemical industry and widely used as comonomers for the production of linear lowdensity polyethylene 1.
Technical descriptions and economic analysis are provided herein for the following technologies. Engage, a relatively new copolymer of ethylene and 1octene, is a commercially available polyole. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1 octene in selectivities exceeding 70%, using an aluminoxaneactivated. The improvement of chloride on 1 octene formation selectivity and catalytic activity was much better than that of a corresponding bromide. A highly selective ethylene tetramerization catalyst shaikh. Preparation of 1octene by ethylene tetramerization with. Ethylene trimerization and tetramerization route largely avoids the production of undesired olefins that conventional fullrange olefin. Recent work includes the development of increasingly more active systems for fullrange oligomerization,1 a variety of crbased ethylene trimerization systems,24 and the first example of selective ethylene tetramerization to 1octene. Mao is requisite in forming active species for ethylene tetramerization toward 1 octene. On the basis of the previous work of bollmann, a diphosphinoamine ligand ar 2 p 2 nr 1 r 1 cyclopentyl was synthesized by introducing cyclopentyl.
Catalysts that can selectively generate 1hexene or 1octene from. The results show that these catalyst systems are able to catalyze ethylene tetramerization, with high catalytic activity up to 0. Publishers pdf, also known as version of record includes final. We were attracted by the potential for using chromium as an ethylene tetramerization active center because of its high catalytic activity and high selectivity to 1octene. For ethylene1octene copolymers, the activity of the supported catalysts and the amount of 1octene incorporated into the copolymer is dependent upon the substituents on the cyclopentadienyl. Template for electronic submission to acs journals technische. While there exists several processes for producing 1hexene via ethylene trimerization, a similar route for. Recent years have witnessed considerable activity in the tri and tetramerization of ethylene for the production of 1hexene and 1. Dec 11, 2019 method for producing ethylene tetramerization catalyst system and 1octene using the same. Further studies were conducted at pressures up to 35 bar at which a change in the primary reaction selectivity from 1hexene to 1octene could be observed.
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