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Ethylene

Ethylene is a colorless, flammable gas that plays a crucial role in plant growth and development.
As a key phytohormone, ethylene regulates a wide range of physiological processes, including fruit ripening, flower senescence, and stress responses.
Researchers studying ethylene's impact on plant biology can leverage PubCompare.ai to optimize their research workflow.
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Most cited protocols related to «Ethylene»

Synthesis of Photopolymerizable PEGDA

Cited 75 times

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Publication 2009

acryloyl chloride Anabolism Ethyl Ether Hydroxyl Radical Molar poly(ethylene glycol)diacrylate Toluene triethylamine

SARS-CoV-2 RBD-ACE2 Complex Purification and Crystallization

Cited 63 times

To purify the RBD/ACE2 complex, human ACE2 and RBD were incubated together, and then the complex was purified on Superdex200 gel filtration chromatography. RBD/ACE2 crystals were grown in sitting drops at room temperature over wells containing 100 mM Tris (pH 8.5), 18-20% PEG 6000, and 100 mM NaCl. Crystals were soaked briefly in 100 mM Tris (pH 8.5), 30% PEG 6000, 100 mM NaCl, and 30% ethylene glycol before being flash-frozen in liquid nitrogen. X-ray diffraction data were collected at the Advanced Photon Source beamline 24-ID-E. The structure was determined by molecular replacement using the structure of human ACE2 complexed with SARS-CoV RBD as the search template (Protein Data Bank accession code 2AJF). Structure data and refinement statistics are shown in Extended Data Table.1.

Shang J., Ye G., Shi K., Wan Y., Luo C., Aihara H., Geng Q., Auerbach A, & Li F. (2020). Structural basis of receptor recognition by SARS-CoV-2. Nature, 581(7807), 221-224.

Publication 2020

ACE2 protein, human Freezing Gel Chromatography Glycol, Ethylene Homo sapiens Nitrogen Polyethylene Glycol 6000 Severe acute respiratory syndrome-related coronavirus Sodium Chloride Tromethamine X-Ray Diffraction

Accurate Annotation of Biologically Relevant Ligands

Cited 45 times

An accurate annotation of the biological relevance of the ligand entries is essential to the BioLiP data collection. A ligand molecule present in a target protein is considered as biologically relevant if it interacts with the protein and plays certain biological roles, such as inhibitor, activator and substrate analog (3 (link),7 (link)). To guarantee the high accuracy and speed, we developed a composite automated and manual procedure as outlined in Figure 1. First, an automated four-step hierarchical procedure is used to verify the biological relevance of a ligand. After the automated procedure is completed, a careful manual check is performed to eliminate possible false positives, which can occur for entries with the commonly used crystallization additives.
To speed up the annotation procedure as well as increase the accuracy, we manually pre-collected a set of 353 suspiciously non-biological ligands, which are frequently used for the protein structure determination (including crystallization additives, non-biological ions, heavy metal and so on.) To generate this list, we first collected all ligands that are observed for >20 times in known protein structures. This list was refined further by analyzing the possible biological role of these ligands, e.g. a ligand is removed from the list if it is found to have biological relevance in the related literature of the structure file or is present in the KEGG database (26 (link)). This list is used to help assess the biological relevance of each ligand in PDB automatically (Figure 1) and is available at http://zhanglab.ccmb.med.umich.edu/BioLiP/ligand_list.
The automated filtering procedure consists of four steps:

First, if the candidate ligand is in the artifact list and appears >15 times in the same structure file, then it is likely to be crystallization additive and is considered as biologically irrelevant.

Second, the contacts between the receptor and ligand atoms are computed. The record ‘REMARK 350’ in the asymmetric unit files is used to exclude crystallization neighbors. This record presents which chains of the structure should be put together and the mathematical transformations (i.e. rotation and translation matrices) operated on each chain to generate biomolecules (i.e. biological unit files). The contacts between two chains are evaluated only when both chains are used to generate a biomolecule. For a receptor residue, if the closest atomic distance between the residue and the ligand is within certain distance cutoff, then the residue is defined as a ligand-binding site residue. The cutoff is set to be 0.5 plus the sum of the Van der Waal’s radius of the two atoms under investigation (7 (link)). If the number of binding site residues (i.e. number of contacts) is less than two or all the binding site residues are consecutive, it is deemed to be biologically irrelevant because most biological relevant ligands are usually tethered by multiple residues, which are further apart in the sequence space.

Third, if the ligand is not present in the artifact list, then it is considered as biologically relevant and kept in the pipeline for further manual verifications.

Fourth, the PubMed abstract is used to filter out biologically irrelevant ligands. If the ligand is in the artifact list, the simplest way is to treat it as biologically irrelevant and discard it. But this will miss some ligands (false negatives) that are indeed biologically relevant in some cases. For instance, the ligand molecule ‘glycerol’ (with ligand ID ‘GOL’) is one of the most frequently used crystallization additives and it is thus regarded as biologically irrelevant by many existing databases. However, this ligand can have a biological role in some proteins. For example, the ligand molecule glycerol binds to the protein ‘enzyme diol dehydratase’ (PDB ID: 3AUJ) with binding affinity K_m = 1.2 ± 0.02 mM with its biological role described as ‘glycerol is bound to the substrate binding site in the (β/α)₈ or TIM barrel of the diol dehydratase α subunit’ in (27 (link)). Thus, this ligand is considered as biologically relevant for this protein and added to BioLiP. We found that if a ligand present in a protein has its relevant biological role, it is often mentioned in the PubMed abstract. Based on such observation, we propose to use the PubMed abstract as an additional filter. To this end, the chemical names/synonyms of the ligand (curated from ChEBI, PubChem and PDB databases) are compared with the PubMed abstract. If there is no hit in this comparison procedure, the ligand is deemed to be biologically irrelevant. Otherwise, the ligand is possible to be biologically relevant, which remains to be verified by hand in the next step.

Finally, the manual verification is performed to check for suspicious or ambiguous entries, which are referred to those entries related with the commonly used crystallization additives, such as glycerol, ethanol, methanol, 2-propanol, ethylene glycol, hexylene glycol and polyethylene glycol. Ligands filtered from the above four steps can sometimes still be false positives, which is usually caused by unexpected match between the ligand names/synonyms and the PubMed abstract. In the same example of the ligand ‘glycerol’, it has the synonym ‘glycyl alcohol’, which leads to an unexpected match of the term ‘alcohol’ for the protein ‘arylesterase’ (PDB ID: 3HI4). Therefore, manual verification for ligands that are commonly used as crystallization additives is necessary to ensure the quality of BioLiP. Currently, we do this manual verification mainly by reading the original literatures and consulting other secondary databases. In the current version of BioLiP, manual verifications helped us to remove ∼12 500 entries that were false positives and we added ∼3000 entries that would have been missed by using the automated procedure alone.

Yang J., Roy A, & Zhang Y. (2012). BioLiP: a semi-manually curated database for biologically relevant ligand–protein interactions. Nucleic Acids Research, 41(Database issue), D1096-D1103.

Publication 2012

arylesterase Binding Sites Biopharmaceuticals Crystallization Enzymes Ethanol Glycerin Glycol, Ethylene hexylene glycol Ions Isopropyl Alcohol Ligands Metals, Heavy Methanol Polyethylene Glycols Propanediol Dehydratase Proteins Protein Subunits Protein Targeting, Cellular Radius Staphylococcal Protein A

Lentivirus Production and Purification

Cited 35 times

Lentiviruses were produced by transfecting the HEK293T cells with the pFUGW vectors expressing GFP and three helper plasmids (pVSVg, RRE, and REV)14 (link). The transfections were carried out using the Polyethylenimine (PEI) method with the ratio at PEI:pFUGW:pVSVg:RRE:REV = 24:3:1:2:2. The virus-containing medium was harvested 48 or 72 hours after transfection and subsequently pre-cleaned with a 3,000 g centrifuge and a 0.45 μm filtration (Millipore). The virus-containing medium was overlaid on a sucrose-containing buffer (50 mM Tris-HCl, pH 7.4,100 mM NaCl, 0.5 mM ethylene diamine tetra acetic acid [EDTA]) at a 4:1 v/v ratio and centrifuged at the indicated RCF at 4 °C. After centrifugation, the supernatant was carefully removed, and the tube was placed on the tissue paper for 3 minutes. Phosphate Buffered Saline (PBS) was added to the semi-dried tube for re-suspension, and then the tube was placed in the 4 °C fridge with a cover for recovery overnight.

Jiang W., Hua R., Wei M., Li C., Qiu Z., Yang X, & Zhang C. (2015). An optimized method for high-titer lentivirus preparations without ultracentrifugation. Scientific Reports, 5, 13875.

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Publication 2015

Acetic Acids Centrifugation Cloning Vectors ethylenediamine Filtration Lentivirus Phosphates Plasmids Polyethyleneimine Saline Solution Sodium Chloride Sucrose Tetragonopterus Tissues Transfection Tromethamine Virus

Human Placental Aromatase Structure

Cited 33 times

Aromatase was purified from term human placenta by immuno-affinity chromatography in a highly active form. It was complexed with androstenedione and crystallized at 4 °C in the oxidized high-spin ferric state of the haem iron with poly(ethylene glycol) 4000 as the precipitant. The space group was P3₂21 and the unit cell parameters are a =b =140.2 Å, c =119.3 Å, α = β =90°, γ =120°, having one aromatase molecule in the asymmetric unit. Diffraction data at about 100 K were collected initially at the Cornell High Energy Synchrotron Source (CHESS) and then to 2.90 Å resolution at the Advanced Photon Source, Argonne National Laboratory, with glycerol as a cryoprotectant. Two data sets at the Fe absorption edge were also collected at the CHESS. The structure was solved by the molecular replacement method coupled with Bijvoet difference Fourier synthesis for identifying the correct solution. Model building and refinement were performed with Coot and Refmac5, respectively. The final model contained 452 amino acid residues; 44 N-terminal and 7 C-terminal residues could not be built because of weakness of their electron densities. The final R factor for all reflections between 38 and 2.90 Å resolution was 0.214, and the R-free value was 0.244. The r.m.s. deviations of bond lengths and angles from ideal values were 0.009 Å and 1.32°, respectively. The average isotropic thermal factor for all atoms was 77.3 Å². There were only two violations in the backbone torsion angle Ramachandran plot, both in the loop regions. The oxyferryl Fe(IV)=O moiety was generated by adding an oxygen atom to Fe with the modelling software MOE (Chemical Computing Group) The exemestane molecule was built into the active site by superimposing it on the experimentally derived androstenedione atomic positions with MOE.

Ghosh D., Griswold J., Erman M, & Pangborn W. (2009). Structural basis for androgen specificity and oestrogen synthesis in human aromatase. Nature, 457(7226), 219-223.

Publication 2009

Amino Acids Anabolism Androstenedione Aromatase Asthenia Cells Chromatography, Affinity Cryoprotective Agents Electrons exemestane Glycerin Heme Homo sapiens Iron Oxygen Placenta polyethylene glycol 4000 Reflex R Factors Vertebral Column

Most recents protocols related to «Ethylene»

Ethylene Oligomerization in High-Pressure Reactor

The oligomerization of ethylene was conducted in a 500 mL high-pressure, stainless-steel reactor with a magnetic stirring bar and temperature detection device. The reactor was vacuum-dried at 120 °C for 4 h and the ethylene gas was replaced three times. The reactor was then cooled to the desired temperature using circulating water cooling. The solvents, cocatalysts, ligands, and chromium sources were sequentially injected into the reactor under vacuum. The experiment began by introducing ethylene to the set pressure and activating the stirring and flow meters. Timing started at this point. After the reaction was complete, the reactor was cooled to room temperature, the pressure was released, and acidified ethanol (30 mL) was used to quench any oligomerization. The liquid phase was separated, and the product distribution was analyzed using gas chromatography mass spectrometry (GC-MS).

Meng X., Ding Z., Gao H., Ma Z., Pan L., Wang B, & Li Y. (2024). Chromium Catalysts for Selective Ethylene Oligomerization Featuring Binuclear PNP Ligands. Molecules, 29(9), 2158.

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Publication 2024

Ethylene Production Quantification in Fruits

The ethylene gas was obtained in the same way as the respiratory intensity and was measured by GC-14 gas chromatograph (Shimadzu, Kyoto, Japan) and repeated three times. The setup parameters and calculation formula were referred from Li Ling et al. [16 (link)] with some modification. The experimental parameters were set as follows: the chromatographic column was a GDX-502 stainless steel packed column; the detector used was a hydrogen flame ionization detector; and the carrier gas was N₂. The inlet temperature, column temperature box, and detector temperature were all set at 60 °C, and the unit was expressed in μL kg⁻¹·h⁻¹.

E t h y l e n e P r o d u c t i o n = \frac{C \times V}{M \times T \times 1000}

in which C is the ethylene content in the sample gas, with the unit as µL L⁻¹;

V is the volume of the enclosed space, with the unit as mL;

M is the mass of fruits, with the unit as kg; and

T is the smothering time, with the unit as h.

Zhang H., Han Y., Liang L, & Deng B. (2024). Rapid Cooling Delays the Occurring of Core Browning in Postharvest ‘Yali’ Pear at Advanced Maturity by Inhibiting Ethylene Metabolism. Foods, 13(7), 1072.

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Publication 2024

Evaluating Ethylene Adsorption Performance

The evaluation of ethylene adsorption performance was conducted in a 10 mm fixed-bed reactor, as illustrated in Figure S1. In this setup, a mixture of 500 mg of Ag/NZ5(X) and 500 mg of silicon dioxide (used as physical supports) were packed in the reactor. The composition of the ethylene standard gas comprised 100 ppm of ethylene, 21 wt.% oxygen, and approximately 79 wt.% nitrogen.
Breakthrough curves were used to evaluate the ethylene adsorption capacity and the reusability of Ag/NZ5(X). For measuring the breakthrough curves, an Agilent 7820A gas chromatograph (GC) was used to determine the ethylene concentrations of the gas stream. The flow rate of the gas stream was kept at 85 mL·min⁻¹ by using a mass flow controller (MFC) under the conditions of 25 °C and atmospheric pressure. Finally, the ethylene removal rate (R) and adsorption capacity (C) of Ag/NZ5(X) were calculated by using equations provided in the Supporting Information. The optimal performance among the samples is defined by the longest sustained near-complete ethylene removal (i.e., R > 99%) coupled with the highest adsorption capacity. This dual metric serves as the benchmark for determining the best ethylene adsorption performance in the study.

Qi Y., Yang H., Li C, & Li H. (2024). Enhanced Adsorption of Trace Ethylene on Ag/NZ5 Modified with Ammonia: Hierarchical Structure and Metal Dispersion Effects. Molecules, 29(5), 981.

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Publication 2024

Ethylene Oligomerization with Chain Transfer Agents

Not available on PMC !

Example 1

In an argon atmosphere dry box, a 500 mL flask equipped with a stirrer is charged with 20 mmol of zirconium tetrachloride anhydride (ZrCl4) and 250 mL of dry cyclohexane. The mixture is then stirred for 10 minutes at room temperature. To the stirred mixture is added triethylaluminum (TEA) and then ethylaluminum sesquichloride (EASC) to provide a mixture that has a EASC:TEA molar ratio of 3.5:1 and an aluminum to zirconium molar ratio of 7:1. The resultant mixture is then heated at 70° C. for 2 hours. The mixture is then cooled to room temperature. A 50 mL portion of the cooled mixture and is transferred to a one liter volumetric flask along with an amount of thiophene to thiophene:zirconium molar ratio of 3:1. The one liter volumetric is then charged with enough dry cyclohexane to provide one liter of catalyst system mixture. The zirconium concentration of the thus prepared catalyst system mixture/liter of cyclohexane and has an aluminum to zirconium molar ratio of 7:1, a EASC:TEA molar ratio of 3.5:1, and a thiophene:zirconium molar ratio of 3:1. The catalyst system mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

Run 1-1 (Comparative)

The oligomerization apparatus as previously described is utilized using only the primary catalyst system solution pump. The oligomerization reactor is prepared for ethylene oligomerization by charging the high pressure product tank to the desired pressure using the high pressure N₂fill line. The reactor is also cycled through three high pressure N₂fill (to 800 psig-5.5 MPa) and vent cycles while isolated from the primary catalyst system solution pump. Each nitrogen purge is performed by closing the valve leading to the product tank, charging nitrogen to the autoclave through the spare entry port to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen of the final nitrogen purge is released, the autoclave is maintained with a slight residual nitrogen pressure. Catalyst system mixture, 200 mL, is then transferred to the catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. The reactor is then quickly filled organic reaction medium (cyclohexane). The diluent pump is then turned on at rate of 335 mL per hour to bring the reactor up to a reaction pressure of 925 psi (6.37 MPa). When the reactor achieves the reaction pressure, the overhead magnetic stirrer is started and set for ˜1200 rpm and the heating jacket turned on and set for 120° C. When the reactor achieves a stable temperature of 120° C., the catalyst system ISCO pump is turned on and set to feed the catalyst system mixture to the reactor at a rate of 15 mL/hr. After 30 minutes, ethylene is then introduced into the reactor at an initial rate of at 50 grams/hour and gradually increased, over a 30 minute period, to a final rate of 175 grams/hour. The oligomerization temperature is maintained by using the internal cooling coils and external heating jacket as needed. After 6 hours, the oligomerization is terminated by decreasing the catalyst system flowrate to zero, decreasing the ethylene flow rate to zero, and turning off the heating jacket. When the reactor attains room temperature, the organic reaction medium flow rate is decreased to zero, and the liquid contents of the reactor pressured into the high pressure product tank using high pressure N₂.

The reactor is then opened and the solids inside the reactor and covering the internal reactor surfaces collected and added to the reactor effluent collected in the high pressure product tank. A liquid sample, 250 grams, of the product tank is collected and a known amount of internal standard (e.g. nonane) is added to the sample. The sample is then treated with 5 wt. % sodium hydroxide solution to deactivate the catalyst system. The organic layer of the sodium hydroxide treated sample is then analyzed using gas chromatographic analysis to determine oligomer product distribution, Schulz-Flory K value, carbon number purities, and catalyst system productivities. The remaining contents of the product tank are then homogenized and a second sample, 250 grams, of the product tank is taken. The second sample is then subjected to rotary evaporation for 1 h at 100° C. at −30 in Hg to effectively remove all the liquid. The mass of the remaining wax and polymer is determined. A portion of the wax is then analyzed by thermogravimetric analysis (TGA) to calculate the fraction of the solid sample that is polymer using the cutoffs of A) liquid (≤175° C.), B) waxes (175° C. to 420° C., and C) polymer ≥420° C. A second portion of the wax and polymer is analyzed by HPLC to determine the molecular weight distribution of the polymer produced in the oligomerization including Mw, Mn, and Mp. The liquid and polymer analysis results are used to determine the oligomer product distribution, Schulz-Flory K value, carbon number purities, catalyst system productivities, polymer Mw, polymer Mw maximum peak, percentage of polymer in the oligomer product, percentage of polymer having an Mw greater than 100,000, and percentage of oligomer product having a Mw greater than 1,000 g/mol.

Run 1-2.

In an argon atmosphere dry box, a 250 mL volumetric flask is charged with 0.1 mole of triethylsilane (a chain transfer agent) and then charged with enough dry cyclohexane to provide 250 mL of chain transfer agent mixture. The chain transfer agent mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

A chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 1-1 is repeated but with the addition of the triethylsilane solution to the suction side of the diluent pump metered to provide a triethylsilane to ethylene mole ratio of 1×10⁻³:1 (˜15 mL/hour when ethylene flowrate is 175 grams/hour) throughout the ethylene oligomerization.

Run 1-3

In an argon atmosphere dry box, a 250 mL volumetric flask is charged with 0.1 mmole of iron(III) octanoate (a transition metal compound chain transfer agent) and then charged with enough dry cyclohexane to provide 250 mL of transition metal compound chain transfer agent mixture. The chain transfer agent mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

A transition metal compound chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 1-1 is repeated but with the addition of the iron(III) octanoate solution to the suction side of the diluent pump metered to provide an iron(III) octanoate to ethylene mole ratio of 1×10⁻⁶:1 (˜15 mL/hour when ethylene flowrate is 175 grams/hour) throughout the ethylene oligomerization.

Run 1-4

A hydrogen feed line is connected to the ethylene feedline of the ethylene oligomerization apparatus. The procedure of Run 1-1 is repeated but with hydrogen being metered into the ethylene at a rate to provide a hydrogen to ethylene mass ratio of (1 g hydrogen)/(kg ethylene) throughout the ethylene oligomerization.

The gas chromatographic analyses and HPLC analyses of ethylene oligomerization Runs, 1-2, 1-3, and 1-4 using a chain transfer agent were reviewed and compared to the gas chromatographic analyses and HPLC analyses of ethylene oligomerization Run 1-1. The analyses show that the oligomer product that is produced in ethylene oligomerization Runs 1-2, 1-3, and 1-4 using a chain transfer agent has less than 1 wt. % of polymer and/or less than 1 wt. % compounds having a weight average molecular weight of greater than 1000 g/mol, when compared to ethylene oligomerization Run 1-1 which did not utilize a chain transfer agent. The analyses also show that the oligomer product that is produced in ethylene oligomerization Runs 1-2, 1-3, and 1-4 using a chain transfer agent produces an oligomer product comprising a polymer having a lower Mw, a polymer having a lower Mw maximum peak, a reduced percentage of polymer, and/or a polymer having a reduced percentage of polymer having a Mw greater than 100,000 when compared to ethylene oligomerization Run 1-1 which did not utilize a chain transfer agent. The gas chromatographic analyses of the oligomer product of Runs, 1-1, 1-2, 1-3, and 1-4 indicate that there is no significant discernable impact on the Schulz-Flory K value, carbon number purities, and catalyst system productivities when a chain transfer agent is utilized in the ethylene oligomerization.

US11873264B2. Ethylene oligomerization processes (2024-01-16). Chevron Phillips Chemical Company LP [US]. Inventors: Brooke L. Small [US], Orson L. Sydora [US], Ronald D. Knudsen [US].

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Patent 2024

Ethylene Oligomerization with Chain Transfer Agents

Not available on PMC !

Example 2

In an argon atmosphere dry box, a first 500 mL flask equipped with a stirrer is charged with zirconium(IV) isopropylcarboxylate (60 mmol), anisole (45 mmol), and dry toluene (200 mL). This first mixture is then stirred for 10 minutes at room temperature. In the argon dry box, a second 500 mL flask equipped with a stirrer is charged with 2-pyrrolidone (43 mmol) and dry toluene (200 mL). To this second mixture is added neat diethylaluminum chloride (1.2 mol) over a period of 30 minutes. This second mixture is then stirred for an additional 10 minutes. The first mixture is then transferred to a one liter volumetric flask. The second mixture is then added to the first mixture in the volumetric flask and then the volumetric flask is charged with enough dry toluene to provide a one liter solution of the first catalyst system mixture. After through mixing, a 200 mL portion of the first catalyst system mixture is transferred to a second one liter volumetric flask along with enough dry toluene to provide one liter of a second catalyst system mixture. The zirconium concentration of the thus prepared second catalyst system mixture is 12 mmol/liter and has an anisole to zirconium molar ratio of 0.75:1, an aluminum:zirconium molar ratio of 20:1, and 2-pyrrolidone:Al ratio of 0.15:1. The second catalyst system mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

Run 2-1 (Comparative)

The oligomerization apparatus as previously described is utilized using only the primary catalyst system solution pump. The oligomerization reactor is prepared for ethylene oligomerization by charging the high pressure product tank to the desired pressure using the high pressure N₂fill line. The reactor is also cycled through three high pressure N₂fill (to 800 psig-5.5 MPa) and vent cycles while isolated from the primary catalyst system solution pump. Each nitrogen purge is performed by closing the valve leading to the product tank, charging nitrogen to the autoclave through the spare entry port to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen of the final nitrogen purge is released, the autoclave is maintained with a slight residual nitrogen pressure. Second catalyst system mixture, 200 mL, is then transferred to the catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. The reactor is then quickly filled organic reaction medium (cyclohexane). The diluent pump is then turned on at rate of 485 mL per hour to bring the reactor up to a reaction pressure of 450 psi (3.1 MPa). When the reactor achieves the reaction pressure, the overhead magnetic stirrer is started and set for ˜1200 rpm and the heating jacket turned on and set for 70° C. When the reactor achieves a stable temperature of 70° C., the catalyst system ISCO pump is turned on and set to feed the catalyst system mixture to the reactor at a rate of 15 mL/hr. After 30 minutes, ethylene is then introduced into the reactor at an initial rate of at 50 grams/hour and gradually increased, over a 30 minute period, to a final rate of 175 grams/hour. The oligomerization temperature is maintained by using the internal cooling coils and external heating jacket as needed. After 6 hours, the oligomerization is terminated by decreasing the catalyst system flowrate to zero, decreasing the ethylene flow rate to zero, and turning off the heating jacket. When the reactor attains room temperature, the organic reaction medium flow rate is decreased to zero, and the liquid contents of the reactor pressured into the high pressure product tank using high pressure N₂.

Run 2-2.

A chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 2-1 is repeated but with the addition of the triethylsilane solution to the suction side of the diluent pump metered to provide a triethylsilane to ethylene mole ratio of 1×10⁻³:1 (˜15 mL/hour when ethylene flowrate is 175 grams/hour) throughout the ethylene oligomerization.

Run 2-3

A transition metal compound chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 2-1 is repeated but with the addition of the iron(III) octanoate solution to the suction side of the diluent pump metered to provide an iron(III) octanoate to ethylene mole ratio of 1×10⁻⁶:1 (˜15 mL/hour when ethylene flowrate is 175 grams/hour) throughout the ethylene oligomerization.

Run 2-4

A hydrogen feed line is connected to the ethylene feedline of the ethylene oligomerization apparatus. The procedure of Run 2-1 is repeated but with hydrogen being metered into the ethylene at a rate to provide a hydrogen to ethylene mass ratio of (1 g hydrogen)/(kg ethylene) throughout the ethylene oligomerization.

The gas chromatographic analyses and HPLC analyses of ethylene oligomerization Runs, 2-2, 2-3, and 2-4 using a chain transfer agent were reviewed and compared to the gas chromatographic analyses and HPLC analyses of ethylene oligomerization Run 2-1. The analyses show that the oligomer product that is produced in ethylene oligomerization Runs 2-2, 2-3, and 2-4 using a chain transfer agent has less than 1 wt. % of polymer and/or less than 1 wt. % compounds having a weight average molecular weight of greater than 1000 g/mol, when compared to ethylene oligomerization Run 2-1 which did not utilize a chain transfer agent. The analyses also show that the oligomer product that is produced in ethylene oligomerization Runs 2-2, 2-3, and 2-4 using a chain transfer agent produces an oligomer product comprising a polymer having a lower Mw, a polymer having a lower Mw maximum peak, a reduced percentage of polymer, and/or a polymer having a reduced percentage of polymer having a Mw greater than 100,000 when compared to ethylene oligomerization Run 1-1 which did not utilize a chain transfer agent. The gas chromatographic analyses of the oligomer product of Runs, 2-1, 2-2, 2-3, and 2-4 indicate that there is no significant discernable impact on the Schulz-Flory K value, carbon number purities, and catalyst system productivities when a chain transfer agent is utilized in the ethylene oligomerization Example 3

In an argon atmosphere dry box, a first 500 mL flask equipped with a stirrer is charged with zirconium tetrachloride (100 mmol), isodecylacetates (105 mmol), and dry ortho-xylene (200 mL). This zirconium mixture is then stirred for 10 minutes at room temperature. The first zirconium mixture then transferred to a one liter volumetric flask and the one liter volumetric flask is then charged with enough ortho-xylene to provide a one liter solution of first zirconium solution. After through mixing, a 200 mL portion of the first zirconium solution is transferred to a second one liter volumetric flask along with enough dry ortho-xylene to provide one liter of a second zirconium solution. The second zirconium solution has an isodecylacetates:Zr molar ratio of 1.05:1. The second zirconium solution volumetric flask is then capped and removed from the argon atmosphere dry box.

In the argon dry box, a second 500 mL flask equipped with a stirrer is charged with dry ortho-xylene (500 mL). To the ortho-xylene added, with stirring, neat diethylaluminum chloride (1.2 mol) over a period of 30 minutes. This mixture is then stirred for an additional 10 minutes. This diethylaluminum chloride solution is then transferred to a one liter volumetric flask and the one liter volumetric flask is then charged with enough ortho-xylene to provide a one liter solution of first zirconium solution. After through mixing, a 200 mL portion of the first diethylaluminum chloride solution is transferred to a second one liter volumetric flask along with enough dry ortho-xylene to provide one liter of a second diethylaluminum chloride solution. The second diethylaluminum chloride solution volumetric flask is then capped and removed from the argon atmosphere dry box.

Run 3-1 (Comparative)

The oligomerization apparatus as previously described is utilized with the following modification: the 500 mL autoclave is replaced by a 200 mL autoclave (also equipped with an overhead magnetic mechanical stirrer to provide mixing of the reaction mixture, and internal cooling coils and external heating jacket) and both the primary and secondary catalyst system pumps are utilized. The oligomerization reactor is prepared for ethylene oligomerization by charging the high pressure product tank to the desired pressure using the high pressure N₂fill line. The reactor is also cycled through three high pressure N₂fill (to 800 psig-5.5 MPa) and vent cycles while isolated from the primary and secondary catalyst system solution pump. Each nitrogen purge is performed by closing the valve leading to the product tank, charging nitrogen to the autoclave through the spare entry port to a pressure of 800 psig (5.5 MPa), holding the nitrogen pressure on the autoclave for 5 minutes and then releasing the nitrogen pressure on the autoclave by opening the valve leading to the product tank. After the nitrogen of the final nitrogen purge is released, the autoclave is maintained with a slight residual nitrogen pressure. Second zirconium mixture, 200 mL, is transferred to the primary catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. Second diethylaluminum chloride solution, 200 mL, is transferred to the secondary catalyst system ISCO syringe pump of the prepared ethylene oligomerization apparatus. The reactor is then quickly filled dry organic reaction medium (ortho-xylene). The diluent pump is then turned on at rate of 680 mL per hour to bring the reactor up to a reaction pressure of 3000 psi (20.7 MPa). When the reactor achieves the reaction pressure, the overhead magnetic stirrer is started and set for ˜1200 rpm and the heating jacket turned on and set for 165° C. When the reactor achieves a stable temperature of 70° C., the primary and secondary catalyst system ISCO pumps are turned on and set to feed the second zirconium solution and the second diethylaluminum chloride solutions at a rate of 11 mL/hr. The feed rate of the zirconium solution and the diethylaluminum chloride solution provide an Al:Zr ratio of 12:1. After 30 minutes, ethylene is then introduced into the reactor at an initial rate of at 50 grams/hour and gradually increased, over a 30 minute period, to a final rate of 600 grams/hour. The oligomerization temperature is maintained by using the internal cooling coils and external heating jacket as needed. After 4 hours, the oligomerization is terminated by decreasing the flowrate of the zirconium solution and the diethylaluminum chloride solution feed rates to zero, decreasing the ethylene flow rate to zero, and turning off the heating jacket. When the reactor attains room temperature, the organic reaction medium flow rate is decreased to zero, and the liquid contents of the reactor pressured into the high pressure product tank using high pressure N₂.

Run 3-2.

In an argon atmosphere dry box, a 250 mL volumetric flask is charged with 360 mmol of triethylsilane (a chain transfer agent) and then charged with enough dry ortho-xylene to provide 250 mL of chain transfer agent mixture. The chain transfer agent mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

A chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 3-1 is repeated but with the addition of the triethylsilane solution to the suction side of the diluent pump metered to provide a triethylsilane to ethylene mole ratio of 1×10⁻³:1 (˜15 mL/hour when ethylene flowrate is 600 grams/hour) throughout the ethylene oligomerization.

Run 3-3

In an argon atmosphere dry box, a 250 mL volumetric flask is charged with 0.36 mmole of iron(III) octanoate (a transition metal compound chain transfer agent) and then charged with enough dry cyclohexane to provide 250 mL of transition metal compound chain transfer agent mixture. The chain transfer agent mixture volumetric flask is then capped and removed from the argon atmosphere dry box.

A transition metal compound chain transfer agent feed line is connected to organic reaction medium feedline on the suction side of the organic reaction medium pump. The procedure of Run 3-1 is repeated but with the addition of the iron(III) octanoate solution to the suction side of the diluent pump metered to provide an iron(III) octanoate to ethylene mole ratio of 1×10⁻⁶:1 (˜15 mL/hour when ethylene flowrate is 175 grams/hour) throughout the ethylene oligomerization.

Run 3-4

A hydrogen feed line is connected to the ethylene feedline of the ethylene oligomerization apparatus. The procedure of Run 3-1 is repeated but with hydrogen being metered into the ethylene at a rate to provide a hydrogen to ethylene mass ratio of (1 g hydrogen)/(kg ethylene) throughout the ethylene oligomerization.

The gas chromatographic analyses and HPLC analyses of ethylene oligomerization Runs, 3-2, 3-3, and 3-4 using a chain transfer agent were reviewed and compared to the gas chromatographic analyses and HPLC analyses of ethylene oligomerization Run 3-1. The analyses show that the oligomer product that is produced in ethylene oligomerization Runs 3-2, 3-3, and 3-4 using a chain transfer agent has less than 1 wt. % of polymer and/or less than 1 wt. % compounds having a weight average molecular weight of greater than 1000 g/mol, when compared to ethylene oligomerization Run 3-1 which did not utilize a chain transfer agent. The analyses also show that the oligomer product that is produced in ethylene oligomerization Runs 3-2, 3-3, and 3-4 using a chain transfer agent produces an oligomer product comprising a polymer having a lower Mw, a polymer having a lower Mw maximum peak, a reduced percentage of polymer, and/or a polymer having a reduced percentage of polymer having a Mw greater than 100,000 when compared to ethylene oligomerization Run 3-1 which did not utilize a chain transfer agent. The gas chromatographic analyses of the oligomer product of Runs, 3-1, 3-2, 3-3, and 3-4 indicate that there is no significant discernable impact on the Schulz-Flory K value, carbon number purities, and catalyst system productivities when a chain transfer agent is utilized in the ethylene oligomerization

Illustrative statements of the subject matter claimed herein below will now be provided. In the interest of clarity, not all features of an actual implementation are described in this specification. It can be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which can vary from one implementation to another. Moreover, it can be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. Furthermore, various modifications can be made within the scope of the invention as herein intended, and embodiments of the invention can include combinations of features other than those expressly claimed. In particular, flow arrangements other than those expressly described herein are within the scope of the invention.

Statement 1. A process comprising: a) contacting i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, n is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a chain transfer agent comprising a compound having a hydrogen silicon bond, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or any combination thereof, and iv) optionally, an organic reaction medium; and b) forming an oligomer product in the reaction zone.

Statement 2. A process comprising: a) introducing i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a chain transfer agent comprising a compound having a hydrogen silicon bond, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or any combination thereof, and iv) optionally, an organic reaction medium into a reaction zone; and b) forming an oligomer product in a reaction zone.

Statement 3. The process of statement 1 or 2, wherein the chain transfer agent comprises a compound having the formula R³¹SiH₃, (R³¹)₂SiH₂, (R³¹)₃SiH, R³¹OSiH3, (R³¹O)₂SiH₂, (R³¹O)₃SiH, R³²SH, R³²CO₂CH₂SH, R³²CO₂CH₂CH₂SH, R³³PH₂, (R³³)₂PH, R³³OPH₂, (R³³O)₂PH, or any combination thereof wherein each R³¹, R³², and R³³independently are a C₁to C₁₅hydrocarbyl group.

Statement 4. The process of any one of statements 1-3, wherein the reaction zone has any hydrogen of the chain transfer agent to ethylene mole ratio disclosed herein e.g., (a minimum value of 1×10⁻⁵: 1, 5×10⁻⁴:1, 1×10⁻⁴:1, or 5×10⁻³:1; a maximum value of 5×10⁻¹: 1, 1×10⁻¹: 1, 5×10⁻²:1, or 1×10⁻²:1; in a range from 1×10⁻⁵:1 to 5×10⁻¹:1, 5×10⁻⁴:1 to 1×10⁻¹:1, 1×10⁻⁴:1 to 5×10⁻²:1, or 5×10⁻³:1 to 1×10⁻²:1; among others values and ranges).

Statement 5. A process comprising: a) contacting i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) hydrogen, and iv) optionally, an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Statement 6. A process comprising: a) introducing i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) hydrogen, and iv) optionally, an organic reaction medium into a reaction zone; and b) forming an oligomer product in the reaction zone.

Statement 7. The process of statement 5 or 6, wherein the reaction zone has any hydrogen to ethylene mass ratio disclosed herein (e.g., a minimum value of (0.05 g hydrogen)/(kg ethylene), (0.1 g hydrogen)/(kg ethylene), (0.25 g hydrogen)/(kg ethylene), (0.4 g hydrogen)/(kg ethylene), or (0.5 g hydrogen)/(kg ethylene); a maximum value of (5 g hydrogen)/(kg ethylene), (3 g hydrogen)/(kg ethylene), (2.5 g hydrogen)/(kg ethylene), (2 g hydrogen)/(kg ethylene), or (1.5 g hydrogen)/(kg ethylene); in a range from (0.05 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (4 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (3 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2.5 g hydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene), or from (0.5 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene); among others values and ranges.

Statement 8. A process comprising: a) contacting i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a transition metal compound chain transfer agent, and iv) optionally, an organic reaction medium; and b) forming an oligomer product in a reaction zone.

Statement 9. A process comprising: a) introducing i) ethylene, ii) a catalyst system (or catalyst system components) comprising 1) a zirconium compound having the formula ZrX¹_mY¹_q, where each X¹independently is a halide, each Y¹independently is a hydrocarboxide, a dihydrocarbylazanide, a hydrocarbylcarboxylate, a hydrocarbylsulfonate, or a β-diketonate, n is a range from 0 to 4, q is in a range from 0 to 4, and m+q is an integer from 2 to 4, and 2) a hydrocarbylmetal compound, iii) a transition metal compound chain transfer agent, and iv) optionally, an organic reaction medium into a reaction zone; and b) forming an oligomer product in the reaction zone.

Statement 10. The process of statement 8 or 9, wherein the transition metal compound chain transfer agent is any transition metal compound chain transfer agent having the formula MX⁴_pwhere M is the transition metal, X⁴is a mono anion, and p is an integer from 2 to 4.

Statement 11. The process of statement 10, wherein the transition metal compound chain transfer agent is any described herein having the formula MX⁴_pwhere M is iron, cobalt, or nickel.

Statement 12. The process of statement 10 or 11, wherein transition metal compound chain transfer agent is any transition metal compound chain transfer agent having the formula MX⁴_pdescribed herein where X⁴is a C₄to C₁₉carboxylate.

Statement 13. The process of statement of any one of statements 8 to 12, wherein the reaction zone has any transition metal of the transition metal compound chain transfer agent to ethylene mole ratio disclosed herein (a minimum value of 1×10⁻⁹:1, 5×10⁻⁸:1, 1×10⁻⁸:1, 5×10⁻⁷:1, or 1×10⁻⁷:1; a maximum value of 5×10⁻³:1, 1×10⁻³:1, 5×10⁻⁴:1, 1×10⁻⁴:1, or 5×10⁻⁵:1; in a range from 1×10⁻⁹:1 to 5×10⁻³:1, 5×10⁻⁸:1 to 1×10⁻³:1, 1×10⁻⁸:1 to 5×10⁻⁴:1, 5×10⁻⁷:1 to 1×10⁻⁴:1, or 1×10⁻⁷:1 to 5×10⁻⁵:1; among others values and ranges).

Statement 14. The process of any one of Statements 1-13, wherein the hydrocarbylmetal compound is any hydrocarbylmetal compound disclosed herein (e.g., comprise any metal disclosed herein—a group 1, 2, 11, 12, 13, or 14 metal, among other metal groups disclosed herein—and any hydrocarbyl group disclosed herein—a C₁to C₂₀, a C₁to C₁₀, or a C₁to C₆hydrocarbyl group and other more specific hydrocarbyl groups disclosed herein).

Statement 15. The process of any one of Statements 1-14, wherein the metal of the hydrocarbylmetal compound to zirconium of the zirconium compound is any value disclosed herein (e.g., a minimum value of 0.1:1, 0.2:1, 0.6:1, 1:1, 2:1 10:1; a the maximum value or 100:1 75:1, 50:125:1, 15:1, or 10:1; or in a range of from 0.1:1 to 100:1, 0.2:1 to 75:1, 0.6:1 to 25:1, 1:1 to 50:1, 2:1 to 25:1, 1:1 to 15:1, 2:1 to 10:1, 10:1 to 50:1, or 10:1 to 25:1; among others values and ranges).

Statement 16. The process of any one of statement 1-15, wherein the catalyst system (or catalyst system components) further comprises a neutral non-ionic organic modifier.

Statement 17. The process of statement 16, wherein the neutral non-ionic organic modifier comprises any an ether, an ester, a ketone, an aldehyde, an alcohol, an anhydride, an acid chloride, a nitrile, a sulfide, a disulfide, a phosphine, an amine, or an amide described herein.

Statement 18. The process of statement 16 or 17, wherein the neutral non-ionic organic modifier to zirconium of the zirconium compound molar ratio can have any values described herein (e.g., a minimum value of 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1; a maximum value of 20:1, 15:1, 10:1 7.5:1, or 5:1; or in a range from 0.5:1 20:1, 0.5:1 to 15:1, 0.75:10:1, 1:1 to 15:1, 1:1 to 10:1, 1:1 to 5:1, 0.5:1 to 5:1, 0.75:1 to 3:1, 0.8:1 to 2:1, 0.9:1 or 1.25; among other values and ranges.

Statement 19. The process of any one of statements 16-18, wherein neutral non-ionic organic modifier to hydrocarbylmetal (or hydrocarbylaluminum) compound molar ratio can have any value described herein (e.g., an minimum value of be 0.05:1, 0.1:1, 0.5:1, 0.75:1 0.8:1, 0.9:1, or 1:1; a maximum value of 5:1, 3:1, 2:1, 1.5:1, 1:1, 0.75:1, or 0.5:1; or in a range from 0.05:1 to 5:1, 0.1 to 1:1, 0.1:1 to 0.5:1, 0.5:1 to 5:1, 0.5:1 to 3:1, 0.75:1 to 2:1, or 0.75:1 to 1.5:1; among other values and ranges.

Statement 20. The process of any one of statements 1-19, wherein the zirconium compound has the formula ZrX¹_mY¹_q, where each X¹independently is chloride or bromide, each Y¹independently is a C₁to C₁₀hydrocarboxide (e.g., any described herein), a C₁to C₁₅hydrocarbylcarboxylate (e.g., any described herein), or a C₁to C₁₅hydrocarbylsulfonate (e.g., any described herein), m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is 4.

Statement 21. The process of any one of statements 1-20, wherein the hydrocarbylmetal compound comprises an alkylaluminum compound having the formula AlX²_3-nR¹_n, Al₂X²_6-q-R¹_q, R¹₂Zn, or any combination thereof, where each R¹independently is a C₁to C₁₀alkyl group, each X²independently is chloride, bromide, or iodide, n is an integer from 0 to 3, and q is an integer for 0 to 6.

Statement 22. The process of any one of statements 20-22, wherein the neutral non-ionic organic modifier comprises any C₂to C₂₀ether, C₃to C₂₀ester, C₃to C₂₀ketone, C₂to C₂₀nitrile, C₂to C₂₀sulfide, C₂to C₂₀disulfide, C₃to C₂₀phosphine, C₁to C₂₀amine, or C₂to C₂₀amide described herein.

Statement 23. The process of any one of statements 1-19, wherein the zirconium compound has the formula ZrX¹_mwhere each X¹independently is a chloride or bromide and m is 4, the hydrocarbylmetal compound has the formula AlX²_nR¹_3-n, Al₂X²₃R¹₃, R¹₂Zn, or any combination thereof where each X²independently is a halide and each R¹independently is C₂to C₄alkyl group, and the metal of the hydrocarbylmetal (or aluminum of the hydrocarbylaluminum) compound to zirconium of the zirconium compound molar ratio is in any range disclosed herein (e.g., in a range of from 1:1 to 50:1).

Statement 24. The process of statement 23, wherein the catalyst system (or catalyst system components) further comprise a neutral non-ionic organic modifier comprising C₂to C₂₀ester, and wherein the neutral non-ionic organic modifier to zirconium of the zirconium compound molar ratio is in is in any range disclosed herein (e.g., in a range of from 0.5:1 to 5:1), and the metal of the hydrocarbylmetal (or aluminum of the hydrocarbylaluminum) compound to zirconium of the zirconium compound molar ratio is in any range disclosed herein (e.g., in a range of from 10:1 to 25:1).

Statement 25. The process of statement 24, wherein the neutral non-ionic organic modifier is contacted with the zirconium compound prior to the zirconium compound contacting ethylene and/or the hydrocarbylmetal compound (and/or being introduced into the reaction zone).

Statement 26. The process of statement 23 or 24, wherein the catalyst system (or catalyst system components) further comprise a neutral non-ionic organic modifier comprising a C₂to C₂₀ether, a C₂to C₂₀sulfide, a C₁to C₂₀amine, a C₃to C₂₀phosphine, or any combination thereof, and wherein the neutral non-ionic organic modifier to zirconium of the zirconium compound molar ratio is in any range disclosed herein (e.g., in a range of from 0.5:1 to 20:1), and the metal of the hydrocarbylmetal (or aluminum of the hydrocarbylaluminum) compound to zirconium of the zirconium compound molar ratio is in any range disclosed herein (e.g., in a range of from 1:1 to 15:1).

Statement 27. The process of any one of statements 1-19, where the zirconium compound has the formula ZrX¹_mY¹_q, where each X¹independently is chloride or bromide, each Y¹independently is a C₁to C₁₀hydrocarboxide (e.g., any described herein), a C₁to C₁₀hydrocarbylcarboxylate (e.g., any described herein), or a C₁to C₁₅hydrocarbylsulfonate (e.g., any described herein), m is a range from 0 to 4, q is in a range from 0 to 4, and m+q is 4, the hydrocarbylmetal compound comprises a hydrocarbylmetal compound having the formula AlX²_nR¹_3-n, Al₂X²₃R¹₃, or any combination thereof where each X²independently is a halide and each R¹independently is C₂to C₄alkyl group, and the metal of the hydrocarbylmetal (or aluminum of the hydrocarbylaluminum) compound to zirconium of the zirconium compound molar ratio is in a range of from 1:1 to 50:1.

Statement 28. The process of statement 27, wherein the zirconium compound is at least partially hydrolyzed by contacting the zirconium compound with water using any water to zirconium molar ratio disclosed herein (e.g., 0.01:1 to 3:1, 0.1: to 2:1, 0.25:1 to 1.75:1).

Statement 29. The process of statement 27 or 28, wherein the catalyst system (or catalyst system components) further comprise a neutral non-ionic organic modifier comprising a C₂to C₁₅amide, and wherein the neutral non-ionic organic modifier to metal of the hydrocarbylmetal (or aluminum of the hydrocarbylaluminum) compound molar ratio is in a range of 0.1:1 to 1:1.

Statement 30. The process of statement 29, wherein the neutral non-ionic organic modifier is contacted with the hydrocarbylmetal (or hydrocarbylaluminum) compound prior to the hydrocarbylmetal (or hydrocarbylaluminum) compound contacting ethylene (and/or being introduced into the reaction zone).

Statement 31. The process of any one of statements 27-30, wherein the catalyst system (or catalyst system components) further comprise a neutral non-ionic organic modifier comprising a C₂to C₂₀ether, a C₂to C₂₀sulfide, a C₁to C₂₀amine, or any combination thereof, and wherein the neutral non-ionic organic modifier to zirconium of the zirconium compound is in any range disclosed herein (e.g., in a range of from 0.1:1 to 10:1).

Statement 32. The process of statement 31, wherein the neutral non-ionic organic modifier is contacted with the zirconium compound prior to the zirconium compound contacting ethylene and/or the hydrocarbylmetal compound (and/or being introduced into the reaction zone).

The process of any one of statements 1-32, wherein the oligomer product is formed at (or the reaction zone has) any reaction zone zirconium of the zirconium compound to ethylene molar ratio described herein (e.g., a minimum reaction zone zirconium of the zirconium compound to ethylene molar ratio of 5×10⁻⁷:1, 1×10⁻⁶:1, 5×10⁻⁵:1, or 2.5×10⁻⁵:1; a maximum reaction zone zirconium of the zirconium compound to ethylene molar ratio of 7.5×10⁻⁴:1, 5×10⁻⁴:1, 2.5×10⁻⁴:1, or 1×10⁻⁴:1; a reaction zone zirconium of the zirconium compound to ethylene molar ratio ranging from 5×10⁻⁷:1 to 1×10⁻⁴:1, 1×10⁻⁶:1 to 2.5×10⁻⁴:1, 5×10⁻⁵:1 to 5×10⁻⁴:1, or 2.5×10⁻⁵:1 to 7.5×10⁻⁴:1; among other reaction zone zirconium of the zirconium compound to ethylene molar ratios and ranges).

Statement 34. The process of any one of statements 1-33, wherein the oligomer product is formed at (or the reaction zone has) any pressure described herein (e.g., a minimum pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); a maximum pressure of 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa); or a pressure in the range of from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa); among other pressures and pressure ranges).

Statement 35. The process of any one of statements 1-34, wherein the oligomer product is formed at (or the reaction zone has) any ethylene partial pressure described herein (e.g., a minimum ethylene partial pressure of 100 psi (689 kPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), 750 psi (5.17 MPa), 900 psi (6.21 MPa), or 1000 psi (6.89 MPa); a maximum ethylene partial pressure of 5000 psi (34.5 MPa), 4500 psi (31 MPa), 4,000 psi (27.6 MPa), 3500 psi (24.1 MPa), 3000 psi (20.7 MPa), 2,500 psi (17.2 MPa), 2,000 psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi (6.89 MPa); or an ethylene partial pressure in the range of from 100 psi (689 kPa) to 5000 psi (34.5 MPa), 100 psi (689 kPa) to 2,500 psi (17.2 MPa), 100 psi (689 kPa) to 1000 psi (6.89 MPa), 500 psi (3.45 MPa) to 4500 psi (31 MPa), 500 psi (3.45 MPa) to 2,500 psi (17.2 MPa), 500 psi (3.45 MPa) to 1000 psi (6.89 MPa), 750 psi (5.17 MPa) to 4500 psi (31 MPa), 900 psi (6.21 MPa) to 4,000 psi (27.6 MPa), or 1000 psi (6.89 MPa) to 3500 psi (24.1 MPa); among other ethylene partial pressures and pressure ranges).

Statement 36. The process of any one of statements 1-35, wherein the oligomer product is formed at (or the reaction zone has) any temperature described herein (e.g., a minimum temperature of 0° C., 25° C., 40° C., 50° C., 75° C., 100° C. or 125° C.; a maximum temperature of 250° C., 200° C., 150° C., 125° C., 100° C., or 90° C.; a temperature in ranging from 0° C. to 250° C., from 25° C. to 200° C., from 40° C. to 150° C., from 40° C. to 100° C., from 50° C. to 100° C., from 50° C. to 150° C., from 75° C. to 125° C., from 75° C. to 250° C., from 100° C. to 200° C., or from 100° C. to 200° C.; among other temperature values and ranges).

Statement 37. The process of any one of statements 1-36, wherein the oligomer product is formed at (or the reaction zone has) any ethylene:organic reaction medium mass ratio described herein (e.g., a minimum ethylene:organic reaction medium mass ratio of 0.5:1, 0.75:1, 1:1, 1.25:1, or 1.5:1; a maximum ethylene:organic reaction medium mass ratio of 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, or 2:1; an ethylene:organic reaction medium mass ratio ranging from 0.5:1 to 4.5:1, from 0.75:1 to 4:1, from 0.75:1 to 2:1, from 1:1 to 3:1, or from 1.5:1 to 2.5:1; among other ethylene:organic reaction medium mass ratio values and ranges).

Statement 38. The process of any one of statements 1-37, wherein the oligomer product is formed at (or the reaction zone has) any reaction zone residence time (or average reaction zone residence time) described herein (e.g., a minimum reaction zone residence time (or average reaction zone residence time) of 10 minutes, 20 minutes, or 30 minutes; a maximum reaction zone residence time (or average reaction zone residence time) of 3 hours, 2.5 hours, 2 hours, or 1.5 hours; a reaction zone residence time (or average reaction zone residence time) ranging from 10 minutes to 2.5 hours, from 20 minutes to 2 hours, from 30 minutes to 2 hours, or from 30 minutes to 1.5 hours; among other reaction zone residence time (or average reaction zone residence time) values and ranges.

Statement 39. The process of any one of statements 1-38, wherein the oligomer product can be formed at any ethylene conversion (or single pass ethylene conversion) described herein (e.g., a minimum ethylene conversion (or single pass ethylene conversion) of 30%, 35%, 40%, 45%, 50% or 55%; additionally or alternatively, a maximum ethylene conversion (or single pass ethylene conversion) of 95%, 90%, 87.5% 85%, or 80%; an ethylene conversion (or single pass ethylene conversion) ranging from 30% to 90%, from 35% to 90%, from 40% to 87.5%, from 45% to 87.5%, from 50% to 85%, or from 55% to 85%; among other ethylene conversion (or single pass ethylene conversion) values and ranges.

Statement 40. The process of any one of statements 1-39, wherein the oligomer product can have any Schulz-Flory K value disclosed herein (e.g., a minimum Schulz-Flory K value of 0.4, 0.45, 0.5, or 0.55; a maximum Schulz-Flory K value of 0.9, 0.85, 0.8, 0.75, 0.7, or 0.65; a Schulz-Flory K ranging from 0.4 to 0.9, from 0.4 to 0.8, from 0.5 to 0.8, from 0.5 to 0.7, or from 0.55 to 0.7; among other Schulz-Flory K values and ranges.

Statement 41. The process of any one of statements 1-40, wherein the process produces an oligomer product comprising (a) polymer having a lower Mw, (b) a polymer having a lower Mw maximum peak, (c) a reduced percentage of polymer, (d) a polymer having a reduced percentage of polymer having a Mw greater than 100,000, or (e) any combination thereof relative to the same process not using a) the chain transfer agent comprising a compound having a hydrogen silicon bond, a compound having a hydrogen sulfur bond, a compound having a hydrogen phosphorus bond, or any combination thereof in any one of statements 1-4, 2) hydrogen in any one statements 5-7, and/or 3) the transition metal compound chain transfer agent in any one of statements 8-13.

Statement 42. The process of any one of statements 1-41, wherein the oligomer product comprises (a) less than 1 wt. % of polymer, (b) less than 1 wt. % compounds having a weight average molecular weight of greater than 1000 g/mol, or (c) any combination thereof wherein the wt. % is based on the total weight of the oligomer product.

All publications and patents mentioned herein are incorporated herein by reference. The publications and patents mentioned herein can be utilized for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

US11873264B2. Ethylene oligomerization processes (2024-01-16). Chevron Phillips Chemical Company LP [US]. Inventors: Brooke L. Small [US], Orson L. Sydora [US], Ronald D. Knudsen [US].

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Patent 2024

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