Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene

Definitions

• the invention relates to a method for adjusting molecular weight distribution and molecular weight of oligomerization/polymerization product of ethylene, wherein nickel ylide linked to a cross-bonded ⁇ ⁇ polystyrene or to be used together with a promoter is used as a catalyst in the oligomerization/polymerization process of ethylene.
• the known catalysts for oligomerization of olefines are generally organometallic compounds, such as organoaluminium compounds, which are in contact with a transition metal compound comprising low molecular weight 0 ligands, which include substances of the group V or VI (nitrogen, oxygen, phosphor or sulphur).
• organometallic compounds such as organoaluminium compounds
• transition metal compound comprising low molecular weight 0 ligands, which include substances of the group V or VI (nitrogen, oxygen, phosphor or sulphur).
• the US patent No. 4 115 468 describes a two-component catalyst, which contains an organoaluminium compound and for example a vinyl-containing siloxane rubber, which is bonded to a nickel salt for dimerization of olefines. 5
• This patent application relates to a method, by means of which the molecular weight distribution and molecular weight of oligomerization ⁇ J5 products of ethylene can be adjusted, when catalysts of the type described above are used as catalysts.
• the inventive method for adjusting the molecular weight distribution and molecular weight of oligomerization products of ethylene is 20 mainly characterized in that the product distribution and/or molecular weight is adjusted by modifying the catalyst system by varying the cross-bonding degree of polystyrene serving as a catalyst carrier and/or the quality and/or quantity of the promoter.
• the invention is especially related to methods, wherein the oligo- 5 merization of ethylene is performed by using as a catalyst the nickel ylide according to the following formula I, which is either bonded to a carrier, especially a cross-linked polystyrene containing preferably 1-4% divinyl benzene or used in combination with triphenyl phosphine or bis-cyclooctadiene nickel chelate.
• the invention is especially related to methods, wherein the molecular distribution of an oligomerization product prepared with a nickel ylide catalyst is on the basis of the application adjusted in the direction of either long- or short-chained ⁇ -olefines.
• a significant transition into the range of long-chained, even polymer products is possible, when the cross-bonding degree of a polystyrene carrier increases (e.g. polystyrene cross-bonded by 2% or 4%).
• An increase in bis-cyclooctadiene in the oligomerization phase also brings about transition of the oligomerization distribution into the range of long-chained products.
• a suitable quantity of (COD ⁇ Ni is 3 to 5 times the quantity of nickel contained in the catalyst.
• phosphine catalysts When adjusted in accordance with the method of the invention phosphine catalysts directly produce high-quality LLPDE.
• the inventive reaction products can be used e.g. for adjusting the working proper ⁇ ties of polyolefines and as reactants for synthetic lubricants. Products with a higher molecular weight can already as such be utilized as diverse polyethylene grades.
• Suitable solvents for completing the oligomerization reaction of ethylene include aromatic or aliphatic hydrocarbons or their mixtures.
• Methods suitable for recycling the catalyst bonded to the carrier include e.g. film separation methods (1-% and 2-% cross-bonded poly ⁇ styrene) or filtration (polystyrene cross-bonded by 4%).
• a more detailed preparation method od catalysts according to the invention is as follows.
• the solution is decanted from the top of the precipitate, sucked from the top of the precipi- tate with a Pasteur-pipette or precipitated with an excess of methanol, and in the second phase the solution is sucked from the top of the precipitate with a double-headed needle or decanted from the top of the gel.
• the precipitate is flushed with water and THF or methanol.
• the product is dried with a Leybold vacuum pump.
• the phosphinated PS is placed in a reaction vessel in a nitrogen cabinet.
• the phosphonium salt is placed in the reaction vessel.
• a pressure reactor was loaded with a catalyst I of formula I and a solvent, and in Examples 3 and 4, (COD ⁇ Ni in a nitrogen cabinet.
• the reactor was heated to 50°C and pressurized with ethylene to a pressure of 50-60 bar.
• the pressure was held constant (50 bar) by means of the ethylene supply during the entire reaction (2 h).
• the gaseous and liquid products were analyzed gas chromatographically and the yield of solids was determined by weighing and the molecular weight distribution was determined by means of a gel permeation chromatographic (GPG) method.
• GPG gel permeation chromatographic
• a pressure reactor was loaded with a catalyst II of formula II and a
• 25 degree (ca. 1%) produces a large quantity of Cg-C 2 g products and a high cross-bonding degree produces polymers of a higher-order.
• the catalyst samples were weighed in brown phials, 10 ml toluene was ⁇
• the results of the oligomerization reactions are summarized in Table 4 and drawings 6-8.
• the reaction mixture 11 was heated to 65°C by means of a rapid heating control, after which the heating advanced 0 at a slow heating rate.
• the reaction temperature increased to over 75°C (max. 138°C) for 6 minutes.
• the quantity of PPh 3 was 1.5 times the molar mass of PPh 3 used in the preparation of the catalyst.
• the quantity of PPh 3 is double with respect to the experiments 12 and 13. 1
• the reaction time is 4 hours (like in 12 and 13), but the autoclave with its reaction mixture was pressurized to 34 bar at room temperature for 2 days, during which period the reaction advanced, consuming all ethylene.
• the quantity of the gases was calculated from the weighing results 25 of the autoclave by means of single responses (autoclave weighing when the gases are inside and after they have been released) .
• the quantity of wax can be decreased by admixing triphenyl phosphine into the autoclave together with the catalyst. However, the total activity of the catalyst will then decrease as a function of the molar mass of the triphenyl phosphine added. Owing to triphenyl phosphine, the share of light C ⁇ -C ⁇ Q 1-alkenes increases in comparison
• triphenyl phosphine to the reaction causes an increase in the weight-average molecular mass of wax and also an increase in the numeral-average molecular mass.
• the quantity of triphenyl phosphine used for preparing the catalyst is reduced, the total activity of the catalyst decreases, but the share
• the most active of the catalysts linked to a cross-bonded polystyrene was the catalyst containing the 1-% PS, with respect to the production 5 °f both oligomers and wax.
• the share of wax of the total product quantity was in the products of the 1-% PS containing catalyst less than 50%, when the catalyst dispersion contained 59 mg/40 ml nickel.
• the 4-% cross-bonded PS containing catalyst with the weakest total 0 activity produced relatively the highest amount of wax, i.e. 90% of the total product quantity.
• the increase in the share of wax was affected by the low amount of catalyst (nickel) , an increase 5 in the solvent volume and a decrease in the reaction temperature.
• the molecular weight distributions varied widely on waxes.
• the lowest polydispersity value 4 was found in the waxes produced by the 4-% cross-bonded PS containing catalyst and the highest value 94 on 2-% waxes.
• the 1-% cross-bonded PS containing catalyst produced wax, whose polydispersity was 12. Mw was 5600 and Mn 460. As the cross-bonding of polystyrene increases, it resulted in polymers of ethylene with a higher molecular mass. The highest molecular masses were achieved with 2-% cross-bonded PS containing catalysts.
• a catalyst containing a non-cross-bonded PS (Mw 209000) produced wax with a low molecular mass.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)

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• 1989
  • 1989-06-05 FI FI892742A patent/FI85588C/fi not_active IP Right Cessation
• 1990
  • 1990-05-23 EP EP19900907088 patent/EP0427830A1/en not_active Ceased
  • 1990-05-23 JP JP50763190A patent/JPH04503375A/ja active Pending
  • 1990-05-23 WO PCT/FI1990/000144 patent/WO1990015085A1/en not_active Application Discontinuation

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