WO2017031395A1 - Désactivateurs de catalyseurs à base d'amines pour des procédés impliquant du polyéthylène contenant du vanadium - Google Patents

Désactivateurs de catalyseurs à base d'amines pour des procédés impliquant du polyéthylène contenant du vanadium Download PDF

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WO2017031395A1
WO2017031395A1 PCT/US2016/047696 US2016047696W WO2017031395A1 WO 2017031395 A1 WO2017031395 A1 WO 2017031395A1 US 2016047696 W US2016047696 W US 2016047696W WO 2017031395 A1 WO2017031395 A1 WO 2017031395A1
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vanadium
catalyst
composition
absorbent
compound
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PCT/US2016/047696
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English (en)
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Jeffrey C. Haley
Robert L. SHERMAN
Douglas C. Mcfaddin
Karl C. KOCH
Michael W. Lynch
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Equistar Chemicals, Lp
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    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • 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 present disclosure relates to chemistry and polyolefin chemistry. In some embodiments, the present disclosure relates to methods of deactivating catalysts.
  • Solution-based polymerization processes are widely used for the manufacture of polyolefms such as high density polyethylene (HOPE).
  • HOPE high density polyethylene
  • One such process is a vanadium and titanium catalyzed polymerization of ethylene to form polyethylene.
  • Efficiently removing the catalyst from the product mixture to obtain the purified polymer is one of the challenges.
  • Some processes use deactivating agents, e.g. , acetylacetone, to separate the catalyst from the product mixture; however, acetylacetone decomposes under the polymerization conditions.
  • Analysis of the recycle steams have identified organic compounds from acetylacetone decomposition, such as acetone, eihanol, and more complex compounds such as isophorone and 3,5-dimethylphenol.
  • the present disclosure provides methods comprising:
  • n 1, 2, 3, or 4;
  • n 1, 2, 3, or 4;
  • Ri is alkyl(cg-24), alkenyl(cg-24), or a substituted version of either of these groups; to a polymerization composition to form a first reaction mixture; (b) contacting the first reaction mixture with absorbent to form a second reaction mixture, whereby a portion of the vanadium is adsorbed onto the absorbent to form vanadium adsorbed absorbent; and
  • Ri is alkyl(cio-20)-
  • R) is dodecanyl or tetradecanyl.
  • the deactivating composition is a mixture comprising a compound wherein Ri is dodecanyl and a compound wherein Ri is tetradecanyl.
  • the compound is cocobis(2- hydroxyethyl)amine.
  • the polymerization composition is a reaction product from a polyethylene production process.
  • the reaction product is from a vanadium catalyzed polyethylene production process.
  • the vanadium catalyst is a vanadium(V) compound.
  • the reaction product further comprises a titanium catalyst.
  • the titanium catalyst is a titanium(IV) compound.
  • the vanadium catalyst is VOCI3 and the titanium catalyst is T1CI .
  • the reaction product further comprises a trialkylaluminum.
  • the trialkylaluminum is triethylaluminum.
  • the absorbent is alumina.
  • the method comprises admixing the compound of formula I in a weight ratio from about 1 : 1 to about 10: 1 relative to the total weight of the catalysts and co-catalysts. In some embodiments, the weight ratio is from about 4:1 to about 5:1 relative to the total weight. In some embodiments, the reaction product comprises a molar ratio of the vanadium catalyst to the titanium catalyst from about 10:1 to about 1 : 10. In some embodiments, the amount of vanadium in the product composition is less than 2.0 ppm.
  • the present disclosure provides methods comprising:
  • n 1, 2, 3, or 4;
  • n 1, 2, 3, or 4;
  • Ri is alkyl(C8-24), alkenyl(c 8 -24), or a substituted version of either of these groups; to a product composition from a vanadium catalyzed polyethylene polymerization reaction to form a first reaction mixture; (b) contacting the first reaction mixture with absorbent to form a second reaction mixture, whereby a portion of the vanadium is adsorbed onto the absorbent to form vanadium adsorbed absorbent; and
  • m and n are 2.
  • Rj is alkyl(eio-20)- h
  • R 5 is dodecanyl or tetradecanyl.
  • the deactivating composition is a mixture comprising a compound wherein 3 ⁇ 4 is dodecanyl and a compound wherein R
  • the compound is cocobis(2- hydroxyethyl)amine,
  • the polymerization composition is a reaction product from a polyethylene production process, In some embodiments, the reaction product is from a vanadium catalyzed polyethylene production process. In some embodiments, the vanadium catalyst is a vanadium ⁇ V) compound. In some embodiments, the reaction product further comprises a titanium catalyst. In some embodiments, the titanium catalyst is a titanium(IV) compound. In some embodiments, the vanadium catalyst is VOCI 3 and the titanium catalyst is TiCLs, I some embodiments, the reaction product further comprises a tria!kylaluminum. In some embodiments, the irialkylal ummiini is triethylaluminum. In some embodiments, the absorbent is alumina.
  • the method comprises admixing the compound of formula ⁇ in a weight ratio from about 1:1 to about 10:1 relative to the total weight of the catalysts and co-catalysts. In some embodiments, the weight ratio is from about 4:1 to about 5:1 relative to the total weight. In some embodiments, the reaction product comprises a molar ratio of the vanadium catalyst to the titanium catalyst from about 10:1 to about 1: 10. In some embodiments, the amount of vanadium in the product composition is less than 2,0 ppm.
  • the present disclosure provides methods comprising: (a) admixing a deactivating compositio comprising a compound of the formula:
  • n 1, 2, 3, or 4;
  • n 1, 2, 3, or 4;
  • Rj is alkyl(cg-24), alkenyl(C8-24), or a substituted version of either of these groups; in a first vessel with a composition from a vanadium catalyzed polyethylene polymerization reaction thereby forming a first reaction mixture;
  • concentration of vanadium of the product mixture is lower that the vanadium concentration in the first reaction mixture.
  • m and n are 2.
  • Rj is alkyl(cio-20).
  • Ri is dodecanyl or tetradecanyl.
  • the deactivating composition is a mixture comprising a compound wherein Rj is dodecanyl and a compound wherein Ri is tetradecanyl.
  • the compound is cocobis(2- hydroxyethyl)amine.
  • the polymerization composition is a reaction product from a polyethylene production process.
  • the reaction product is from a vanadium catalyzed polyethylene production process.
  • the vanadium catalyst is a vanadium(V) compound.
  • the reaction product further comprises a titanium catalyst.
  • the titanium catalyst is a titanium(IV) compound.
  • the vanadium catalyst is VOC3 ⁇ 4 and the titanium catalyst is TiCLt.
  • the reaction product further comprises a trialkylaluminum.
  • the trialkylaluminum is triethylaluminum.
  • the absorbent is alumina.
  • the method comprises admixing the compound of formula I in a weight ratio from about 1: 1 to about 10: 1 relative to the total weight of the catalysts and co-catalysts. In some embodiments, the weight ratio is from about 4: 1 to about 5: 1 relative to the total weight. In some embodiments, the reaction product comprises a molar ratio of the vanadium catalyst to the titanium catalyst from about 10: 1 to about 1 : 10. In some embodiments, the amount of vanadium in the product composition is less than 2.0 ppm.
  • FIG. 1 shows the X P spectra centered on the vanadium emission peak XRF results are shown for acetylacetone deactivated samples, samples not treated with a deactivating agent, and fresh alumina.
  • Fresh untreated alumina contains no vanadium
  • Alumina contacted with catalyst solution with no added deactivating agent contains a detectable level of vanadium.
  • Alumina contacted with catalyst solution in the presence of acetylacetone contained a higher level of vanadium than alumina taken from the deactivator-free experiments. It was estimated that the acetylacetone samples contained approximately 2.5 times the level of vanadium based on measurements of the relative peak heights.
  • FIG. 2 shows the XRF peak height corresponding to vanadium plotted as a function of the quantity of deactivating agent for the deactivator concentration study.
  • the deactivating compounds are labeled m the figure as acetyl acetone ($), ArmostatTM 400 (dark *), ArmostatTM 700 (light *), acetic acid (g), DEG (A), and adspic acid (*).
  • the curves are drawn as a guide. Multiple date points for ArmostatTM 400 at each concentration were collected during individual experiments and provide some information on experimental reproducibility.
  • Both ArmostatTM 400 and ArmostatTM 700 increase the amount of vanadium adsorbed when compared with experiments where no deactivator was added. Additionally, for both compounds the amount of vanadium adsorbed increases with increasing deactivator level.
  • FIG. 3 shows the XRF peak height corresponding to vanadium plotted as a function of the quantity of deactivating agent for the catalyst concentration study
  • the deactivating compounds are labeled in the figure as acetyl acetone (s), ArmostatTM 400 (&), acetic acid (*), and no deactivating compound (*),
  • the curves are drawn as a guide.
  • the data show that acetic acid resulted in similar amounts of vanadium being adsorbed relative to experiments where no deactivating agent was used. This observation seems to hold over the range of catalyst concentrations studied.
  • ArmostatTM 400 and acetyl acetone both show a tendency to increase the quantity of vanadium adsorbed onto the alumina.
  • the effects of ArmostatTM 400 and acetyl acetone are similar in magnitude.
  • the present disclosure provides methods for removing catalysts from polymerization solutions, including polymerization product mixtures.
  • the methods may be used to remove vanadium and titanium catalysts from such solutions and mixtures.
  • such methods comprise admixing a composition comprising a compound of formula I to a solution or mixture and exposing the solution or mixture to alumina.
  • these methods are used to treat the product mixture that results from a vanadium catalyzed polyethylene production process.
  • the methods described herein may be used to obtain polyethylene products, which contains a reduced concentration of vanadium and/or improved physical properties, such as color, taste, or odor.
  • the present disclosure provides methods of using a catalyst deactivating composition comprising a compound of the formula:
  • n 1, 2, 3, or 4;
  • n 1, 2, 3, or 4;
  • Ri is alkyl(C8-24), alkenyl ⁇ c8-24), or a substituted version of either of these groups.
  • m is 1, 2, or 3. In some embodiments, m is 2. In some embodiments, n is 1, 2, or 3. In some embodiments, n is 2. In some embodiments, Rj of the compound is an alkyl(C8-24) or alkenyl(cs-24). In some embodiments, Ri is an alkyl(C8-24). In some embodiments, 3 ⁇ 4 is alkyl ( cio-20)- Some non-limiting examples of alkyl groups at the Ri position include decanyl, dodecanyl, tetradecanyl, hexadecanyl, octadecanyl, or eicosanyl. In other embodiments, Ri is alkenyl(cg.
  • Rj is alkenyl(cio- 2 o).
  • alkenyl groups at the R] position include 9-hexadecenyl, 9-octadecenyl, 9,12-octadecadienyl, 9,12,15-octadecatrienyl, 6,9, 12-octadecatrienyl, 5,8,11,14-eicosatetraenyl, or 5,8, 11 , 14,17-eicosapentaenyl.
  • Rj is an alkyl or alkenyl group derived from a fatty acid.
  • the method comprises using a single compound of formula I.
  • the method comprise adding a catalyst deactivating composition comprising a mixture of compounds of formula I wherein the different compounds have different carbon lengths on the alkyl or alkenyl group of Rj.
  • the compound that may be used is a deactivating composition of compounds with two or more different Ri group lengths which comprises greater than 60%, greater than 80%, or greater than 90% of the composition.
  • the catalyst deactivating composition consists essentially of a mixture of compounds of formula I wherein each compound has a different Rj group.
  • One catalyst deactivating composition that may be used in the method described herein comprises a mixture of compounds of formula I wherein the mixture consisting of at least 50% of compounds with dodecanyl and tetradecanyl Rj groups.
  • the amount of the catalyst deactivating compositions used is proportional to the amount of catalyst, co-catalyst, and/or activator used. In some embodiments, the amount of the catalyst deactivating compositions used can stoichiometrically chelate the catalyst and any additional metal components such as co -catalyst and/or activators.
  • the catalyst deactivating compositions may be used to chelate to the vanadium and titanium in the catalyst at a ratio of 3 moles of the catalyst deactivating compositions to 1 mole of vanadium and a ratio of 4 moles of the catalyst deactivating compositions to 1 mole of titanium.
  • the catalyst deactivating compositions may be used to chelate the aluminum compound by adding a ratio of 3 moles of the catalyst deactivating compositions to 1 mole of aluminum.
  • the amount of the catalyst deactivating compositions that is used is present in a ratio from about 1 : 1 to about 10: 1 weight catalyst deactivating compositions to the weight of the catalyst, co-catalyst, and/or activators.
  • the ratio is relative to the weight of the catalyst and co-catalysts.
  • the ratio is from about 2: 1 to about 5: 1 wt/wt.
  • the ratio is about 4.4:1 wt/wt.
  • the methods may further comprise adding a second deactivating compound such as acetyl acetone.
  • a second deactivating compound such as acetyl acetone.
  • the molar ratio of the second deactivating compound to the catalyst deactivating compositions that may be used is from about 0.1 : 1 to about 2: 1.
  • the methods use an absorbent to remove the catalyst from the reaction mixture.
  • the absorbent is a porous material which absorbs or collects certain compounds or compositions such as catalysts and co-catalysts while allowing other materials such as a polyolefin or a solvent to pass with little to no absorbance.
  • Some non- limiting examples of absorbents include alumina, bentonite, silica, clay, metal oxides, molecular sieves, zeolites, diatomaceous earth, activated carbon, carbon black, magnesia, or a mixture of any of these absorbents. Additional examples of absorbents are described in U.S. Patent Nos.
  • the absorbent is alumina, silica, or mixed alumina-silica particles. In some embodiments, the absorbent is alumina. In some aspects, the absorbent is contacted with the reaction mixture for a period of time to cause vanadium to deposit on the absorbent.
  • the absorbent is dried before the use in the methods described herein.
  • Methods of drying the absorbent that may be used include heating the absorbent to an elevated temperature and/or exposing the absorbent to a vacuum.
  • the absorbent is dried at a temperature greater than 50 °C.
  • the absorbent is dried at a temperature great than 50 °C in the presence of a vacuum.
  • the absorbent is dried at a temperature of about 90 °C in the presence of a vacuum.
  • the absorbent is dried for a time period from about 1 hour to about 48 hours. In some embodiments, the time period is about 3 hours to about 18 hours. In some embodiments, the absorbent is dried overnight.
  • the shape and form of the absorbent is optimized to remove the catalyst from the reaction mixture.
  • the absorbent is formed as a powder, as a particle, or as a bead. In some embodiments, the absorbent is formed as a particle or as bead. In some embodiments, absorbent is characterized by an average particle size or average particle diameter of from about 1 um to about 500 urn. In some embodiments, the average particle size is from about 60 um to about 150 um. In some embodiments, the average particle size is from about 70 um to about 100 um. In other embodiments, the absorbent is in the form of spheres or beads that have a larger particle size. The particle size of the spheres or beads may be from about 0.1 mm to about 30 mm. In some embodiments, the average particle size is from about 2 mm to about 25 mm. In some embodiments, the average particle size is from about 3 mm to about 10 mm.
  • the absorbent comprises a high surface area or porosity.
  • the absorbent has a surface area greater than 10 m 2 /g.
  • the surface area is from about 50 m 2 /g to about 10,000 m 2 /g.
  • the surface area is from about 50 m 2 /g to about 1,000 m 2 /g.
  • the surface area of the absorbent is measured using the BET method or other methods known to a person of skill in the art.
  • the absorbent has a pore volume of greater than 0.25 mlVg. In some embodiments, the pore volume is greater than 0.4 mL/g. Methods of determining pore volume that may be used include helium or mercury displacement.
  • the catalyst deactivating compositions described herein may be used in a vanadium and titanium catalyzed polyolefin polymerization process.
  • the polyolefin is a polyethylene such a low density polyethylene or a high density polyethylene.
  • the method comprises a catalyst composition comprising a vanadium source and a titanium source.
  • vanadium sources may be used in the catalyst composition for the polymerization process described herein.
  • the vanadium source is a vanadium compound or complex wherein the vanadium is in the +5 oxidation state.
  • Some non-limiting examples of vanadium sources include VOX 3 wherein X is a halide, VO(OR)3 wherein R is an alky cw ) , or VCI 4 .
  • the vanadium compound or complex has one or more organic chelating ligands.
  • the vanadium source is VOCI3.
  • the titanium source is a titanium compound or complex wherein the titanium is in the +4 oxidation state.
  • Some non-limiting examples of examples of titanium sources include T1X4 wherein X is a halide, Ti(OR)4. y X y , wherein y is less than or equal to 4, X is a halide and R is an alkyl(Ci-6 Ti(QR)4 wherein R is an alkyl ( ci-6).
  • the titanium source is TiCL».
  • the catalyst composition comprises a ratio of the vanadium source to the titanium source from about 10:1 to about 1 :10. In some embodiments, the ratio of the vanadium source to the titanium source is about 5:1 to about 1:5. In some embodiments, the ratio is about 5:1 to about 1 :1. In some embodiments, the ratio is about 4:1 of the vanadium source to the titanium source.
  • the polymerization method further comprises adding an alkylalummum reagent.
  • the alkyl aluminum reagent has a formula: Al(OR) 3-!C R'x wherein R and R' are each independently alkyl ( ci-cs ) - In some embodiments, x is 3.
  • the alkylalummum reagent is triethylaluminum (TEAL).
  • TEAL triethylaluminum
  • the alkylaluminum reagent is added to the polymerization process relative to the vanadium and titanium in a molar ratio from about 5: 1 to about 1 :1. In some embodiments, the molar ratio is about 3: 1 to about 1.1 :1 relative to the vanadium and titanium. In some embodiments, the molar ratio is from about 2:1 to about 1.3: 1.
  • the polymerization may comprise one or more additional elements such as a magnesium reagent, an alkyl halide, and/or hydrogen gas.
  • additional elements such as a magnesium reagent, an alkyl halide, and/or hydrogen gas.
  • the polymerization process may comprise running the process at an elevated temperature from about 50 °C to about 350 °C. In some embodiments, the process is run from about 150 °C to about 300 °C. Additionally, the polymerization process may be performed at conditions comprising a pressure from about 2 MPa to about 20 MPa. In some embodiments, the pressure is form about 8 MPa to about 20 MPa.
  • the polymerization process may also comprise the use of a solvent. In some embodiments, the solvent is a hydrocarbon solvent with 6-18 carbon atoms.
  • hydrocarbon solvents include hexane, heptane, octane, cyclohexane, methylcyclohexane, hexadecane, hydrogenated naphtha, and decalin.
  • the polymerization process is an ethylene polymerization process.
  • a co-monomer comprising a C3- C12 olefin may also be added to the reaction to obtain copolymer.
  • the co-monomer comprises from 1-20% of the polymer composition. Additional characteristics of the polymerization process are described in U.S. Patent Nos. 5,589,555 and 6,084,042.
  • the methods described herein comprise removing vanadium from a solution such that the vanadium concentration in the polymer is less than 5 parts per million. In some embodiments, the vanadium concentration in the polymer is less than 3 parts per million. In some embodiments, the vanadium concentration is from about 0.5 parts per million to about 5 parts per million. In some embodiments, the vanadium concentration is less than 2 parts per million. In some embodiments, vanadium concentration can be measured using atomic absorbance spectroscopy or x-ray fluorescence.
  • the methods described herein may be used to obtain a polymer composition with improved stability, taste, odor, and/or color.
  • the lightness scale is greater than 78. In some embodiments, the lightness scale is greater than 80. In some embodiments, the lightness scale is greater than 82. In some embodiments, the lightness scale is greater than 85.5.
  • the color of the object may show a measurement on the red green scale with an upper limit of about 1 with a lower limit of about -3. In some embodiments, the red green scale has an upper limit of about 0 with a lower limit of about -2.3. In some embodiments, the red green scale has an upper limit of about -0.8 with a lower limit of about -2.
  • the red green scale is less than about -1.6.
  • the yellow blue scale of the polymer shows an upper limit of about 2.5 with a lower limit of about -12.
  • the yellow blue scale has an upper limit of about 2 with a lower limit of about -8.
  • the yellow blue scale has an upper limit of about 0.0 with a lower limit of about -3.
  • the yellow blue scale is greater than -1.
  • the lightness, red green scale, and yellow blue scale can be measured as described in the ASTM 1331 :ASTM 313 standards and ASTM standards E308 and ASTM standards D6290.
  • absorbent or "absorbent material” is used to describe a material which has a porous nature which selective absorbs one or more compounds while not absorbing the polyoiefin or the solvent.
  • absorbent include alumina, bentonite, silica, clay, metal oxides, molecular sieves, zeolites, diatomaceous earth., activated carbon, carbon black, magnesia, or a mixture thereof.
  • acetylaeetone acetyl acetone
  • acetyl acetone acetyl acetone
  • aeetoacsione acetylaeetone
  • alky when used in the context of this application is a saturated aliphatic, straight or branched chain radical consisting of carbon and hydrogen atoms consistent with standard IUPAC nomenclature.
  • substituted one or more of the hydrogen atoms of the alkyl group has been replaced with ⁇ OH, -F, -CI, -Br, -I, -N3 ⁇ 4 -N0 2 , -C0 2 H, -C0 2 CH 3) -CN, -SH, -OCH 3 , -OCH 2 CH 3 , -C(G)CH 3; -NHCH 3 , - HCH2CH3, -N(CH 3 ) 2 , -C(0)N3 ⁇ 4, -OC(0)CH 3 , or -S(0) 2 NH 2 .
  • alkenyl when used in the context of this application is an aliphatic, straight or branched chain radical consisting of only carbon and hydrogen atoms containing one or more carbon-carbon double bonds consistent with standard IUPAC nomenclature.
  • one or more of the hydrogen atoms of the alkyl group has been replaced with -OH, -F, -CI, -Br, -I, -NH 2 , -NO 3 ⁇ 4 -C0 2 H, -C0 2 CH 3 , -CN, -SH, -OCH3, -OCH2CH3, -C(0)CH 3 , -NHCH3, -NHCH 2 C3 ⁇ 4 -N(CH 3 ⁇ 2 , -C(0)NH 2 , -OC(0)CH 3 , or -S(G ⁇ 2 N3 ⁇ 4.
  • ArmostatTM 400 and “ArmostatTM 410” are used to described cocobis(2-hydroxyethyl)amine (CAS Registry No. 61791-31-9).
  • ArmostatTM 700 is used to described oleylbis(2-hydroxyethyl)amine (CAS Registry No. 25307-17-9).
  • UV-3853 is used to described 2,2,6,6-tetramethyl -piperidinyl stearate (CAS Registry No. 167078-06-0).
  • olefin refers to an alkene or aralkene wherein at least one carbon-carbon double bond in the molecule is a terminal double bond.
  • olefins include styrene, ethylene, propylene, butene, pentene, hexene, heptene, octenc, nonene, decene, or dodecene.
  • a commercially available basic alumina (LZ060000) was used. Alumina was dried in a vacuum oven overnight at 90 °C. Dried alumina was stored in an inert atmosphere glove box until it was used. VOCI3, TiCLi, and triethyl aluminum (TEA1) solutions in heptane were prepared and used in the polymerization reactions.
  • Hexadecane (Aldrich), acetylacetone (Aldrich), acetic acid (Aldrich), benzoylacetone (Aldrich), diethylene glycol (Aldrich), adipic acid (Aldrich), stearic acid (Aldrich), glycerol monostearate (Aldrich), sodium stearate (Baerlocher), ArmostatTM 700 (AkzoNobel), and UV-3853 (Cytec) were used as received without additional purification.
  • the stirrer was turned on and the reaction vessel was heated to 280 °C. Once the vessel reached its target temperature, 0.05 mM of TEA1 was injected into the reactor and allowed to stir for 5 min. At this point, 0.022 mM of VOCI3 and 0.006 mM of T1CI4 were injected into the solution, and the catalysf ' cocatalyst solution was stirred for 30 min. A fine precipitate of catalyst particles was formed. Stirring was sufficient to keep the particles suspended in solution.. After 30 min, 0.35 mM of deactivator were injected into the solution.
  • deactivators were dissolved in hexadecane. If deactivator did not dissolve on its own at room temperature then the hexadecane solution was heated to 80 °C to dissolve the deactivator. If heated, the deactivator hexadecane solution was maintained at elevated temperature prior to injection, and a hot injection syringe that had been stored in an oven was used to prevent the deactivator from precipitating in the syringe. Adipic acid, glycerol monosiearate, and sodium stearate did not completely dissolved in the hexadecane solution.
  • the resulting solution was allowed to stir for 5 min. After 5 min, the basket containing 5 g of alumina was lowered into the solution. The alumina was held in the stirring solution for 1 hour. After 1 hour, the alumina basket was raised and the reactor was allowed to cool off. The alumina was first dried overnight in a fume hood, and then was dried in a vacuum oven at 80 °C. The dried alumina was characterized by x-ray fluorescence (XRF) for vanadium.
  • XRF x-ray fluorescence
  • Alumina contacted with catalyst solution in the presence of acetylacetone contained a higher level of vanadium than alumina taken from the deactivator-free experiments. It was estimated that the acetylacetone samples contained approximately 2.5 times the level of vanadium based on measurements of the relative peak heights in FIG. 1.
  • Example 1 The basic apparatus and experimental procedures used herein are described in Example 1.
  • Example 1 Based upon the experiments carried out in Example 1, a number of potential deactivating compounds were determined as potential replacements for acetyl acetone.
  • ArmostatTM 700, acetic acid, adipic acid, and diethylene glycol (DEG) were identified as potential replacement compounds.
  • ArmostatTM 400 was added.
  • the catalyst concentration was maintained at a fixed level that is approximately 1 order of magnitude greater than the actual catalyst concentration used commercially (See Example 2A).
  • the relative amount of vanadium adsorbed onto the alumina by XRF was determined. The XRF signal strength is proportional to the quantity of adsorbed vanadium.
  • FIG. 2 plots the XRF signal intensity as a function of the amount of deactivator added to the system.
  • FIG. 2 illustrates how increasing the amount of each deactivator used affects vanadium adsorption. Results for the 6 different compounds are shown in FIG. 2.
  • Acetyl acetone is used as a deactivating agent for the V Ti catalyst system in solution processes. The amount of vanadium adsorbed during a given experiment is proportional the XRF peak height. The amount of vanadium adsorbed by the alumina increases as the amount of acetyl acetone increases. The amount of vanadium adsorbed in the presence of the lowest quantity of acetyl acetone shown in FIG. 2 is three times the amount of vanadium adsorbed without any added acetyl acetone. These data show that acetyl acetone aids the adsorption process for vanadium in these experiment.
  • ArmostatTM 700 showed promise as a potential deactivating compound.
  • ArmostatTM 700 and ArmostatTM 400 were tested.
  • ArmostatTM 400 is structurally similar to ArmostatTM 700, but is somewhat lower in molecular weight.
  • the results for both ArmostatTM 400 and ArmostatTM 700 are shown in FIG. 2. Multiple data points for ArmostatTM 400 at each concentration were collected during individual experiments and provide some information on experimental reproducibility.
  • Both ArmostatTM 400 and ArmostatTM 700 increase the amount of vanadium adsorbed when compared with experiments where no deactivator was added. Additionally, for both compounds the amount of vanadium adsorbed increases with increasing deactivator level.
  • ArmostatTM 400 is more effective as a deactivator, on a per mole basis, than ArmostatTM 700. This difference would be magnified on a per mass basis, as ArmostatTM 400 is lower in molecular weight than ArmostatTM 700.
  • ArmostatTM 400 appears to increase vanadium absorption values and thus might be capable of replace acetyl acetone in a HDPE solution process. ArmostatTM 400 and acetyl acetone seem to have similar effectiveness when used at the same molar concentration.
  • a catalyst concentration experiment was performed as described in section A. In these experiments, a fixed quantity of deactivating agent (0.35 mmoles) and varied the concentration of catalyst and cocatalyst were used. The experiments conducted at the lowest catalyst concentration in this experiment are equivalent to the experiments conducted in Example 1. This catalyst concentration experiment served to further validate the data described in Example 1. The remaining catalyst concentrations bridge the gap between Example 1 and the deactivator concentration experiments described above in section B.
  • Example 3 Polyethylene Composition Properties
  • the deactivator was added as a molar ratio to the amount of catalyst added and runs between 1.3 and 1.5 dependent on the adsorber conditions and polymer color. For the experiments, a 1.3 deactivator/catalyst ratio was used. Four different compositions were tested. The compositions were as follows:
  • composition 1 25 mole% ArmostatTM 410 and 75 mole% Acetyl Acetone
  • composition 2 50 mole% ArmostatTM 410 and 50 mole% Acetyl Acetone
  • composition 3 75 mole% ArmostatTM 410 and 25 mole% Acetyl Acetone
  • composition 4 100 mole% ArmostatTM 410 and 0 mole% Acetyl Acetone
  • the produced polymers were evaluated for polymer color by the following method: A 0.10-inch thick plaque was molded from the sample of interest. The sample plaque was placed over the viewing port of the spectrocolorimeter. An opaque backing plate backed the sample since the polyethylene sample was translucent. The spectrophotometer measured the reflectance of the sample as a function of wavelength. The microprocessor used the reflectance data to calculate the L, a, b, values consistent with ASTM 1331 :ASTM 313 standard.
  • composition from a vanadium catalyzed polyethylene reaction was treated with different mixtures of acetyl acetone and ArmostatTM 410.
  • Each of the compositions treated with ArmostatTM 410 showed higher lightness and red green scales and a lower yellow blue scale with decreased vanadium concentrations relative to a composition treated with acetyl acetone.
  • Composition 3 85.88 -1.51 -1.43 0.9

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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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des procédés d'élimination de métaux de transition hors de compositions polyoléfiniques, lesdits procédés comprenant l'addition d'un composé de formule I à une composition et la mise en contact de la composition avec de l'alumine. La formule I est définie comme suit : les variables étant telles que définies dans la description. Selon certains aspects, ces procédés peuvent être utilisés pour l'élimination de vanadium hors d'un mélange de produits à base de polyéthylène catalysé par du vanadium (par exemple le HPDE). <i />
PCT/US2016/047696 2015-08-20 2016-08-19 Désactivateurs de catalyseurs à base d'amines pour des procédés impliquant du polyéthylène contenant du vanadium WO2017031395A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10941228B2 (en) * 2016-07-29 2021-03-09 Exxonmobil Chemical Patents Inc. Polymerization processes using high molecular weight polyhydric quenching agents

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991017193A1 (fr) * 1990-05-02 1991-11-14 Du Pont Canada Inc. Procede de polymerisation en solution pour la preparation de polymeres d'alpha-olefines
EP0604958A2 (fr) * 1992-12-28 1994-07-06 Union Carbide Chemicals & Plastics Technology Corporation Procédé de finition d'un polymère
US20090152169A1 (en) * 2007-12-17 2009-06-18 Etherton Bradley P Removal of metal contaminants from polyethylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991017193A1 (fr) * 1990-05-02 1991-11-14 Du Pont Canada Inc. Procede de polymerisation en solution pour la preparation de polymeres d'alpha-olefines
EP0604958A2 (fr) * 1992-12-28 1994-07-06 Union Carbide Chemicals & Plastics Technology Corporation Procédé de finition d'un polymère
US20090152169A1 (en) * 2007-12-17 2009-06-18 Etherton Bradley P Removal of metal contaminants from polyethylene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10941228B2 (en) * 2016-07-29 2021-03-09 Exxonmobil Chemical Patents Inc. Polymerization processes using high molecular weight polyhydric quenching agents

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