METHODS OF PREPARATION OF A CATALYST, METHOD OF PREPARATION OF A POLYMER, COMPOSITION OF PRE-CATALYS

专利摘要:
a method for preparing a catalyst comprising a) placing (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound and (iv) an optional solvent in contact to form a first aqueous mixture comprising a pre-catalyst and a reaction medium having from about 1% by weight to about 99% by weight of water; b) heat treating the pre-catalyst by heating at a temperature of about 400 ° C to about 1,000 ° C for a period of time from about 1 minute to about 24 hours to form the catalyst. a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with a chromium-containing compound to form a first aqueous mixture comprising a chrome support; placing the first aqueous mixture comprising a chrome support in contact with a solution comprising (i) a solvent and (ii) an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst; and thermally treating the pre-catalyst to form the catalyst.
公开号:BR112019005929B1
申请号:R112019005929-6
申请日:2017-09-26
公开日:2021-03-30
发明作者:Max P Mcdaniel；Eric D Schwerdtfeger；Jeremy M. Praetorius；Alan L Solenberger；Kathy S Clear
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] The present disclosure relates to catalytic compositions. More specifically, the present disclosure relates to methods of preparing catalytic polymerization compositions of olefins and polymers prepared therefrom. FUNDAMENTALS
[0002] Improvements in the methods of preparing olefin polymerization catalysts can reduce the costs associated with the production of catalysts and improve the economics of the process. Thus, there is an ongoing need to develop new methods for preparing olefin polymerization catalysts. SUMMARY
[0003] Here is disclosed a method for preparing a catalyst comprising a) placing (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound and (iv) an optional solvent in contact to form a first aqueous mixture. comprising a pre-catalyst and a reaction medium having from about 1% by weight to about 99% by weight of water; b) thermally treat the pre-catalyst by heating at a temperature of about 400 ° C to about 1,000 ° C for a period of time from about 1 minute to about 24 hours to form the catalyst.
[0004] Also disclosed herein is a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with a chromium-containing compound to form a first aqueous mixture comprising a chrome support; placing the first aqueous mixture comprising a chrome support in contact with a solution comprising (i) a solvent and (ii) an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst; and thermally treating the pre-catalyst to form the catalyst.
[0005] Also disclosed herein is a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with an oxotitanium compound to form a first aqueous mixture comprising a titanated support; placing the first aqueous mixture comprising a titanated support in contact with a chromium-containing compound to form a second aqueous mixture comprising a pre-catalyst; and heat treating the pre-catalyst to form the catalyst.
[0006] Also disclosed herein is a method for preparing a catalyst comprising a) contacting (i) a silica support material comprising from about 0.1% to about 20% by weight of water, (ii) a solution comprising (1) 2,4-oxotitanium pentadionate, (2) a solvent and (3) from about 0.1% by weight to about 80% by weight of water based on the total weight of the solution and (iii ) a chromium-containing compound to form a pre-catalyst in which the liquid present in (i), (ii) and (iii) comprises a reaction medium; and b) heat treating the pre-catalyst by heating to a temperature in the range of about 500 ° C to about 900 ° C for a period of time from about 3 hours to about 12 hours to form a catalyst. BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Figure 1 is a graph of the shear response of the polyethylene resins of example 3. DETAILED DESCRIPTION
[0008] Methods for preparing olefin polymerization catalysts and olefin polymerization catalyst supports are described here. In one aspect of the present disclosure, the olefin polymerization catalyst support comprises a silica-titania (Si-Ti) support that is used to produce an olefin polymerization catalyst, such as a chromium-silica-titania catalyst ( Cr / Si-Ti). In one aspect of the present disclosure, the compositions and methodologies disclosed herein allow the production of a chromium-silica-titania catalyst, hereinafter an olefin polymerization catalyst, in the presence of water.
[0009] In one aspect of the present disclosure, the olefin polymerization catalyst comprises titanium. The source of the titanium can be any compound containing titanium capable of supplying a sufficient amount of titanium to the olefin polymerization catalyst in the presence of an aqueous reaction medium as described herein. In one aspect of the present disclosure, the compound containing titanium is an oxotitanium compound. An example of an oxotitanium compound suitable for use in the present description is characterized by the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, an alkoxide, a dicarboxylate, a tricarboxylate, a diketonate, an amino acid, a-hydroxycarboxylate , an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof.
[0010] In one aspect, R1 and R2 are each independently a carboxylate, a dicarboxylate, an ammonium salt of a dicarboxylate or an a-hydroxycarboxylate. Generally, the carboxylate can be a C1 to C20 carboxylate; or alternatively, a C1 to C10 carboxylate. In another aspect, R1 and R2 can each independently be a dicarboxylate, such as oxalate, malonate, fumarate or malate. In yet another aspect, R1 and R2 can each independently be an ammonium salt of a dicarboxylate, such as ammonium oxalate, ammonium malonate, ammonium fumarate or ammonium malate. In yet another aspect, R1 and R2 can each independently be a tricarboxylate, such as citrate. In one aspect of the present disclosure, R1 and R2 are each independently acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate or dodecanoate; or alternatively, a pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate or dodecanoate. For example, R1 and R2 can each be independently format, acetate or propionate. Yet another example, R1 and R2 can each independently be an oxalate. In yet another example, R1 and R2 can each be independently a diketonate. In another example, R1 and R2 can each independently be unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate. In one aspect of the present disclosure, the source of the titanium excludes a titanium tetra-alkoxide.
[0011] The amount of titanium present in the olefin polymerization catalyst can vary from about 0.01% by weight to about 10% by weight of titanium by weight of the olefin polymerization catalyst, alternatively from about 0.5 % by weight to about 5% by weight, alternatively from about 1% by weight to about 4% by weight or alternatively from about 2% by weight to about 4% by weight. In another aspect of the present disclosure, the amount of titanium in the olefin polymerization catalyst can vary from about 1% by weight to about 5% by weight. Here, the percentage of titanium refers to the final weight in percentage of titanium associated with the olefin polymerization catalyst by the total weight of the olefin polymerization catalyst after all the processing steps (for example, after the final activation by means of calcination) ).
[0012] In one aspect of the present disclosure, the olefin polymerization catalyst comprises chromium. The source of chromium can be any compound containing chromium capable of supplying a sufficient amount of chromium to the olefin polymerization catalyst. For example, the chromium-containing compound can be a water-soluble compound or a hydrocarbon-soluble compound. Examples of water-soluble chromium compounds include chromium trioxide, chromium acetate, chromium nitrate or combinations thereof. Examples of hydrocarbon-soluble chromium compounds include tertiary butyl chromate, a diarene-chromium compound (0), bisciclopentadienyl chromium (II), chromium acetylacetonate (III) or combinations thereof. In one aspect of the present disclosure, the chromium-containing compound can be a chromium (II) compound, a chromium (III) compound or combinations thereof. Suitable chromium (III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium sulfate, chromium nitrate, chromium dionates or combinations thereof. Specific chromium (III) compounds include, but are not limited to, chromium (III) sulfate, chromium (III) chloride, chromium (III) nitrate, chromium bromide, chromium (III) acetylacetonate and chromium acetate (III). Suitable chromium (II) compounds include, but are not limited to, chromium chloride, chromium bromide, chromium iodide, chromium (II) sulfate, chromium (II) acetate or combinations thereof.
[0013] The amount of chromium present in the olefin polymerization catalyst can vary from about 0.01% by weight to about 10% by weight of chromium by weight of the olefin polymerization catalyst, alternatively from about 0.5 % by weight to about 5% by weight, alternatively from about 1% by weight to about 4% by weight or alternatively from about 2% by weight to about 4% by weight. In another aspect of the present disclosure, the amount of chromium present in the olefin polymerization catalyst can vary from about 1% by weight to about 5% by weight. Here, the percentage of chromium refers to the final weight in percentage of chromium associated with the olefin polymerization catalyst by the total weight of the olefin polymerization catalyst after all the processing steps (for example, after the final activation by means of calcination) ).
[0014] In one aspect of the present disclosure, the olefin polymerization catalyst comprises a silica support. A silica support suitable for use in the present disclosure may have an effective surface area and pore volume to provide for the production of an active olefin polymerization catalyst. In one aspect of the present disclosure, the siliary support has a surface area in the range of about 100 m2 / gram to about 1,000 m2 / gram, alternatively from about 250 m2 / gram to about 1,000 m2 / gram, alternatively from about from 250 m2 / gram to about 700 m2 / gram, alternatively from about 250 m2 / gram to about 600 m2 / gram or alternatively greater than 250 m2 / gram. The silica support can also be characterized by a pore volume greater than about 0.9 cm3 / gram, alternatively greater than about 1.0 cm3 / gram or alternatively greater than about 1.5 cm3 / gram. In one aspect of the present disclosure, the silica support is characterized by a pore volume ranging from about 1.0 cm3 / gram to about 2.5 cm3 / gram. The silica support can further be characterized by an average particle size of about 10 microns to about 500 microns, alternatively about 25 microns to about 300 microns or alternatively about 40 microns to about 150 microns. Generally, the average pore size of the silica support ranges from about 10 Angstroms to about 1,000 Angstroms. In one aspect of the present disclosure, the average pore size of the silica support material is in the range of about 50 Angstroms to about 500 Angstroms, while in another aspect of the present disclosure the average pore size varies between about 75 Angstroms to about 350 Angstroms.
[0015] The silica support may contain more than about 50 percent (%) silica, alternatively greater than about 80% silica, alternatively greater than about 95% silica by weight of the silica support. The silica support can be prepared using any suitable method, for example, the silica support can be prepared synthetically by hydrolysis of tetrachlorosilane (SiCl4) with water or by contacting sodium silicate with a mineral acid. An example of a silica support suitable for use in this disclosure includes, without limitation, ES70 which is a silica support material with a surface area of 300 m2 / gram and a pore volume of 1.6 cm3 / gram which is commercially available at PQ Corporation. The silica support may include additional components that do not adversely affect the catalyst, such as zirconia, alumina, thorium, magnesia, fluoride, sulfate, phosphate or mixtures thereof.
[0016] The silica support can be present in the olefin polymerization catalyst in an amount of about 50% by weight (% by weight) to about 99% by weight or alternatively from about 80% by weight to about 99% by weight. Here, the percentage of silica support refers to the final weight percentage of silica support associated with the olefin polymerization catalyst by the total weight of the olefin polymerization catalyst after all processing steps (for example, after final activation by means of calcination).
[0017] Methods for preparing a catalyst composition comprising contacting one or more catalyst components are disclosed herein. Various sequences for contacting the catalyst components are also disclosed here. It is contemplated that other sequences for contacting the catalyst components can also produce a catalyst of the type disclosed herein. Consequently, in one aspect of the present disclosure, the catalyst components (e.g., oxotitanium compound, chromium-containing compound, silica) can be brought into contact in any order or manner to produce a catalyst of the type disclosed herein.
[0018] In one aspect of the present disclosure, a method for preparing an olefin polymerization catalyst of the type disclosed herein comprises contacting an oxotitanium compound (for example, R1R2TiO with a silica support to form a titanated support. In one aspect of the present disclosure, the preparation of an olefin polymerization catalyst of the type disclosed herein excludes drying of the silica support prior to contacting the silica support with any other catalyst component. the present disclosure can be a "hydrated" silica support containing more than about 1% by weight of water with respect to the total weight of the silica support. For example, the silica support can contain about 0.1% by weight to about 20% by weight of water, alternatively from about 0.1% by weight to about 15% by weight of water or alternatively from about 0.1% by weight to about 10% by weight of water. In the same mod o, the oxotitanium compound can be a component of an aqueous solution when placed in contact with hydrated silica. By placing the oxotitanium compound and the silica support in contact, the first resulting aqueous mixture comprising the titanated support and the water can be stirred at room temperature for a period of time from about 5 minutes to about 30 hours, alternatively about 15 minutes to about 12 hours or alternatively between about 30 minutes and about 5 hours.
[0019] In one aspect of the present disclosure, the method for preparing an olefin polymerization catalyst of the type disclosed herein comprises contacting the first aqueous mixture (comprising water and the titanated support) with a chromium-containing compound to form a second aqueous mixture comprising water and a pre-catalyst (for example, a titanium, chrome-plated support). It is contemplated that the chromium-containing compound may be a component of an aqueous solution when placed in contact with the first aqueous mixture (comprising the titanium support and water). In one aspect of the present disclosure, the second aqueous mixture comprising the water and the pre-catalyst (for example, a titanium, chrome-plated support) is then treated to remove the water, for example, by means of a heat treatment. For example, the second aqueous mixture comprising water and the pre-catalyst (for example, a titanium, chrome-plated support) can be dried at temperatures ranging from about 25 ° C to about 300 ° C, alternatively from about 50 ° C at about 200 ° C or alternatively about 80 ° C and about 150 ° C to form a dry pre-catalyst. In one aspect of the present disclosure, the dry pre-catalyst can then be activated by means of a calcination step by heating it in an oxidizing environment to produce the olefin polymerization catalyst. For example, the dry pre-catalyst can be calcined in the presence of air at a temperature in the range of about 400 C to about 1,000 C, alternatively from about 500 ° C to about 900 ° C, alternatively from about 500 ° C at about 850 ° C and for a period of about 1 min to about 24 hours, alternatively about 1 minute to about 10 hours, alternatively about 1 hour to about 24 hours, alternatively about 1 hour to about 12 hours to about 12 hours, alternatively about 20 min to about 5 hours or alternatively about 1 hour to about 3 hours to produce the olefin polymerization catalyst.
[0020] In one aspect of the present disclosure, a method for preparing an olefin polymerization catalyst of the type disclosed herein comprises contacting a chromium-containing compound with a silica support to form a first aqueous mixture comprising a chrome support and Water. In an aspect like this of the present disclosure, the silica support can be a hydrated silica. Likewise, the chromium-containing compound can be a component of an aqueous solution when placed in contact with hydrated silica. When adding the chromium-containing compound to the silica support, the first resulting aqueous mixture comprising the chrome support and the water can be stirred at room temperature for a period of time from about 5 minutes to about 30 hours, alternatively from about 15 minutes to about 12 hours or alternatively between about 30 minutes and about 5 hours.
[0021] In one aspect of the present disclosure, the method for preparing an olefin polymerization catalyst of the type disclosed herein comprises contacting the first aqueous mixture (comprising the chrome support and water) with an oxotitanium compound (for example , R1R2TiO) to form a second aqueous mixture comprising water and a pre-catalyst (for example, a titanium, chrome-plated support). It is contemplated that the oxotitanium compound (for example, R1R2TiO) can be a component of an aqueous solution when placed in contact with the first aqueous mixture (comprising the chrome support and water).
[0022] In one aspect of the present disclosure, the second aqueous mixture comprising the water and the pre-catalyst (for example, a titanium, chrome-plated support) is then treated to remove the water, for example, by means of a heat treatment. For example, the second aqueous mixture comprising water and the pre-catalyst (for example, a titanium, chrome-plated support) can be dried at temperatures ranging from about 25 ° C to about 300 ° C, alternatively from about 50 ° C at about 200 ° C or alternatively about 80 ° C and about 150 ° C to form a dry pre-catalyst. In one aspect of the present disclosure, the dry pre-catalyst can then be activated by means of a calcination step by heating it in an oxidizing environment to produce the olefin polymerization catalyst. For example, the dry pre-catalyst can be calcined in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively from about 500 ° C to about 900 ° C, alternatively from about 500 ° C to about 850 ° C and for a period of about 1 min to about 24 hours, alternatively about 1 minute to about 10 hours, alternatively about 1 hour to about 24 hours, alternatively about 1 hour to about 12 hours to about 12 hours, alternatively about 20 min to about 5 hours or alternatively about 1 hour to about 3 hours to produce the olefin polymerization catalyst.
[0023] In one aspect of the present disclosure, a method for preparing an olefin polymerization catalyst of the type disclosed herein comprises contacting an oxotitanium compound (for example, R1 R 2TiO) with a silica support and a compound containing chromium to form a first aqueous mixture comprising water and a pre-catalyst (for example, a titanium, chrome-plated support). In one aspect of the present disclosure, the silica support is a hydrated silica. Likewise, the oxotitanium compound and / or the chromium-containing compound can be a component of an aqueous solution when placed in contact with hydrated silica. Upon contact of the silica support, the chromium-containing compound and the oxotitanium compound, the first aqueous mixture comprising water and the pre-catalyst (for example, a titanium, chrome-plated support) can be stirred at room temperature for a period of time. about 5 minutes to about 30 hours, alternatively about 15 minutes to about 12 hours or alternatively about 30 minutes to about 5 hours.
[0024] In one aspect of the present disclosure, the first aqueous mixture comprising the water and the pre-catalyst (for example, a titanium, chrome-plated support) is then treated to remove the water, for example, by means of a heat treatment. For example, the first aqueous mixture comprising water and the pre-catalyst (for example, a titanium, chrome-plated support) can be dried at temperatures ranging from about 25 ° C to about 300 ° C, alternatively about 50 ° C at about 200 ° C or alternatively about 80 ° C and about 150 ° C to form a dry pre-catalyst. In one aspect of the present disclosure, the dry pre-catalyst can then be activated by means of a calcination step by heating it in an oxidizing environment to produce the olefin polymerization catalyst. For example, the dry pre-catalyst can be calcined in the presence of air at a temperature in the range of about 400 ° C to about 1,000 ° C, alternatively from about 500 ° C to about 900 ° C, alternatively from about 500 ° C to about 850 ° C and for a period of about 1 min to about 24 hours, alternatively about 1 minute to about 10 hours, alternatively about 1 hour to about 24 hours, alternatively about 1 hour to about 12 hours to about 12 hours, alternatively about 20 min to about 5 hours or alternatively about 1 hour to about 3 hours to produce the olefin polymerization catalyst.
[0025] In an optional aspect of the present disclosure, the contact of one or more components used to prepare the olefin polymerization catalyst is carried out in the presence of water, as well as an additional solvent, for example, water combined with a non-aqueous solvent . In one aspect, the solvent comprises alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, halocarbons, ethers, acetonitrile, esters or combinations thereof. Alternatively, the solvent comprises alcohols, ketones, esters or combinations thereof.
[0026] Aliphatic hydrocarbons that may be useful as a solvent include aliphatic hydrocarbons C3 to C20; alternatively aliphatic hydrocarbons C4 to C15; or alternatively aliphatic hydrocarbons C5 to C10. Aliphatic hydrocarbons can be cyclic or acyclic and / or they can be linear or branched, unless otherwise specified. Non-limiting examples of suitable acyclic aliphatic hydrocarbon solvents that can be used alone or in any combination include propane, isobutane, n-butane, butane (n-butane or a mixture of straight and branched C4 acyclic aliphatic hydrocarbons), pentane (n- pentane or a mixture of linear or branched C5 acyclic hydrocarbons), hexane (n-hexane or mixture of linear and branched C6 acyclic hydrocarbons), heptane (n-heptane or mixture of linear and branched C7 acyclic hydrocarbons), octane ( n-octane or a mixture of linear and branched C8 acyclic hydrocarbons) and combinations thereof. Aromatic hydrocarbons that may be useful as a solvent include aromatic hydrocarbons C6 to C20; or alternatively aromatic hydrocarbons C6 to C10. Non-limiting examples of suitable aromatic hydrocarbons that can be used alone or in any combination in the present disclosure include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene or mixtures thereof), ethylbenzene or combinations thereof.
[0027] Halogenated aliphatic hydrocarbons that may be useful as a solvent include halogenated aliphatic hydrocarbons C1 to C15; alternatively halogenated aliphatic hydrocarbons C1 to C10; or alternatively halogenated aliphatic hydrocarbons C1 to C5. Halogenated aliphatic hydrocarbons may be cyclic or acyclic and / or may be linear or branched, unless otherwise specified. Non-limiting examples of suitable halogenated aliphatic hydrocarbons that can be used include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and combinations thereof; alternatively, methylene chloride, chloroform, dichloroethane, trichloroethane and their combinations. Halogenated aromatic hydrocarbons that may be useful as a solvent include halogenated aromatic hydrocarbons C6 to C20; or alternatively C6 to C10 halogenated aromatic hydrocarbons. Non-limiting examples of suitable halogenated aromatic hydrocarbons include chlorobenzene, dichlorobenzene and combinations thereof.
[0028] Esters, ketones or alcohols that may be useful as a solvent include esters, ketones or alcohols C1 to C20; alternatively, esters, ketones, aldehydes or alcohols C1 to C10; or alternatively, esters, ketones, aldehydes or alcohols C1 to C5. Non-limiting examples of suitable esters that can be used as a solvent include ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate and combinations thereof. Non-limiting examples of suitable ketones that can be used as a solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone and combinations thereof. Non-limiting examples of suitable alcohols that can be used as a solvent include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol and the like or combinations thereof. In one aspect, the solvent comprises methanol, ethanol, isopropanol, propanol, butanol, acetone, methyl ethyl ketone, ethyl acetate, heptane or combinations thereof.
[0029] In one aspect of the present disclosure, an additional solvent additionally comprises a polyol or polyhydric alcohol (for example, a polyalcohol or polyol). In some respects, the polyol can comprise any hydrocarbon having at least 2 alcohol groups (or alternatively called hydroxy groups); alternatively, at least 3 alcohol groups; or alternatively, at least 4 alcohol groups. In one aspect, the polyol is an aliphatic hydrocarbon comprising at least two groups of alcohol. In some respects, the polyol is a glycol, a sugar, a reduced sugar, an oligomer of a glycol or combinations thereof.
[0030] In one aspect, the polyol can be an aliphatic polyol, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycols with a molecular weight of 106 to 8,500, polyethylene glycols with a molecular weight of 400 to 2,000, 1.2 -propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentylglycol, 1,2-hexanediol, 1,6-hexanediol, 1,2 -octanediol, 1,8-octanediol, 1,2-decanediol, 1,10-decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1,2,4-butanotriol, 2,2 , 4-trimethyl-1,3-pentanediol or combinations thereof.
[0031] In one aspect, the polyol may be a cyclic aliphatic polyol, such as 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4- cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxy-cyclohexyl) propane or any combination thereof .
[0032] In one aspect, the polyol may be an aralkyl polyol, such as 1-phenyl-1,2-ethanediol, 1,2-benzene dimethanol, 1,3-benzene-di-methanol, 1,4-benzene-dimethanol or their mixtures. In one aspect, the polyol can be an aromatic polyol, such as 1,2-benzenediol (pyrocatechol), 1,3-benzenediol (resorcinol), 1,4-benzenediol, methyl catechol, methyl resorcinol, 1,2,4- benzenotriol, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 3,5-dihydroxybenzyl alcohol, 2- (2-hydroxyphenyl) ethanol, 2- (3-hydroxy-phenyl) -ethanol, 2- ( 4-hydroxyphenyl) -ethanol, 2-phenyl-1,2-propanediol or mixtures thereof.
[0033] In one aspect, the polyol is a sugar alcohol that refers to the hydrogenated forms of the aldoses or ketosis of a sugar. For example, glucitol, also known as sorbitol, has the same linear structure as the glucose chain form, but the aldehyde group (-CHO) is replaced by a - CH2OH group. Other common sugar alcohols include the monosaccharides erythritol and xylitol and the disaccharides lactitol and maltitol.
[0034] Generally, sugar alcohols can be characterized by the general formula HO-CH2- (CH-OH) n-CH2-OH, where n is typically 1 to 22. For example, when n = 2, alcohol sugar can be erythritol, tritol, etc. For example, when n = 3, the sugar alcohol can be arabitol, xylitol, ribitol, etc. For example, when n = 4, the sugar alcohol can be mannitol, sorbitol, etc. The most common sugar alcohols have 5 or 6 carbon atoms in their structure; where n is 3 or 4, respectively. In one aspect, sugar alcohol comprises mannitol, sorbitol, arabitol, tritol, xylitol, ribitol, galactitol, fruitol, iditol, inositol, volemitol, isomalt, malitol, lactitol or combinations thereof.
[0035] In one aspect, the polyol comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycols with a molecular weight of 106 to 1,000, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol 1,4-butanediol, 1,5 Pentanedial, Neopentyl glycol, 1,2-hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol , 1,2-octanediol, 1,8-octanediol, 1,2-decanediol, 1,10-decanediol, glycerol, 2,2-dimethylpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1, 2,4-butanediol , 2,2,4-trimethyl-1,3-pentanediol, 1-phenyl-1,2-ethanediol, 1,2-benzenediol (catechol), 1,3-benzenediol (resorcin), 1,4-benzenediol catechol methyl methyl resorcinol, 1, 2,4-benzenotriol, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 3,5-dihydroxybenzyl alcohol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4 -benzenedimethanol, 2- (2-hydroxyphenyl) ethanol, 2- (3-hydroxyphenyl) ethanol, 2- ( 4-hydroxyphenyl) ethanol, 2-phenyl-1,2-propanediol, bisphenol A (2,2-di (4-hydroxyphenyl) propane), bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol S (4, 4 '-dihydroxydiphenylsulfone), bisphenol Z (4, 4'-cyclohexylidenobisphenol), bis (2-hydroxyphenyl) methane or combinations thereof. In one aspect, the polyol is selected from the group consisting of ethylene glycol, glycerol, propylene glycol, butanoglycol, lactic acid or combinations thereof.
[0036] In some respects, polyols, such as glycols, glycol mono- and diesters, glycerol and glycerates are added to the solvent to further reduce HRVOC emissions. The use of polyols in an olefin polymerization catalyst preparation is described in more detail in US Patent Application Serial No. 14 / 699,533 entitled "Methods of Preparing a Catalyst" which is incorporated herein by reference in its entirety.
[0037] In some aspects of the present disclosure, any contact of the components of the olefin polymerization catalyst can be carried out in the presence of a reaction medium. Specifically, the liquid associated with each component used in the preparation of the olefin polymerization catalyst (for example, water associated with hydrated silica, the oxotitanium compound, the chromium-containing compound, etc.) and, optionally, an added solvent (for example, example, an aqueous solvent) can form the reaction medium at each contact step described here. In one aspect, the reaction medium excludes any solid component used in the preparation methodology disclosed herein (for example, excludes the silica support and any solids associated with it). In some respects, the sum of an amount of water present in any reaction medium formed during the preparation of the olefin polymerization catalyst is from about 1% by weight to about 99% by weight based on the total weight of the media. reaction (for example, liquid components including water and any non-aqueous liquids, such as one or more optional organic solvents), alternatively from about 1% by weight to about 50% by weight, alternatively from about 1% by weight to about 20% by weight, or alternatively from about 1% by weight to about 10% by weight. In one aspect of the present disclosure, the reaction media formed during one or more contact steps carried out during the preparation of the olefin polymerization catalyst (for example, the liquid components of a mixture that includes the titanated support, the liquid components of a mixture that includes the chrome support, the liquid components of a mixture that includes the pre-catalyst, etc.) can contain more than about 1% by weight of water, alternatively more than about 5% by weight, alternatively more than about 10% by weight, alternatively more than about 20% by weight, alternatively more than about 30% by weight, alternatively more than about 40% by weight, Alternatively more than about 50% by weight, alternatively more than about 60% by weight, alternatively more than about 70% by weight, alternatively more than about 80% by weight or alternatively more than about 90% by weight of water based on the total weight of the reaction medium, where the water can originate from one or more components used to form the mixture. In another aspect, an anhydrous reaction medium (for example, 100% organic medium) is excluded as a component for the preparation of an olefin polymerization catalyst of the type disclosed herein.
[0038] During the production of the catalyst, materials such as highly reactive volatile organic compounds (HRVOC) can be emitted. HRVOCs play a role in ozone formation in areas of non-ozone depletion, that is, areas that do not meet the air quality standards of the Environmental Protection Agency for ground-level ozone. In one aspect of the present disclosure, an olefin polymerization catalyst prepared as disclosed herein results in a reduction in the level of HRVOCs produced during the preparation of olefin polymerization catalyst. For example, HRVOCs can comprise hydrocarbons, aromatics, alcohols, ketones or combinations thereof. In one aspect of the present disclosure, HRVOCs comprise alkenes, alternatively propylene, butene, ethylene or combinations thereof. The olefin polymerization catalysts produced as disclosed herein can be characterized by HRVOC emissions that are reduced from about 50% to about 99% when compared to the emissions of a similar olefin polymerization catalyst, prepared in the absence of a compound of oxotitanium. Alternatively, emissions of HRVOCs from olefin polymerization catalysts prepared as disclosed herein are reduced by more than about 50%, alternatively more than about 75%, alternatively more than about 90% or alternatively more than about 99% in comparison to the otherwise similarly olefin polymerization catalyst prepared in the absence of an oxotitanium compound (e.g., an otherwise similar olefin polymerization catalyst prepared in the presence of a Ti (isopropoxide) 4). In one aspect of the present disclosure, emissions of HRVOCs during the preparation of olefin polymerization catalysts of the type disclosed herein are less than about 2% by weight based on the total weight of the olefin polymerization catalyst, alternatively less than about 1% by weight, alternatively less than about 0.5% by weight, or alternatively less than about 0.1% by weight. In one aspect of the present disclosure, HRVOC is propylene and the olefin polymerization catalyst production process has emissions from about 50% by weight to about 1% by weight based on the percentage by weight of titanium in the polymerization catalyst of olefins, alternatively less than about 20% by weight, alternatively less than about 10% by weight or alternatively less than about 1% by weight. In one aspect, the oxotitanium compound used in the preparation of the olefin polymerization catalyst has a carbon: oxygen ratio of about 0.3 to about 3.0, alternatively from about 0.5 to about 3.5 or alternatively from about 1.0 to about 3.0. In some respects, the oxotitanium compound used in the preparation of an olefin polymerization catalyst of the type disclosed herein has a carbon: oxygen ratio greater than about 0.5.
[0039] The olefin polymerization catalysts of the present disclosure are suitable for use in any method of polymerization of olefins, using various types of polymerization reactors. In one aspect of the present disclosure, a polymer of the present disclosure is produced by any method of polymerizing olefins, using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and / or copolymers. Homopolymers and / or copolymers produced in the reactor can be referred to as resin and / or polymers. The various types of reactors include, but are not limited to, those that can be referred to as batch, slurry, gas phase solution, high pressure, tubular, autoclave or other reactor and / or reactors. The gas phase reactors can comprise fluidized bed reactors or horizontal stacked reactors. The slurry reactors can comprise vertical and / or horizontal loops. High pressure reactors may comprise autoclave and / or tubular reactors. Reactor types can include batch and / or continuous processes. Continuous processes may use intermittent and / or continuous discharge or transfer of the product. The processes may also include direct partial or complete recycling of unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents and / or other materials from the polymerization process.
[0040] The polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different types, operated in any suitable configuration. The production of polymers in multiple reactors can include several phases in at least two separate polymerization reactors interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors may include transferring, either manually or automatically, the polymer from one reactor to the reactor or subsequent reactors for further polymerization. Alternatively, polymerization in multiple stages or multiple stages can occur in a single reactor, where the conditions are changed in such a way that a different polymerization reaction occurs.
[0041] The desired polymerization conditions in one of the reactors can be the same or different from the operating conditions of any other reactors involved in the overall polymer production process of the present disclosure. Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors or a combination of high pressure reactors with loop and / or gas. The multiple reactors can be operated in series or in parallel. In one aspect of the present disclosure, any arrangement and / or any combination of reactors can be employed to produce the polymer of the present disclosure.
[0042] According to one aspect of the present disclosure, the polymerization reactor system may comprise at least one loop slurry reactor. Such reactors are common and may include vertical or horizontal loops. Monomer, diluent, catalyst system and, optionally, any comonomer can be fed continuously to a loop slurry reactor, where polymerization takes place. Generally, continuous processes can comprise the continuous introduction of a monomer, a catalyst and / or a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymeric particles and the diluent. The effluent from the reactor can be washed to remove liquids that comprise the solid polymer, monomer and / or comonomer diluent. Various technologies can be used for this separation step including, but not limited to, washing which can include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydro cyclone; centrifugation separation; or another appropriate method of separation.
[0043] Typical slurry polymerization processes (also known as particle form processes) are described in US Patents 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833 .415, for example; each of which is incorporated herein by reference in its entirety.
[0044] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer to be polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons, such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop polymerization reactions can occur in volume conditions where no diluent is used. An example is the polymerization of the propylene monomer as disclosed in US Patent 5,455,314, which is incorporated herein by reference in its entirety.
[0045] According to yet another aspect of the present disclosure, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back into the reactor. Simultaneously, the polymeric product can be removed from the reactor and new or freshly prepared monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for the polymerization of gas phase olefins in multiple stages, in which the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones by feeding a polymer containing catalyst formed in a first polymerization zone for a second polymerization zone. A type of gas phase reactor is disclosed in US Patents 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated herein by reference in its entirety.
[0046] According to yet another aspect of the present disclosure, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where monomers, initiators or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a zone of the reactor. Primers, catalysts and / or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. The gas streams can be mixed by polymerization. Heat and pressure can be used appropriately to obtain the ideal polymerization reaction conditions.
[0047] Still in accordance with another aspect of the present disclosure, the polymerization reactor may comprise a solution polymerization reactor in which the monomer is brought into contact with the catalyst composition by suitable stirring or other means. A carrier comprising an organic diluent or excess monomer can be employed. If desired, the monomer can be placed in the vapor phase in contact with the product of the catalytic reaction, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Stirring can be used to obtain better temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
[0048] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feedstock for catalyst or catalyst components and / or at least one recovery system polymer. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis and process control.
[0049] Conditions that are controlled for polymerization efficiency and to provide the properties of the polymer include, but are not limited to, temperature, pressure, type and amount of catalyst or cocatalyst and the concentrations of various reagents. The polymerization temperature can affect the productivity of the catalyst, the molecular weight of the polymer and the distribution of the molecular weight. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs Free Energy Equation. Typically, this includes from about 60 ° C to about 280 ° C, for example, and / or from about 70 ° C to about 110 ° C, depending on the type of polymerization reactor and / or polymerization process.
[0050] Adequate pressures will also vary according to the reactor and the polymerization process. The pressure for liquid phase polymerization in a loop reactor is typically less than 1,000 psig (6.9 MPa). The pressure for gas phase polymerization is usually about 200 psig (1.4 MPa) to 500 psig (3.45 MPa). High pressure polymerization in tubular or autoclave reactors is generally carried out at about 20,000 psig (138 MPa); to 75,000 psig (518 MPa). Polymerization reactors can also be operated in a supercritical region that occurs at generally higher temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
[0051] The concentration of various reagents can be controlled to produce polymers with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer and the method of forming that product may vary to determine the desired properties of the final product. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, creep, stress relaxation and hardness tests. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, short chain branching, branching long-chain and rheological measurements.
[0052] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in the production of specific properties of the polymer. Comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate poisons and / or control molecular weight. The concentration of poisons can be minimized, as the poisons can affect the reactions and / or affect the properties of the polymeric product. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
[0053] Polymers, such as polyethylene homopolymers and ethylene copolymers with other monoolefins can be produced in the manner described above using the polymerization catalysts prepared as described herein. Polymers produced as disclosed herein can be formed into articles of manufacture or articles of end use using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and casting. For example, a polymeric resin can be extruded into a sheet, which is then thermoformed into an end-use article, such as a container, a glass, a tray, a pallet, a toy or a component of another product. Examples of other end-use articles in which polymer resins can be formed include tubes, films and bottles.
[0054] In one aspect of the present disclosure, an olefin polymerization catalyst of the type described herein can be used to prepare polyethylene. The PE prepared as described herein can be characterized by a melt index, MI, ranging from about 0 g / 10 min. at about 10 g / 10 min., alternatively about 0.1 g / 10 min. at about 5 g / 10 min. or alternatively about 0.2 g / 10 min. at about 2 g / 10 min. The melting index (MI) refers to the amount of a polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 2,160 grams in ten minutes at 190 ° C, as determined according to ASTM D1238.
[0055] In addition, PE can be characterized by a high melt load index, HLMI, ranging from about 1 g / 10 min. at about 1,000 g / 10 min., alternatively about 3 g / 10 min. at about 300 g / 10 min., about 10 g / 10 min. at about 100 g / 10 min or alternatively from about 10 g / 10 min to about 60 g / 10 min. The HLMI represents the flow rate of a polymer melted through a 0.0825 inch diameter orifice when subjected to a force of 21,600 grams at 190 ° C, as determined according to ASTM D1238.
[0056] In one aspect of the present disclosure, PE can be characterized by a shear response ranging from about 30 to about 1,000, alternatively from about 30 to about 200, less than 60 or less than 45 or alternatively less to 40. The shear response refers to the ratio between high melt load index and melt index (HLMI / MI).
[0057] Catalysts of the present disclosure tend to produce a polymer with a wide molecular weight distribution, as indicated by the polydispersity index that results from the average molecular weight by weight (Mw) divided by the numerical average molecular weight (Mn). Mw describes the molecular weight distribution of a polymer and is calculated according to Equation 1:
where Ni is the number of molecules of molecular weight Mi.
[0058] Mn is the common average of the molecular weights of the individual resins and can be calculated according to Equation 2:
where Ni is the number of molecules of molecular weight Mi. A polymer (e.g., polyethylene) prepared as disclosed herein can be characterized by a polydispersity index of about 10 to about 30, alternatively from about 12 to about 25, alternatively from about 15 to about 25 or alternatively greater than about 15. EXAMPLES
[0059] The following examples are given as a particular aspect of the present disclosures of the present disclosure and to demonstrate the practice and benefits of it. It is understood that the examples are given by way of illustration and are not intended to limit the following specification or claims in any way.
[0060] The olefin polymerization catalysts of the type described here were prepared as follows: 7.3 grams of HA30W were weighed into a beaker. HA30W is a commercial Cr / silica material obtained from WR Grace, having a surface area of about 500 m2 / gram, a pore volume of about 1.6 mL / g, an average particle size of about 90 microns and containing 1% by weight.% of Cr and about 8% by weight of moisture. 2.3 grams of titanium oxide acetylacetonate, i.e., TiO (AcAc) 2 were then dissolved in 150 ml of moist methanol (ie, methanol that had not been specifically dried). The Ti compound dissolved to make a yellow solution. Then, HA30W was added to the solution and the methanol was evaporated in a vacuum oven at 100 ° C. Subsequently, the solid catalyst was calcined by fluidization in dry air for three hours at 650 ° C. It was then stored in an airtight container in dry nitrogen until it was tested in a polymerization test.
[0061] In another experiment, 4.08 grams of ammonium titanyloxylate, that is, (NH4) 2TiO (C2O4) 2 * 1H2O were dissolved in 40 ml of deionized water. 13.3 grams of HA30W catalyst was then added to this solution to make a wet paste. It was placed in a vacuum oven at 100 ° C overnight, producing a light blue dry material. Finally, the material was calcined as previously described at 650 ° C to produce the orange polymerization catalyst.
[0062] The melting index (MI, g / 10 min) was determined according to ASTM D1238 at 190 ° C, with a weight of 2,160 grams. I10 (g / 10 min) is the polymer flow using a weight of 10 kg. The high melt load index (HLMI) of a polymer resin represents the flow rate of a molten resin through a 0.0825 inch diameter orifice when subjected to a force of 21,600 grams at 190 ° C. HLMI values are determined according to condition E. ASTM D1238.
[0063] Polymerization tests were conducted in a 2.2 liter stainless steel reactor equipped with a marine stirrer rotating at 500 rpm. The reactor was surrounded by a steel jacket, through which a mixture of cold water and steam was passed to precisely control the temperature in half a degree centigrade, with the help of electronic control instruments.
[0064] Unless otherwise indicated, a small amount (0.01 to 0.10 grams normally) of the solid catalyst was first charged under nitrogen in the dry reactor. Then, 1.2 liters of liquid isobutane was loaded and the reactor was heated to 105 ° C. Finally, ethylene was added to the reactor to maintain a fixed pressure, 550 psig, during the experiment. Stirring was continued for the specified time, usually around one hour, and activity was recorded by recording the flow of ethylene in the reactor to maintain the set pressure.
[0065] After the predicted time, the flow of ethylene was interrupted and the reactor depressurized slowly and opened to recover a granular polymer powder, which was weighed. In all cases, the reactor was clean, with no indication of any wall scale, coating or other encrustation. The polymer powder was then removed and weighed. The activity was specified as gram of polymer produced per gram of solid catalyst loaded per hour. Example 1
[0066] The results of the polymerization tests using an olefin polymerization catalyst of the type disclosed here are shown in Table 1. The table lists which titanium compound was used, the running conditions and various properties of the polymer, including melt index , high load melting index and polydispersity. Table 1

[0067] The results demonstrate that the olefin polymerization catalyst of the present disclosure was effective in increasing the polymer melting index and showed a higher catalyst activity when compared to the use of a chrome support as an olefin polymerization catalyst ( that is, control test no. 7). Example 2
[0068] HRVOC emissions during the preparation of an olefin polymerization catalyst of the type disclosed here were investigated and compared with the emissions observed when preparing an olefin polymerization catalyst using a non-oxo-titanium compound. The results of these experiments, the percentage of carbon emissions and the oxygen / carbon ratio (O / C) are shown in Table 2. Table 2

[0069] As one skilled in the art would understand, the more carbons present in the titanium compound, the more emissions are expected during calcination to activate the catalyst. This is observable for Tioxo (AcAc) 2 and Tioxo (oxylate) 2 have less% carbon than the control (ie, Ti (isopropoxide) 4). In addition, given the oxygen-to-carbon (O / C) ratio for the oxo compounds, pyrolysis would result in the carbon being released as CO2 or CO as opposed to the propylene production observed when the control compound is pyrolyzed.
[0070] The shear response, which is HLMI / MI, can also be calculated from the values in Table 1. It is interesting that the shear response values of the Ti-oxo catalysts in Table 1 are considerably lower than normal for these broad MW distribution polymers. Figure 1 says about this point, showing a graph of the MI as a function of the HLMI. Races using catalysts from the present disclosure of Table 1 are represented here together with numerous other polymers prepared from the same Cr / silica catalyst, but using other titanium compounds, mainly titanium tetraisopropoxide. Note that inventive runs stand out as having a higher MI for a given HLMI. In other words, the catalysts of the invention produce a lower shear response, although all catalysts have been calcined at 650 ° C and tested under the same polymerization conditions. The results demonstrate that polymers prepared using an olefin polymerization catalyst of the type disclosed herein have a narrow HLMI / MI ratio (i.e., shear response) when compared to polymers prepared using non-oxo-titanic compounds. This attribute is useful in the production of film resins. ADDITIONAL DISCLOSURE
[0071] The following listed aspects of the present disclosures are provided as non-limiting examples.
[0072] A first aspect which is a method for preparing a catalyst comprising a) placing (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound and (iv) an optional solvent in contact to form a first aqueous mixture. comprising a pre-catalyst and a reaction medium having from about 1% by weight to about 99% by weight of water and b) heat treating the pre-catalyst by heating at a temperature of about 400 ° C to about 1,000 ° C over a period of about 1 minute to about 24 hours to form the catalyst.
[0073] A second aspect which is the method of the first aspect in which the reaction medium comprises from about 1% by weight to about 20% by weight of water.
[0074] A third aspect that is the method of any one of the first to the second aspects in which the reaction medium comprises a liquid associated with the silica support, a liquid associated with the oxotitanium compound, a liquid associated with the compound containing chromium and, when present, the solvent.
[0075] A fourth aspect that is the method of any of the first to the third aspects in which the silica support is characterized by a surface area of about 100 m2 / gram to about 1,000 m2 / gram and a higher pore volume at about 1.0 cm3 / gram.
[0076] A fifth aspect that is the method of any one of the first to four aspects in which the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a chromium diamine compound (0) , bisciclopentadienil chromo (II), chromium (III) acetylacetonate or their combinations.
[0077] A sixth aspect which is the method of any of the first to the fifth aspects in which an amount of chromium present in the olefin polymerization catalyst can vary from about 0.01% to about 10% by weight of the polymerization catalyst of olefin and an amount of titanium present in the olefin polymerization catalyst can vary from about 0.01% to about 10% by weight of the olefin polymerization catalyst.
[0078] A seventh aspect that is the method of any of the first to sixth aspects, in which the pre-catalyst excludes a titanium tetra-alkoxide.
[0079] An eighth aspect that is the method of any of the first to seventh aspects in which the oxotitanium compound is characterized by the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof.
[0080] A ninth aspect which is the method of the eighth aspect in which R1 and R2 are each independently format, acetate, propionate, ammonium oxalate, ammonium malonate, ammonium fumarate or ammonium malate.
[0081] A tenth aspect which is the method of the eighth aspect in which R1 and R2 are each independently unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate.
[0082] An eleventh aspect which is the method of any one of the first to eleventh aspects, further comprising the contact of the catalyst with an ethylene monomer under conditions.
[0083] An twelfth aspect which is the polymer of the eleventh aspect with a high charge melt index of about 10 g / 10 min and at about 60 g / 10 min, a polydispersity index greater than about 15 and a shear response of less than about 60.
[0084] A thirteenth aspect which is the polymer of the eleventh aspect with a high charge melt index of about 10 g / 10 min to about 60 g / 10 min, a polydispersity index greater than about 15 and a shear response of less than about 45.
[0085] A fourteenth aspect which is a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with a chromium-containing compound to form a first aqueous mixture comprising a chrome support; placing the first aqueous mixture comprising a chrome support in contact with a solution comprising (i) a solvent and (ii) an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst; and thermally treating the pre-catalyst to form the catalyst.
[0086] A fifteenth aspect which is the method of the fourteenth aspect in which the first aqueous mixture comprises a liquid associated with the hydrated support material comprising silica and a liquid associated with the chromium-containing compound and in which the second aqueous mixture comprises a liquid associated with the hydrated support material comprising silica, a liquid associated with the compound containing chromium, a liquid associated with the oxotitanium compound and the solvent.
[0087] A sixteenth aspect which is the method of any of the fourteenth to the fifteenth aspects in which an amount of water present in the first or second aqueous mixture is in a range of about 1% by weight to about 50% by weight of the total weight of the pre-catalyst.
[0088] A seventeenth aspect which is the method of any one of the fourteenth to the sixteenth aspects in which the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a chromium diamine compound (0), bisciclopentadienil chromo (II), chromium acetylacetonate (III) or combinations thereof.
[0089] An eighteenth aspect which is the method of any of the fourteenth to the seventeenth aspects in which the oxotitanium compound is characterized by the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, an alkoxide, a salt of ammonium from a dicarboxylate, an ammonium salt from a tricarboxylate or their combinations.
[0090] A nineteenth aspect which is the method of the eighteenth aspect in which R1 and R2 are each independently format, acetate, propionate, ammonium oxalate, ammonium malonate, ammonium fumarate or ammonium malate.
[0091] A twentieth aspect which is the method of the eighteenth aspect in which R1 and R2 are each independently unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate.
[0092] A twenty-first aspect which is a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with an oxotitanium compound to form a first aqueous mixture comprising a titanated support; placing the first aqueous mixture comprising a titanated support in contact with a chromium-containing compound to form a second aqueous mixture comprising a pre-catalyst; and heat treating the pre-catalyst to form the catalyst.
[0093] A twelfth aspect which is a method for preparing a catalyst comprising a) contacting (i) a silica support material comprising from about 0.1% to about 20% by weight of water, (ii ) a solution comprising (1) 2,4-oxotitanium pentadionate, (2) a solvent and (3) from about 0.1% by weight to about 80% by weight of water based on the total weight of the solution and (iii) a chromium-containing compound to form a pre-catalyst in which the liquid present in (i), (ii) and (iii) comprises a reaction medium; and b) heat treating the pre-catalyst by heating to a temperature in the range of about 500 ° C to about 900 ° C for a period of time from about 3 hours to about 12 hours to form a catalyst.
[0094] A twenty-third aspect which is the method of the twenty-second aspect in which the heat treatment of the pre-catalyst produces emission products comprising less than about 2% by weight of hydrocarbons based on the total weight of the emission products.
[0095] A twenty-fourth aspect which is a pre-catalyst composition comprising: (i) a silica support (ii) an oxotitanium compound characterized by the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate , a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof and (iii) a compound containing chromium.
[0096] A twenty-fifth aspect which is the composition of the twenty-fourth aspect in which titanium is present in an amount of about 0.5% by weight to about 10% by weight and chromium is present in an amount of about from 0.2% by weight to about 2% by weight based on the total weight of the composition.
[0097] A twenty-sixth aspect that is the composition of any of the twenty-fourth to twenty-fifth aspects in which the silica support is characterized by a surface area greater than about 250 m2 / g and a pore volume greater than about 0 , 9 cm3 / g.
[0098] A twenty-seventh aspect that is a pre-catalyst prepared by contacting (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound, and (iv) an optional solvent to form a first mixture comprising the pre-catalyst and a reaction medium having from about 1% to about 99% by weight of water.
[0099] A twenty-eighth aspect that is the pre-catalyst for the twenty-seventh aspect in which titanium is present in an amount of about 0.5% by weight to about 10% by weight and chromium is present in an amount from about 0.2% by weight to about 2% by weight based on the total weight of the composition.
[00100] A twenty-ninth aspect that is the pre-catalyst for any of the twenty-seventh to the twenty-eighth aspects in which the silica support is characterized by a surface area greater than about 250 m2 / g and a pore volume greater than about 0.9 cm3 / g.
[00101] A thirtieth aspect that is the method of any of the twenty-seventh to the twenty-ninth aspects in which the oxotitanium compounds have a carbon: oxygen ratio equal to or greater than about 0.5.
[00102] m thirty-first aspect which is a method of preparing a catalyst composed by contacting a hydrated support material with one comprising silica with a compound containing chromium to form a chrome support in which the hydrated support material contains about 1% by weight to about 20% by weight of water based on the weight of the support material and in which the chromium-containing compound is in a water or an alcohol, contacting the chrome support with a solution composed of (i) a solvent selected from the group consisting of water or C1-C4 alcohol and (ii) an oxotitanium compound to form a pre-catalyst, wherein the oxotitanium compound is characterized by the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof and in which the titanated pre-catalyst mixture comprises about 1% by weight about 99% by weight of water; and heat treating the pre-catalyst by heating to a temperature in the range of about 500 ° C to about 900 ° C for a period of time from about 1 minute to about 24 hours to form a catalyst.
[00103] A thirty-second aspect which is a method for preparing a catalyst comprising placing a hydrated support material comprising silica in contact with a chromium-containing compound to form a first aqueous mixture comprising a chrome support; placing the first aqueous mixture comprising a chrome support in contact with an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst; and heat treating the pre-catalyst to form the catalyst.
[00104] A thirty-third aspect which is the thirty-second aspect method in which the first aqueous mixture comprises a liquid associated with the hydrated support material comprising silica, a liquid associated with the compound containing chromium and an optional solvent (for example, non-solvent) aqueous), when present.
[00105] A thirty-fourth aspect which is the method of any of the thirty-second to the thirty-third aspects in which the second aqueous mixture comprises a liquid associated with the hydrated support material comprising silica, a liquid associated with the compound containing chromium, a liquid associated to the oxotitanium compound and an optional solvent (for example, non-aqueous solvent), when present.
[00106] A thirty-fifth aspect which is a method of preparing a catalyst comprising contacting a hydrated support material comprising silica with an oxotitanium compound, optionally in the presence of a first solvent (for example, water and / or a solvent non-aqueous) to form a first aqueous mixture comprising a titanated support; placing the first aqueous mixture comprising the titanated support in contact with a chromium-containing compound, optionally in the presence of a second solvent (for example, water and / or a non-aqueous solvent) to form a second aqueous mixture comprising a pre-catalyst, in that the first solvent and the second solvent can be the same or different; and heat treating the pre-catalyst to form the catalyst.
[00107] A thirty-sixth aspect which is a method of preparing a catalyst comprising placing a hydrated support material comprising silica in contact with a solution comprising (i) an oxotitanium compound and (ii) a first solvent (for example, water and / or a non-aqueous solvent) to form a first aqueous mixture comprising a titanated support; bringing the first aqueous mixture comprising the titanated support into contact with a solution comprising (i) a chromium-containing compound and (ii) a second solvent (for example, water and / or a non-aqueous solvent) to form a second aqueous mixture comprising a pre-catalyst, wherein the first solvent and the second solvent can be the same or different; and heat treating the pre-catalyst to form the catalyst.
[00108] A thirty-seventh aspect that is a pre-catalyst prepared by contacting (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound, and (iv) an optional solvent to form a first mixture comprising the pre-catalyst and a reaction medium having from about 1% to about 99% by weight of water.
[00109] A thirty-eighth aspect which is the pre-catalyst for the thirty-seventh aspect in which titanium is present in an amount of about 0.5% by weight to about 10% by weight and chromium is present in an amount from about 0.2% by weight to about 2% by weight based on the total weight of the composition.
[00110] A thirty-ninth aspect that is the pre-catalyst for any of the thirty-seventh to thirty-eighth aspects in which the silica support is characterized by a surface area greater than about 250 m2 / g and a pore volume greater than about 0.9 cm3 / g.
[00111] Although various aspects of the present disclosure have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. Aspects of the present disclosures described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the invention disclosed in this document are possible and are within the scope of the invention. When ranges or numerical limitations are expressly stated, such ranges or limitations should be understood to include iterative ranges or limitations of equal magnitude within the ranges or limitations explicitly expressed (for example, 1 to 10, 2, 3, 4, etc. ., greater than 0.10 includes 0.11, 0.12, 0.13, etc.). The use of the term "optionally" in relation to any element of a claim is intended to mean that the element in question is necessary or, alternatively, not necessary. Both alternatives are intended to be within the scope of the claim. The use of broader terms, such as understand, include, having, etc. is to be understood as providing support for more restricted terms, such as consisting of, consisting essentially of, composed substantially of, etc.
[00112] Consequently, the scope of protection is not limited by the description set out above, but is limited only by the claims that follow, whose scope includes all equivalents of the subject in question of the claims. Each of the claims is incorporated into the specification as an aspect of the present disclosure of the present invention. Thus, the claims are an additional description and are an addition to the aspect of the present disclosures of the present disclosure. The discussion of a reference in the present disclosure is not an admission that it is the prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this patent application. The present disclosures of all patents, patent applications and publications cited herein are hereby incorporated by reference, insofar as they provide exemplary, procedural or other details complementary to those set forth herein.

权利要求:
Claims (29)
[0001]
1. Method of preparing a catalyst characterized by comprising: a) contacting (i) a silica support, (ii) an oxotitanium compound, (iii) a chromium-containing compound and (iv) an optional solvent, to form a first aqueous mixture comprising a pre-catalyst and a reaction medium in which the reaction medium comprises from 1% by weight to 20% by weight of water; and b) heat treating the pre-catalyst by heating at a temperature from 400 ° C to 1,000 ° C for a period of time from 1 minute to 24 hours to form the catalyst.
[0002]
2. Method according to claim 1, characterized by the fact that the reaction medium comprises a liquid associated with the silica support, a liquid associated with the oxotitanium compound, a liquid associated with the compound containing chromium and, when present, with solvent.
[0003]
3. Process according to claim 1, characterized by the fact that the silica support has a surface area comprised between 100 m2 / gram and 1,000 m2 / gram and a pore volume greater than 1.0 cm3 / gram.
[0004]
4. Method according to claim 1, characterized by the fact that the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a diaromo-chromium compound (0), bisciclopentadienyl chromium (II), chromium acetylacetonate (III) or combinations thereof.
[0005]
5. Method according to claim 1, characterized by the fact that the amount of chromium present in the catalyst varies from 0.01% to 10% by weight of the catalyst and the amount of titanium present in the catalyst varies from 0.01% 10% by weight of the catalyst.
[0006]
6. Method according to claim 1, characterized by the fact that the reaction mixture excludes a titanium tetra-alkoxide.
[0007]
7. Method of preparing a catalyst characterized by comprising: a) contacting (i) a silica support, (ii) an oxotitanium compound with a general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof, (iii) a compound containing chromium and (iv) an optional solvent, to form a first aqueous mixture comprising a pre-catalyst and a reaction medium having from 1% by weight to 99% by weight of water; and b) heat treating the pre-catalyst by heating at a temperature from 400 ° C to 1,000 ° C for a period of time from 1 minute to 24 hours to form the catalyst.
[0008]
8. Method according to claim 7, characterized by the fact that R1 and R2 are each independently format, acetate, propionate, ammonium oxalate, ammonium malonate, ammonium fumarate or ammonium malate.
[0009]
9. Method according to claim 7, characterized in that R1 and R2 are each independently unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate.
[0010]
10. Method of preparing a polymer characterized in that it comprises contacting a catalyst prepared by the method, as defined in claim 1, with an ethylene monomer under conditions suitable for the formation of an ethylene polymer; and recovering the polymer.
[0011]
11. Method according to claim 10, characterized by the fact that the polymer has a high melt index of 10 g / 10 min at 60 g / 10 min, a polydispersity index greater than 15 and a response of shear less than 60.
[0012]
12. Method according to claim 10, characterized by the fact that the polymer has a high charge melting index of 10 g / 10 min at 60 g / 10 min, a polydispersity index greater than 15 and a response of shear less than 45.
[0013]
13. Method of preparing a catalyst characterized by comprising: contacting a hydrated support material comprising silica with a compound containing chromium to form a first aqueous mixture comprising a chrome support; contacting the first aqueous mixture comprising a chrome support with a solution comprising (i) a solvent and (ii) an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst, wherein the oxotitanium compound has a general formula R1R2TiO wherein R1 and R2 are each independently a carboxylate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof; and heat treating the pre-catalyst to form the catalyst.
[0014]
Method according to claim 13, characterized in that the first aqueous mixture comprises a liquid associated with the hydrated support material comprising silica and a liquid associated with the chromium-containing compound and in which the second aqueous mixture comprises an associated liquid to the hydrated support material comprising silica, a liquid associated with the chromium-containing compound, a liquid associated with the oxotitanium compound and the solvent.
[0015]
15. Method according to claim 13, characterized in that an amount of water present in the first or second aqueous mixture is in the range of 1% by weight to 50% by weight.
[0016]
16. Method according to claim 13, characterized by the fact that the compound containing chromium comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a chromium (0) compound, bisciclopentadienyl chromium (II), chromium acetylacetonate (III) or combinations thereof.
[0017]
17. Method according to claim 13, characterized by the fact that R1 and R2 are each independently format, acetate, propionate, ammonium oxalate, ammonium malonate, ammonium fumarate or ammonium malate.
[0018]
18. Method according to claim 13, characterized in that R1 and R2 are each independently unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate.
[0019]
19. Method of preparing a catalyst characterized by comprising: contacting a hydrated support material comprising silica with an oxotitanium compound to form a first aqueous mixture comprising a titanated support and a first reaction medium in which the first reaction medium comprises from 1% by weight to 20% by weight of water; contacting the first aqueous mixture comprising a titanated support with a compound containing chromium to form a second aqueous mixture comprising a pre-catalyst and a second reaction medium in which the second reaction medium comprises from 1% by weight to 20% by weight. water weight; and heat treating the pre-catalyst to form the catalyst.
[0020]
20. Method of preparing a catalyst characterized by comprising: a) contacting (i) a silica support material comprising from 0.1% by weight to 20% by weight of water, (ii) a solution comprising (1 ) a 2,4-pentadionate oxotitanium compound, (2) a solvent and (3) from 0.1% by weight to 80% by weight of water based on the total weight of the solution and (iii) a compound containing chromium for forming a pre-catalyst in which the liquid present in (i), (ii) and (iii) comprises a reaction medium; and b) thermally treating the pre-catalyst by heating to a temperature in the range of 500 ° C to 900 ° C for a period of time from 3 hours to 12 hours to form a catalyst.
[0021]
21. Method according to claim 20, characterized in that the heat treatment of the pre-catalyst produces emission products comprising less than 2% by weight of hydrocarbons based on a total weight of the emission products.
[0022]
22. Pre-catalyst composition characterized by comprising: (i) a silica support (ii) an oxotitanium compound with the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof, and (iii) a compound containing chromium.
[0023]
23. Composition according to claim 22, characterized by the fact that titanium is present in an amount of 0.5% by weight to 10% by weight and chromium is present in an amount of 0.2% by weight to 2% by weight of the total composition.
[0024]
24. Composition according to claim 22, characterized by the fact that the silica support has a surface area greater than 250 m2 / g and a pore volume greater than 0.9 cm3 / g.
[0025]
25. Pre-catalyst characterized by being prepared by a process that comprises contacting (i) a silica support, (ii) an oxotitanium compound having a general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or combinations thereof, (iii) a compound containing chromium and (iv) an optional solvent, to form a first aqueous mixture comprising pre-catalyst and a reaction medium having from 1% by weight to 99% by weight of water.
[0026]
26. Pre-catalyst according to claim 25, characterized by the fact that titanium is present in an amount of 0.5% by weight to 10% by weight and chromium is present in an amount of 0.2% by weight at 2% by weight based on the total weight of the composition and where the silica support has a surface area greater than 250 m2 / g and a pore volume greater than 0.9 cm3 / g.
[0027]
27. Method according to claim 19, characterized in that the amount of chromium present in the catalyst varies from 0.01% to 10% by weight of the catalyst and the amount of titanium present in the catalyst varies from 0.01% 10% by weight of the catalyst.
[0028]
28. Method according to claim 19, characterized in that the oxotitanium compound has the general formula R1R2TiO in which R1 and R2 are each independently a carboxylate, a dicarboxylate, a diketonate, an alkoxide, an ammonium salt of a dicarboxylate, an ammonium salt of a tricarboxylate or their combinations.
[0029]
29. Method according to claim 28, characterized in that R1 and R2 are each independently unsubstituted 2,4-pentadionate or substituted 2,4-pentadionate.

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US9725530B2|2012-04-20|2017-08-08|East China University Of Science And Technology|Supported metal oxide double active center polyethylene catalyst, process for preparing the same and use thereof|US9023967B2|2011-11-30|2015-05-05|Chevron Phillips Chemical Company Lp|Long chain branched polymers and methods of making same|

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US10889664B2|2019-06-12|2021-01-12|Chevron Phillips Chemical Company Lp|Surfactant as titanation ligand|

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US11242416B2|2019-06-12|2022-02-08|Chevron Phillips Chemical Company Lp|Amino acid chelates of titanium and use thereof in aqueous titanation of polymerization catalysts|

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US10858456B1|2019-06-12|2020-12-08|Chevron Phillips Chemical Company Lp|Aqueous titanation of Cr/silica catalysts by the use of acetylacetonate and another ligand|

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法律状态:
2020-12-22| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/09/2017, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US15/281,538|US9988468B2|2016-09-30|2016-09-30|Methods of preparing a catalyst|

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US15/281,538|2016-09-30|

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PCT/US2017/053468|WO2018064050A2|2016-09-30|2017-09-26|Methods of preparing a catalyst|

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