Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • 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 invention relates to a catalyst for polymerization and co- polymerization of ethylene, or more particularly to a solid titanium catalyst supported onto a carrier containing magnesium, which has a very high catalytic activity with excellent catalyst morphology.
• Catalysts containing magnesium for polymerization and co-polymerization of ethylene are known to have very high catalytic activities and to accord high bulk density, which are suitable for liquid or gas phase polymerization.
• liquid phase polymerization of ethylene it denotes a polymerization process performed in a medium such as bulk ethylene, isopentane, or hexane, and as for the important characteristics of the catalyst used in this process, they are as follows: high activity, bulk density of produced polymers, the amount of low molecular weight polymer dissolved in a medium, etc. Of these characteristics, it could be said that catalytic activity is the most important characteristics of a catalyst.
• US Patent No. 5,459,1 16 discloses a method of producing a solid titanium catalyst by contact-reacting a magnesium solution having an ester of at least one hydroxy group as an electron donor with a titanium compound. By using this method, a catalyst with a high polymerization activity and superior bulk density of polymers can be obtained. Yet. there are disadvantages at the production stage, such as a large quantity of expensive TiCl 4 in use, and a large amount of hydrogen chloride produced during the manufacturing process.
• US Patent No. 4,843,049 discloses a method of producing a catalyst having high titanium content by reacting a magnesium chloride-ethanol substrate produced by means of a spray-drying with titanium alkoxide. followed by reacting diethyl aluminum chloride or ethyl aluminum sesquichloride.
• this method has disadvantages of having alcohol content outside the range of 18- 25% and deteriorating bulk density of polymers produced when compounds other than diethyl aluminum chloride or ethyl aluminum sesquichloride are used.
• US Patent Nos. 5,726,261 and 5.585,317 disclose a method of producing a catalyst having porosity of 0.35-0.7, supported with a titanium compound having at least one titanium-halogen and one hydroxy group, by treating the magnesium- ethanol substrate produced by means of a spray-drying method with triethyl aluminum, or heat-treating the same, and then treating it with a titanium alkoxide compound, titanium alkoxide or silicon tetraethoxide, etc. Yet, this method has a disadvantage of somewhat low catalytic activity. Disclosure of Invention
• the objective of the present invention is to provide a new catalyst for polymerization or co-polymerization of ethylene. wherein said catalyst has enhanced catalytic activity and is capable of producing polymers of high bulk density.
• Another objective of the present invention is to provide a simple process as disclosed specifically for producing a catalyst for polymerization or co- polymerization of ethylene.
• the solid titanium catalyst of high catalytic activity capable of producing polymers having high bulk density as provided in the present invention, is produced by a simple yet efficient manufacturing process, which comprises (i) preparing a magnesium solution by contact-reacting a halogenated magnesium compound with alcohol; (ii) reacting the same with an ester compound containing at least one hydroxy group, or a silicon compound containing an alkoxyl group and a phosphorous compound; (iii) reacting the same with an aluminum compound, and then producing a solid titanium catalyst by adding a titanium compound, or a titanium compound and a vanadium compound.
• halogenated magnesium compounds used in the present invention are as follows: di-halogenated magnesium such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; alkymagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, and amylmagnesium halide; alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagensium halide, isopropoxymagnesium halide, butoxymagnesium halide, octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methyl-phenoxymagnesium halide.
• di-halogenated magnesium such as magnesium chloride, magnesium iodide, magnesium flu
• the preferable magnesium compounds are magnesium halides, especially magnesium chlorides or alkylmagnesium chlorides, preferably those having an alkyl group of 1- 10 carbons; alkoxymagnesium chlorides, preferably those having an alkoxy group of 1 ⁇ 10 carbons; and aryloxymagnesium chlorides, preferably those having an aryloxy group of 6 ⁇ 20 carbons.
• the magnesium solution used in the present invention is made by dissolving the aforementioned compounds in alcohol solvent in the presence or absence of a hydrocarbon solvent.
• hydrocarbon solvents used in the present invention are as follows: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane. and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.
• aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene
• alicyclic hydrocarbons such as cyclobenzene, methylcyclobenz
• the types of alcohol include those containing 1 - 20 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol. octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl benzyl alcohol, and cumyl-alcohol, or preferably an alcohol containing 1 - 12 carbon atoms.
• the average size of a target catalyst and its particle distribution can vary according to the following factors: types of alcohol, the total contents, types of magnesium compounds, the ratio of magnesium to alcohol, etc.
• the total amount of alcohol required to obtain magnesium solution is at least 0.5 mol per each mole of a magnesium compound, preferably about 1.0 - 20 mol, or more preferably about 2.0 - 10 mol.
• the reaction of a magnesium compound with alcohol for producing magnesium solution is preferably carried out in the presence of a hydrocarbon medium. While it varies depending on the types and the amounts of alcohol and aromatic ether, the reaction temperature should be at least -25 ° C . preferably -10 - 200 ° C , or more preferably about 0 - 150 ° C . It is preferable to carry out the reaction for about 15 minutes - 5 hours, preferably for about 30 minutes - 4 hours.
• the ester compounds containing at least one hydroxy group include unsaturated aliphatic acid esters having at least one hydroxy group such as 2-hydroxy ethylacrylate, 2-hydroxy ethylmethacrylate. 2-hydroxypropyl acrylate. 2-hydroxypropylmethacrylate, 4- hydroxybutylacrylate, pentaerithritol triacrylate; aliphatic monoesters or polyesters containing at least one hydroxy group such as 2-hydroxy ethyl acetate, methyl 3 -hydroxy butylate, ethyl 3 -hydroxy butylate.
• diethyl bis-(hydroxy methyl) malonate aromatic esters having at least one hydroxy group such as 2-hydroxy ethyl benzoate, 2-hydroxy ethylsalicylate. methyl-4-(hydroxy methyl) benzoate, methyl-4-hydroxy benzoate. ethyl-3- hydroxy benzoate, 4-methyl salicylate, ethyl salicylate, phenyl salicylate. propyl- 4-hydroxy benzoate, phenyl-3 -hydroxy naphthanoate. monoethylene glycol monobenzoate, diethylene glycol monobenzoate. triethylene glycol benzoate; alicyclic esters having at least one hydroxy group such as hydroxy butyl lactone.
• the amount of an ester compound containing at least one hydroxy group should be 0.001 - 5 mol per mole of magnesium compound, or preferably 0.01 - 2 mol per mole.
• Another electron donor compound used in the present invention is expressed by the following general formula: PX a R' b (OR 2 ) c or POX d R 3 e (OR 4 ) f .
• X is a halogen atom
• R 1 , R 2 , R 3 , or R 4 is a hydrocarbon of an alkyl, alkenyl or aryl group, having 1-20 carbon atoms.
• it includes phosphorus trichloride, phosphorus tribromide. diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite.
• diphenylbromophosphite dimethylchlorophosphite, phenylchlorophosphite, trimethylphosphite, triethylphosphite, tri-n- butylphosphite, trioctylphosphite, tridecylphosphite, triphenylphosphite, triethylphosphate, tri-n-butylphosphate, and triphenylphophate.
• Other phosphor compounds satisfying the aforementioned formula may be used.
• 0.25 mole or below per 1 mole of magnesium compound is appropriate, or more preferably 0.2 mole or below per 1 mole.
• silicone compound having an alkoxy group another electron donor, it is preferable to use a compound having a general formula of R_Si(OR) 4 . n
• R is a hydrocarbon having 1-12 carbon atoms, and n is a natural number of 1-3).
• the amount used 0.05 - 3 moles per 1 mole of magnesium compound is preferable, or more preferably 0.1 - 2 moles.
• the temperature used during contact-reaction of a liquid magnesium compound solution with an ester compound having at least one hydroxy group, or a phosphorous compound and silicon solution having an alkoxy group the temperature of 0 - 100 ° C is appropriate, or more preferably 10 - 70 ° C .
• the magnesium compound solution reacted with said electron donors causes re-crystallization of catalyst particles by reacting with a mixture of a liquid titanium compound of general formula of Ti(OR) a X 4 .
• a (R for a hydrocarbon group, X for a halogen atom, and "a" for a natural number of 0 ⁇ a ⁇ 4) and a silicon compound of a general formula of R_SiCl n _ 4 (R for hydrogen, an alkyl group of 1 - 10 carbons, an alkoxy. haloalkyl. aryl, halosilylalkyl group, or a halosilyl group of 1-8 carbon atoms, and n for a natural number of 0 ⁇ a ⁇ 3).
• Ti(OR) a X 4 _ a include 4-halogenated titanium such as TiCl 4 . TiBr 4 . and Til 4 ; 3- halogenated alkoxy-titanium such as Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(OC 2 ) 3 , Ti(O(I-C 4 H 9 ))Br 3 , and Ti(O(i-C 4 H 9 )Br 3 ; 2-halogenated alkoxy-titanium such as Ti(OCH 3 ) 2 Cl 2 . Ti(OC 2 H 5 ) 2 Cl : .
• a mixture of the above titanium compounds can also be used in the present invention.
• the preferable titanium compounds are those containing halogen, or more preferably titanium tetrachloride.
• R_SiCl 4 . n include silicon tetrachloride; trichlorosilane such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane; dichlorosilane such as dimethylchlorosilane, diethyldichlorosilane. di-phenyldichlorosilane, and methylphenyldichlorosilane; monochlorosilane such as trimethylchlorosilane; and a mixture of these silicon compounds can also be used in the present invention, or more preferably silicon tetrachloride can be used.
• the amount of the mixture of a titanium compound and a silicon compound used during re-crystallization of the magnesium compound solution is appropriately 0.1 - 200 mol per mole of a halogenated magnesium compound, preferably 0.1 - 100 mol, or more preferably 0.2 - 80 mol.
• the molar ratio of a titanium compound to a silicon compound in the mixture is appropriately 0.05 - 0.95, or more preferably 0.1 - 0.8.
• the shape and the size of the resultant re- crystallized solid components vary a great deal according to the reaction conditions at the time when the magnesium compound solution is reacted with the mixture of a titanium compound and a silicon compound.
• the reaction of a magnesium compound with the mixture of a titanium compound and a silicon compound should be carried out preferably at a sufficiently low temperature to result in formation of solid components. More preferably, the reaction should be carried out by contact-reaction at -70 - 70 ° C , or more preferably at -50 - 50 ° C . After the contact-reaction, the reaction temperature is slowly raised for sufficient reaction for the duration of 0.5 - 5 hours at 50 - 150 ° C .
• the solid components obtained as above are activated by reacting the same with an aluminum compound.
• the aluminum compounds used in the present invention for examples include trialkylaluminum having an alkyl group of 1-6 carbon atoms, such as triethylaluminum and triisobutylaluminum; an aluminum compound having one more halogens, such as ethylaluminum dichloride, diethylaluminum chloride, and ethylaluminum sesquichloride; or the mixtures thereof.
• an aluminum compound can be used by diluting it to the solvent. At the time of reacting aluminum, it should be carried out at 0 - 100 ° C . or more preferably at 20 - 80 ° C .
• the solid catalyst is produced by reacting a titanium compound or a mixture of a titanium compound and a vanadium compound with said activated solid components.
• These titanium compounds used in the present invention are titanium halides, and halogenated alkoxy titanium with an alkoxy functional group of 1 - 20 carbons. At times, a mixture of these compounds can also be used. Of these compounds, titanium halide and a halogenated alkoxy titanium compound having an alkoxy functional group of 1-8 carbons can be appropriately used, or more preferably titanium tetrahalide.
• the vanadium compound used in the present invention is a compound with the maximum atomic valence of 4, or the maximum atomic valence of VO of a vanadyl group of 3. It has a general formula of V(OR) 4 . n X n . or VO(OR) 3 . m X,_.
• R is an aliphatic or aromatic hydrocarbon group having 1-14 carbons, or COR 1 (R 1 is an aliphatic or aromatic hydrocarbon group having 1-14 carbons).
• X is Cl, Br or I
• n is an integer of 0-4, or the ratio thereof.
• An m is an integer of 0-3, or the ratio thereof.
• These compounds include vanadium tetrachloride, vanadyl trichloride, vanadyl tri-n-propoxide. vanadyl triisopropoxide, vanadyl tri-n-butoxide, vanadyl tetra-n-butoxide and vanadyl tetra-n-propoxide.
• vanadium tetrachloride vanadyl trichloride
• vanadyl tri-n-propoxide vanadyl triisopropoxide, vanadyl tri-n-butoxide, vanadyl tetra-n-butoxide and vanadyl tetra-n-propoxide.
• vanadium tetrachloride vanadyl trichloride
• vanadyl tri-n-propoxide vanadyl triisopropoxide
• vanadyl tri-n-butoxide vanadyl
• the catalysts produced according to the present invention can be utilized during polymerization or co-polymerization of ethylene.
• the catalyst is used in polymerization of ethylene, and also in co-polymerization of ethylene and a -olefin having three or more carbons, such as propylene, 1- butene, 1-pentene, 4-methyl-l-pentene, or 1-hexene.
• the polymerization reaction in the presence of the catalyst of the present invention is carried out by means of using (a) the solid catalyst of the present invention, comprising magnesium, titanium, aluminum, halogen, electron donors. and optionally vanadium, and (b) a catalyst system comprising compounds of organic metals of Groups II and III of the Periodic Table.
• the solid titanium catalyst (a) of the present invention can be used after pre-polymerization to ethylene or a -olefin prior to the use in the aforementioned polymerization reaction.
• the pre-polymerization can be carried out in the presence of a hydrocarbon solvent such as hexane, at a sufficiently low temperature, with ethylene or a -olefin under pressure, in the presence of the above catalyst component and an organic aluminum compound such as triethylaluminum.
• Pre-polymerization by maintaining the shape of the catalyst by surrounding the catalyst particles with polymers, is helpful in producing good- quality post-polymerization shape in polymers.
• the weight ratio of the polymers to the catalysts after pre-polymerization is ordinarily 0.1 : 1 to 20 : 1.
• the organometallic compound (b) used in the polymerization reaction using the catalyst of the present invention can be represented by a general formula of MR_. wherein, M stands for a metal component of Group II or IIIA in the
• Periodic Table such as magnesium, calcium, zinc, boron, aluminum, and gallium
• R for an alkyl group with 1 - 20 carbons such as a methyl, ethyl, butyl, hexyl, octyl. or decyl group; and n for the atomic valence of the metal component.
• organometallic compounds trialkyl aluminum having an alkyl group of 1 - 6 carbons, such as triethylaluminum and triisobutylaluminum, or the mixture thereof can be utilized.
• an organic aluminum compound having one or more halogen, or a hydride group such as ethylaluminum dichloride, diethylaluminum chloride, ethyl-aluminum sesquichloride, or diisobutylaluminum hydride can also be used.
• polymerization reaction it is possible to carry out either gas phase or bulk polymerization in the absence of an organic solvent, or liquid slurry polymerization in the presence of an organic solvent. These polymerization methods, however, are carried out in the absence of oxygen, water, or other compounds that may act as catalytic poison.
• the concentration of the solid titanium compound (a) with respect to the polymerization reaction system, in the case of a liquid phase slurry polymerization, is approximately 0.001 - 5 mmol in terms of titanium atom of catalysts per one liter of solvent, or more preferably approximately 0.001 - 0.5 mmol.
• the solvent the following compounds or the mixtures thereof can be used: alkanes or cycloalkanes such as pentane.
• alkylaromatic such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, di ethylbenzene
• halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene; and the mixtures
• the amount of solid titanium catalysts (a) could be approximately 0.001 - 5 mmol in terms of titanium atom of catalysts per one liter of a polymerization volume, preferably approximately 0.001 - 1.0 mmol, or more preferably approximately 0.01 - 0.5 mmol.
• the preferable concentration of an organometallic compound (b) is about 1 - 2,000 mol, as calculated by aluminum atoms, per mole of titanium atoms in the catalyst (i), or more preferably about 5 - 500 mol.
• the polymerization herein is carried out at a sufficiently high temperature, irrespective of the polymerization manufacturing process.
• the temperature of 20 - 200 ° C is appropriate, or more preferably approximately 20 - 95 ° C .
• the appropriate pressure of monomers at the time of polymerization is the atmospheric to 100 atm. or more preferably 2 - 50 atm.
• the molecular weight is expressed as a melting index (ASTM D 1238), which is generally known in the art.
• the value of the melting index generally becomes greater as the molecular weight decreases.
• the products obtained by the method of polymerization using the catalyst of the present invention are solid ethylene polymer or copolymers of ethylene and a -olefin, which have excellent bulk density and fluidity. Since the yield of polymers is sufficiently high, there is no need for the removal of catalyst residues.
• a 2-L high-pressure reactor was dried in an oven and assembled while hot. In order to make the inside of the reactor nitrogen atmosphere, nitrogen and vacuum were alternatively manipulated three times in the reactor. It was then instilled with 1 ,000 ml of n-hexane, after which 2 mmols of triethylaluminum and 0.01 mmol of the solid catalyst, in terms of titanium atoms or titanium + vanadium metal atoms, were added thereto. Then, 1 ,000 ml of hydrogen was added. The temperature was raised to 80 ° C while stirring at 700 rpm. The pressure of ethylene was adjusted to 100 psi, and the polymerization was allowed to continue for 20 minutes.
• the temperature of the reactor was lowered to room temperature, and an excessive amount of ethanol solution was added to the polymerized matter.
• the polymers thus produced were collected by separation and was vacuum-dried in an oven at 50 ° C for at least six hours, whereby polyethylene was obtained in the form of white powder.
• the polymerization activities (kg of polyethylene divided by g of catalyst) were calculated as the weight (kg) ratio of the polymers as produced per amount of the catalysts so used (g of catalyst).
• the results of polymerization are shown in Table 1 , together with bulk densities (g/ ml) and melting indexes (g/10 minutes) of the polymers.
• the catalyst was produced by treating 15g of the catalyst produced in Step
• the polymerization reaction was carried out under the conditions of Example 1 , the results of which are shown in Table 1.
• the polymerization reaction was carried out under the conditions of Example 1 , the results of which are shown in Table 1.
• the polymerization reaction was carried out under the conditions of Example 1, the results of which are shown in Table 1.
• the catalyst was produced by treating 15g of the catalyst produced in Step
• the catalyst was produced by treating 15g of the catalyst produced in Step
• Step (ii) of the catalyst production process of Example 1 76.0 ml of tributylphosphate and 100 ml of silicon tetraethoxide were used to produce a catalyst as in Example 1.
• the titanium content of the catalyst thus produced was
• the polymerization reaction was carried out under the conditions of Example 1. the results of which are shown in Table 1.
• the polymerization reaction was carried out under the conditions of Example 1. the results of which are shown in Table 1.
• the catalyst was produced by treating 15g of the catalyst produced in Step
• the catalyst was produced by treating 15g of the catalyst produced in Step
• Example 13 The catalyst was produced by treating 15g of the catalyst produced in Step
• the polymerization reaction was carried out under the conditions of Example 1. the results of which are shown in Table 1.
• the polymerization reaction was carried out under the conditions of Example 1. the results of which are shown in Table 1.
• the polymerization reaction was carried out under the conditions of Example 1 , the results of which are shown in Table 1.
• the catalyst of the present invention for polymerization and co-polymerization of ethylene involves a simple production process and results in excellent catalytic activity. Further, the present invention produces polymers of high bulk density and narrow particle distribution with the effect of reducing the amount of fine particles.

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