• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides a polymerization process using a single site catalyst, by using a physical property modifier selected from the group consisting of aliphatic hydrocarbons, aliphatic ring hydrocarbons, aromatic hydrocarbons, and mixtures thereof for the polymerization reaction. Molecular weight, molecular weight distribution, or an improved method of controlling both.
    公开号:KR20000077306A
    申请号:KR1020000026460
    申请日:2000-05-17
    公开日:2000-12-26
    发明作者:바이 진라이；무루가난담 나타라얀
    申请人:조셉 에스. 바이크；유니온 카바이드 케미칼즈 앤드 플라스틱스 테크날러지 코포레이션；
    IPC主号:
    专利说明:

    Method for Controlling Molecular Weight and Molecular Weight Distribution in Polymers Produced Using a Single Site Catalyst}
    Field of invention
    The present invention relates to a method for controlling the molecular weight, molecular weight distribution, or both of polymers prepared using single site catalysts (metallocenes, etc.). More specifically, the present invention relates to a polymer (polymer such as alpha olefin and / or diolefin) using a physical property modifier selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof in a polymerization process using a single site catalyst. It relates to a method of adjusting the above characteristics.
    Background of the Invention
    Molecular weight (MW) and molecular weight distribution (MWD) influence the properties of the final polymer produced in the polymerization process. More important is the role of MW and MWD in the manufacturing process or end use to which the final polymer is added. That is, because the polymer does not have specific MW and MWD values, the Mooney viscosity properties desired by end users or process designers may be lacking. Therefore, there is a need for a method of controlling / manipulating MW and MWD in the polymerization process itself in order to produce a particularly desired polymer product. This control is particularly necessary when single site catalysts such as metallocenes are used in the polymerisation process.
    It is an object of the present invention to provide a method of controlling the molecular weight, molecular weight distribution, or both of polymers produced using single site catalysts by varying the physical property modifiers depending on the type of polymerization and the type of catalyst used.
    Another object of the present invention is to provide a method for controlling the molecular weight, molecular weight distribution, or both in the polymerization process itself in order to make polymer products having Mooney viscosity properties required by end users or process designers.
    Another object of the present invention is to prepare polymers having a full range of MW and MWD by adjusting the mixing ratios of aliphatic hydrocarbons and physical property modifier combinations of aromatic hydrocarbons.
    The above and other objects of the present invention can be achieved by the present invention described below.
    Physical properties modifiers
    Compounds useful in modulating or modifying the molecular weight (Mw), molecular weight distribution (MWD or Mw / Mn), or both, of a polymer are referred to as physical property modifiers. There are two kinds of physical property modifiers used in the present invention: (1) aliphatic hydrocarbon compounds including ring compounds (ie, aliphatic ring hydrocarbons) and (2) aromatic hydrocarbon compounds. In the present invention, it is preferred that the modifier is in liquid form. Only one of the two modifiers may be used, or mixtures thereof, to obtain the specific molecular weight and / or molecular weight distribution of the polymer.
    Aliphatic hydrocarbon compounds have 4 to 12 carbon atoms. Preferably, aliphatic hydrocarbon compounds except aliphatic ring hydrocarbon compounds used as physical property modifiers in the present invention have a solubility parameter of 7.5 (cal / cm 3 ) 1/2 or less. Aliphatic ring hydrocarbon compounds have a solubility parameter of at least 7.7 (cal / cm 3 ) 1/2 . Examples of such saturated compounds may be selected from the group consisting of butane, pentane, isopentane, hexane, heptane, decane, cyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. More preferably, the liquid aliphatic hydrocarbon used in the present invention is isopentane, hexane, heptane, and mixtures thereof. When only aliphatic hydrocarbon compounds are used as physical property modifiers in the present invention, the Mooney viscosity (ie, high molecular weight) of the produced polymer has a high range of values of about 50 to 150, and has a molecular weight distribution (Mw / Mn or PDI: Polydispersity). Index) has a narrow range of values of about 1.5 to 4.5.
    Aromatic hydrocarbon compounds have 6 to 20 carbon atoms. Preferably the aromatic hydrocarbon compound used as physical property modifier in the present invention has a solubility parameter of at least 7.7 (cal / cm 3 ) 1/2 . Examples of such saturated compounds may be selected from the group consisting of benzene, azobenzene, toluene, xylene (olso, meta, para isomers), and mixtures thereof. More preferably, the liquid aromatic hydrocarbons used in the present invention are azobenzene, toluene, xylene (olso, meta, para isomers), and mixtures thereof. When only aromatic hydrocarbon compounds are used as physical property modifiers in the present invention, the Mooney viscosity of the produced polymer has a low range of values of about 10 to 100, and a molecular weight distribution of a narrow range of values of about 1.5 to 4.5.
    Two kinds of physical property modifiers (aliphatic and aromatic hydrocarbons) may be used alone. In the present invention, when two kinds of physical property modifiers (aliphatic and aromatic hydrocarbons) are used in combination, an intermediate molecular weight and a wide molecular weight distribution are obtained. In the combination of an aliphatic physical property modifier (1) or an aromatic physical property modifier (2), the mixing ratio is a volume ratio and varies to some extent depending on the compound selected from (1) or (2). Generally, however, the mixing ratio is 99/1 to 1/99, preferably 90/10 to 10/90 and most preferably 85/15 to 60/40. Preferred combinations of aliphatic (1) or aromatic hydrocarbon compounds (2) are hexane-toluene, isopentane-toluene, heptane-toluene, hexane-xylene, isopentane-xylene, and heptane-xylene. Most preferred combinations are hexane-toluene, isopentane-toluene. By adjusting the mixing ratio of the two types of physical property modifier combinations, it is possible to produce polymers having a full range of MW and MWD.
    Physical Properties Modifiers can be used in various ways depending on the type of polymerization (solution / slurry or gas polymerization) and the type of catalyst used (liquid or supported catalyst).
    In slurry / solution processes using liquid or soluble catalysts, one or more of these physical property modifiers may be used with the catalyst (solid or liquid) dissolved in one or both of them. When only one physical property modifier is used, the catalyst precursor enters the reaction and can be dispersed / dissolved in the modifier. When two or more physical property modifiers are used, one way to do this is to disperse or dissolve the catalyst precursor in one of the physical property modifiers, and to add the other physical property modifier separately and / or continuously. Another way to do this is to disperse or dissolve the catalyst compound in a mixture in two or more physical property modifier mixtures. Next, when the dispersion / solution of the catalyst is injected into the slurry / solution polymerization reaction using a compound having the same or different physical properties as the dispersion medium / solvent (reaction medium), the monomer is preferably introduced into the polymerization reactor.
    In a gas phase process using a liquid or soluble catalyst as in the slurry / solution polymerization described above, the catalyst precursor may be dispersed or dissolved in the modifier when only one physical property modifier enters the polymerization process. Alternatively, when two or more physical property modifiers are used, the catalyst precursor is dispersed or dissolved in one of the physical property modifiers, followed by the continuous addition of the remaining physical property modifiers. Another method when two types of modifiers are used is to mix the two modifiers in some specific proportion to disperse or dissolve the catalyst precursor and inject the mixture / solution into the fluidization polymerization of the gas. Typically, the catalyst dispersion / solution is introduced into the gas phase polymerization reactor together with the cocatalyst or separately (continuously or intermittently) and the monomers are continuously or intermittently introduced respectively.
    Generally, soluble / solution catalysts are used for solution / slurry polymerization, and supported catalysts are used for gas phase polymerization. In the present invention, the support catalyst may be combined with one or more physical property modifiers and used in the solution / slurry process. This can be done by the following method. The catalyst precursor is dissolved (in certain desired proportions) in one or both of them if one physical property modifier or several kinds of physical property modifiers are used. Next, individual particulate support catalysts (silica, carbon black, alumina, magnesia) are added to the mixture. Preferably, the support material is silica, carbon black, or mixtures thereof. The slurry thus prepared is dried by removing excess liquid (physical property modifier) by purifying or vacuuming under inert air to form a free-flowing powdered catalyst. The support catalyst thus produced is continuously or intermittently introduced into the polymerization reactor in such a manner that another support catalyst is introduced. In other variations of this embodiment, additional modifiers may be introduced with or separately from support catalysts that have been treated with physical property modifiers.
    polymer
    The olefin polymers prepared according to the invention range from about 0.84 to 0.96 ethylene homopolymers, homopolymers of linear or branched higher alpha olefins having 3 to 20 carbon atoms, and interpolymers of ethylene and higher alpha olefins. Include but are not limited to. Homopolymers and copolymers of propylene can also be prepared by the catalysts and processes of the present invention. Examples of suitable higher alpha olefins are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene. The olefin polymers according to the invention may also comprise or be based on conjugated or nonconjugated dienes such as linear, branched, or cyclic hydrocarbon dienes having about 4 to 20, preferably 4 to 12 carbon atoms. have. Examples of preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-novorene, 1,7-octadiene, 7-methyl-1,6-octadiene (MOD), vinyl Cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene noborene (ENB) and the like. Aromatic compounds having vinyl unsaturated compounds such as styrene and substituted styrene, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, and vinyl trialkyl silanes are polymerized according to the present invention. It is good. Specific olefin polymers prepared according to the invention include, for example, polyethylene, polypropylene, ethylene / propylene rubber (EPR's), ethylene / propylene / diene terpolymers (EPDM's), ethylene-butene copolymers, ethylene-butene-diene polymers, Polybutadiene, polyisoprene and the like. In the present invention, the specific gravity of EPR's and EPDM's is 0.84 to 0.89.
    Polymerization Process and Conditions
    The polymers are prepared by polymerizing one or more monomers (olefins, diolefins, and / or vinyl aromatic compounds) in suspension, slurry, or gas phase processes in known equipment and reaction conditions, but are not limited to specific reactions. . However, a preferred polymerization process is a gas phase process using a fluidized bed. Gas phase processes used in the present invention are well known to those skilled in the art and may include so-called "normal" gas phase processes and "condensation mode" processes, and recent "liquid mode" processes.
    In many processes it is desirable to add a scavenger to the reactor to remove accidental toxic substances such as water or oxygen before they lower the catalytic activity. Trialkylaluminum species is used as the Ziegler catalyst, and methylalumoxane is preferably used in the process using a metallocene catalyst to achieve the above object.
    Examples of conventional fluidization processes are disclosed in US Pat. Nos. 3,922,322, 4,035,560, 4,994,534, and 5,317,036.
    Examples of condensation mode polymerization processes, including induced condensation modes, are disclosed in US Pat. Nos. 4,543,399, 4,588,790, 4,994,534, 5,317,036, 5,352,749, and 5,462,999. Condensation mode operation is preferred for polymerization processes for preparing alpha olefin homopolymers and copolymers.
    Liquid mode or liquid monomer gas phase polymerization processes are disclosed in U.S. Patent 5,453,471, U.S. Patent Application 510,375, WO 96/04322 (PCT / US95 / 09826) and WO 96/04323 (PCT / US95 / 09827). It is. It is preferred to use liquid mode when one or more dienes are used.
    Inert particulates called fluidizing agents in polymerization processes such as ethylene-propylene copolymers (eg EPMs), ethylene-propylene-diene terpolymers (eg EPDMs), diolefins (eg butadiene), and vinyl aromatics polymerization Preference is given to using materials. Examples of inert particulates are disclosed in US Pat. No. 4,994,534 and include silica, carbon black, clay, talc, and mixtures thereof. Of these, silica, carbon black, and mixtures thereof are more preferable. When used as a glidant, such inert particulates are used in amounts of about 0.3 to 80% by weight, preferably about 5 to 50% by weight, based on the polymer weight produced. Inert particulates may comprise modified carbon blacks disclosed in WO 98/34960 and / or activated carbons disclosed in EP 0 727,447. The use of inert particulates as glidants in the polymerization process can produce polymers having a core-shell arrangement as disclosed in US Pat. No. 5,304,588. In the case of a tacky polymer, these resin particles are prepared by a fluidized bed polymerization process at or above the softening point of the tacky polymer.
    The polymerization process may be carried out in a single reactor or in multiple reactors, typically two or more reactors may be used in succession. When a gas phase reactor is used, it is helpful to use an agitator or paddle for gas fluidization. Essential parts of the reactor are vessels, beds, gas distribution plates, inlet and outlet pipes, one or more compressors, one or more circulating gas coolers, and product outlet systems. The vessel above the bed has a deceleration zone and the bed has a reaction zone.
    Generally all of the above polymerization modes are carried out in a gas phase fluidized bed comprising a "seed bed" of the same or different polymer as the polymer produced. Preferably the bed consists of a granular resin such as produced in a reactor.
    The bed is composed of monomers or monomers to be polymerized, initial feed, supplementary feed, circulating (recirculating) gas, inert medium gas (e.g. nitrogen, argon, or inert hydrocarbons such as ethane, propane, butane, pentane, isopentane). Fluidized with a configured fluidizing gas and, if necessary, a modifier (eg hydrogen). Thus, during the polymerization process, the bed is optionally used and acts as a fluid and fluidizes by fluidizing by polymerizing and polymerizing the incoming gas components at a flow rate suitable for separating particles, polymer forming particles, increasing Polymer particles, and catalyst particles.
    In general, the polymerization condition temperature of the gas phase reactor may be in the range below the atmosphere, but is typically about 0 to 120 ℃, preferably about 40 to 100 ℃, most preferably about 40 to 80 ℃. The partial pressure varies depending on the specific monomer and polymerization temperature used, and may range from about 1 to 300 psi (6.89 to 2,067 kiloPascals), preferably from about 1 to 100 psi (6.89 to 689 kiloPascals). Condensation temperatures of monomers such as butadiene, isoprene and styrene are well known. In general, in a gas fluidized polymerization process, the diene is the only monomer or occupies a major proportion in the monomer being polymerized, and it is desirable to operate at temperatures slightly above or below the dew point of one or more monomers (ie, ± 10 ° C.). .
    Single site catalyst
    The single site catalyst used in the present invention is a metallocene, i.e., an organometallic having one or more π bonds (i.e., a cycloalkadienyl group) bonded to a group IIIB to Group VI or lanthanide metal atoms on the periodic table. It can be a coordination complex. Bridged and unbridged mono, di, and tricycloalkadienyl / metal compounds are the most common metallocenes, with the general formula:
    (L) y R 1 z (L ') MX (xy-1) (Ⅰ)
    Wherein M is a rare earth metal on the periodic table or a metal from Group IIIB to Group VIII; L and L 'are π-bonding ligands coordinated to M which may be the same or different, preferably one or more hydrocarbon groups having 1 to 20 carbon atoms and optionally substituted cyclopentadienyl, indenyl, or Cycloalkadienyl groups such as fluorenyl groups; R 1 is a C 1 -C 4 substituted or unsubstituted alkylene radical, a dialkyl or diaryl germanium or silicon group, and an alkyl or aryl phosphine or amine radical bridged to L and L '; Each X is hydrogen, an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms, or a hydrocarbon radical having 1-20 carbon atoms; y is 0, 1, or 2; x is 1, 2, 3, or 4 depending on the equilibrium with M; z is 0 or 1 and is 0 when y is 0; And xy≥1.
    Examples of metallocenes represented by Formula I include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium Diphenyl, bis (cyclopentadienyl) hafnium methyl and diphenyl, bis (cyclopentadienyl) titanium di-neopentyl, bis (cyclopentadienyl) zirconium di-neopentyl, bis (cyclopentadienyl) titanium Dialkyl metallocenes such as dibenzyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) vanadium dimethyl; Bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium ethyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl Monoalkyl metallocenes such as zirconium ethyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, and bis (cyclopentadienyl) titanium methyl bromide; Trialkyl metals such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, and cyclopentadienyl hafnium trimethyl Rosene; Monocyclopentadienyl titanocene such as pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, and bis (pentamethylcyclopentadienyl) titanium diphenyl; Carbene represented by the formula bis (cyclopentadienyl) titanium = CH 2 and derivatives of this reagent; Substituted bis (cyclopentadienyl) titanium (IV) compounds such as bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dihalide; Dialkyl, trialkyl, tetraalkyl and pentaalkyl such as bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride Cyclopentadienyl titanium compounds; Such as dimethyl cyryldicyclopentadienyl titanium diphenyl or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride and other dihalide complexes, and Isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) Zirconium Dichloride, Diisopropylmethylene (cyclopentadienyl) (fluorenyl) Zirconium Dichloride, Diisobutylmethylene (cyclopentadienyl) (fluorenyl) Zirconium Dichloride, Ditertbutylmethylene (cyclopentadiene Nil) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirco Dichloride, diisopropylmethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclo Pentadienyl) (fluorenyl) hafnium dichloride, diisopropylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diisobutylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride , Dibutyl butylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diisopropyl methylene (2,5-dimethylcyclo Pentadienyl) (fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, Isopropylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisobutylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ditertbutylmethylene (cyclopentadienyl) (fluorene Nitrile) titanium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, diisopropylmethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, racene Mic-ethylene bis (1-indenyl) zirconium (IV) dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic-dimethyl Cyryl bis (1-indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic-1, 1,2,2-tetramethylsilanylene bis (1-indenyl) zirconium (IV) dichloride, racemic-1 , 1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) dichloride, ethylidene (1-indenyl tetramethylcyclopentadienyl) Zirconium (IV) dichloride, racemic-dimethylsilyl bis (2-methyl-4-t-butyl-1-cyclopentadienyl) zirconium (IV) dichloride, racemic-ethylene bis (1-indenyl) hafnium (IV) Dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) hafnium (IV ) Dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis (1-indenyl) hafnium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) Dichloride, ethylidene (1-indenyl-2,3,4,5-tetramethyl-1 -Cyclopentadienyl) hafnium (IV) dichloride, racemic-ethylene bis (1-indenyl) titanium (IV) dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-1- Indenyl) titanium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) titanium (IV) dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1- Nil) titanium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis (1-indenyl) titanium (IV) dichloride, racemic-1,1,2,2-tetra Methylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV) dichloride, and ethylidene (1-indenyl-2,3,4,5-tetramethyl-1- Cyclopentadienyl) silicones such as titanium (IV) dichloride, phosphines, amines, or carbon bridged cyclopentadiene complexes.
    Another class of single site catalysts used in the present invention is transition metals, such as those disclosed in U.S. Patent No. 5,527,752, substituted or unsubstituted pibond ligands, and one or more hetero allyl moieties. Is expressed:
    In the above, M is a transition metal, preferably Zr or Hf;
    L is a pibond ligand, preferably a cycloalkadienyl ligand, coordinated to M, which is unsubstituted or substituted;
    Each Q is independently selected from the group consisting of —O—, —NR—, —CR 2 , and —S—, preferably oxygen;
    Y is C or S, preferably carbon;
    Z is selected from the group consisting of -OR, -NR 2 , -CR 3 , -SR, -SiR 3 , -PR 2 , -H, and unsubstituted or aryl group, if Q is -NR- Z is selected from the group consisting of -OR, -NR 2 , -SR, -SiR 3 , -PR 2 , and -H, preferably Z is from the group consisting of -OR, -CR 3 , and -NR 2 Selected;
    n is 1 or 2;
    A is a divalent anion if n is 1, a monovalent anion if n is 2, preferably A is a carbamate, carboxylate, or other heteroallyl moiety represented by a bond of Q, Y, and Z; And
    Each R is independently selected from the group consisting of carbon, silicon, nitrogen, oxygen, and / or phosphorus, one or more R groups can be bonded to an L substituent, preferably R is from 1 to 20 carbon atoms A hydrocarbon having, more preferably an alkyl, cycloalkyl, or aryl group, one or more of which may be bonded to an L substituent;
    or
    In the above, M is a transition metal, preferably Zr or Hf;
    L is a pibond ligand, preferably a cycloalkadienyl ligand, coordinated to M, which is unsubstituted or substituted;
    Each Q is independently selected from the group consisting of —O—, —NR—, —CR 2 , and —S—, preferably oxygen;
    Y is C or S, preferably carbon;
    Z is selected from the group consisting of -OR, -NR 2 , -CR 3 , -SR, -SiR 3 , -PR 2 , -H, and unsubstituted or aryl group, if Q is -NR- Z is selected from the group consisting of -OR, -NR 2 , -SR, -SiR 3 , -PR 2 , and -H, preferably Z is from the group consisting of -OR, -CR 3 , and -NR 2 Selected;
    n is 1 or 2;
    A is a divalent anion if n is 1, a monovalent anion if n is 2, preferably A is a carbamate, carboxylate, or other heteroallyl moiety represented by a bond of Q, Y, and Z;
    Each R is independently selected from the group consisting of carbon, silicon, nitrogen, oxygen, and / or phosphorus, one or more R groups can be bonded to an L substituent, preferably R is from 1 to 20 carbon atoms A hydrocarbon having, most preferably an alkyl, cycloalkyl, or aryl group and one or more may be bonded to an L substituent;
    T is a bridging group selected from the group consisting of alkylene and arylene groups having 1 to 10 carbon atoms optionally substituted with carbon or heteroatoms, germanium, silicon, and alkyl phosphines; And
    m is 2 to 7, preferably 2 to 6, more preferably 2 or 3.
    In structures II and III, the supported substituents formed by Q, Y, and Z are single-charged polydentate ligands that contribute to the electronic effect because of the high polarization similar to cyclopentadienyl groups. In the most preferred embodiment of the invention, the double substituted carbamate
    And the carboxylate
    This is used.
    Examples of complex compounds according to Structural Formulas II and III include indenyl zirconium tris (diethyl carbamate), indenyl zirconium tris (trimethylacetate), indenyl zirconium tris (p-toluate), indenyl zirconium tris (benzoate), (1-methylindenyl) zirconium tris (trimethyl acetate), (2-methylindenyl) zirconium tris (diethyl carbamate), (methylcyclopentadienyl) zirconium tris (trimethyl acetate), cyclopentadienyl tris ( Trimethyl acetate), tetrahydroindenyl zirconium tris (trimethyl acetate), and (pentamethylcyclopentadienyl) zirconium tris (benzoate). Most preferred examples are indenyl zirconium tris (diethylcarbamate), indenyl zirconium tris (trimethylacetate), and (methylcyclopentadienyl) zirconium tris (trimethylacetate).
    One method of preparing the most preferred catalyst precursor, indenyl zirconium tris (diethylcarbamate), is a metal compound of formula M (NR 2 ) 4 , wherein M and R are the above to link the cycloalkadienyl ligand to the metal compound. And the source of the cycloalkadienyl ligand are reacted first. The product is then dissolved in an inert solvent such as toluene, and the heterocumene CO 2 is brought into contact with the dissolved product to inject one or more M-NR 2 bonds to form carbamate.
    Another type of single bond catalyst that can be used in the present invention is a constrained geometry catalyst represented by the following formula:
    In the above, M is a metal of Group VIII in IIIB on the periodic table;
    Cp is a cyclopentadienyl group or a substituted cyclopentadienyl group bonded with M in a η 5 mode;
    Z 'is a boron or group consisting of elements of group IVB on the periodic table and sulfur or oxygen optionally used, a portion containing up to 20 non-hydrogen atoms, and optionally Z' is a ring bonded with Cp To form a system;
    X 'is an anionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms;
    a is 0, 1, 2, 3, or 4 depending on equilibrium with M;
    Y 'is an anionic or non-anionic ligand group combined with Z' and M and is a nitrogen, phosphorus, oxygen, or sulfur having up to 20 non-hydrogen atoms, and optionally a ring system in which Y 'is bonded with Z' Forming.
    Forced geometry catalysts are well known to those skilled in the art and are also disclosed in US Pat. Nos. 5,026,798, 5,055,438, and European Patent Application No. 0 416 815 A2.
    Examples of substituents Z ', Cp, Y', X ', and M of formula IV are as follows:
    Z 'CpY 'X 'M DimethylsilylCyclopentadienylt-butyl amidoChloridetitanium MethylphenylsilylFluorenylPhenylamidomethylzirconium DiphenylsilylIndenilCyclohexyl amido hafnium Tetramethylethylene Oxo EthyleneTetramethylcyclopentadienyl Diphenylmethylene
    The most preferred forced geometry catalyst is a cyrylamide catalyst (ACT): (C 5 Me 4 ) Me 2 Si (Nt-Bu) TiCl 2 , Me is methyl and Bu is butyl.
    The invention is also useful for other classes of single site catalysts, die (imine) metal complexes and the like as disclosed in PCT application WO 96/23010. Such di (imine) metal complexes are transition metal complexes of bidentate ligands selected from the group consisting of:
    In the above, the transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, rare earth metals, Fe, Co, Ni, and Pd;
    R 2 and R 5 are each independently a hydrocarbon or a substituted hydrocarbon, provided that the carbon atom bonded to the imino nitrogen atom has two or more carbon atoms bonded thereto;
    R 3 and R 4 are each independently hydrogen, hydrocarbon, or substituted hydrocarbon, or R 3 and R 4 together are hydrocarbylene or substituted hydrocarbylene to form a carbon ring;
    R 44 is hydrocarbyl or substituted hydrocarbyl, R 28 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, or R 44 and R 28 together may form a ring;
    R 45 is hydrocarbyl or substituted hydrocarbyl, R 29 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, or R 45 and R 29 together may form a ring;
    Each R 30 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, or both R 30 may together form a ring;
    Each R 31 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
    R 46 and R 47 are each independently hydrocarbyl or substituted hydrocarbyl if the carbon atom bonded to the imino nitrogen atom has two or more carbon atoms bonded thereto;
    R 48 and R 49 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
    R 20 and R 23 are each independently hydrocarbyl or substituted hydrocarbyl;
    R 21 and R 22 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; And
    n is 2 or 3; And
    The transition metal is combined with a ligand added to or substituted with an olefin monomer to be polymerized, and if the transition metal is lead (Pd), the bidentate ligand is (V), (iii), or (iii).
    The catalyst may be a soluble or insoluble, supported or unsupported, spray dried in the presence or absence of a filler, or a preformed catalyst. Techniques for preparing preformed catalysts or prepolymers are well known in the art.
    Cocatalysts used with the precursors listed above are aluminoxanes such as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).
    The catalyst and / or cocatalyst can be injected into the reactor either continuously or intermittently by various known techniques. Gases or liquids that are inert to the catalyst and polymerization are useful for delivering the catalyst into the bed.
    The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
    Example
    Example 1 Polymerization Under ACT Catalyst Using Only Hexane as Polymerization Medium
    In a glove box under nitrogen, 0.0184 g of ACT catalyst was placed in an oven dried vial. The bottle was sealed and taken out of the glove box. Toluene (10 ml, Aldrich, anhydrous, packaged under nitrogen) was placed in the flask to make a 0.005 M concentration solution.
    1L Stainless Steel Fluitron Nitrogen was constantly passed through the reactor at 100 ° C. for 1 hour. The reactor was cooled to 40 ° C. and 500 ml of hexane, 1 ml of tri-isobutyl aluminum (TIBA) (0.87 M concentration in heptane) and 2 ml (purified) ENB were added. The reactor was sealed and heated to 65 ° C. Ethylene (C 2 ) and propylene (C 3 ) gas (C 3 / C 2 fill ratio = 0.75 to 1) were charged until the reactor pressure was 90 psi. At this time, the ratio of gas was adjusted to C 3 / C 2 = 0.20. The polymerization was initiated by injection under 2.77 ml pressurization of 5 μmol Ti or ACT 0.005 M, and 1.8 M MAO (Al / Ti = 1000) in toluene solution. The polymerization was carried out for 1 hour after ACT and MAO injection. ENB (0.5 ml) was injected under pressure at the time of polymerization for 10 minutes and 30 minutes, respectively, until 3 ml of ENB was added.
    Ethanol removal solvent {0.5 g of BHT in 125 ml of ethanol, ie 2,6-di-t-butylate-4-methylphenol; Kemamine 1.0 g (# AS-900, manufactured by Witco Corp.); Irganox (# 1076, manufactured by Ciba-Geigy) 0.5 g} 2 ml were injected to terminate the polymerization. The C 2 and C 3 gases were stopped and the reactor was cooled to room temperature and vented.
    The polymer was removed, blended in methanol and dried overnight in a vacuum oven at 40 ° C. The collected polymer was 34.4 g and the catalytic activity was 6.88 kg (EPDM) / mmol Ti / hr. Polymer FI was 1.7. Based on SEC measurements, Mw was 2.04 (× 10 5 ) and Mn was 0.96 (× 10 5 ). Therefore, PDI (Mw / Mn) was 2.1.
    Example 2 Polymerization with ACT Catalyst Using Hexane / Toluene = 5: 1 as Reaction Medium
    In a glove box under nitrogen, 0.0184 g of ACT catalyst was placed in an oven dried 10 ml volumetric flask. The bottle was sealed and taken out of the glove box. Toluene (10 ml, Aldrich, anhydrous, packaged under nitrogen) was placed in the flask to make a 0.005 M concentration solution.
    1L Stainless Steel Fluitron Nitrogen was constantly passed through the reactor at 100 ° C. for 1 hour. The reactor was cooled to 40 ° C. and 500 ml of hexane, 100 ml of toluene (Aldrich, anhydride, packed under nitrogen), 1 ml of 0.87 M TIBA, and 2 ml of ENB (purified) were added. The reactor was sealed and heated to 65 ° C. Ethylene (C 2 ) and propylene (C 3 ) gas (C 3 / C 2 fill ratio = 0.75 to 1) were charged until the reactor pressure was 90 psi. At this time, the ratio of gas was adjusted to C 3 / C 2 = 0.20.
    The polymerization was initiated by injecting toluene solution under pressure of 2.77 ml of Ti 5μmol or ACT 0.005M and 1.8M MAO (Al / Ti = 1000). The polymerization was carried out for 1 hour after ACT and MAO injection. At 10 and 30 minutes respectively, ENB (0.5 ml) was injected into the reactor under pressure. A total of 3 ml of ENB was added to the reactor. 2 ml of ethanol removal solvent (0.5 g of BHT in 125 ml of ethanol, 1.0 g of Kemamine 1.0 g, Irganox 0.5 g) was injected to terminate the polymerization. The C 2 and C 3 gases were stopped and the reactor was cooled to room temperature and vented.
    The polymer was removed, blended in methanol and dried overnight in a vacuum oven at 40 ° C. The collected polymer was 41.3 g and the catalytic activity was 8.26 kg (EPDM) / mmol Ti / hr. Polymer FI was 3.6. Based on SEC measurements, Mw was 1.97 (× 10 5 ) and Mn was 0.93 (× 10 5 ). Therefore, PDI (Mw / Mn) was 2.1.
    Example 3: Polymerization under ACT Catalyst Using Hexane / Toluene = 1: 1 as Reaction Medium
    The procedure of Example 2 was repeated except that 250 ml of hexane and 250 ml of toluene were added to the reactor instead of 500 ml of hexane and 100 ml of toluene as the polymerization medium. Therefore, the ratio of hexane / toluene is 1: 1. The amount of EPDM polymer collected after the polymerization was 51.3 g and the catalytic activity was 10.26 kg (EPDM) / mmol Ti / hr. Polymer FI was 2.04. Based on the SEC measurements, Mw was 2.06 (× 10 5 ) and Mn was 0.73 (× 10 5 ). Therefore, PDI (Mw / Mn) was 2.8.
    Example 4: Polymerization under ACT Catalyst Using Hexane / Toluene = 1: 5 as Reaction Medium
    The procedure of Example 2 was repeated except that 100 ml of hexane and 500 ml of toluene were added to the reactor instead of 500 ml of hexane and 100 ml of toluene as the polymerization medium. Therefore, the ratio of hexane / toluene is 1: 5. EPDM polymer collected after the polymerization was 38.6g, catalytic activity was 7.72kg (EPDM) / mmol Ti / hr. Polymer FI was 4.7. Based on SEC measurements, Mw was 1.89 (× 10 5 ) and Mn was 0.74 (× 10 5 ). Therefore, PDI (Mw / Mn) was 2.5.
    Example 5 Polymerization Under ACT Catalyst Using Toluene Only as Polymerization Medium
    The procedure of Example 2 was repeated except that 500 ml of toluene was added to the reactor instead of 500 ml of hexane and 100 ml of toluene as the polymerization medium. The EPDM polymer collected after the polymerization was 9.1 g and the catalytic activity was 1.82 kg (EPDM) / mmol Ti / hr. Polymer FI was 26.2. Based on SEC measurements, Mw was 0.94 (E + 05) and Mn was 0.54 (E.05). Therefore, PDI (Mw / Mn) was 1.7.
    Example 6 Polymerization Under ACT Catalyst Using Only m-Xylene as Polymerization Medium
    The procedure of Example 1 was repeated except that 500 ml of m-xylene was added to the reactor instead of 500 ml of hexane as the polymerization medium. The amount of EPDM polymer collected after the polymerization was 34.4 g and the catalytic activity was 6.88 kg (EPDM) / mmol Ti / hr. Polymer FI was 0.54 and calculated Mooney was 98.
    Example 7 Polymerization Under ACT Catalyst Using Only Cyclohexane as Polymerization Medium
    The procedure of Example 1 was repeated except that 500 ml of cyclohexane was added to the reactor instead of 500 ml of hexane as the polymerization medium. The amount of EPDM polymer collected after the polymerization was 38.8 g and the catalytic activity was 7.77 kg (EPDM) / mmol Ti / hr. Polymer FI was 2.5 and calculated Mooney was 58.
    Example 8 Polymerization Under ACT Catalyst Using Hexane / m-Xylene = 1: 1 as Reaction Medium
    The procedure of Example 1 was repeated except that 250 ml of hexane was used as the polymerization medium and hexane / m-xylene solvent mixture in which ACT catalyst was dissolved in 250 ml of m-xylene was added to the reactor. The amount of EPDM polymer collected after the polymerization was 39.4 g and the catalytic activity was 7.88 kg (EPDM) / mmol Ti / hr. Polymer FI was 0.71 and calculated Mooney was 89.
    Example 9 Polymerization under ACT Catalyst Using Hexane / o-Xylene = 1: 1 as Reaction Medium
    The procedure of Example 8 was repeated except that 250 ml of hexane as the polymerization medium and hexane / m-xylene solvent mixture in which ACT catalyst was dissolved in 250 ml of o-xylene were added to the reactor. The amount of EPDM polymer collected after the polymerization was 45.9 g and the catalytic activity was 9.18 kg (EPDM) / mmol Ti / hr. Polymer FI was 1.4 and calculated Mooney was 71.
    Polymerization conditions and polymer properties from Examples 1 to 9 are summarized in Table 1.
    Example 10 EPDM Polymerization in Cp * Ti (BzO) 3 / MeOH / DTBP / MMAO Catalyst System Using Hexane to Dissolve Catalyst Precursor
    In a glove box under nitrogen, 0.027 g of Cp * Ti (BzO) 3 was placed in a jar equipped with a magnetic stirring bar. The bottle was sealed, taken out of the glove box and 5 ml hexane (nitrogen sprayed) was added via syringe to make a 0.01 (M) Cp * Ti (BzO) 3 precursor solution. Then 1.6 ml of 0.123 (M) MeOH / hexane solution (4eq. Methanol for Ti) was added to the solution, and the whole solution was stirred at room temperature for 1 hour 30 minutes.
    The 100 ml glass jar containing the stir bar was closed with a rubber membrane and nitrogen was sparged for a while. Hexane (60 ml) was added to the bottle. In the bottle, 0.65 ml of a catalyst precursor premixed in methanol, 0.8 ml of 1.74 (M) MMAO, 1 ml of 0.5 (M) 2,6-di-t-butylphenol (DTBP), and 2 ml of ENB were mixed with stirring. The active catalysts in the bottles were DTBP / Ti = 100, MeOH / Ti = 4, MMAO / Ti = 200. ENB was used as a trimer in EPDM polymerization.
    1L stainless steel (Fluitron ) The reactor was sparged with nitrogen constantly for at least 1 hour and cooled to 40 ° C. 500 ml of hexane was added to the reactor. The catalyst solution prepared in the bottle was delivered to the reactor under nitrogen pressurization. The reactor was sealed and warmed to 60 ° C. The reactor is ethylene (C2) And propylene (C3) Gas was charged 1: 1. When reactor pressure reaches 90 psi, C3And C2The ratio of was adjusted to 1: 3. The polymerization was carried out for 1 hour. During the polymerization, 0.5 ml of ENB was injected into the reactor under pressure at 10 and 20 minute intervals. 3 ml of ENB was added to the polymerization.
    After the completion juhap was injected inhibitor (in ethanol 125ml BHT 0.5g, Kemamine 1.0g, Irganox 0.5g) 2ml. The C 2 and C 3 gases were stopped and the reactor was cooled to room temperature and vented. The polymer was removed from the reactor, blended in methanol and dried overnight in a vacuum oven at 40 ° C. The collected polymer was 29 g and the catalytic activity was 6.0 kg (EPDM) / mmol Ti / hr. The polymer had a flow rate of 0.44 and a calculated Mooney 105.
    Example 11 EPDM Polymerization in a Cp * Ti (BzO) 3 / MeOH / DTBP / MMAO Catalyst System Using Toluene to Dissolve the Catalyst Precursor
    An experiment similar to Example 10 is run except that toluene is used instead of hexane to mix with methanol in the toluene solution and dissolve the Cp * Ti (BzO) 3 precursor. The polymer collected after the polymerization was 22.3 g, and the catalytic activity was 4.46 kg (EPDM) / mmol Ti / hr. The FI of the polymer was 1.1 and the calculated Mooney was 77.
    It can be seen that the molecular weight of EPDM rubber is increased when hexane is used when the other conditions are the same in Example 10 and Example 11.
    Examples 12-15 Preparation of EPDM by Gas Phase Polymerization in Stirred Bed Reactors
    The reactor used is a dual phase (gas / solid) stirred bed, backmix reactor. Four sets of plows are horizontally coupled to a central column that rotates at 200 rpm to mechanically fluidize the reactor particles. The cylinders swept by these flows had a diameter of 39.7 cm (15.6 in) and a length of 40.6 cm (16 in), so the mechanical fluidized volume was 45 liters (1.65 ft 3 ). The gas volume was larger than the mechanical fluidization volume, totaling 62.6 liters (2.21 ft 3 ), due to the presence of other incidental devices along with the vertical cylindrical chamber in the reaction system.
    Reactor pressure was 350 psi. Ethylene, propylene, and diene monomers were continuously injected into the reactor through control valves. The ethylene partial pressure was 240 to 320 psia and the propylene partial pressure was 35 to 90 psia. Gas composition was analyzed by gas chromatography. Freed through the small outlet of the reactor, the composition of the gas and nitrogen entering the catalyst were in equilibrium. Outlet holes were adjusted through a computer to maintain a constant overall pressure in the reactor. The diene (ENB) dosage varied from 30 to 50 cc / lb of the resulting polymer.
    The reactor was cooled by an outer jacket of glycol. Bed temperature was measured with an RTD thermometer in a thermowell protruding into the bed between the inner set of flows. The reactor temperature was adjusted to a value in the range of 20-80 ° C. for EPDM production.
    The solution catalyst was added continuously during one operation with ethylene, propylene and diene monomers. The solution catalyst was delivered by nitrogen through the solution catalyst input. Alkyl cocatalysts were also added continuously at a constant molarity relative to the catalyst injection rate. As in the fluidized bed reactor, the cocatalyst injection rate was fixed, so that the catalytic activity was not degraded. The single yield of granular polymer was 4-10 pounds (lbs). It took 2 to 10 hours per batch. A glidant (carbon black N-650) was used in an amount of 10 to 20% by weight to prevent sticking.
    The work was initiated by passivating the carbon black with the alkyl (cocatalyst) used in the work and placing the required amount of carbon black into the reactor. The monomer was injected into the reactor and the injection amount (nitrogen and monomer) was adjusted until the desired gas composition was reached. After the catalyst injection began, the monomers were added sufficiently to the reactor to maintain the gas composition. As the catalyst piled up the polymer production rate increased from 3 to 10 lbs / hr, at which point catalyst injection was reduced to maintain a constant polymer production rate. The alkyl rate was maintained in proportion to the catalyst injection rate. After the desired amount of work was completed, the monomers were washed off, the catalyst was deactivated by isopropanol, and the polymer was stabilized to the appropriate amount of stabilizer consisting of BHT / ZnO. The remaining diene was washed off with nitrogen for several hours until only a small amount remained in the polymer. The work vessel was emptied into a bag and left open in air.
    Example 12
    Dry carbon black (2.1 lb) was placed in a stirred bed reactor and deactivated with MMAO 0.19 mM / g. Ethylene, propylene, and hydrogen were added so as to have a C 2 pressure of 240 psia, an ethylene / propylene mixing ratio of 0.2, and 0.1 mol% of hydrogen. The ACT catalyst in toluene was contacted with 10% MMAO in the isopentane stream at 1 mM / l concentration and then passed through the reactor. When the polymerization rate was constant, the level was maintained by constant injection of ethylene, propylene and ENB. Cocatalyst and catalyst were injected at a ratio of 460: 1 of Al / Ti. After 10 hours, isopropanol was added to terminate the reaction. Stabilizer was added. The unreacted monomer was washed with nitrogen and the work vessel was emptied. The daily work load was 6 lbs.
    The polymer composition was 36% propylene, 5.4% ENB, and 58.6% ethylene. Ti residue in the polymer was 10.6 ppm. The molecular weight of the polymer by SEC was as follows: Mw = 152,000; Mn = 39,000. The gum Mooney of the product was 50 ml.
    Example 13
    Dry carbon black (2.1 lb) was placed in a stirred bed reactor and deactivated with MMAO 0.19 mM / g. Ethylene, propylene, and hydrogen were used so as to have a C 2 pressure of 240 psia, an ethylene / propylene mixing ratio of 0.2, and 0.1 mol% of hydrogen. Reactor temperature was maintained at 60 ° C. The ACT catalyst in hexane was contacted with 10% MMAO in the isopentane stream at a concentration of 1 mM / l for about 10 minutes and then passed through the reactor. When the polymerization rate was constant, the level was maintained by constant injection of ethylene, propylene and ENB. The cocatalyst and the catalyst were injected in an Al / Ti ratio of 430: 1. After 9.5 hours, isopropanol was added to terminate the reaction. Stabilizer was added. The unreacted monomer was washed with nitrogen and the work vessel was emptied. The daily work volume was 11.3 lbs.
    The polymer composition was 36% propylene, 6.9% ENB, and 57.1% ethylene. Ti residue in the polymer was 6.0 ppm. The molecular weight of the polymer by SEC was as follows: Mw = 212,000; Mn = 56,000. The gum Mooney of the product was 67 ml.
    It can be seen that the molecular weight of EPDM rubber is increased when hexane is used when the other conditions are almost the same in Example 12 and Example 13.
    Example 14
    Dry carbon black (2.1 lb) was placed in a stirred bed reactor and deactivated with MMAO 0.19 mM / g. Ethylene and propylene were used to have a C 2 pressure of 320 psia and an ethylene / propylene mix ratio of 0.2. Reactor temperature was maintained at 60 ° C. The ACT catalyst in toluene was contacted with 10% MMAO in the isopentane stream at a concentration of 7 mM / l for about 10 minutes and then passed through the reactor. When the polymerization rate was constant, the level was maintained by constant injection of ethylene, propylene and ENB. The cocatalyst and catalyst were injected at an Al / Ti ratio of 850: 1. After 8.5 hours, isopropanol was added to terminate the reaction. Stabilizer was added. The unreacted monomer was washed with nitrogen and the work vessel was emptied. The amount of work was 13 lbs.
    The polymer composition was 37.2% propylene, 3.7% ENB, and 59.1% ethylene. Ti residue in the polymer was 4 ppm. The molecular weight of the polymer by SEC was as follows: Mw = 159,000; Mn = 38,000. The gum Mooney of the product was 70 ml.
    Example 15
    Dry carbon black (2.1 lb) was placed in a stirred bed reactor and deactivated with MMAO 0.19 mM / g. Ethylene and propylene were used to have a C 2 pressure of 320 psia and an ethylene / propylene mix ratio of 0.2. Reactor temperature was maintained at 60 ° C. The ACT catalyst in hexane was contacted with 10% MMAO in the isopentane stream at a concentration of 1 mM / l for about 10 minutes and then passed through the reactor. When the polymerization rate was constant, the level was maintained by constant injection of ethylene, propylene and ENB. The cocatalyst and the catalyst were injected at an Al / Ti ratio of 820: 1. After 6.5 hours, the reaction was terminated by adding isopropanol. Stabilizer was added. The unreacted monomer was washed with nitrogen and the work vessel was emptied. The amount of work was 10.3 lbs.
    The polymer composition was 35% propylene, 7.8% ENB, and 57.2% ethylene. Ti residue in the polymer was 3.8 ppm. The molecular weight of the polymer by SEC was as follows: Mw = 257,000; Mn = 67,000. The gum Mooney of the product was 112 ml.
    It can be seen that the molecular weight of EPDM rubber is increased when hexane is used when the other conditions are almost the same in Example 14 and Example 15.
    The present invention is to provide a method for controlling the molecular weight, molecular weight distribution, or both of the polymer produced using a single site catalyst by using a variety of physical property modifiers depending on the type of polymerization and the type of catalyst used, (B) Adjust the molecular weight, molecular weight distribution, or both in the polymerization process itself to produce polymer products with the Mooney viscosity properties required by the process designer, and adjust the mixing ratios of the physical property modifier combinations of aliphatic hydrocarbons and aromatic hydrocarbons. Adjustments have the effect of providing polymers with all ranges of MW and MWD.
    Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
    权利要求:
    Claims (14)
    [1" claim-type="Currently amended] In a polymerization process using a single site catalyst, by introducing a physical property modifier selected from the group consisting of aliphatic hydrocarbons, aliphatic ring hydrocarbons, aromatic hydrocarbons, and mixtures thereof, the molecular weight, molecular weight distribution, or both of the polymers produced. Adjusting method characterized in that to adjust.
    [2" claim-type="Currently amended] The method of claim 1 wherein the solubility parameter of the aliphatic hydrocarbon is 7.5 (cal / cm 3 ) 1/2 or less, the solubility parameter of the aliphatic ring hydrocarbon is 7.7 (cal / cm 3 ) 1/2 or more, and the aromatic hydrocarbon Solubility parameter is a control method, characterized in that more than 7.7 (cal / cm 3 ) 1/2 .
    [3" claim-type="Currently amended] The method of claim 2, wherein the aliphatic hydrocarbon and the aliphatic ring hydrocarbon are each composed of 4 to 12 carbon atoms, and the aromatic hydrocarbon is 6 to 20 carbon atoms.
    [4" claim-type="Currently amended] The method of claim 3, wherein the physical property modifier is selected from the group consisting of butane, pentane, isopentane, hexane, heptane, decane, cyclopentane, cyclohexane, benzene, azobenzene, toluene, xylene, and mixtures thereof. How to adjust.
    [5" claim-type="Currently amended] 3. The method according to claim 2, wherein the physical property modifier is an aliphatic hydrocarbon or aliphatic ring hydrocarbon (i) and aromatic hydrocarbon (ii) in a ratio of 90:10 to 10:90.
    [6" claim-type="Currently amended] 6. The method of claim 5, wherein the physical property modifier is a combination of aliphatic and aromatic hydrocarbons selected from the combination of hexane-toluene, isopentane-toluene, heptane-toluene, hexane-xylene, isopentane-xylene, and heptane-xylene. Adjusting method characterized in that.
    [7" claim-type="Currently amended] 3. The process according to claim 2, wherein the polymerization process used is a gas fluidized bed process.
    [8" claim-type="Currently amended] 8. The process of claim 7, wherein the polymerization process comprises (a) ethylene, or propylene homopolymers; (b) copolymers of ethylene with one or more alpha olefins having 3 to 20 carbon atoms; (c) a copolymer of propylene with one or more alpha olefins having 4 to 20 carbon atoms; (d) terpolymers of ethylene, propylene, and dienes; (e) polymers of aromatic compounds having vinyl unsaturated groups; And (f) a polar vinyl monomer selected from the group consisting of styrene, substituted styrene, acrylonitrile, maleic acid ester, vinyl acetate, acrylate ester, methacrylate ester, vinyl trialkyl silane, and mixtures thereof. A control method characterized by producing a polymer of choice.
    [9" claim-type="Currently amended] The method according to claim 1, wherein the polymerization reaction is carried out in the presence of 0.3 to 80% by weight of the inert particulate material.
    [10" claim-type="Currently amended] 10. The method of claim 9, wherein said inert particulate material is selected from the group consisting of carbon assays, activated carbon, silica, clay, talc, and mixtures thereof.
    [11" claim-type="Currently amended] The method of claim 1, wherein the single site catalyst is (C 5 Me 4 ) Me 2 Si (Nt-Bu) TiCl 2 .
    [12" claim-type="Currently amended] The process of claim 1 wherein the polymerization process is performed using a liquid single site catalyst having a catalyst precursor compound dispersed or dissolved in one or more physical property modifiers.
    [13" claim-type="Currently amended] The method of claim 1 wherein the physical property modifier is added to at least one polymerization reaction.
    [14" claim-type="Currently amended] The method of claim 1, wherein the polymerization step,
    a. Dissolving the catalyst precursor compound in one or more physical property modifiers to make a solution;
    b. Adding a support material to the solution to make a slurry; And
    c. Drying the slurry to make a catalyst;
    A control method characterized in that it is carried out using a supported single site catalyst prepared by the process.
    类似技术:
    公开号 | 公开日 | 专利标题
    USRE40751E1|2009-06-16|Polymerization catalyst systems comprising substituted hafnocenes
    JP3429026B2|2003-07-22|Preparation of catalyst systems, homo- and copolymerization of olefins and polymers and copolymers of at least one olefin
    US6489413B1|2002-12-03|Olefin polymerization process with alkyl-substituted metallocenes
    US5693727A|1997-12-02|Method for feeding a liquid catalyst to a fluidized bed polymerization reactor
    Kaminsky2001|Olefin polymerization catalyzed by metallocenes
    ES2331341T3|2009-12-29|Gaseous phase polymerization process.
    AU2002320636B8|2005-09-15|Mixed metallocene catalyst systems containing a poor comonomer incorporator and a good comonomer incorporator
    KR100284211B1|2001-03-02|Polyolefin wax and process for its preparation
    US5096867A|1992-03-17|Monocyclopentadienyl transition metal olefin polymerization catalysts
    AU763151B2|2003-07-17|A polymerization process for producing easier processing polymers
    US5324800A|1994-06-28|Process and catalyst for polyolefin density and molecular weight control
    JP4298794B2|2009-07-22|Highly active metallocene polymerization method
    US5084534A|1992-01-28|High pressure, high temperature polymerization of ethylene
    CA2277057C|2005-01-04|Catalyst composition for the production of olefin polymers
    AU718884B2|2000-04-20|Mixed transition metal catalyst systems for olefin polymerization
    KR0137960B1|1998-05-01|Method for preparing polyethylene wax by gas phase polymerization
    AU697056B2|1998-09-24|Production of polyolefins containing long chain branches by a gas phase process
    EP0868445B1|2002-02-27|High temperature olefin polymerization process
    JP5603595B2|2014-10-08|Ethylene / α-olefin / diene solution polymerization method and polymer
    RU2142953C1|1999-12-20|Transition metal complexes, catalyst system comprising thereof, method of preparing polyolefins, and polyolefinic composition
    EP0643078B1|2003-01-22|Process for the preparation of ethylene polymers and products obtained therefrom
    AU689178B2|1998-03-26|Spray dried metallocene catalyst composition for use in polyolefin manufacture
    JP3760130B2|2006-03-29|Process for the production of supported catalyst systems and their use in polymerization processes
    US5317036A|1994-05-31|Gas phase polymerization reactions utilizing soluble unsupported catalysts
    AU743509B2|2002-01-24|Mixed catalysts and their use in a polymerization process
    同族专利:
    公开号 | 公开日
    EP1054025A1|2000-11-22|
    JP2000327702A|2000-11-28|
    CN1277211A|2000-12-20|
    BR0002755A|2001-01-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-05-19|Priority to US31519499A
    1999-05-19|Priority to US9/315,194
    2000-05-17|Application filed by 조셉 에스. 바이크, 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크날러지 코포레이션
    2000-12-26|Publication of KR20000077306A
    优先权:
    申请号 | 申请日 | 专利标题
    US31519499A| true| 1999-05-19|1999-05-19|
    US9/315,194|1999-05-19|
    [返回顶部]