EP0880549A2 - Systeme catalyseur et composants - Google Patents

Systeme catalyseur et composants

Info

Publication number
EP0880549A2
EP0880549A2 EP97905946A EP97905946A EP0880549A2 EP 0880549 A2 EP0880549 A2 EP 0880549A2 EP 97905946 A EP97905946 A EP 97905946A EP 97905946 A EP97905946 A EP 97905946A EP 0880549 A2 EP0880549 A2 EP 0880549A2
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
naphthyl
catalyst
polynuclear
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97905946A
Other languages
German (de)
English (en)
Inventor
Gary F. Licciardi
Lawrence C. Debolt
Donna Jean Crowther
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0880549A2 publication Critical patent/EP0880549A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • this invention relates to organosilane modifiers for catalyst systems and processes to make such modifiers.
  • this invention relates to catalyst systems and processes for polymerization of olefins using organosilane modifiers external to supported catalyst components.
  • this invention relates to bulky organosilane modifiers which are useful to produce polypropylene having both high crystallinity and broad molecular weight distribution.
  • Olefin polymerization catalyst systems comprising (i) a catalyst component of titanium, magnesium, and an "internal modifier" or “first electron donor”; (ii) a cocatalyst or “activator” such as an alkyl aluminum compound; and (iii) an "external modifier” or “second electron donor” are very well known in the art.
  • a catalyst component of titanium, magnesium, and an "internal modifier” or “first electron donor” such as an alkyl aluminum compound
  • a cocatalyst or “activator” such as an alkyl aluminum compound
  • an "external modifier” or “second electron donor” are very well known in the art.
  • a variety of diesters, esters, amines, and silanes have been used as external modifiers, and in particular, certain alkoxysilanes have been used as external electron donors, including specific aromatic and aliphatic alkoxysilanes.
  • organosilanes used as external donors such as diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxy-silane, and dicyclopentyldimethoxysilane, enable production of polypropylene with increased crystallinity, such donors unfortunately also produce polymer with narrow molecular weight distributions (“MWD”) and narrow ranges of melt flow rate (“MFR").
  • MFD molecular weight distributions
  • MFR melt flow rate
  • Patent 5,218,052 discusses polymer data derived from use of diisopropyldimethoxysilane, diisobutyldimethoxysilane and di-t- butyldimethoxysilane as external donors in a two step polymerization process seeking to make a reactor blend of high and low molecular weight polymers.
  • the reactor blend is to have a synthetic broad molecular weight distribution but such blended polymer has low melting points and low melt flow rates.
  • Patent 5,218,052 treats silane donors generically and cites as donors, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxy-silane, t-butyldimethoxysilane, diisopentyldimethoxysilane, di-t-pentyldimethoxy-silane, dineopentyldimethoxysilane, neopentyldimethoxysilane, isobutylisopropyl- dimethoxysilane, isobutyl-t-butyldimethoxysilane, isopropyl-t-butyldimethoxy- silane and di-p-tolyldimethoxysilane.
  • U.S. Patent 5,218,052 fails to recognize the advantage of certain classes or types of silane donors in making highly crystalline polypropylene in a single step process.
  • silane donors having a bulky structure preferably those comprising a polynuclear group of nine or more carbons, enhance the performance of olefin polymerization catalyst systems.
  • silane donors with bulky substituents produce polymers with improved desirable polymer properties while other bulky silane donors do not.
  • bulky indenyl, fluorenyl and Co. and C]o and higher polynuclear aromatic radicals are effective as Si donor constituent groups when the remaining Si donor constituents have only one or two carbons, such as methyl or ethyl radicals.
  • the silane donors of this invention are thus a unique class of silane donors, being very bulky at a portion of the zone around the Si atom and having essentially very small bulk at the remaining portion of the zone around the Si atom.
  • donors of this invention produce polypropylenes which have high crystallinity and which exhibit unique molecular weight distribution and melt flow rate characteristics. While prior art donors that produce high crystallinity polymer unfortunately produce polymer with narrow molecular weight distributions and narrow MFR ranges, we have produced novel silane donors that give high crystallinity polypropylene as well as broad molecular weight distribution with wide melt flow rate ranges. These donors of our invention also produce polypropylene with excellent flex modulus.
  • R ⁇ and R2 are the same or different and are selected from the group consisting of alkyl radicals, cycloalkyi radicals, and polynuclear radicals, said polynuclear radicals having nine or more carbon atoms, wherein at least one of Rj or R2 is a polynuclear radical of nine or more carbon atoms, with the proviso that where either R] or R2 is indenyl or fluorenyl, the other of Rj or R2 is a substituted or unsubstituted bridged cyclic aliphatic radical or is a polynuclear aromatic radical of ten or more carbon atoms, and wherein Ry and Rz are the same or different and each Ry and Rz are selected from alkyl radicals having one or two carbon atoms
  • silane compounds of Structure I wherein Ri is a polynuclear aromatic radical having ten or more carbon atoms, and wherein R2, Ry and Rz are the same or different and each R2, Ry and Rz are selected from alkyl radicals having one or two carbon atoms.
  • silane compounds having the following Structure II:
  • Rj is a polynuclear aromatic radical having ten or more carbon atoms, and wherein Rx, Ry and Rz are the same or different and each
  • Rx, Ry and Rz are selected from alkyl radicals having one or two carbon atoms.
  • polynuclear radical means fused ring hydrocarbons sharing at least one pair of carbon atoms.
  • polynuclear radical may also include “indenyl” radicals means C9H7" radical from indene, and other radicals having indenyl structures such as "fluorenyl” C13H9” radical derived from fluorene and fluoranthenyl C19H13" radical derived from fluoranthene.
  • indenyl containing structures include all of the various indenyl isomers.
  • alkyl means branched and straight chain hydrocarbon radicals, having from one up to 20 carbon atoms, which may be substituted or unsubstituted with one or more radicals containing other than hydrogen and carbon such as those selected from halo, amino, nitro, and other radicals.
  • cycloalkyi as used herein means an alicyclic hydrocarbon radical having from seven up to 20 carbon atoms, which may be substituted or unsubstituted with one or more radicals containing other than hydrogen and carbon such as those selected from halo, amino, nitro, and other radicals.
  • preferred polynuclear radicals include but are not limited to indenyl, fluorenyl, fluoranthenyl and preferred polynuclear aromatic radicals include, but are not limited to, naphthyl; naphthylenyl, naphthylidenyl, naphthindenyl, alkyl- and dialkyl- naphthyls such as methylnaphthyl, dimethylnaphthyl, ethylnaphthyl , and propylnaphthyl; phenylnaphthyl; anthracyl, phenanthryl; l-methyl-7-isopropylphenanthyl; halonaphthyls such as bromo- and chloro- naphthyls; nitronaphthyls, and amine substituted naph
  • naphthalene alkylnaphthalenes such as 1-methylnaphthalene, 2-methylnaphthalene, ethyl naphthalene, and propylnaphthalene; phenylnaphthalene; anthracene; phenanthrene; l-methyl-7-isopropylphenanthalene; halonaphthalenes such as 1- bromonaphthalene, 2-bromonaphthalene, 1 -chloronaphthalene, and 2- chloronaphthalene as well as fluoranthene; nitronaphthyls such as 1- nitronaphthalene, 2-nitronaphthalene, and amine substituted naphthylenes such as 1-naphthylamine and 2-naphthylamine.
  • Ri or R2 has ten carbon atoms
  • R ⁇ and R2 are different and one of R] or R2 is polynuclear radical of nine or more carbons and the other of R ⁇ and R2 has 7 or more carbons and is selected from the group consisting of, saturated and unsaturated and substituted and unsubstituted, straight chain aliphatics, branched aliphatics, and unbridged and bridged cyclic aliphatics.
  • K ⁇ and R2 are different and one ofRi or R2 is selected from indenyl, fluorenyl, or a polynuclear aromatic of ten or more carbons and the other of Rj and R2 is a substituted or unsubstituted bridged cyclic aliphatic group.
  • Preferred bridged cyclic aliphatic groups include without limitation norbornyl and alkyl substituted norbornyls such as methylnorbornyl, ethylnorbornyl, and propylnorbornyl.
  • Preferred norbornylindenyldimethoxysilane compounds include those having a structure of
  • organosilane dinaphthyldimethoxysilane compounds of the formula (CioHy)2Si(OCH3)2 Preferred dinaphthyldimethoxysilane compounds include those having a structure of
  • a method to prepare norbornylindenyldimethoxysilane comprising (a) reacting indene with methyllithium in a diluent to form indenyllithium, (b) reacting indenyllithium with norbornyltrichlorosilane in a solvent to form LiCl and norbornylindenyldichlorosilane, (c) separating said LiCl from said norbornylin- denyldichlorosilane, (d) reacting norbornylindenyldichlorosilane with methyl alcohol and pyridine in presence of a first solvent; (e) separating a HCl'pyridine complex from norbornyl-indenyldimethoxysilane, and (f) recovering said norbornyl-indenyldimethoxysilane
  • the above method can be used to make various isomers of said norbornylindenyldimethoxysilane.
  • a method to prepare bis-(naphthyl)dimethoxysilane comprising (a) reacting bromonaphthalene with magnesium to form a magnesium salt CioH7MgBr « (CH3CH2)2O)x, where x > 0; (b) reacting said salt with SiCl4 in the presence of a first solvent at an elevated temperature to form a heated solution containing bis-(naphthyl)silicondichloride; (c) cooling said heated solution to crystallize at least a portion of said bis-(naphthyl)silicondichloride; (d) removing said first solvent; (e) reacting bis-(naphthyl)silicondichloride with pyridine and methanol in the presence of a second solvent to form bis-(naphthyl) dimethoxysilane; and (f) recovering said bis- (naphthyl)dimethoxys
  • an olefin polymerization catalyst system comprising (a) a catalyst component comprising titanium, magnesium, and a first electron donor; (b) an organometallic cocatalyst; and, (c) one or more organosilanes having Structure I or having Structure II.
  • organosilanes include 1 -naphthyl trimethoxysilane, 1 -naphthyltriethoxysilane, and indenyltriethoxysilane.
  • the organosilane is bis-(l -naphthyl) dimethoxysilane or is norbomylindenyldimethoxysilane.
  • the catalyst system further comprises hydrogen as a chain transfer agent.
  • a process for polymerizing one or more alpha-olefins comprises contacting, at polymerization conditions, one or more alpha-olefins with a catalyst system comprising (a) a catalyst component comprising titanium, magnesium, and a first electron donor; (b) an organometallic cocatalyst; and, (c) one or more organosilanes having Structure I or having Structure ⁇ .
  • a catalyst system comprising (a) a catalyst component comprising titanium, magnesium, and a first electron donor; (b) an organometallic cocatalyst; and, (c) one or more organosilanes having Structure I or having Structure ⁇ .
  • Preferred alpha-olefins in the various embodiments of this invention are C3 to CIO alpha-olefins such as propylene, butene- 1, pentene-1, 4-methyl-l-pentene, hexene, octene, and decene.
  • a process for polymerizing ethylene and one or more alpha-olefins comprising contacting, at polymerization conditions, ethylene and one or more alpha-olefins with a catalyst system comprising (a) a catalyst component comprising titanium, magnesium, and a first electron donor; (b) an organometallic cocatalyst; and, (c) one or more organosilanes having Structure I or having Structure II.
  • a process for polymerizing ethylene comprising contacting, at polymerization conditions, ethylene with a catalyst system comprising (a) a catalyst component comprising titanium, magnesium, and a first electron donor; (b) an organometallic cocatalyst; and, (c) one or more organosilanes having Structure I or having Structure II.
  • the polymerization is conducted in the presence of hydrogen.
  • the polymerization is conducted in the presence of a hydrogenation catalyst.
  • the hydrogenation catalyst is used in a manner such that the hydrogenation catalyst removes hydrogen or consumes hydrogen.
  • Preferred hydrogenation agents are metallocenes where the metal is selected from the group consisting of titanium, zirconium and hafnium.
  • Preferred metallocenes include alkyl organocyclic metal halides, where the organocyclic has two or more conjugated double bonds.
  • a preferred titanocene is bis(n-butylcyclopentadiene) titanium dichloride.
  • MWD molecular weight distribution
  • the MWD can preferably be from 6 to 7, and still more preferably can be from 8 to 9.
  • a true homopolymer of propylene having a crystallinity melt temperature exceeding 164°C, a percent crystallinity exceeding 55%, and a molecular weight distribution of from 5 to 10 is provided.
  • the term "true homopolymer” means a polymer prepared at polymerization conditions of uniform or substantially constant polymerization temperature, catalyst concentration, hydrogen concentration, and propylene (excess) concentration.
  • substantially constant is meant within normal process operating variability for target operating conditions, which by way of example and not limitation may be 5°C ⁇ or more for polymerization temperature and 100 kPa ⁇ or more for hydrogen pressure.
  • One of the most preferred polymerization processes of this invention is a "single stage" process wherein the term "single stage” means one or more reactors operating at balanced conditions or operating at substantially similar conditions which are maintained substantially constant, except preferably for differing hydrogen concentrations or preferably differing concentrations of hydrogenation catalyst.
  • Balanced conditions and balanced reactors differ from unbalanced conditions and unbalanced reactors, at least in part, in that unbalanced reactors have two reactors or reactor stages operating at substantially differing hydrogen concentration or other conditions and producing differing polymers.
  • the catalyst modifiers of this invention are useful with olefin polymerization catalyst systems for polymerization of ethylene or alpha-olefins as well as polymerization of mixtures of one or more alpha-olefins with ethylene.
  • the modifiers are particularly effective with conventional olefin polymerization catalyst systems for polymerization of propylene or mixtures propylene and ethylene.
  • Conventional olefin polymerization catalyst systems typically comprise (a) a catalyst component of titanium, magnesium and a first, internal electron donor, (b) a cocatalyst component or "activator", usually a Group II or III metal alkyl such as an alkyl aluminum and (c) a second, external electron donor.
  • a catalyst component is a solid component, having a titanium constituent supported on a compound of magnesium and combined with a first electron donor compound.
  • Catalyst components generally comprise from 1 to 10 wt% titanium, from 5 to 35 wt% magnesium, and from 40 to 70 wt% halogen based on 100 wt% of titanium, magnesium and halogen, with internal electron donor being present in the range from 0.03 to 0.6 grams internal modifier per gram of magnesium compound.
  • Various methods to produce such catalyst components are well known.
  • Such catalyst components are typically prepared, in an inert atmosphere, by reacting a titanium halide with a compound of magnesium in the presence of the first electron donor.
  • Titanium compounds useful in preparing such catalyst component may be one or more of titanium halides and haloalcoholates.
  • examples of such compounds include titanium tetrahalides, preferably as TiCLj and TiBr. ⁇ , and Ti(OCH3)Cl3, - 12 -
  • Magnesium compounds useful in preparing such catalyst component may be one or more of a magnesium alcoholate; a magnesium alkyl; a magnesium halide; or a reaction product of a magnesium halide with an alcohol or an organic acid ester or with an organometallic compound of metals of Groups I-III.
  • Electron donors useful as internal donors in preparing such catalyst component may be one or more organic compounds containing one or more of oxygen, nitrogen, sulfur, and phosphorus. Such compounds include organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines and other compounds.
  • the Ci -Cg alkyl benzoates, C] and C2 halobenzoates, and dialkyl phthalates are well known internal donors.
  • the catalyst component is typically "washed” with an inert liquid and “washed” again with one or more Lewis acids such TiCl4, SiC.4, SnCl4, BCI3, AlBr3, or others.
  • a common commercial catalyst component comprises TiCl4 supported onto a MgCl2 surface with a diester as internal donor being co-milled or otherwise combined with the TiCl4 and MgCl2 in the steps of producing the supported titanium.
  • the amount of catalyst component to be employed varies depending on choice of polymerization technique, reactor size, monomer to be polymerized, and other factors known to persons of skill in the art, and can be determined on the basis of the examples appearing hereinafter.
  • catalyst components are used in an amount from 2 to 3 x 10" 5 grams of catalyst to gram of polymer produced; however, catalyst usage varies with activity of the catalyst.
  • cocatalysts or "activators" are also well known and this invention is not limited to specific cocatalysts.
  • Commonly used cocatalysts include Group II and IIIA metal alkyls such as A1(CH 3 ) 3 , A1(C 2 H 5 ) 3 , A1(C 3 H 7 ) 3 , A1(C 4 H 9 )3, Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 2 H5)(C4H9), Mg(C 4 H 9 ) 2 , Zn(CH 3 ) 2 , Zn(C H5)2, and Zn(C4H9)2 and others.
  • cocatalyts also include metal alkyls having one or more halogen or hydride groups, and mixtures thereof, such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride and others.
  • cocatalyst is employed in an amount so that the atomic ratio of cocatalyst component metal atoms to catalyst metal is in the range of 1 to 100.
  • a preferred ratio of Al metal atoms to Ti metal atoms is in the range of 5 to 50.
  • Triethylaluminum is a prefered activator.
  • the catalyst component may be combined with the cocatalyst and external donor in one step in the polymerization reactor.
  • the catalyst component, the cocatalyst and external donor may be contacted in a first prepolymerization step with an olefin, preferably in the presence of an inert compound as inactive diluent, to form a polymer coated catalyst particle which is then fed to the polymerization reactor.
  • the catalyst system of this invention may include, in addition to one or more donors of this invention, one or more additional other external silane donors such as dinorbornyldimethoxysilane; tetramethoxysilane; dicyclopentyl- dimethoxysilane; methylcyclohexyldimethoxysilane; diphenyldimethoxysilane; tetraethoxysilane; and cyclopentyl-t-butoxydimethoxysilane and such other donors as organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines and other compounds.
  • the silane compound donor is preferably added so that the molar ratio of cocatalyst metal to silane is 1 to 50.
  • Preferred catalyst systems of this invention have external silane donors of this invention present in an amount ranging from 0.05 to 1.0 moles of silane donor per moles of cocatalyst metal.
  • One preferred catalyst system of this invention will include the above described catalyst components in the following amounts, each amount is based on one gram of magnesium halide: (i) from 0.08 to 0.12 grams titanium tetrahalide, (ii) from 0.06 to 0.24 grams internal modifier, (iii) from 2 to 75 grams cocatalyst activator aluminum, (iv) from 0 14 to 28 grams external modifier and (v) one gram of magnesium halide
  • NIMS 2-norbornyl-l-indenyldimethoxysilane
  • Indenyllithium was prepared by reacting indene with one equivalent of methyllithium in diethylether Solid indenyllithium (0 034 mol) was placed in 50 ml of diethylether and was then added to a cold ether solution of 2-norbornyltrichlorosilane (0 034 mol) dropwise over approximately one hour The reaction was allowed to proceed overnight LiCl was then removed by vacuum filtration 2-norbornyl-l-(indenyl)dichlorosilane was purified via vacuum distillation (1 10-115°C @ 10 torr) Purification analysis by HNMR yielded 2- norbornyl-l-(indenyl)dichlorosilane, at 69 6% yield 2-norbornyl-l-
  • All polymer produced was stabilized with 0 1-0 6 wt% of 2,6-di-tert-butyl- 4-methylphenol by mixing the powdered 2,6-di-tert-butyl-4-methylphenol with the polymer particles or granules as the case may be, before the polymer was extruded "Activities" were calculated using an inductively coupled plasma emission spectroscopy (ICPES) determination of Mg content Approximately 20-100g of polymer sample is burned to ash. The ash is then digested in 3 ml of a first acid (HF) to remove silica and 3 ml of a second acid (HNO3) for dissolving the ash.
  • ICPES inductively coupled plasma emission spectroscopy
  • a 4% boric acid solution (20 ml) is added as a buffer.
  • the solution is then diluted to 100 ml and run through the ICPES to measure Mg levels in the ash.
  • Mg level is used for calculating the amount of catalyst in the ash and activity. Activity is indicated by grams of polymer produced per gram of catalyst.
  • Tm Melting temperature
  • Tc crystallinity
  • DSC differential scanning calorimetry
  • Xc was calculated by dividing the heat of fusion during crystallization of the melt (Joules/gram or ""J/g"), taken from the DSC, by 212 (J/g) which is the theoretical value for 100% crystalline isotactic polypropylene.
  • the DSC instrument used was a DuPont 912 DSC equipped with a mechanical cooling accessory. Analysis was done on a TA2100 system.
  • Method of analysis was as follows: (1) equilibrate at 25°C; (2) ramp 50°C / minute to 230°C; (3) isotherm for 10 minutes; (4) ramp 5°C / minute to 25°C; (5) ramp 10°C / minute to 230°C; (6) integrate heat area of crystallization " ⁇ H C - (step 4) from 75°C to 140°C and (7) integrate heat area of melting " ⁇ H m " (step 4) from 100°C to 175°C.
  • ⁇ H C generally correlates to polymer crystallinity, with some consideration of MFR effect on crystallinity.
  • ⁇ H C generally correlates to flex modulus.
  • MFR Melt Flow rate
  • a timer is started when the timer arm comes into contact with a 2060 g weight, used to push the sample through the extrusion chamber.
  • Piston travel distance for measurement is 1/4" for MFR 0.5 - 10 and 1 " for MFR >10. For 1" travel distance more sample should be used such as approximately 5-7 g.
  • FM Flexible Modulus
  • Frax Modulus was measured according to ASTM standard D-790 by using injection molded samples from a small injection molding machine which is a reciprocating screw-type machine having hydraulic clamping forces. Sample preparation of injection molded bars for flex modulus measurement was done by pelletizing 250-400 g samples with a 3/4" Killion Extruder. Injection molded bars were prepared on a lab scale 655 kPa (95 psi) Hi Tech Butler 10/90V Injection Molder.
  • MWD Molecular Weight Distribution
  • Decalin solubles Samples of selected weight (1 gram) of polypropylene are placed in an excess quantity of decalin (100 ml) and then are dissolved in the decalin by heating the combination while stirring to a temperature less decalin's boiling point. The heated solution is removed from heat, allowed to stand and cool to room temperature for 16 to 20 hours in order to cause the crystalline component of the polypropylene to precipitate. The precipitate is then filtered. After filtration, an aliquot of filtered solution is evaporated and weighed for a total solubles. Test Materials used in Examples III through VII:
  • Propylene commercially available propylene of Exxon Chemical Company (99.8% pure propylene) was first passed in series through two 500 ml stainless steel vessels containing a bed of 3 A molecular sieves. The propylene was then passed through a 500 ml stainless steel vessel containing 1/8 inch beads of alumina (Selexorb COS, obtained from Alcoa Separations Technology, Inc. to selectively remove COS, CO2, H2S, & CS2. The propylene was further passed through 1/8 inch beads of alumina (Selexorb CD, also obtained from Alcoa Separations Technology, Inc) to selectively remove alcohols, ketones, aldehydes, carboxylic acids, and H S and other mercaptans.
  • Selexorb COS 1/8 inch beads of alumina
  • TEAL triethylaluminum
  • Hydrogen hydrogen gas (99.99% purity from Matheson) was used after passing through a 500 ml stainless steel vessel containing an oxygen remover. This vessel was prepacked and purchased from Matheson as Model 64- 1050 A with a maximum flow of 50 SCFH (standard cubic feet per hour) and a maximum oxygen removal of 1% by volume.
  • Catalyst components Commercially available catalyst components were obtained from Toho Titanium Company Limited, Japan (referred to herein as “TOHO A” and “TOHO B”) and AKZO Chemical (referred to herein as “AKZO TK”). Titanium content in catalyst powder ranged from 2.0 wt% to 2.5 wt%, and magnesium content ranged from 15 wt% to 20 wt%.
  • the catalyst components were received in a powder form and prepared with white oil as follows: (i) 9.85 g powder of catalyst TOHO A was placed in a 125 ml wheaton vial with 55.82 g of white oil (Precision-technical grade, purged for 24 h by nitrogen prior to use) and a magnetic stir bar.
  • Tetraethoxysilane was acquired from Aldrich Chemical Co., product number 33,385-9. Cyclopentyl-t-butoxydimethoxysilane was obtained from Tonen Chemical Company. Dicyclopentyldimethoxysilane (DCPMS) was obtained from Shinetsu Chemical Company, Japan. Diphenyldimethoxysilane (DPMS) and tetramethoxysilane (TMOS) were obtained from Gelest, Inc. product numbers SID4535.0 and SIT7510.1, respectively. Dinorbornyldimethoxysilane (DNMS) was also acquired from Gelest, Inc. Dinaphthyldimethoxysilane (DNAMS) and norbomylindenyldimethoxysilane (NIMS) were prepared according to the procedures of Examples I and II, respectively.
  • DNMS dinorbornyldimethoxysilane
  • NIMS norbomylindenyldimethoxysilane
  • TMOS tetramethoxysilane
  • DCPMS dicyclopentyldimethoxysilane
  • DNAMS dinaphthyl dimethoxysilane
  • MCMS methylcyclohexyldimethoxysilane
  • DPMS diphenyldimethoxysilane
  • TEOS tetraethoxysilane
  • CPBS cyclopentyl-t-butoxydimethoxysilane.
  • nucleating agent 0.6 gram per 100 grams of polymer sample was added as a stabilizer during extrusion of the polymer to enhance the crystalline properties of the polymer.
  • the nucleating agent consisted of a blend ("pbw", parts by weight) of 25 pbw sodium benzoate, 42 pbw sorbitol based nucleating agent (Millad 3988 obtained Milliken Chemicals), 8.3 pbw stablizer ( Cyanox 1790 obtained from Cytec Industries, Inc.); 8.3 pbw other stablizer (Ultranox 626 GE Chemicals), 8.3 pbw of a mold release agent (Acrawax C Lonza Inc.), and neutralizer (DHT4A, Kyowa Chemical Industries Company, Ltd, Japan).
  • Example III The polymerization procedures and materials used in Example III were repeated in this Example IV to produce polymer using the external donors methylcyclohexyldimethoxysilane (MCMS), dicyclopentyldimethoxysilane (DCPMS), dinorbornyldimethoxysilane (DNMS), dinaphthyl dimethoxysilane (DNAMS), and norbomylindenyldimethoxysilane (NIMS).
  • MCMS methylcyclohexyldimethoxysilane
  • DCPMS dicyclopentyldimethoxysilane
  • DNMS dinorbornyldimethoxysilane
  • DNAMS dinaphthyl dimethoxysilane
  • NIMS norbomylindenyldimethoxysilane
  • Table II compares physical and mechanical properties of polymers made using various donors where the polymer produced was treated a nucleating agent.
  • MFR (range) ⁇ 0.5 - 25 ⁇ 0.5 - 116 0.5 - 120 0.5 - 40 0.5 - 25
  • Example V The polymerization procedure of Examples I-IV was repeated in this Example V with the additional step of the addition of a titanocene hydrogenation catalyst at a concentration 25-to-l ratio (based on respective Ti content) of catalyst component to titanocene hydrogenation catalyst
  • the hydrogenation catalyst consumes hydrogen and can enable production of a high molecular weight polymer fraction to broaden the MWD and possibly increase flexural modulus
  • a high crystalline fraction with MFR > 70 with a Flex Modulus > 260 kpsi is increased Bis(n-butylcyclopentadiene)titaniumdichloride (0 023 g, 6 37 x 10" 5 m ), obtained from Boulder Scientific, was mixed with 0 38 ml of a 1 0M solution of triisobutylaluminum (obtained from Aldrich Chemical Co ) to solubilize such titanocene which would otherwise be insoluble in mineral oil To this solution, 24 6 g of mineral oil, which had been purged
  • Example V The polymerization procedure of Example V was repeated in this Example VI with the additional step of, after polymerizing for 1 hour at maximum hydrogen 1724kPa (250 psi) in the reactor, a titanocene hydrogenation catalyst was added to the reactor via 250 ml of propylene at a concentration ratio of 1 : 1 Ti of catalyst component: Ti of titanocene hydrogenation catalyst. This reaction was allowed to continue for an additional hour.
  • the donor performance described in Table IV shows a larger MWD obtained by use of hydrogenation catalyst.
  • Example VI To evaluate performance of mixtures of extemal donors, the polymerization procedure of Example III was repeated in this Example VII, with the additional step of mixing two external donors, 50% by weight TEOS plus 50% by weight of the donor shown in Table VI. Comparative data for systems with single donors (100% one donor) was found to be as follows in Table V:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des composés d'organosilane ayant la structure (I) dans laquelle R1 et R2 sont identiques ou différents et sélectionnés dans le groupe constitué par des radicaux alkyle, des radicaux cycloalkyle et des radicaux polynucléaires possédant au moins neuf atomes de carbone. Au moins un des radicaux R1 et R2 est un radical polynucléaire d'au moins neuf atomes de carbone à condition que l'un ou l'autre des radicaux R1 et R2 représente indényle ou fluorényle, et que l'un ou l'autre de R1 ou R2 représente un radical aliphatique, cyclique, ponté, substitué ou non substitué ou un radical aromatique polynucléaire d'au moins dix atomes de carbone. Dans cette formule, Ry et Rz sont identiques ou différents et chacun d'eux est sélectionné parmi des radicaux alkyles possédant un ou deux atomes de carbone. Selon une variante préférée, R1 représente un radical aromatique polynucléaire possédant au moins dix atomes de carbone, et R2, Ry et Rz sont identiques ou différents et chacun d'eux est sélectionné parmi des radicaux alkyles possédant un ou deux atomes de carbone. L'invention concerne également des organosilanes ayant la structure (II) dans laquelle R1 représente un radical aromatique polynucléaire possédant au moins dix atomes de carbone et dans laquelle Rx, Ry et Rz sont identiques ou différents et chacun d'eux étant sélectionné parmi des radicaux alkyles possédant un ou deux atomes de carbone. Ces organosilanes sont destinés à être utilisés comme modificateurs de systèmes catalyseurs de polymérisation oléfinique. L'invention concerne encore des polymères de propylène dont la température de fusion dépasse 164 °C et dont le pourcentage de crystallinité dépasse 55 %, mesures obtenues par DSC (ΔHf=212J/g pour 100 %), la répartition du poids moléculaire étant comprise entre 5 et 10.
EP97905946A 1996-02-13 1997-02-13 Systeme catalyseur et composants Withdrawn EP0880549A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US600838 1984-04-16
US60083896A 1996-02-13 1996-02-13
PCT/US1997/002271 WO1997030096A2 (fr) 1996-02-13 1997-02-13 Systeme catalyseur et composants

Publications (1)

Publication Number Publication Date
EP0880549A2 true EP0880549A2 (fr) 1998-12-02

Family

ID=24405246

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97905946A Withdrawn EP0880549A2 (fr) 1996-02-13 1997-02-13 Systeme catalyseur et composants

Country Status (5)

Country Link
EP (1) EP0880549A2 (fr)
JP (1) JP2001509182A (fr)
CN (1) CN1213382A (fr)
CA (1) CA2244803A1 (fr)
WO (1) WO1997030096A2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376628B1 (en) * 1998-05-21 2002-04-23 Grand Polymer Co., Ltd. Process for polymerization of alpha-olefin and alpha-olefin polymer
EP2028199B1 (fr) † 1998-06-25 2010-05-26 Idemitsu Kosan Co., Ltd. polymère de propylène et composition le contenant, objet moulé et stratifié les comprenant, et procédés pour la fabrication de polymère de propylène et composition le contenant
JP4758583B2 (ja) * 1999-12-22 2011-08-31 バセル テクノロジー カンパニー ビー．ブイ． 芳香族シラン化合物を含むα−オレフィン重合触媒系
US20100036068A1 (en) * 2008-08-08 2010-02-11 Sumitomo Chemical Company, Limited Hydrogenation catalyst and process for producing olefin polymer
EP2679609A1 (fr) * 2012-06-28 2014-01-01 Lummus Novolen Technology Gmbh Dialkoxydialkylsilanes stériquement exigeants en tant que donneurs externes pour catalyseurs ziegler pour la polymérisation de propylène
CN113248535B (zh) * 2021-04-20 2022-07-26 国家能源集团宁夏煤业有限责任公司 硅杂1,3-二醚化合物及其制备方法、烯烃聚合催化剂及烯烃聚合方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427273A (en) * 1964-08-10 1969-02-11 Owens Illinois Inc Process for making luminescent organopolysiloxanes and compositions thereof
ES2052004T5 (es) * 1988-06-17 2002-05-16 Mitsui Chemicals Inc Procedimiento de preparacion de poliolefinas y catalizador de polimerizacion.
JP2564713B2 (ja) * 1991-07-02 1996-12-18 大和紡績株式会社 熱接着性複合繊維およびその繊維集合体
JPH06329726A (ja) * 1993-03-26 1994-11-29 Ube Ind Ltd 高流動性、高融点、高結晶性ポリプロピレン
ES2136212T3 (es) * 1994-01-31 1999-11-16 Toho Titanium Co Ltd Catalizador para la polimerizacion de olefinas y procedimiento de polimerizacion que utiliza este.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9730096A2 *

Also Published As

Publication number Publication date
CA2244803A1 (fr) 1997-08-21
WO1997030096A2 (fr) 1997-08-21
JP2001509182A (ja) 2001-07-10
WO1997030096A3 (fr) 1997-10-16
CN1213382A (zh) 1999-04-07

Similar Documents

Publication Publication Date Title
KR101278336B1 (ko) 안사-메탈로센 화합물의 라세모선택적 합성, 안사-메탈로센 화합물, 이를 포함하는 촉매, 그 촉매를 이용한 올레핀 폴리머 제조 공정, 그리고 올레핀 호모- 및 코폴리머
EP0821011B1 (fr) Procédé de préparation de polymères à base d'éthylène
KR20100101092A (ko) 메탈로센 화합물, 이를 포함하는 촉매, 이 촉매를 사용한 올레핀 폴리머생산방법, 및 올레핀 호모- 및 코폴리머
CS275682B6 (en) Compounds of transient metals bridged with silicon
EP1632506A1 (fr) Polymère à base de propylène
WO1992005204A1 (fr) Procede servant a produire des poly-alpha-olefines avec un systeme catalytique comportant un metal de transition combine avec du monocyclopentadienyle
CA2262396A1 (fr) Systeme de catalyseur sur support, procede permettant de le produire et son utilisation pour la polymerisation d'olefines
WO2001070395A2 (fr) Catalyseurs
KR20150052804A (ko) 프로필렌-1-부텐 공중합체 수지 조성물의 제조방법 및 이로부터 수득되는 프로필렌-1-부텐 공중합체 수지 조성물
JP3168341B2 (ja) オレフィン重合触媒及び方法
CN113840845B (zh) 丙烯-乙烯无规共聚物
JP2005510591A (ja) プロピレンの多孔性ポリマー
WO2005044870A1 (fr) Compose de metaux de transition organometallique, systeme de ligand bicyclopentadienyle, systeme de catalyseur et procede de preparation de polyolefines
US20100240846A1 (en) Catalyst component for the polymerization of olefins based on 1,3-diethers
WO1997030096A2 (fr) Systeme catalyseur et composants
AU2004268892B2 (en) High stereospecific polybutylene polymer and highly active process for preparation thereof
WO2003014167A1 (fr) Procede de polymerisation utilisant un organosilane specifique en tant que donneur externe
CN114761449A (zh) 催化剂
JP2003528028A (ja) アンサ基−４−金属ビス（μ−置換）アルミニウムメタロセン
JP2008534722A (ja) オレフィン類の重合用触媒成分
JP3704205B2 (ja) 遷移金属化合物および該遷移金属化合物からなるオレフィン重合用触媒成分
AU667292C (en) Process for producing crystalline poly-alpha-olefins with a monocyclopentadienyl transition metal catalyst system
JPH10231316A (ja) α−オレフィンの重合方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980910

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 19990128

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20000901