WO2001058970A1 - Propylene impact copolymers - Google Patents
Propylene impact copolymers Download PDFInfo
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- WO2001058970A1 WO2001058970A1 PCT/US2001/004126 US0104126W WO0158970A1 WO 2001058970 A1 WO2001058970 A1 WO 2001058970A1 US 0104126 W US0104126 W US 0104126W WO 0158970 A1 WO0158970 A1 WO 0158970A1
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- zirconium dichloride
- dimethylsiladiyl
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Definitions
- FIELD This invention relates to propylene impact copolymer compositions.
- these unique and improved compositions can be produced using metallocene catalysts in commercial-scale processes.
- Propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they are too brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these.
- a typical propylene impact copolymer contains two phases or components, a homopolymer component and a copolymer component. These two components are usually produced in a sequential polymerization process wherein the homopolymer produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component.
- the copolymer component has rubbery characteristics and provides the desired impact resistance, whereas the homopolymer component provides overall stiffness.
- U.S. Patent No. 5,166,268 describes a "cold forming" process for producing propylene impact copolymers where finished articles are fabricated at temperatures below the melting point of the preform material, in this case, the propylene impact copolymer.
- the patented process uses a propylene impact copolymer comprised of either a homopolymer or crystalline copolymer matrix (first component) and at least ten percent by weight of an "interpolymer" of ethylene and a small amount of propylene (the second component). Adding comonomer to the first component lowers its stiffness.
- the ethylene/propylene copolymer second component enables the finished, cold-formed article to better maintain its shape.
- nucleating agent is added to propylene impact copolymers having a numerical ratio of the intrinsic viscosity of the copolymer rubber phase (second component) to the intrinsic viscosity of the homopolymer phase (first component) which is near unity, and an ethylene content of the copolymer phase in the range of 38% to 60% by weight.
- second component the intrinsic viscosity of the copolymer rubber phase
- first component the intrinsic viscosity of the homopolymer phase
- ethylene content of the copolymer phase in the range of 38% to 60% by weight.
- U.S. Patent No. 5,250,631 describes a propylene impact copolymer having a homopolypropylene first component and an ethylene/butene/propylene terpolymer second component. Again, the goal is to obtain high impact strength coupled with resistance to stress whitening.
- Propylene impact copolymers are also used to produce films as described in U.S. Patent No. 5,948,839.
- the impact copolymer described in this patent contains a conventional first component and 25 to 45 weight percent ethylene/propylene second component having from 55 to 65 weight percent ethylene.
- This impact copolymer composition has a melt flow of from 7 to 60 dg/min. Such films are used in articles such as diapers.
- U.S. 5,990,242 approaches this problem by using an ethylene/butene (or higher ⁇ -olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type metallocene.
- hafnocene type metallocene such hafnium metallocenes in general are known for producing relatively higher molecular weight polymers; however, their activities are much lower than the more commonly used zirconocenes.
- the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
- the present inventors have discovered new propylene impact copolymer compositions having the benefits of metallocene catalyzed polymers in addition to properties needed for high impact strength. Importantly, these polymers can be economically produced using commercial-scale processes.
- the present invention provides reactor produced propylene impact copolymer compositions comprising:
- Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
- Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
- (i) has a weight average molecular weight of at least 100,000; (ii) a composition distribution of greater than 60%; and (iii) an intrinsic viscosity of greater than 1.00 dl/g.
- This invention also provides a process for producing propylene impact copolymer in a multiple stage process wherein Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer is produced in a primary stage and Component B is produced in a subsequent stage, Component B comprising propylene copolymer wherein the copolymer comprises from about
- Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[l -naphthyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl) 2 zirconium dichloride; and
- Figure 1 is a plot of Notched Isod values as a function of Flexural Modulus data from Table 8.
- the propylene impact copolymers (“ICPs”) of this invention comprise at least two major components, Component A and Component B.
- Component A is preferably an isotactic propylene homopolymer, though small amounts of a comonomer may be used to obtain particular properties.
- Such copolymers of Component A contain 10% by weight or less, preferably less than 6% by weight or less, comonomer such as ethylene, butene, hexene or octene. Most preferably less than 4% by weight ethylene is used.
- the end result is usually a product with lower stiffness but with some gain in impact strength compared to homopolymer Component A.
- Component A refers generally to the xylene insoluble portion of the ICP composition
- Component B refers generally to the xylene soluble portion.
- the xylene soluble portion clearly has both a high molecular weight component and a low molecular weight component, we have found that the low molecular weight component is attributable to amorphous, low molecular weight propylene homopolymer. Therefore, Component B in such circumstances refers only to the high molecular weight portion.
- Component A preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 4.0, preferably lower than 3.5, more preferably lower than 3.0, and most preferably 2.5 or lower. These molecular weight distributions are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight.
- Component A preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 200,000 and a melting point (Mp) of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C.
- ICPs Another important feature of ICPs is the amount of amorphous polypropylene they contain.
- the ICPs of this invention are characterized as having low amorphous polypropylene, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably there is no measurable amorphous polypropylene.
- Component B is most preferably a copolymer consisting essentially of propylene and ethylene although other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired.
- propylene/butene, hexene or octene copolymers, and ethylene/butene, hexene or octene copolymers may be used, and propylene/ethylene/hexene-1 terpolymers may be used.
- Component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% by weight to about 30% by weight propylene, even more preferably from about 70% by weight to about 35% by weight propylene.
- the comonomer content of Component B is preferably in the range of from about 20% to about 70% by weight comonomer, more preferably from about 30% to about 65% by weight comonomer, even more preferably from about 35% to about 60% by weight comonomer.
- Most preferably Component B consists essentially of propylene and from about 20% to about 70% ethylene, more preferably from about 30% to about 65% ethylene, and most preferably from about 35% to about 60% ethylene.
- Component B For other Component B copolymers, the comonomer contents will need to be adjusted depending on the specific properties desired. For example, for ethylene/hexene copolymers, Component B should contain at least 17% by weight hexene and at least 83% by weight ethylene.
- Component B preferably has a narrow molecular weight distribution Mw/Mn ("MWD"), i.e., lower than 5.0, preferably lower than 4.0, more preferably lower than 3.5, even more preferably lower than 3.0 and most preferably 2.5 or lower. These molecular weight distributions should be obtained in the absence of visbreaking or peroxide or other post reactor treatment designed to reduce molecular weight.
- Component B preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
- Component B preferably has an intrinsic viscosity greater than 1.00 dl/g, more preferably greater than 1.50 dl/g and most preferably greater than 2.00 dl/g.
- intrinsic viscosity or "IN” is used conventionally herein to mean the viscosity of a solution of polymer such as Component B in a given solvent at a given temperature, when the polymer composition is at infinite dilution.
- IN measurement involves a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at the given temperature are determined.
- decalin is a suitable solvent and a typical temperature is 135°C. From the values of the viscosity of solutions of varying concentrations, the "value" at infinite dilution can be determined by extrapolation.
- Component B preferably has a composition distribution (CD) of greater than 60%, more preferably greater than 65%, even more preferably greater than 70%o, even more preferably greater than 75%, still more preferably greater than 80%, and most preferably greater than 85%.
- CD defines the compositional variation among polymer chains in terms of ethylene (or other comonomer) content of the copolymer as a whole. The measurement of CD is described in detail U.S. Patent No. 5,191,042 which is hereby fully incorporated by reference. CD is defined herein as the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content. As described in U.S. Patent No.
- CD is determined by first determining the mean ethylene (or other comonomer) content of the copolymer by a suitable test such as ASTM D-3900. Next, the copolymer sample is dissolved in solvent such as hexane and a number of fractions of differing composition are precipitated by the addition of incremental amounts of a liquid such as isopropanol in which the copolymer is insoluble. Generally from about 4 to 6 fractions are precipitated in this way and the weight and ethylene (or other comonomer) content of each fraction are determined after removing the solvent. From the weight of each fraction and its ethylene content, a plot is prepared of weight percent composition vs. cumulative weight percent of polymer, and a smooth curve is drawn through the points.
- Component B of the ICPs preferably has low crystallinity, preferably less than 10% by weight of a crystalline portion, more preferably less than 5% by weight of a crystalline portion. Where there is a crystalline portion of Component
- composition is preferably the same as or at least similar to (within 15% by weight) the remainder of Component B in terms of overall comonomer weight percent.
- the ICPs of this invention are "reactor produced” meaning Components A and B are not physically or mechanically blended together. Rather, they are interpolymerized in at least one reactor. The final ICP as obtained from the reactor or reactors, however, can be blended with various other components including other polymers.
- the preferred melt flow rate ("MFR") of these ICPs depends on the desired end use but is typically in the range of from about 0.2 dg min to about 200 dg/min, more preferably from about 5 dg/min to about 100 dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min are obtainable. MFR is determined by a conventional procedure such as ASTM-1238 Cond. L.
- the ICP preferably has a melting point of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C.
- the ICPs comprise from about 40% to about 95% by weight Component A and from about 5% to about 60% by weight Component B, preferably from about 50% to about 95% by weight Component A and from about 5% to about 50% Component B, even more preferably from about 60% to about 90% by weight
- Component A and from about 10 % to about 40% by weight Component B.
- the ICP consists essentially of Components A and B.
- the overall comonomer (preferably ethylene) content of the total ICP is preferably in the range of from about 2% to about 30% by weight, preferably from about 5% to about 25% by weight, even more preferably from about 5% to about
- additives may be incorporated into the ICP for various purposes.
- Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents and mold release agents.
- the ICP compositions of this invention may be prepared by conventional polymerization processes such as a two-step process. It is conceivable, although currently impractical, to commercially produce ICPs in a single reactor. Each step may be independently carried out in either the gas or liquid slurry phase. For example the first step may be conducted in the gas phase and the second in liquid slurry or vice versa. Alternatively, each phase may be the same.
- the ICPs of this invention are produced in multiple reactors, preferably two or three, operated in series, Component B is preferably polymerized in a second, gas phase reactor. Component A is preferably polymerized first, in a liquid slurry or solution polymerization process.
- Component A is made in at least two reactors in order to obtain fractions with varying melt flow rate. This has been found to improve the processability of the ICP.
- stage is defined as that portion of a polymerization process during which one component of the ICP, Component A or Component B, is produced- One or multiple reactors may be used during each stage.
- Hydrogen may be added to one or both reactors to control molecular weight, IN and MFR.
- the use of hydrogen for such purposes is well known to those skilled in the art.
- a metallocene catalyst system is used to produce the ICP compositions of this invention.
- the most suitable metallocenes are those in the generic class of bridged, substituted bis(cyclopentadienyl) metallocenes, specifically bridged, substituted bis(indenyl) metallocenes known to produce high molecular weight, high melting, highly isotactic propylene polymers.
- those of the generic class disclosed in U.S. Patent No. 5,770,753 should be suitable, however, it has been found that the exact polymer obtained is highly dependent on the metallocene's specific substitution pattern.
- racemic metallocenes are most suitable for preparing the ICP compositions of this invention: rac-dimethylsiladiyl(2-iPr,4 ⁇ phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[ 1 - naphthyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5- dimethylphenyl]indenyl) 2 zircor ⁇ ium dichloride; rac-dimethylsiladiyl(2-iPr, 4-
- Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system.
- activator is defined herein to be any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins.
- Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes contain 5 to 40 of the repeating units:
- R is a Cj-Cg alkyl including mixed alkyls.
- Compounds in which R is methyl are particularly preferred.
- Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Patent No.
- Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928.
- ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and US patent 5,198,401 and WO-A- 92/00333 (incorporated herein by reference for purposes of U.S. patent practice). These teach desirable methods of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
- Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorided aryl-constituents such as phenyl, biphenyl and napthyl.
- noncoordinating anion means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
- “Compatible” noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion.
- Particularly useful noncoordinating anions are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient liability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
- ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a noncoordinating anion is also known. See, for example, EP-A-0 426 637 and EP-A- 0 573 403 (incorporated herein by reference for purposes of U.S. patent practice).
- An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated herein by reference for purposes of U.S. patent practice).
- Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference for purposes of U.S. patent practice).
- metal ligands include halogen moieties (for example, bis- cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP- Al-0 570 982 (incorporated herein by reference for purposes of U.S. patent practice) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds. '
- the activator for the metallocene supported catalyst composition is a
- NCA preferably the NCA is first added to the support composition followed by the addition of the metallocene catalyst.
- the activator is MAO
- the MAO and metallocene catalyst are dissolved together in solution.
- the support is then contacted with the MAO/metallocene catalyst solution.
- a porous particulate material such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
- the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
- Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable.
- Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
- the support material is porous silica which has a surface area in the range of from 10 to 700 " m-2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 ⁇ m. More preferably, the surface area is in the range of from 50 to 500 m- ⁇ /g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 ⁇ m.
- the surface area is in the range of from 100 to 400 m-2/g
- the pore volume is in the range of from 0.8 to 3.0 cc/g
- the average particle size is in the range of from 30 to 100 ⁇ m.
- the average pore size of typical porous support materials is in the range of from 10 to 1000 A.
- a support material is used that has an average pore diameter of from 50 to 50 ⁇ A, and most desirably from 75 to 35 ⁇ A. It may be particularly desirable to dehydrate the silica at a temperature of from 100°C to 800°C anywhere from 3 to 24 hours.
- the metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U. S Patent Nos.
- the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/ 28034, WO 96/00243, and WO 96/00245 (each folly incorporated herein by reference for purposes of U.S. patent practice).
- the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
- the total volume of reaction solution applied to porous support is desirably less than 4 times the total pore volume of the porous support, more desirably less than 3 times the total pore volume of the porous support and even more desirably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support.
- Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental
- the methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the
- Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
- the supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
- Metallocene A racemic dimethylsiladiyl(2-isopropyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene B racemic dimethylsiladiyl(2-isopropyl-4-[l-naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene C racemic dimethylsiladiyl(2-isopropyl-4-[2-methyl- phenyl]indenyl) 2 zirconium dichloride was prepared as follows:
- Metallocene D racemic dimethylsiladiyl(2- isopropyl-4-[3,5- dimethylphenyl]indenyl) 2 zirconium dichloride was prepared as follows:
- Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindene] (2.1g, 3.6 mmol) was dissolved in 60 mL of Et 2 O. While stirring, 2.9 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35°C and ZrCl (0.83 g, 3.6 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in toluene and filtered to remove
- Metallocene E racemic diphenylsiladiyl(2-methyl-4-[l-naphthyl]indenyl) 2 zirconium dichloride was prepared as follows. Ph2Si(2-Methyl-4-ri-na ⁇ thyllindene)2
- 4-[l-napthyl]indenyl lithium to form the ligand system with a Ph2Si bridge is a general one.
- a wide variety of cyclopentadienyl or indenyl metal salts can be reacted with Ph2Si(OSO2CF3)2 when Ph2Si(Cl)2 is unreactive or slow with the cyclopentadienyl or indenyl metal salt reagent.
- Ph2Si(2-Methyl-4-[l-napthyl]indenyl lithium)2 was prepared from addition of a 2.0 M solution of n-Butyl lithium and pentane (1.5 mL, 3.0 mmol) to a mixture of Ph2Si(2-Methyl, 4-napthyl indene)2 (1.0 g, 1.44 mmol) and diethyl ether (20 mL). After stirring for two hours, trimethyl tin chloride (0.6 g, 3.0 mmol) was added. The color changed instantly from an intense to light yellow. The ether was removed and the product extracted with pentane (3 x 20 mL). Removal of solvent yielded product. Yield 0.88 g, 60 %.
- Comparison Metallocene 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 2 racemic dimethylsiladiyl(2- methyl-4-[l- naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 3 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 4 racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- dimethylsiladiyl(2-iPr-4-phenyl indenyl)2 zirconium dichloride (A, 0.060 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration).
- dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride F, 0.065 g was added to the MAO-toluene solution (5.1 g, 5.35 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration).
- dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (G, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.4 mL) and stirred fifty minutes. This was filtered through a medium glass frit funnel and washed with toluene (13 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, dried at 40 °C for ten minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 3 hours. The supported catalyst was recovered as a purple, free flowing solid (5.45 g).
- racemic dimethylsiladiyl(2-methyl-4- phenylindenyl) 2 zirconium dichloride (Comparison metallocene 3, 13.0 g) was dissolved in a MAO solution (300 mL). This was added to a MAO solution (800 mL diluted with 1600 mL toluene) and an additional 150 mL of toluene was added. This was mixed one hour. One half of this solution was added to dehydrated silica (802.2 g, Davison 948 Regular, 600°C dehydration) and stirred five minutes- The remaining solution was then added and stirred twenty minutes. Additional toluene was added (450 mL). This slurry was stirred for twenty minutes then dried at 46 °C for 11.5 hours under nitrogen flow. The supported catalyst was recovered as an orange, free flowing solid (1092.2 g) which was passed through a 25 mesh screen.
- the polymerization procedure for producing homopolymers with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70 °C , the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented- The polymer was removed and dried. Results are shown in Tables 1 A and 2A.
- the polymerization procedure for producing ICP with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added.
- Results are shown in Tables IB, 2B and 3-8.
- DSC melting points were determined on commercial DSC instruments and are reported as the second melting point.
- the polymer sample was heated to 230.0°C for ten minutes and then cooled from 230°C to 50°C at 10°C/minute. The sample is held at 50°C for five minutes.
- the second melt is then recorded as the sample is heated from 50°C to 200°C at a rate of 10°C/minute.
- the peak temperature is recorded as the second melting point.
- the ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubes are dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV of the recovered soluble material was measured in decalin at 135°C by using known methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler. At very high ICP MFR this method can extract some low molecular weight isotactic PP and thus lower the observed IV.
- the ICP products from the reactor were dry blended with additives (lOOOppm Irganox 3114; 600ppm Irgafos 168; 500ppm Kemamide U; 2000ppm sodium benzoate; 600ppm DSTDP), followed by compounding/pelletization on a laboratory extrusion line to make pellets. After pelletization, injection molded bars (127 mm x 12.7 mm x 3.2 mm) were fabricated using a Butler laboratory injection molding machine (Model No. 10/90V).
- ASTM type tests were conducted on the molded samples to measure 1% secant flexual modulus (ASTM D-790A); Heat Distortion Temperature at 66 psi (455 kPa) (ASTM D-648); Izod impact strength (notched at 23°C and unnotched at -40°C, ASTM D-256).
- the impact copolymers of this invention display improved impact properties as measured by the room temperature notched Izod values at similar Flexural Modulus. This can be seen by examining Table 8.
- the ICP from inventive run 43 with inventive metallocene F has a Flexural Modulus of 151.8 kpsi (1046.9 MPa) with a Notched Izod of 1.57 ft-lb/inch (83.8 J/m) value
- the ICP from inventive run 50 with inventive metallocene G has a Flexural Modulus of 158.3 kpsi (1091.5 MPa) with a Notched Izod of 1.7 ft-lb/inch (90.7 J/m) value.
- the improved impact strength at comparable modulus results from a higher molecular weight, as measured by IV, of Component B.
- the known metallocenes comparison 1 and 2 are limited to low values for this molecular weight as measured by the IV of Component B.
- the maximum value of IN for the comparative metallocenes was a value of about 1.7 dl/g for run 9 (Table IB) with the ethylene/propylene at a 4.2/0.8 ratio.
- Inventive metallocene B at this ratio produced an IV that ranged from 1.99 dl/g in run 13 to 2.338 dl/g in run 18.
- the inventive metallocene D produced an ICP with an IV of 3.508 dl/g in run 40.
Abstract
Description
Claims
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AT01910477T ATE286082T1 (en) | 2000-02-08 | 2001-02-08 | IMPACT RESISTANT PROPYLENE COPOLYMERS |
KR1020027010213A KR20020074509A (en) | 2000-02-08 | 2001-02-08 | Propylene impact copolymers |
EP01910477A EP1254186B1 (en) | 2000-02-08 | 2001-02-08 | Propylene impact copolymers |
JP2001558115A JP2003522259A (en) | 2000-02-08 | 2001-02-08 | Propylene impact copolymer |
BR0108150-0A BR0108150A (en) | 2000-02-08 | 2001-02-08 | Propylene Impact Copolymers |
CA002398509A CA2398509A1 (en) | 2000-02-08 | 2001-02-08 | Propylene impact copolymers |
DE60108075T DE60108075T2 (en) | 2000-02-08 | 2001-02-08 | PEDESTAL PROPYLENE COPOLYMERISATE |
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US09/534,556 | 2000-03-24 | ||
US09/535,357 US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/535,357 | 2000-03-24 | ||
US09/534,556 US6492465B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
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EP (2) | EP1254186B1 (en) |
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AT (1) | ATE286082T1 (en) |
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US9708481B2 (en) | 2013-10-24 | 2017-07-18 | Borealis Ag | Blow molded article based on bimodal random copolymer |
US9751962B2 (en) | 2013-11-22 | 2017-09-05 | Borealis Ag | Low emission propylene homopolymer with high melt flow |
US9777142B2 (en) | 2013-08-21 | 2017-10-03 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness |
US9802394B2 (en) | 2013-10-11 | 2017-10-31 | Borealis Ag | Machine direction oriented film for labels |
US9828698B2 (en) | 2013-12-04 | 2017-11-28 | Borealis Ag | Phthalate-free PP homopolymers for meltblown fibers |
WO2017204830A1 (en) | 2016-05-27 | 2017-11-30 | Exxonmobil Chemical Patents, Inc. | Metallocene catalyst compositions and polymerization process therewith |
US9890275B2 (en) | 2013-08-21 | 2018-02-13 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness |
US10030109B2 (en) | 2014-02-14 | 2018-07-24 | Borealis Ag | Polypropylene composite |
US10040930B2 (en) | 2013-09-27 | 2018-08-07 | Abu Dhabi Polymers Co. Ltd (Borouge) Llc. | Polymer composition with high XS, high Tm suitable for BOPP processing |
US10100185B2 (en) | 2014-02-06 | 2018-10-16 | Borealis Ag | Soft copolymers with high impact strength |
US10100186B2 (en) | 2014-02-06 | 2018-10-16 | Borealis Ag | Soft and transparent impact copolymers |
US10227427B2 (en) | 2014-01-17 | 2019-03-12 | Borealis Ag | Process for preparing propylene/1-butene copolymers |
US10280235B2 (en) | 2015-06-05 | 2019-05-07 | Exxonmobil Chemical Patents Inc. | Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers |
US10280233B2 (en) | 2015-06-05 | 2019-05-07 | Exxonmobil Chemical Patents Inc. | Catalyst systems and methods of making and using the same |
US10287372B2 (en) | 2015-06-05 | 2019-05-14 | Exxonmobil Chemical Patents Inc. | Bimodal propylene polymers and sequential polymerization |
US10294316B2 (en) | 2015-06-05 | 2019-05-21 | Exxonmobil Chemical Patents Inc. | Silica supports with high aluminoxane loading capability |
US10329360B2 (en) | 2015-06-05 | 2019-06-25 | Exxonmobil Chemical Patents Inc. | Catalyst system comprising supported alumoxane and unsupported alumoxane particles |
US10450451B2 (en) | 2014-05-20 | 2019-10-22 | Borealis Ag | Polypropylene composition for automotive interior applications |
US10465025B2 (en) | 2014-01-15 | 2019-11-05 | Exxonmobil Chemical Patents Inc. | Low comonomer propylene-based impact copolymers |
US10519259B2 (en) | 2013-10-24 | 2019-12-31 | Borealis Ag | Low melting PP homopolymer with high content of regioerrors and high molecular weight |
US10723821B2 (en) | 2015-06-05 | 2020-07-28 | Exxonmobil Chemical Patents Inc. | Supported metallocene catalyst systems for polymerization |
WO2020170046A1 (en) * | 2019-02-19 | 2020-08-27 | Braskem S.A. | No break polypropylene impact copolymers with melt flow rate higher than 90 g/10 min |
US10759886B2 (en) | 2015-06-05 | 2020-09-01 | Exxonmobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
EP3722363A1 (en) * | 2019-04-12 | 2020-10-14 | Thai Polyethylene Co., Ltd. | Impact copolymer polypropylene for thin-wall injection packaging |
US10920053B2 (en) | 2017-10-16 | 2021-02-16 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymer blends with improved gloss |
US11472828B2 (en) | 2019-10-11 | 2022-10-18 | Exxonmobil Chemical Patents Inc. | Indacene based metallocene catalysts useful in the production of propylene polymers |
Families Citing this family (156)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7919561B2 (en) * | 1996-09-04 | 2011-04-05 | Exxonmobil Chemical Patents Inc. | Process of producing thermoplastic polymer blends |
US6635715B1 (en) * | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6921794B2 (en) * | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US7232871B2 (en) * | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
WO2002083754A1 (en) | 2001-04-12 | 2002-10-24 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
EP1098934A1 (en) * | 1998-07-01 | 2001-05-16 | Exxon Chemical Patents Inc. | Elastic blends comprising crystalline polymer and crystallizable polymers of propylene |
JP2000072933A (en) * | 1998-08-31 | 2000-03-07 | Asahi Chem Ind Co Ltd | Olefin elastomer composition |
CA2398529A1 (en) * | 2000-02-08 | 2001-08-16 | Exxonmobil Chemical Patents Inc. | Method of preparing group 14 bridged biscyclopentadienyl ligands |
US6492465B1 (en) * | 2000-02-08 | 2002-12-10 | Exxonmobil Chemical Patents, Inc. | Propylene impact copolymers |
GB0008690D0 (en) * | 2000-04-07 | 2000-05-31 | Borealis Polymers Oy | Process |
US6870016B1 (en) * | 2000-06-30 | 2005-03-22 | Exxonmobil Chemical Patents Inc. | Polymerization process and polymer composition |
US7217463B2 (en) | 2002-06-26 | 2007-05-15 | Avery Dennison Corporation | Machine direction oriented polymeric films and methods of making the same |
US7998579B2 (en) * | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
US7271209B2 (en) * | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
US7531594B2 (en) * | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
CA2492839C (en) * | 2002-08-12 | 2011-02-01 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
US8003725B2 (en) * | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
ATE445651T1 (en) * | 2002-09-06 | 2009-10-15 | Basell Polyolefine Gmbh | METHOD FOR COPOLYMERIZING ETHYLENE |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
EP1558655B1 (en) | 2002-10-15 | 2012-08-29 | ExxonMobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7459500B2 (en) * | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US20040147169A1 (en) | 2003-01-28 | 2004-07-29 | Allison Jeffrey W. | Power connector with safety feature |
EP1630197B1 (en) * | 2003-05-28 | 2011-03-02 | Mitsui Chemicals, Inc. | Propylene polymer composition and use thereof |
US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
CN1849350A (en) * | 2003-09-11 | 2006-10-18 | 巴塞尔聚烯烃股份有限公司 | Multistep process for preparing heterophasic propylene copolymers |
CN1878806A (en) * | 2003-09-11 | 2006-12-13 | 巴塞尔聚烯烃股份有限公司 | Multistep process for preparing heterophasic propylene copolymers |
US6995213B2 (en) * | 2003-09-29 | 2006-02-07 | Fina Technology, Inc. | Oriented films prepared using impact copolymer polypropylene |
JP4590037B2 (en) * | 2003-09-30 | 2010-12-01 | 日本ポリプロ株式会社 | Olefin polymerization catalyst component, α-olefin polymerization catalyst and method for producing α-olefin polymer |
US7458839B2 (en) | 2006-02-21 | 2008-12-02 | Fci Americas Technology, Inc. | Electrical connectors having power contacts with alignment and/or restraining features |
CN101882718B (en) | 2003-12-31 | 2012-11-21 | Fci公司 | Electrical power contacts and connectors comprising same |
EP1718700B8 (en) | 2004-02-12 | 2012-10-03 | ExxonMobil Chemical Patents Inc. | Plasticized polyolefin compositions |
US20050234172A1 (en) * | 2004-04-19 | 2005-10-20 | Fina Technology, Inc. | Random copolymer-impact copolymer blend |
US20050234198A1 (en) * | 2004-04-20 | 2005-10-20 | Fina Technology, Inc. | Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system |
CN101006132B (en) * | 2004-07-30 | 2010-05-05 | 沙特基础工业公司 | Propylene copolymer compositions with high transparency |
EP1793997A1 (en) * | 2004-09-10 | 2007-06-13 | ExxonMobil Oil Corporation | Cavitated opaque polymer film and methods related thereto |
CN101065437B (en) † | 2004-10-04 | 2010-12-08 | 巴塞尔聚烯烃意大利有限责任公司 | Elastomeric polyolefin compositions |
US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
US7384289B2 (en) | 2005-01-31 | 2008-06-10 | Fci Americas Technology, Inc. | Surface-mount connector |
KR100878869B1 (en) * | 2005-03-18 | 2009-01-15 | 미쓰이 가가쿠 가부시키가이샤 | Propylene polymer composition, use thereof, and process for production of thermoplastic polymer composition |
US8513347B2 (en) | 2005-07-15 | 2013-08-20 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
EP1917304B1 (en) * | 2005-08-22 | 2011-06-22 | Mitsui Chemicals, Inc. | Propylene based resin composition |
JP5379479B2 (en) * | 2005-10-21 | 2013-12-25 | バーゼル・ポリオレフィン・ゲーエムベーハー | Polypropylene for injection molding |
US7709577B2 (en) | 2005-12-07 | 2010-05-04 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
US20090017710A1 (en) * | 2006-02-02 | 2009-01-15 | Basell Polyolefine Gmbh | Propylene Melt Blown Resins, Propylene Melt Blown Resin Fibers and Non-Woven Fabric Made From the Same, and Methods of Making the Same |
CN103121320B (en) | 2006-06-14 | 2015-06-24 | 艾利丹尼森公司 | Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing |
US7726982B2 (en) | 2006-06-15 | 2010-06-01 | Fci Americas Technology, Inc. | Electrical connectors with air-circulation features |
BRPI0713492A2 (en) | 2006-06-20 | 2012-01-24 | Avery Dennison Corp | multi-layer polymeric film for labeling hot melt adhesives and label and label thereof |
ES2313510T5 (en) * | 2006-07-10 | 2012-04-09 | Borealis Technology Oy | Branched Short Chain Polypropylene |
US20080097774A1 (en) * | 2006-08-29 | 2008-04-24 | Rawls-Meehan Martin B | Using a software application to configure a foam spring mattress |
US8198373B2 (en) * | 2006-10-02 | 2012-06-12 | Exxonmobil Chemical Patents Inc. | Plastic toughened plastics |
US7256240B1 (en) * | 2006-12-22 | 2007-08-14 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
US7905731B2 (en) | 2007-05-21 | 2011-03-15 | Fci Americas Technology, Inc. | Electrical connector with stress-distribution features |
WO2009035850A1 (en) * | 2007-09-07 | 2009-03-19 | Dow Global Technologies Inc. | Filled tpo compositions with good low temperature ductility |
US7762857B2 (en) * | 2007-10-01 | 2010-07-27 | Fci Americas Technology, Inc. | Power connectors with contact-retention features |
EP2062937A1 (en) * | 2007-11-26 | 2009-05-27 | Total Petrochemicals Research Feluy | Heterophasic propylene copolymer for corrugated sheet and cast film applications |
JP5156415B2 (en) * | 2008-02-01 | 2013-03-06 | トピー工業株式会社 | High rigidity and high impact resistance resin composition |
WO2009152345A1 (en) | 2008-06-12 | 2009-12-17 | 3M Innovative Properties Company | Biocompatible hydrophilic compositions |
CN102105625B (en) * | 2008-06-12 | 2015-07-08 | 3M创新有限公司 | Melt blown fine fibers and methods of manufacture |
US8062051B2 (en) | 2008-07-29 | 2011-11-22 | Fci Americas Technology Llc | Electrical communication system having latching and strain relief features |
US8246918B2 (en) * | 2008-10-21 | 2012-08-21 | Fina Technology, Inc. | Propylene polymers for lab/medical devices |
US7851554B2 (en) * | 2008-10-27 | 2010-12-14 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymers with balanced impact strength and stiffness |
US8323049B2 (en) | 2009-01-30 | 2012-12-04 | Fci Americas Technology Llc | Electrical connector having power contacts |
USD619099S1 (en) | 2009-01-30 | 2010-07-06 | Fci Americas Technology, Inc. | Electrical connector |
US8366485B2 (en) | 2009-03-19 | 2013-02-05 | Fci Americas Technology Llc | Electrical connector having ribbed ground plate |
MX347301B (en) | 2009-03-31 | 2017-04-21 | 3M Innovative Properties Co | Dimensionally stable nonwoven fibrous webs and methods of making and using the same. |
USD618181S1 (en) | 2009-04-03 | 2010-06-22 | Fci Americas Technology, Inc. | Asymmetrical electrical connector |
USD618180S1 (en) | 2009-04-03 | 2010-06-22 | Fci Americas Technology, Inc. | Asymmetrical electrical connector |
WO2011008589A1 (en) * | 2009-07-14 | 2011-01-20 | Dow Global Technologies Inc. | Polypropylene impact copolymers having high melt flow and izod ductility |
WO2011032917A1 (en) * | 2009-09-21 | 2011-03-24 | Basell Poliolefine Italia S.R.L. | Polymer filament |
EP2488583B1 (en) | 2009-10-13 | 2014-01-15 | Basell Poliolefine Italia S.r.l. | Propylene polymer compositions |
WO2011084670A1 (en) * | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
WO2011075619A1 (en) | 2009-12-17 | 2011-06-23 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs, melt blown fine fibers, and methods of making and using the same |
EP2539496B1 (en) | 2010-02-23 | 2016-02-10 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
TW201221714A (en) | 2010-10-14 | 2012-06-01 | 3M Innovative Properties Co | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
US8980415B2 (en) | 2010-12-03 | 2015-03-17 | Benoit Ambroise | Antistatic films and methods to manufacture the same |
PL2655505T3 (en) * | 2010-12-20 | 2019-03-29 | Braskem America, Inc. | Propylene-based compositions of enhanced appearance and excellent mold flowability |
US20120272468A1 (en) | 2011-04-26 | 2012-11-01 | The Procter & Gamble Company | Oral Care Device Comprising A Synthetic Polymer Derived From A Renewable Resource And Methods Of Producing Said Device |
US8809461B2 (en) * | 2011-04-28 | 2014-08-19 | Braskem America, Inc. | Multimodal heterophasic copolymer and thermoformed articles from same |
US8530581B2 (en) | 2011-12-12 | 2013-09-10 | Exxonmobil Chemical Patents Inc. | Powder, compositions thereof, processes for making the same, and articles made therefrom |
EP2624034A1 (en) | 2012-01-31 | 2013-08-07 | Fci | Dismountable optical coupling device |
USD727268S1 (en) | 2012-04-13 | 2015-04-21 | Fci Americas Technology Llc | Vertical electrical connector |
US8944831B2 (en) | 2012-04-13 | 2015-02-03 | Fci Americas Technology Llc | Electrical connector having ribbed ground plate with engagement members |
USD718253S1 (en) | 2012-04-13 | 2014-11-25 | Fci Americas Technology Llc | Electrical cable connector |
USD727852S1 (en) | 2012-04-13 | 2015-04-28 | Fci Americas Technology Llc | Ground shield for a right angle electrical connector |
US9257778B2 (en) | 2012-04-13 | 2016-02-09 | Fci Americas Technology | High speed electrical connector |
USD751507S1 (en) | 2012-07-11 | 2016-03-15 | Fci Americas Technology Llc | Electrical connector |
US9543703B2 (en) | 2012-07-11 | 2017-01-10 | Fci Americas Technology Llc | Electrical connector with reduced stack height |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
MX2015002874A (en) | 2012-09-11 | 2015-07-17 | Sika Technology Ag | Thermoplastic mixture with high flexibility and high melting point. |
CN104755511B (en) | 2012-10-31 | 2016-12-28 | 埃克森美孚化学专利公司 | Propylene copolymer compositions and preparation method thereof |
US9322114B2 (en) | 2012-12-03 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Polypropylene fibers and fabrics |
WO2014088827A1 (en) | 2012-12-05 | 2014-06-12 | Exxonmobil Chemical Patents Inc. | Hdpe modified polyethylene blown film compositions having excellent bubble stability |
CN106113851A (en) | 2012-12-18 | 2016-11-16 | 埃克森美孚化学专利公司 | Polyethylene film and manufacture method thereof |
USD745852S1 (en) | 2013-01-25 | 2015-12-22 | Fci Americas Technology Llc | Electrical connector |
USD720698S1 (en) | 2013-03-15 | 2015-01-06 | Fci Americas Technology Llc | Electrical cable connector |
BR112015026427B1 (en) | 2013-05-14 | 2020-07-21 | Exxonmobil Chemical Patents Inc. | ethylene-based polymers and articles made of the same |
US20140355122A1 (en) | 2013-05-28 | 2014-12-04 | Tredegar Film Products Corporation | Polyolefin Volumetric Diffuser |
EP3011089B1 (en) * | 2013-06-18 | 2020-12-02 | ExxonMobil Chemical Patents Inc. | Fibers and nonwoven materials prepared therefrom |
US9938364B2 (en) | 2013-07-17 | 2018-04-10 | Exxonmobil Chemical Patents Inc. | Substituted metallocene catalysts |
EP3022236B1 (en) | 2013-07-17 | 2017-11-15 | ExxonMobil Chemical Patents Inc. | Process using substituted metallocene catalysts and products therefrom |
WO2015009471A1 (en) | 2013-07-17 | 2015-01-22 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
WO2015009473A1 (en) | 2013-07-17 | 2015-01-22 | Exxonmobil Chemical Patents Inc. | Cyclopropyl substituted metallocene catalysts |
EP3022234B1 (en) | 2013-07-17 | 2018-12-26 | ExxonMobil Chemical Patents Inc. | Substituted metallocene catalysts |
CN105358589B (en) | 2013-07-17 | 2018-07-03 | 埃克森美孚化学专利公司 | Metallocene and by its derivative carbon monoxide-olefin polymeric |
US10006165B2 (en) | 2013-09-30 | 2018-06-26 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
CN105579630B (en) | 2013-09-30 | 2018-03-23 | 3M创新有限公司 | Fiber, cleaning piece and method |
US20160235057A1 (en) | 2013-09-30 | 2016-08-18 | 3M Innovative Properties Company | Compositions, Wipes, and Methods |
US9266910B2 (en) | 2013-10-29 | 2016-02-23 | Exxonmobil Chemical Patents Inc. | Asymmetric polypropylene catalysts |
US9376559B2 (en) | 2013-11-22 | 2016-06-28 | Exxonmobil Chemical Patents Inc. | Reverse staged impact copolymers |
WO2015085446A1 (en) | 2013-12-10 | 2015-06-18 | Exxonmobil Chemical Patents Inc. | Methods for making multilayer films and films made thereby |
BR112016013611B1 (en) | 2013-12-20 | 2021-01-05 | Saudi Basic Industries Corporation | polyolefin compound, composition and article, heterophasic propylene copolymer and their uses |
MX2016008028A (en) | 2013-12-20 | 2017-05-12 | Saudi Basic Ind Corp | Heterophasic propylene copolymer. |
AU2015270854B2 (en) | 2014-06-02 | 2018-08-02 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
WO2016038211A1 (en) * | 2014-09-12 | 2016-03-17 | Borealis Ag | Process for the preparation of copolymers of propylene |
CN106795237B (en) | 2014-10-03 | 2019-07-26 | 埃克森美孚化学专利公司 | Polyethylene polymer, the film being made from it and its manufacturing method |
JP6663096B2 (en) * | 2015-02-19 | 2020-03-11 | 住友化学株式会社 | Thermoplastic elastomer composition |
CN107531035B (en) | 2015-03-17 | 2022-11-22 | 埃克森美孚化学专利公司 | Multilayer film and method for producing same |
US10618989B2 (en) | 2015-04-20 | 2020-04-14 | Exxonmobil Chemical Patents Inc. | Polyethylene composition |
KR102537802B1 (en) | 2015-06-11 | 2023-05-31 | 다우 글로벌 테크놀로지스 엘엘씨 | Cable insulation comprising a blend of LDPE and polypropylene |
CN109070531B (en) | 2016-03-11 | 2020-09-18 | 埃克森美孚化学专利公司 | Multilayer film and method for producing same |
EP3445808A1 (en) | 2016-04-22 | 2019-02-27 | ExxonMobil Chemical Patents Inc. | Polyethylene sheets |
WO2018102091A1 (en) | 2016-12-02 | 2018-06-07 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
WO2018106480A1 (en) | 2016-12-06 | 2018-06-14 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2018151903A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2018187047A1 (en) | 2017-04-06 | 2018-10-11 | Exxonmobil Chemical Patents Inc. | Cast films and processes for making the same |
WO2018194740A1 (en) | 2017-04-19 | 2018-10-25 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2018226311A1 (en) | 2017-06-08 | 2018-12-13 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and extrudates and methods of making the same |
WO2019027524A1 (en) | 2017-08-02 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
US10913808B2 (en) | 2017-08-04 | 2021-02-09 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with unbridged hafnocenes with -CH2-SiMe3 moieties |
WO2019027586A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with 2, 6-bis(imino)pyridy| iron complexes and bridged hafnocenes |
CN111094366B (en) | 2017-08-04 | 2022-06-24 | 埃克森美孚化学专利公司 | Polyethylene compositions and films made therefrom |
WO2019027605A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Films made from polyethylene compositions and processes for making the same |
US11691398B2 (en) | 2017-11-28 | 2023-07-04 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
CN115850552A (en) | 2017-12-01 | 2023-03-28 | 埃克森美孚化学专利公司 | Catalyst system and polymerization process using the same |
WO2019108327A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Films comprising polyethylene composition |
EP3749707A1 (en) | 2018-02-05 | 2020-12-16 | ExxonMobil Chemical Patents Inc. | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
EP3807358B1 (en) | 2018-06-13 | 2023-11-15 | ExxonMobil Chemical Patents Inc. | Polyolefin blend compositions |
CN112313254B (en) | 2018-06-19 | 2023-04-18 | 埃克森美孚化学专利公司 | Polyethylene compositions and films made therefrom |
WO2020068497A1 (en) | 2018-09-25 | 2020-04-02 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
US20220056168A1 (en) | 2018-11-01 | 2022-02-24 | Exxonmobil Chemical Patents Inc. | Slurry Trim Feeder Modifications |
EP3873950A1 (en) | 2018-11-01 | 2021-09-08 | ExxonMobil Chemical Patents Inc. | On-line adjustment of catalysts by trim and olefin polymerization |
US20220033536A1 (en) | 2018-11-01 | 2022-02-03 | Exxonmobil Chemical Patents Inc. | On-Line Adjustment of Mixed Catalyst Ratio By Trim and Olefin Polymerization with the Same |
WO2020092584A2 (en) | 2018-11-01 | 2020-05-07 | Exxonmobil Chemical Patents Inc. | In-line trimming of dry catalyst feed |
US20220033535A1 (en) | 2018-11-01 | 2022-02-03 | Exxonmobil Chemical Patents Inc. | On-Line Adjustment of Mixed Catalyst Ratio and Olefin Polymerization |
WO2020139499A1 (en) | 2018-12-26 | 2020-07-02 | Exxonmobil Chemical Patents Inc. | Multilayer metallized cast polypropylene films doped with hydrocarbon resin |
WO2020167929A1 (en) | 2019-02-13 | 2020-08-20 | Exxonmobil Chemical Patents Inc. | Methods for making films and films made thereby |
WO2020167441A1 (en) | 2019-02-13 | 2020-08-20 | Exxonmobil Chemical Patents Inc. | Oriented multilayer polyethylene films and laminates thereof |
WO2020190507A1 (en) | 2019-03-19 | 2020-09-24 | Exxonmobil Chemical Patents Inc. | Multilayer oriented films |
US11180646B2 (en) | 2019-08-20 | 2021-11-23 | Exxonmobil Chemical Patents Inc. | Films and methods of making the same |
US11518154B2 (en) | 2020-01-27 | 2022-12-06 | Exxonmobil Chemical Patents Inc. | Barrier films for packaging |
WO2021167739A1 (en) | 2020-02-18 | 2021-08-26 | Exxonmobil Chemical Patents Inc. | High tenacity handwrap stretch film for improved pallet stability |
WO2021195070A1 (en) | 2020-03-26 | 2021-09-30 | Exxonmobil Chemical Patents Inc. | Processes for making 3-d objects from blends of polypropylene and semi-amorphous polymers |
CN116917353A (en) | 2021-03-05 | 2023-10-20 | 埃克森美孚化学专利公司 | Methods of making and using slurry catalyst mixtures |
WO2022203461A1 (en) * | 2021-03-26 | 2022-09-29 | 주식회사 엘지화학 | Polypropylene resin composition and method for preparing same |
WO2022203463A1 (en) * | 2021-03-26 | 2022-09-29 | 주식회사 엘지화학 | Polypropylene resin composition and non-woven fabric prepared using same |
WO2023150480A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | C1 symmetric 5-ome-6-alkyl substituted metallocenes |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0641807A2 (en) * | 1993-08-13 | 1995-03-08 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for preparing polypropylene and a propylene block copolymer |
EP0657500A1 (en) * | 1993-06-30 | 1995-06-14 | Mitsui Petrochemical Industries, Ltd. | Polypropylene composition |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5382631A (en) | 1988-09-30 | 1995-01-17 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions |
US5258464A (en) | 1990-01-29 | 1993-11-02 | Shell Oil Company | Impact copolymer compositions |
US5118757A (en) | 1990-03-26 | 1992-06-02 | Shell Oil Company | Polymer production |
US5166268A (en) | 1990-04-12 | 1992-11-24 | Union Carbide Chemicals & Plastics Technology Corporation | Process for cold forming propylene copolymers |
US5362782A (en) | 1990-05-14 | 1994-11-08 | Shell Oil Company | Polymer compositions |
US5250631A (en) | 1990-06-13 | 1993-10-05 | Shell Oil Company | Polymer compositions |
DE4130429A1 (en) | 1991-09-13 | 1993-03-18 | Basf Ag | METHOD FOR PRODUCING MULTI-PHASE BLOCK COPOLYMERISATS BASED ON ALK-1-ENEN |
US5830821A (en) | 1991-11-30 | 1998-11-03 | Targor Gmbh | Process for olefin preparation using metallocenes having benzo-fused indenyl derivatives as ligands |
TW294669B (en) | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
DE59309424D1 (en) | 1992-08-15 | 1999-04-15 | Targor Gmbh | Process for the production of polyolefins |
EP0812854B2 (en) | 1993-06-07 | 2011-04-20 | Mitsui Chemicals, Inc. | Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer |
WO1995027741A1 (en) * | 1994-04-11 | 1995-10-19 | Mitsui Petrochemical Industries, Ltd. | Process for producing propylene polymer composition, and propylene polymer composition |
CA2157400C (en) | 1994-04-11 | 2003-07-29 | Takashi Ueda | Process for preparing propylene polymer composition, and propylene polymer composition |
JP3357186B2 (en) | 1994-07-14 | 2002-12-16 | 三菱化学株式会社 | Method for producing propylene block copolymer |
KR100359370B1 (en) | 1995-02-07 | 2003-02-11 | 미쓰이 가가쿠 가부시키가이샤 | Manufacturing method of olefin polymer |
US5674630A (en) | 1995-05-08 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Polymer compositions and cast films |
JPH09151294A (en) | 1995-09-29 | 1997-06-10 | Mitsubishi Chem Corp | Talc-containing propylene resin composition |
US5712344A (en) | 1996-01-04 | 1998-01-27 | Union Carbide Chemicals & Plastics Technology Corporation | Modified polypropylene impact copolymer compositions |
JPH09208881A (en) | 1996-02-07 | 1997-08-12 | Mitsubishi Chem Corp | Propylene resin composition for coating |
SG67392A1 (en) | 1996-05-27 | 1999-09-21 | Sumitomo Chemical Co | Propylene/ethylene-alpha-olefin block copolymer and process for producing the same |
AU1211197A (en) | 1997-01-10 | 1998-08-03 | Chisso Corporation | Propylene/ethylene copolymer, process for the production thereof, and molded articles thereof |
WO1998040331A1 (en) | 1997-03-07 | 1998-09-17 | Targor Gmbh | Preparation of preparing substituted indanones |
US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
US6635715B1 (en) * | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6201069B1 (en) * | 1997-08-29 | 2001-03-13 | Chisso Corporation | Polypropylene/propylene-ethylene copolymer composition and process for the preparation thereof |
DE19739946A1 (en) | 1997-09-11 | 1999-03-18 | Targor Gmbh | Process for the production of metallocenes |
US5942587A (en) | 1997-11-21 | 1999-08-24 | Exxon Chemical Patents Inc. | Ethylene polymers with a norbornene comonomer for LLDPE like resins of improved toughness and processibility for film production |
US5986009A (en) * | 1997-12-03 | 1999-11-16 | The Dow Chemical Company | Blends of polypropylenes |
US6469100B2 (en) | 1998-06-04 | 2002-10-22 | Japan Polychem Corporation | Propylene block copolymer and resin composition |
US6492465B1 (en) * | 2000-02-08 | 2002-12-10 | Exxonmobil Chemical Patents, Inc. | Propylene impact copolymers |
-
2000
- 2000-03-24 US US09/534,556 patent/US6492465B1/en not_active Expired - Fee Related
- 2000-03-24 US US09/535,357 patent/US6384142B1/en not_active Expired - Fee Related
-
2001
- 2001-02-08 WO PCT/US2001/004126 patent/WO2001058970A1/en active IP Right Grant
- 2001-02-08 CN CN01804671A patent/CN1398272A/en active Pending
- 2001-02-08 DE DE60108075T patent/DE60108075T2/en not_active Expired - Lifetime
- 2001-02-08 BR BR0108150-0A patent/BR0108150A/en not_active IP Right Cessation
- 2001-02-08 JP JP2001558115A patent/JP2003522259A/en active Pending
- 2001-02-08 KR KR1020027010245A patent/KR20020073209A/en not_active Application Discontinuation
- 2001-02-08 AT AT01910477T patent/ATE286082T1/en not_active IP Right Cessation
- 2001-02-08 KR KR1020027010213A patent/KR20020074509A/en not_active Application Discontinuation
- 2001-02-08 EP EP01910477A patent/EP1254186B1/en not_active Expired - Lifetime
- 2001-02-08 CA CA002398509A patent/CA2398509A1/en not_active Abandoned
- 2001-02-08 EP EP04021067A patent/EP1481997B1/en not_active Expired - Lifetime
- 2001-05-21 US US09/862,667 patent/US6342566B2/en not_active Expired - Lifetime
- 2001-11-27 US US09/996,245 patent/US6472474B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0657500A1 (en) * | 1993-06-30 | 1995-06-14 | Mitsui Petrochemical Industries, Ltd. | Polypropylene composition |
EP0641807A2 (en) * | 1993-08-13 | 1995-03-08 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for preparing polypropylene and a propylene block copolymer |
Cited By (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7026040B2 (en) | 1996-09-04 | 2006-04-11 | Exxon Mobil Chemical Patents Inc. | Oriented films from improved propylene polymers |
US6583227B2 (en) | 1996-09-04 | 2003-06-24 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
US6806316B2 (en) | 1996-09-04 | 2004-10-19 | Exxonmobil Chemical Patents Inc. | Propylene polymers for oriented films |
US7122498B2 (en) | 2000-06-30 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
WO2002070572A3 (en) * | 2001-03-06 | 2002-11-07 | Exxonmobil Chem Patents Inc | Propylene polymers for films |
WO2002070572A2 (en) * | 2001-03-06 | 2002-09-12 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
WO2003002583A2 (en) | 2001-06-29 | 2003-01-09 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
WO2003002583A3 (en) * | 2001-06-29 | 2004-03-04 | Exxonmobil Chem Patents Inc | Metallocenes and catalyst compositions derived therefrom |
WO2003045551A1 (en) * | 2001-11-30 | 2003-06-05 | Basell Polyolefine Gmbh | Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins |
US7109278B2 (en) | 2001-11-30 | 2006-09-19 | Basell Polyolefine Gmbh | Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins |
KR100954975B1 (en) * | 2002-03-29 | 2010-04-30 | 구미아이 가가쿠 고교 가부시키가이샤 | Genes Encoding Acetolactate Synthase |
US8030547B2 (en) | 2002-03-29 | 2011-10-04 | Kumiai Chemical Industry Co., Ltd. | Gene coding for acetolactate synthase |
JP2005528412A (en) * | 2002-04-23 | 2005-09-22 | ダウ・グローバル・テクノロジーズ・インコーポレイテッド | Alkaryl-substituted group 4 metal complex, catalyst, and olefin polymerization method |
US7439312B2 (en) | 2002-10-24 | 2008-10-21 | Exxonmobil Chemical Patents Inc. | Branched crystalline polypropylene |
US8304496B2 (en) | 2005-05-12 | 2012-11-06 | Dow Global Technologies Llc | Thermoformed, extruded sheeting with reduced gloss |
US8299287B2 (en) | 2007-10-25 | 2012-10-30 | Lammus Novolen Technology GmbH | Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers |
WO2009054833A2 (en) | 2007-10-25 | 2009-04-30 | Novolen Technology Holdings, C.V. | Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo and copolymers |
US8507706B2 (en) | 2007-10-25 | 2013-08-13 | Lummus Novolen Technology Gmbh | Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers |
EP2075284A1 (en) * | 2007-12-17 | 2009-07-01 | Borealis Technology OY | Heterophasic polypropylene with high flowability and excellent low temperature impact properties |
WO2009077032A1 (en) * | 2007-12-17 | 2009-06-25 | Borealis Technology Oy | Heterophasic polypropylene with high flowability and excellent low temperature impact properties |
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US8445598B2 (en) | 2007-12-17 | 2013-05-21 | Borealis Technology Oy | Heterophasic polypropylene with high flowability and excellent low temperature impact properties |
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US8404773B2 (en) | 2008-03-17 | 2013-03-26 | Dow Global Technologies Llc | Coating composition, method of producing the same, articles made therefrom, and method of making such articles |
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Also Published As
Publication number | Publication date |
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US6384142B1 (en) | 2002-05-07 |
EP1254186B1 (en) | 2004-12-29 |
BR0108150A (en) | 2003-01-21 |
US6472474B2 (en) | 2002-10-29 |
DE60108075T2 (en) | 2005-12-08 |
EP1481997A1 (en) | 2004-12-01 |
DE60108075D1 (en) | 2005-02-03 |
CA2398509A1 (en) | 2001-08-16 |
US20020086947A1 (en) | 2002-07-04 |
US6342566B2 (en) | 2002-01-29 |
KR20020074509A (en) | 2002-09-30 |
EP1254186A1 (en) | 2002-11-06 |
KR20020073209A (en) | 2002-09-19 |
CN1398272A (en) | 2003-02-19 |
JP2003522259A (en) | 2003-07-22 |
ATE286082T1 (en) | 2005-01-15 |
EP1481997B1 (en) | 2006-08-16 |
US20010034411A1 (en) | 2001-10-25 |
US6492465B1 (en) | 2002-12-10 |
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