bottle closure, process for preparing said closure, polyethylene composition and process for prepari

专利摘要:
POLYETHYLENE COMPOSITIONS HAVING HIGH DIMENSIONAL STABILITY AND EXCELLENT PROCESSABILITY FOR COVERS AND CLOSES A double reactor solution polymerization process provides high density polyethylene compositions containing a first ethylene copolymer and a second ethylene copolymer and which have excellent, high dimensional stability processability as well as good organoleptic properties and resistance to cracking by reasonable stress. Polyethylene compositions are suitable for compression molding or injection molding applications and are particularly useful in the manufacture of bottle caps and closures, especially bottles containing non-pressurized liquids.
公开号:BR112015013775B1
申请号:R112015013775-0
申请日:2013-10-22
公开日:2021-03-16
发明作者:XiaoChuan Wang；Yves Lacombe；Mark Rejman；Douglas Walter Checknita；Matthew Zaki Botros；Renée Laurel Anseeuw
申请人:Nova Chemicals (International) S.A.；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to polyethylene compositions that are useful in the manufacture of molded articles such as bottle closures. TECHNICAL FUNDAMENTALS
[002] Polymeric compositions useful for molding applications, specifically the manufacture of bottle caps and closures are well known. Threaded closures, for example, are typically made of polypropylene (PP) in order to obtain the required cover strength, however, an inner coating composed of a soft polymer is necessary to provide the necessary sealing properties. Also, a typical PP closure alone does not have good organoleptic properties, which is another reason to use a coating. The soft inner lining can be made of ethylene / vinyl acetate (EVA), polyvinyl chloride (PVC), butyl rubber or other suitable material. The two-part lid is expensive, and single-part constructions are preferred to reduce cost.
[003] One-piece closures, such as screw caps, were more recently manufactured from polyethylene (PE) resins. The use of high density resin is necessary if the closures must be sufficiently rigid, while good flow properties combined with an ability to withstand cracking over time (as measured, for example, by environmental stress crack resistance (ESCR) )) is also desirable. In addition, closures that can be produced quickly while not suffering from anisotropic contraction when released from a mold are also desirable. Such closures, for example, screw cap closures for water bottles, must when produced at high turnover, consistently satisfy strict dimensional tolerances to provide a compatible fit and seal and to maintain product integrity. Generally, polyethylene closures alone have better organoleptic properties than PP closures alone.
[004] Polyethylene blends produced with conventional Ziegler-Natta or Phillips type catalyst systems can be manufactured having suitably high density and ESCR properties, see for example, WO 00/71615 and Pat. No. 5,981,664. However, the use of conventional catalyst systems typically produces significant amounts of low molecular weight polymer chains having high comonomer contents, which results in resins having non-ideal organoleptic properties.
[005] Examples of high density multimodal polyethylene blends manufactured using conventional catalyst systems for the manufacture of lids or closures are shown in Pat. No. 7,750,083; 7,750,082; 7,790,826; 8,044,160; and 8,129,472; Pat. Pub. U.S. Nos. 2007/0213468 and 2008/0287608, as well as WO 2007/060007 and EP 2,017,302A1. Other multimodal, high density polyethylene blends manufactured using conventional Ziegler-Natta catalysts are disclosed in Pub. Of Pat. No. Nos. 2009/0198018; 2009/0203848; 2008/0221273; 2010/0084363 and 2012/0022214.
[006] Unlike traditional catalysts, the use of so-called single-site catalysts (such as "metallocene" and "restricted geometry" catalysts) provides resin having lower catalyst residues and improved organoleptic properties as shown by Pat. No. 6,806,338. The disclosed resins are suitable for use in molded articles. Other resins comprising metallocene-catalyzed components that are useful for molding applications are described in U.S. Pat. No. 7,022,770; 7,307,126; 7,396,878; 7,396,881; and 7,700,708.
[007] A monomodal polyethylene composition that is useful in the preparation of a screw closure was manufactured using a mixed metallocene catalyst system as described in Pat. No. 8,039,569.
[008] The Pub. Of Pat. No. 2011 / 0165357A1 discloses a blend of metallocene-catalyzed resins that is suitable for use in pressure resistant pipe applications.
[009] The Pub. Of Pat. No. 2006 / 0241256A1 shows formulated blends of polyethylene manufactured using a hafnocene catalyst in the slurry phase.
[010] A bimodal resin having a relatively narrow molecular weight distribution and long chain branching is described in U.S. Pat. No. 7,868,106. The resin is manufactured using a bis-indenyl metallocene catalyst in a double-flow cycle polymerization process and can be used to manufacture lids and closures.
[011] Pat. No. 6,642,313 discloses multimodal polyethylene resins that are suitable for use in the manufacture of tubes. A dual reactor solution polymerization process is used to prepare the resins in the presence of a phosphinimine catalyst.
[012] Polyethylene blends of narrow molecular weight distribution comprising a polyethylene component produced by metallocene and a polyethylene component produced by Zielger-Natta or metallocene are reported in Pat. No. 7,250,474. Blends can be used in blow molding and injection molding applications such as, for example, milk bottles and bottle caps respectively.
[013] For other references describing relevant polyethylene compositions see: Pat. No. 7,875,690; 6,545,093; 8,129,489; 6,063,871; 5,382,630; 5,382,631; 7,928,051; 6,809,154; 7,592,395; 6,194,520; 5,858,491; 6,946,521; and 5,494,965 as well as Pub. of Pat. U.S. Nos. 2010/0121006 and 2011/0136983.
[014] In Pat. No. 8,022,143 we disclose a resin composition having a good balance of toughness, ESCR, processability, and organoleptic properties for use in the manufacture of lids and closures. The resins were manufactured using a single site catalyst system in a dual reactor solution polymerization process, to provide bimodal polyethylene compositions in which the comonomer was present in both a high molecular weight and a low molecular weight component. The disclosed resins had a normal comonomer distribution in which the low molecular weight component had a greater amount of comonomer than the high molecular weight component.
[015] In patent application CA No. 2,752,407 we disclose resins having improved ESCR, good organoleptic properties, balanced rheological and mechanical properties and which were suitable for use in the manufacture of molded articles such as bottle closures.
[016] We have now discovered a single site catalyzed double reactor resin composition that has high dimensional stability, excellent processability and organoleptic properties as well as reasonable stress crack resistance. The new compositions have a better isotropic contraction ratio (that is, one that is closer to the unit), a lower contraction differential between the TD and MD directions (this is closer to zero) and better processability in the rate range extrusion shear (ie lower melt viscosity) compared to the resins disclosed in U.S. Pat. No. 8,022,143 and Pub. Of Pat. CA No. 2,752,407. The present resins are especially suitable for use in the manufacture of caps and closures for bottles containing water or other non-carbonated drinks. DISCLOSURE OF THE INVENTION
[017] The present invention provides a polyethylene composition that can be used in the manufacture of bottle caps and closures.
[018] The present invention provides a polyethylene composition that has good dimensional stability while maintaining low shear viscosity values at high shear rates which is desirable for high speed injection applications.
[019] The present invention provides lids and closures comprising a polyethylene composition manufactured by a double reactor solution phase polymerization process and a single site catalyst. Molded discs made from polyethylene compositions have good dimensional stability.
[020] A bottle closure is provided, the closure comprising a polyethylene composition, the polyethylene composition comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melt index of 0.1 at 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; an I21 / I-2 melt flow rate of 22 to 50; a voltage exponent of less than 1.40; and an ESCR Condition B (100% IGEPAL) of at least 3.5 h.
[021] In one embodiment of the invention, the closure is manufactured by compression molding.
[022] In one embodiment of the invention, the closure is manufactured by injection molding.
[023] In one embodiment of the invention, the closure is a screw cap.
[024] A polyethylene composition is provided comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melt index of 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; a composition distribution amplitude index (CDBI (50)) greater than 65%; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; a composition distribution amplitude index (CDBI (50)) greater than 65%; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and an ESCR Condition B (100% IGEPAL) of at least 3.5 h.
[025] A polyethylene composition is provided comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melt index of 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and an ESCR Condition B (100% IGEPAL) of at least 3.5 h.
[026] In an embodiment of the invention, the polyethylene composition has an ESCR Condition B (100% IGEPAL) from 3.5 to 15 h.
[027] In one embodiment of the invention, the polyethylene composition has a TD / MD contraction ratio of 0.90 to 1.15 when measured according to the Dimensional Stability Test (DST).
[028] In one embodiment of the invention, the polyethylene composition has an I2 melt index, greater than 5.0 to less than 20 g / 10 min.
[029] In one embodiment of the invention, the first and second ethylene copolymers are manufactured by polymerizing ethylene and an alpha olefin in the presence of a single site catalyst.
[030] In an embodiment of the invention, the density of the second ethylene copolymer is less than 0.030 g / cm3 higher than the density of the first ethylene copolymer.
[031] In one embodiment of the invention, the first ethylene copolymer has an I2 melt index of 0.1 to 3.0 g / 10 min.
[032] In an embodiment of the invention, the second ethylene copolymer has an I2 melt index, from 100 to 5000 g / 10 min.
[033] In one embodiment of the invention, the polyethylene composition has an I2 melt index of 6 to 12 g / 10 min.
[034] In one embodiment of the invention, the polyethylene composition has a bimodal molecular weight distribution as determined by gel permeation chromatography.
[035] In an embodiment of the invention, the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand atoms of carbon in the second ethylene copolymer (SCB2) is at least 1.5.
[036] In an embodiment of the invention, the polyethylene composition has a molecular weight distribution Mw / Mn, from 3.5 to 6.
[037] In an embodiment of the invention, the first ethylene copolymer has a density of 0.936 to 0.952 g / cm3.
[038] In an embodiment of the invention, the second ethylene copolymer has a density of less than 0.965 g / cm3.
[039] In an embodiment of the invention, the polyethylene composition has a density of 0.952 to 0.960 g / cm3.
[040] In one embodiment of the invention, the polyethylene composition has no long chain branches.
[041] In one embodiment of the invention, the polyethylene composition has a composition distribution amplitude index (CDBI (50)) greater than 65%.
[042] In one embodiment of the invention, the polyethylene composition has a composition distribution amplitude index (CDBI (50)) greater than 70%.
[043] In one embodiment of the invention, the first and second ethylene copolymers all have a composition distribution amplitude index (CDBI (50)) greater than 65%.
[044] In an embodiment of the invention, the polyethylene composition comprises: from 25 to 60% by weight of the first ethylene copolymer; and from 75 to 40% by weight of the second ethylene copolymer.
[045] In one embodiment of the invention, the polyethylene composition has a comonomer content of less than 0.5 mol% as determined by 13C NMR.
[046] In an embodiment of the invention, the polyethylene composition further comprises a nucleating agent.
[047] In one embodiment of the invention, the first and second ethylene copolymers are ethylene and 1-octene copolymers.
[048] A process for preparing a polyethylene composition is provided, the polyethylene composition comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melt index, from 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and an ESCR Condition B (100% IGEPAL) of at least 3.5 h; the process comprising contacting at least one single site polymerization catalyst system with ethylene and at least one alpha-olefin under solution polymerization conditions in at least two polymerization reactors.
[049] In an embodiment of the invention, the at least two polymerization reactors comprise a first reactor and a second reactor configured in series.
[050] In an embodiment of the invention, at least one alpha-olefin is fed exclusively to the first reactor. BRIEF DESCRIPTION OF THE DRAWINGS
[051] Figure 1 shows the balance of processability and ESCR for various inventive resins of the present invention and for some comparative resins as demonstrated by a batch of the processability indicator (100 / na 105 s-1 and 240 ° C) against ESCR B100. Inventive resins are particularly suitable for application in the manufacture of lids and closures.
[052] Figure 2 shows the balance of processability and impact resistance for several inventive resins of the present invention and for some comparative resins as demonstrated by a batch of the Notched Izod Impact Resistance (J / m) against the processability indicator ( 100 / na 105 s-1 and 240 ° C). Inventive resins are particularly suitable for application in the manufacture of lids and closures.
[053] Figure 3 shows a graph of the dimensional stability of several inventive resins of the present invention and for some comparative resins, where dimensional stability is demonstrated by a lot of the TD / MD shrinkage ratio (for an injection molded disc of circular shape) against the post-molding time (in hours).
[054] Figure 4 shows the TREF profile of an inventive resin and a comparative resin where each is manufactured with a single site catalyst by solution polymerization. The inventive resin has a CDBI (50) greater than 70% by weight and is particularly suitable for use in the manufacture of lids and closures. The comparative resin has a CDBI (50) of less than 50% by weight. BEST MODE FOR CARRYING OUT THE INVENTION
[055] The present invention relates to bottle caps and closures and the polyethylene compositions and processes used to manufacture them. Polyethylene compositions are composed of at least two ethylene copolymer components: a first ethylene copolymer and a second ethylene copolymer. The polyethylene compositions of the invention have good dimensional stability and are ideal materials for use in the manufacture of caps and closures for bottles containing non-carbonated soft drinks.
[056] The terms "cover" and "closure" are used interchangeably in the present invention, and both connote any properly formed shaped article for containment, sealing, closing or covering etc., a properly formed opening, a properly shaped opening, a structure open-necked or similar used in combination with a container, bottle, jar and the like.
[057] It is well known that metallocene catalysts and other so-called "single site catalysts" generally incorporate comonomer more uniformly than traditional Ziegler-Natta catalysts when used for copolymerization of catalytic ethylene with alpha olefins. This fact is often demonstrated by measuring the composition distribution amplitude index (CDBI) for corresponding ethylene copolymers. The distribution of the composition of a polymer can be characterized by the short chain distribution index (SCDI) or the composition distribution amplitude index (CDBI). The definition of the composition distribution amplitude index (CDBI (50)) can be found in PCT publication WO 93/03093 and Pat. No. 5,206,075. CDBI (50) is conveniently determined using techniques that isolate polymer fractions based on their solubility (and consequently their comonomer content). For example, elution fractionation with elevation of temperature (TREF) as described by Wild et al. J. Poli. Sci., Poli. Phys. Ed. Vol. 20, p441, 1982 or in Pat. No. 4,798,081 can be used. From the fraction by weight versus composition distribution curve, the CDBI (50) is determined by establishing the weight percentage of a copolymer sample that has a comonomer content within 50% of the median comonomer content on each side of the median. Alternatively, the CDBI (25), which is sometimes used in the art, is determined by establishing the weight percentage of a copolymer sample that has a comonomer content within 25% of the median comonomer content on each side of the median . The First Ethylene Copolymer
[058] The first ethylene copolymer of the polyethylene composition of the present invention has a density of about 0.930 g / cm3 to about 0.960 g / cm3; a melt index, I2, of more than 0.1 g / 10 min; a molecular weight distribution, Mw / Mn, below about 3.0 and a weighted average molecular weight Mw, which is greater than the Mw of the second ethylene copolymer. Preferably, the weighted average molecular weight Mw of the first ethylene copolymer is at least 50,000 g / mol.
[059] By the term “ethylene copolymer” it is meant that the copolymer comprises both polymerized ethylene and at least one polymerized alpha-olefin comonomer, with polymerized ethylene being the majority species.
[060] In an embodiment of the invention, the first ethylene copolymer is manufactured with a single site catalyst, such as for example a phosphinimine catalyst.
[061] The comonomer content (i.e. alpha-olefin) in the first ethylene copolymer can be from about 0.05 to about 3.0 mol% as measured by 13C NMR, or FTIR or GPC-FTIR methods , or as calculated from a reactor model (see the Examples section). The comonomer is one or more suitable alpha olefins such as, but not limited to, 1-butene, 1-hexene, 1-octene and the like, with 1-octene being preferred.
[062] The short chain branch in the first ethylene copolymer can be from about 0.25 to about 15 short chain branches per thousand carbon atoms (SCB1 / 1000Cs). In other embodiments of the invention, the short chain branch in the first ethylene copolymer can be 0.25 to 10, or 0.25 to 7.5, or 0.25 to 5, or 0.25 to 3 branches per thousand carbon atoms (SCB1 / 1000Cs). The short chain branch is the branch due to the presence of alpha-olefin comonomer in the ethylene copolymer and for example it will have two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc. The comonomer is one or more suitable alpha-olefins such as, but not limited to 1-butene, 1-hexene, 1-octene and the like, with 1-octene being preferred.
[063] In one embodiment of the invention, the comonomer content in the first ethylene copolymer is greater than the comonomer content of the second ethylene copolymer (as reported for example in mol%).
[064] In one embodiment of the invention, the amount of short chain branching in the first ethylene copolymer is greater than the amount of short chain branching in the second ethylene copolymer (as reported in short chain branches, SCB per thousand carbons in the polymer main chain, 1000Cs).
[065] The I2 melt index of the first ethylene copolymer can in an embodiment of the invention be from 0.1 to 10 g / 10 min and including narrower ranges within this range and any numbers covered by these ranges. For example, the I2 melt index of the first ethylene composition can be from above 0.1 to below 10 g / 10 min, or it can be from 0.1 to 7.5 g / 10 min, or from 0, 1 to 5.0 g / 10 min, or from 0.1 to 3.0 g / 10 min, or from 0.1 to 2.5 g / 10 min, or from 0.1 to 1.0 g / 10 min.
[066] In one embodiment of the invention, the first ethylene copolymer has a weighted average molecular weight Mw of about 50,000 to about 225,000 g / mol including narrower ranges and any numbers covered by these ranges. For example, in another embodiment of the invention, the first ethylene copolymer has a weighted average molecular weight Mw of about 75,000 to about 200,000. In other embodiments of the invention, the first ethylene copolymer has a weighted average molecular weight Mw of about 75,000 to about 175,000, or from about 85,000 to about 150,000, or from about 100,000 to about 150,000.
[067] The density of the first ethylene copolymer in the present invention is from 0.930 to 0.960 g / cm3 or it can be a narrower range within this range and any numbers covered by these ranges. For example, in other embodiments of the invention, the density of the first ethylene copolymer can be from 0.936 to 0.960 g / cm3, or it can be from 0.938 to 0.960 g / cm3, or from 0.936 to 0.952 g / cm3, or 0.938 to 0.952 g / cm3, or from 0.936 to 0.950 g / cm3, or from 0.938 to 0.950 g / cm3, or from 0.936 to 0.947 g / cm3, or from 0.938 to 0.947 g / cm3, or from 0.936 to 0.945 g / cm3 cm3, or from 0.938 to 0.945 g / cm3.
[068] In embodiments of the invention, the first ethylene copolymer has a molecular weight distribution Mw / Mn of <3.0, or <2.7, or <2.7, or <2.5, or < 2.5, or <2.3, or 1.8 to 2.3.
[069] In an embodiment of the invention, the first ethylene copolymer of the polyethylene composition is produced with a single site catalyst and has a weighted average molecular weight MW of at least 50,000 g / mol; a molecular weight distribution, Mw / Mn, of less than 3.0 and a density of 0.936 to 0.950 g / cm3.
[070] In an embodiment of the invention, a single site catalyst that provides an ethylene copolymer having a CDBI (50) of at least 65% by weight, or at least 70%, or at least 75%, or at least at least 80%, or at least 85%, during solution phase polymerization in a single reactor, is used in the preparation of the first ethylene copolymer.
[071] In one embodiment of the present invention, the first ethylene copolymer is an ethylene copolymer that has a CDBI (50) greater than about 60% by weight, or greater than about 65%, or greater than than about 70%, or greater than about 75%, or greater than about 80%, or greater than about 85%.
[072] The first ethylene copolymer can comprise from 10 to 70 weight percent (% by weight) of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the first ethylene copolymer comprises from 20 to 60 weight percent (% by weight) of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the first ethylene copolymer comprises from 25 to 60 weight percent (% by weight) of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the first ethylene copolymer comprises from 30 to 60 weight percent (% by weight) of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the first ethylene copolymer comprises from 40 to 50 weight percent (% by weight) of the total weight of the first and second ethylene copolymers. The second Ethylene Copolymer
[073] The second ethylene copolymer of the polyethylene composition of the present invention has a density below 0.967 g / cm3 but which is higher than the density of the first ethylene copolymer; an I2 melt index of about 50 to 10,000 g / 10 min; a molecular weight distribution, Mw / Mn, below about 3.0 and a weighted average molecular weight Mw that is less than the Mw of the first ethylene copolymer. Preferably, the weighted average molecular weight, Mw of the second ethylene copolymer will be below 45,000 g / mol.
[074] By the term “ethylene copolymer” it is meant that the copolymer comprises both polymerized ethylene and at least one polymerized alpha-olefin comonomer, with polymerized ethylene being the majority species.
[075] In an embodiment of the invention, the second ethylene copolymer is manufactured with a single site catalyst, such as for example a phosphinimine catalyst.
[076] The comonomer content in the second ethylene copolymer can be from about 0.05 to about 3 mol% as measured by the 13C NMR, or FTIR or GPC-FTIR methods, or as calculated from a reactor model (see the Examples section). The comonomer is one or more suitable alpha olefins such as but not limited to 1-butene, 1-hexene, 1-octene and the like, with the use of 1-octene being preferred.
[077] The short chain branch in the second ethylene copolymer can be from about 0.25 to about 15 short chain branches per thousand carbon atoms (SCB1 / 1000Cs). In other embodiments of the invention, the short chain branch in the first ethylene copolymer can be 0.25 to 10, or 0.25 to 7.5, or 0.25 to 5, or 0.25 to 3 branches per thousand carbon atoms (SCB1 / 1000Cs). The short chain branch is the branch due to the presence of alpha-olefin comonomer in the ethylene copolymer and for example it will have two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc. The comonomer is one or more suitable alpha olefins such as but not limited to 1-butene, 1-hexene, 1-octene and the like, with 1-octene being preferred.
[078] In one embodiment of the invention, the comonomer content in the second ethylene copolymer is less than the comonomer content of the first ethylene copolymer (as reported for example in mol%).
[079] In one embodiment of the invention, the amount of short chain branching in the second ethylene copolymer is less than the amount of short chain branching in the first ethylene copolymer (as reported in short chain branches, SCB per thousand carbons in the polymer main chain, 1000Cs).
[080] In the present invention, the density of the second ethylene copolymer is less than 0.967 g / cm3. In another embodiment of the invention, the density of the second ethylene copolymer is less than 0.966 g / cm3. In another embodiment of the invention, the density of the second ethylene copolymer is less than 0.965 g / cm3. In another embodiment of the invention, the density of the second ethylene copolymer is less than 0.964 g / cm3. In an embodiment of the invention, the density of the second ethylene copolymer is from 0.952 to 0.967 g / cm3 or it can be a narrower range within this range, including the entire number falling within these ranges.
[081] In the present invention, the second ethylene copolymer has a density that is higher than the density of the first ethylene copolymer, but less than about 0.037 g / cm3 higher than the density of the first ethylene copolymer . In an embodiment of the invention, the second ethylene copolymer has a density that is higher than the density of the first ethylene copolymer, but less than about 0.035 g / cm3 higher than the density of the first ethylene copolymer. ethylene. In another embodiment of the invention, the second ethylene copolymer has a density that is higher than the density of the first ethylene copolymer, but less than about 0.030 g / cm3 higher than the density of the first copolymer of ethylene. In yet another embodiment of the invention, the second ethylene copolymer has a density that is higher than the density of the first ethylene copolymer, but less than about 0.027 g / cm3 higher than the density of the first ethylene copolymer. In yet another embodiment of the invention, the second ethylene copolymer has a density that is higher than the density of the first ethylene copolymer, but less than about 0.025 g / cm3 higher than the density of the first ethylene copolymer.
[082] In an embodiment of the invention, the second ethylene copolymer has a weighted average molecular weight Mw of less than 45,000 g / mol. In another embodiment of the invention, the second ethylene copolymer has a weighted average molecular weight Mw of about 7,500 to about 40,000. In other embodiments of the invention, the second ethylene copolymer has a weighted average molecular weight Mw of about 9,000 to about 35,000, or from about 10,000 to about 30,000, or from about 10,000 to 25,000.
[083] In embodiments of the invention, the second ethylene copolymer has a molecular weight distribution (Mw / Mn) of <3.0, or <2.7, or <2.7, or <2.5, or <2.5, or <2.3, or 1.8 to 2.3.
[084] In one embodiment of the invention, the I2 melt index of the second ethylene copolymer can be 50 to 10,000 g / 10 min. In another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 100 to 5,000 g / 10 min. In another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 50 to 3,500 g / 10 min. In another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 100 to 10,000 g / 10 min. In yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 1000 to 7000 g / 10 min. In yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 1200 to 10,000 g / 10 min. In yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be from 1200 to 7,000 g / 10 min. In yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be greater than 1200, but less than 5000 g / 10 min. However, in yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be greater than 1000, but less than 3000 g / 10 min. However, in yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be greater than 500, but less than 3000 g / 10 min. However, in yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be greater than 250, but less than 2700 g / 10 min. However, in yet another embodiment of the invention, the I2 melt index of the second ethylene copolymer can be greater than 150, but less than 2700 g / 10 min.
[085] In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 100 g / 10 min. In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 200 g / 10 min. In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 500 g / 10 min. In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 1000 g / 10 min. In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 1200 g / 10 min. In an embodiment of the invention, the I2 melt index of the second ethylene copolymer is greater than 1500 g / 10 min.
[086] In an embodiment of the invention, the second ethylene copolymer of the polyethylene composition is manufactured with a single site catalyst and has a weighted average molecular weight, MW, of a maximum of 45,000; a molecular weight distribution, Mw / Mn, of less than 3.0 and a density higher than the density of said first ethylene copolymer, but less than 0.967 g / cm3.
[087] In one embodiment of the invention, a single site catalyst that provides an ethylene copolymer having a CDBI (50) of at least 65% by weight, or at least 70%, or at least 75%, or at least minus 80%, or at least 85%, during solution phase polymerization in a single reactor, is used in the preparation of the second ethylene copolymer.
[088] In an embodiment of the present invention, the second ethylene copolymer has a CDBI (50) greater than about 60% by weight, or greater than about 65%, or greater than about 70% , or greater than about 75%, or greater than about 80%, or greater than about 85%.
[089] The second ethylene copolymer can comprise 90 to 30% by weight of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the second ethylene copolymer comprises from 80 to 40% by weight of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the second ethylene copolymer comprises from 75 to 40% by weight of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the second ethylene copolymer comprises from 70 to 40% by weight of the total weight of the first and second ethylene copolymers. In an embodiment of the invention, the second ethylene copolymer comprises from 60 to 50% by weight of the total weight of the first and second ethylene copolymers.
[090] In embodiments of the invention, the I2 melt index of the second ethylene copolymer is at least 50 times, or at least 100 times, or at least 1,000 times the I2 melt index of the first ethylene copolymer. The Composition of Polyethylene
[091] At a minimum, the polyethylene composition will contain a first ethylene copolymer and a second ethylene copolymer (as defined above).
[092] In embodiments of the invention, the polyethylene composition has a unimodal, unimodal, bimodal or multimodal molecular weight distribution as determined by gel permeation chromatography.
[093] In one embodiment of the invention, the polyethylene composition that minimally comprises a first ethylene copolymer and a second ethylene copolymer (as defined above) will have a ratio (SCB1 / SCB2) of the number of chain branches short per thousand carbon atoms in the first ethylene copolymer (ie SCB1) for the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (ie SCB2) greater than 1.0 (ie SCB1 / SCB2> 1.0).
[094] In other embodiments of the invention, the ratio of the short chain branch in the first ethylene copolymer (SCB1) to the short chain branch in the second ethylene copolymer (SCB2) is at least 1.25. In yet another embodiment of the invention, the ratio of the short chain branching in the first ethylene copolymer (SCB1) to the short chain branching in the second ethylene copolymer (SCB2) is at least 1.5.
[095] In embodiments of the invention, the ratio (SCB1 / SCB2) of the short chain branch in the first ethylene copolymer (SCB1) to the short chain branch in the second ethylene copolymer (SCB2) will be greater than 1, 0 to about 12.0, or greater than 1.0 to about 10, or greater than 1.0 to about 7.0, or greater than 1.0 to about 5.0, or greater than 1.0 to about 3.0.
[096] In one embodiment of the invention, the polyethylene composition is bimodal as determined by GPC.
[097] Typically, a bimodal or multimodal polyethylene composition can be identified using gel permeation chromatography (GPC). A GPC chromatography can display two or more component ethylene copolymers, where the number of component ethylene copolymers corresponds to the number of discernible peaks. One or more ethylene copolymer components may also exist as a hump, shoulder or tail in relation to the molecular weight distribution of the other ethylene copolymer component. By the phrase “bimodal as determined by GPC” it is meant that in addition to a first peak, there will be a secondary peak or shoulder that represent a component of higher or lower molecular weight (ie the molecular weight distribution, can be said to have two maximum values on a molecular weight distribution curve). Alternatively, the phrase “bimodal as determined by GPC” connotes the presence of two maxima in a molecular weight distribution curve generated according to the ASTM D6474-99 method.
[098] The polyethylene composition of the present invention has a density greater than or equal to 0.950 g / cm3, as measured according to ASTM D792; an I2 melt index, from about 2 to about 22 g / 10 min, as measured according to ASTM D1238 (when conducted at 190 ° C, using a weight of 2.16 kg); a molecular weight distribution, Mw / Mn, of about 2 to about 7, an average molecular weight Z Mz, of less than 300,000; a voltage exponent of less than 1.40; and an ESCR Condition B in 100% Igepal for at least 3 hours.
[099] In embodiments of the invention, the polyethylene composition has a comonomer content of less than 0.75 mol%, or less than 0.70 mol%, or less than 0.65% mol mol, or less than 0.60 mol%, or less than 0.55 mol%, or less than 0.50 mol% as measured by FTIR or 13C NMR methods, with 13C NMR being preferred, where the comonomer is one or more suitable alpha olefins such as but not limited to 1-butene, 1-hexene, 1-octene and the like, with 1-octene being preferred.
[0100] In the present invention, the polyethylene composition has a density of at least 0.950 g / cm3. In other embodiments of the invention, the polyethylene composition has a density of> 0.952 g / cm3, or> 0.953 g / cm3, or> 0.955 g / cm3.
[0101] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.950 to 0.970 g / cm3. In an embodiment of the present invention, the polyethylene composition has a density in the range of 0.950 to 0.965 g / cm3.
[0102] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.950 to 0.962 g / cm3.
[0103] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.952 to 0.960 g / cm3.
[0104] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.950 to 0.960 g / cm3.
[0105] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.950 to 0.959 g / cm3.
[0106] In one embodiment of the invention, the polyethylene composition has a density in the range of 0.951 to 0.957 g / cm3.
[0107] In an embodiment of the invention, the polyethylene composition has a density in the range of 0.952 to 0.957 g / cm3.
[0108] In an embodiment of the invention, the polyethylene composition has an I2 melting index, from 2 to 22 g / 10 min according to ASTM D1238 (when conducted at 190 ° C, using a weight of 2.16 kg) and including narrower ranges within this range and all numbers covered by these ranges. For example, in other embodiments of the invention, the polyethylene composition has an I2 melt index, greater than 2, but less than 22 g / 10 min, or 2 to 15.0 g / 10 min, or from 3 to 12.5 g / 10 min, or from 4 to 12.5 g / 10 min, or greater than 4 to less than 20 g / 10 min, or from 4.5 to 10 g / 10 min, or from 5 to 20 g / 10 min, or greater than 5.0 to less than 20 g / 10 min, or from 3 to 15.0 g / 10 min, or from 6.0 to 12.0 g / 10 min, or from 6.0 to 10.0 g / 10 min, or from about 5.0 to about 12.0 g / 10 min, or from more than 5.0 to less than 10.0 g10 / min.
[0109] In one embodiment of the invention, the polyethylene composition has an I5 "medium charge" melt index of at least 2.5 g / 10 min according to ASTM D1238 (when conducted at 190 ° C, using a weight of 5 kg). In another embodiment of the invention, the polyethylene composition has an average charge melting index I5, greater than about 5.0 g / 10 min, as measured according to ASTM D1238 (when conducted at 190 ° C , using a weight of 5 kg). In other embodiments of the invention, the polyethylene composition has an average charge melt index I5 of at least 10.0 g / 10 min, or at least 4.0 g / 10 min. In still other embodiments of the invention, the polyethylene composition has an average charge melting index I5, from about 5.0 to about 25.0 g / 10 min, or from about 5.0 to about 20.0 g / 10 min, or from about 5.0 to about 17.5 g / 10 min, or from about 5.0 to about 15.0 g / 10 min.
[0110] In an embodiment of the invention, the polyethylene composition has an I21 “high charge” melt index of at least 100 g / 10 min according to ASTM D1238 (when conducted at 190 ° C, using a weight 21 kg). In another embodiment of the invention, the polyethylene composition has a high charge melt index I21, greater than about 150 g / 10 min.
[0111] In one embodiment of the invention, the polyethylene composition has a high charge melt index I21, from 125 to 500 g / 10 min, or from 150 to 450 g / 10 min, or from 150 to 400 g / 10 min
[0112] In one embodiment of the invention, the polyethylene composition has a numerical average molecular weight Mn, below about 30,000 g / mol. In another embodiment of the invention, the polyethylene composition has a numerical average molecular weight Mn, below about 25,000 g / mol. In yet another embodiment of the invention, the polyethylene composition has a numerical average molecular weight Mn, below about 20,000 g / mol.
[0113] In the present invention, the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7 or a narrower range within this range, including all numbers covered within these ranges. For example, in other embodiments of the invention, the polyethylene composition has a molecular weight distribution Mw / Mn, from 3.0 to 7.0, or from 3.5 to 6.0, or from 3.5 to 5 , 5.
[0114] In an embodiment of the invention, the polyethylene composition has an average molecular weight Z MZ, below 300,000 g / mol. In another embodiment of the invention, the polyethylene composition has an average molecular weight Z MZ, below 250,000 g / mol. In yet another embodiment of the invention, the polyethylene composition has an average molecular weight Z MZ, below 200,000 g / mol.
[0115] In embodiments of the invention, the polyethylene composition has an average molecular weight Z to weighted average molecular weight MZ / MW ratio of 2.0 to 4.0, or 2.0 to 3.75, or from 2.25 to 3.75, or from 2.50 to 3.5.
[0116] In embodiments of the invention, the polyethylene composition has a melt flow ratio defined as I21 / I2, from about 15 to about 50, or from about 20 to 50, or from about 22 to 50, or from about 25 to 45, or from about 30 to 45, or from about 30 to 50, or from 22 to 50, or from about 22 to less than 50.
[0117] In one embodiment of the invention, the polyethylene composition has a melt flow rate defined as I21 / I5, of less than 25. In another embodiment of the invention, the polyethylene composition has a melt flow rate melt flow defined as I21 / I5, less than 20. In another embodiment of the invention, the polyethylene composition has a melt flow rate defined as I21 / I5, less than 15.
[0118] In one embodiment of the invention, the polyethylene composition has a shear viscosity around 105 s -1 (240 ° C) of less than about 10 (Pa.s). In other embodiments of the invention, the polyethylene composition has a shear viscosity around 105 s -1 (240 ° C) of less than 7.5 Pa.s, or less than 6.8 Pa.s. At the same time, the polyethylene composition can have a shear viscosity around 100s-1 (240 ° C) of less than about 600 Pa.s, a shear viscosity around 200s-1 (240 ° C) of less than about 500 Pa.se a shear viscosity around 300s-1 (240 ° C) of less than about 400 Pa.s.
[0119] In one embodiment of the invention, the polyethylene composition has at least one type of alpha-olefin that has at least 4 carbon atoms and its content is less than 0.75 mol% as determined by 13C NMR . In an embodiment of the invention, the polyethylene composition has at least one type of alpha-olefin that has at least 4 carbon atoms and its content is less than 0.65 mol% as determined by 13C NMR. In an embodiment of the invention, the polyethylene composition has at least one type of alpha-olefin that has at least 4 carbon atoms and its content is less than 0.55 mol% as determined by 13C NMR. In an embodiment of the invention, the polyethylene composition has at least one type of alpha-olefin which has at least 4 carbon atoms and its content is less than 0.50 mol% as determined by 13C NMR. In an embodiment of the invention, the polyethylene composition has at least one type of alpha-olefin that has at least 4 carbon atoms and its content is greater than 0.20 to less than 0.55% in mol as determined by 13C NMR.
[0120] In one embodiment of the invention, the shear viscosity ratio, SVR (100,100000) at 240 ° C of the polyethylene composition can be 50 to 90, or it can be about 55 to 90, or 55 to 85, or 55 to 75. The SVR shear viscosity ratio (100.100000) is determined by taking the shear viscosity ratio at the 100s-1 shear rate and the shear viscosity at the 100000 s shear rate -1 as measured with a capillary rheometer at constant temperature (for example, 240 ° C), and two molds with an L / D ratio of 20 and a diameter of 0.06 ”(from 3 to 1000 s-1) and a ratio of 20 L / D and 0.012 ”diameter (from about 1000 to 100000 s1) respectively.
[0121] In an embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition, has a Condition B resistance to cracking by 100% environmental stress ESCR of at least 3 h, as measured accordingly with ASTM D1693 (at 50 ° C using 100% Igepal, condition B).
[0122] In an embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition, has a Condition B resistance to cracking by 100% ESCR environmental stress of at least 3.5 h, as measured according to ASTM D1693 (at 50 ° C using 100% Igepal, condition B).
[0123] In an embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition, has a Condition B resistance to cracking by 100% environmental stress ESCR of at least 4.0 h, as measured according to ASTM D1693 (at 50 ° C using 100% Igepal, condition B).
[0124] In an embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition, has a Condition B resistance to cracking by 100% ESCR environmental stress from 3.5 to 15 h, as measured according to ASTM D1693 (at 50 ° C using 100% Igepal, condition B).
[0125] In one embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition, has a Condition B resistance to cracking by 100% ESCR environmental stress from 3.5 to 12 h, as measured according to ASTM D1693 (at 50 ° C using 100% Igepal, condition B).
[0126] In an embodiment of the invention, the polyethylene composition or a molded article manufactured from the polyethylene composition has an Notched Izod Impact Resistance of at least 40 J / m, as measured according to ASTM D256.
[0127] In embodiments of the invention, the polyethylene composition has a contraction ratio of TD / MD (for an injection molded disc within 48 h after molding) from 0.90 to 1.20, or from 0, 90 to 1.15, or from 0.95 to 1.15, or from 0.90 to 1.10, or from 0.95 to 1.10, or from 0.95 to 1.05 when measured according to the Dimensional Stability Test (DST).
[0128] In embodiments of the invention, the polyethylene composition has a TD contraction - MD contraction (for an injection molded disc within 48 h after the molding time) from 0.25 to -0.25, or from 0.20 to -0.20, or from 0.15 to -0.15, or from 0.10 to -0.10, or from 0.075 to -0.075, or from 0.05 to -0.05, when measured according to the Dimensional Stability Test (DST).
[0129] In an embodiment of the invention the polyethylene composition of the present invention has a density of 0.950 to 0.960 g / cm3; an I2 melt index, from 3 to 12 g / 10 min; a MW / Mn molecular weight distribution, from 2.0 to 7.0; a numerical average molecular weight Mn, below 30,000; a shear viscosity at 105s-1 (240 ° C) of less than 10 (Pa.s), a hexane extractable content of less than 0.55%, a Notched Izod Impact Resistance of more than 40 J / m, and a 100% ESCR B of at least 3.5 h.
[0130] In an embodiment of the invention, the polyethylene composition has a hexane extractable content of less than 0.55%. In other embodiments of the invention, the polyethylene composition has a hexane extractable content of less than 0.50%, or less than 0.45%, or less than 0.40%, or less than 0.35%.
[0131] In an embodiment of the invention, the polyethylene composition has a stress exponent, defined as Logio [l6 / l2] / Logio [6.48 / 2.16], which is <1.40. In other embodiments of the invention, the polyethylene composition has a stress exponent, Log10 [I6 / I2] / Log10 [6.48 / 2.16] from 1.22 to 1.40, or from 1.22 to 1.38, or 1.24 to 1.36.
[0132] In one embodiment of the invention, the polyethylene composition has a composition distribution amplitude index (CDBI (50)), as determined by temperature elution fractionation (TREF), of> 60 weight percent . In other embodiments of the invention, the polyethylene composition will have a CDBI (50) greater than 65%, or greater than 70%, or greater than 75%, or greater than 80%.
[0133] In one embodiment of the invention, the polyethylene composition has a composition distribution amplitude index (CDBI (25)), as determined by temperature elution fractionation (TREF), of> 55 weight percent . In other embodiments of the invention, the polyethylene composition will have a CDBI (25) greater than 60%, or greater than 65%, or 55 to 75%, or 60 to 75%.
[0134] The polyethylene composition of this invention can be manufactured using any conventional blending method such as but not limited to physical combination and in situ combination by polymerization in multiple reactor systems. For example, it is possible to mix the first ethylene copolymer with the second ethylene copolymer by mixing by melting the two preformed polymers. Preferred are processes in which the first and second ethylene copolymers are prepared in at least two sequential polymerization stages, however, both a serial reactor and a parallel reactor process are considered for use in the present invention. Gas phase, slurry phase or solution phase reactor systems can be used, with solution phase reactor systems being preferred.
[0135] Mixed catalyst single reactor systems can also be used to manufacture the polymeric compositions of the present invention.
[0136] In an embodiment of the present invention, a dual reactor solution polymerization process is used as described for example in Pat. No. 6,372,864 and Pub. Of Pat. No. 20060247373A1 which are incorporated herein by reference.
[0137] Generally, the catalysts used in the present invention will be so called single site catalysts based on a group 4 metal having at least one cyclopentadienyl ligand. Examples of such catalysts which include metallocenes, restricted geometry catalysts and phosphinimine catalysts are typically used in combination with selected activators of methylaluminoxanes, boranes or ionic borate salts and are further described in Pat. No. 3,645,992; 5,324,800; 5,064,802; 5,055,438; 6,689,847; 6,114,481 and 6,063,879. Such single-site catalysts are distinguished from traditional Ziegler-Natta or Phillips catalysts which are also well known in the art. In general, single-site catalysts produce ethylene copolymers having a molecular weight distribution (MW / Mn) of less than about 3.0 and a distribution amplitude index of the CDBI composition (50) greater than about 65 %.
[0138] In an embodiment of the invention, a single site catalyst that provides an ethylene copolymer having a CDBI (50) of at least 65% by weight, or at least 70%, or at least 75%, or at least minus 80%, or at least 85%, during solution phase polymerization in a single reactor, is used in the preparation of each of the first and the second ethylene copolymers.
[0139] In an embodiment of the invention, homogenously branched ethylene copolymers are prepared using an organometallic complex of a group 3, 4 or 5 metal which is further characterized as having a phosphinimine ligand. Such a complex, when active for olefin polymerization, is generally known as a phosphinimine catalyst (polymerization). Some non-limiting examples of phosphinimine catalysts can be found in U.S. Pat. No. 6,342,463; 6,235,672; 6,372,864; 6,984,695; 6,063,879; 6,777,509 and 6,277,931 all of which are incorporated by reference here.
[0140] Some non-limiting examples of metallocene catalysts can be found in U.S. Pat. No. 4,808,561; 4,701,432; 4,937,301; 5,324,800; 5,633,394; 4,935,397; 6,002,033 and 6,489,413, which are incorporated herein by reference. Some non-limiting examples of restricted geometry catalysts can be found in U.S. Pat. No. 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,703,187 and 6,034,021, all of which are incorporated by reference here in their entirety.
[0141] In an embodiment of the invention, the use of a single site catalyst that does not produce long chain branching (LCB) is preferred. Hexyl (C6) branches detected by NMR are excluded from the definition of a long chain branch in the present invention.
[0142] Without wishing to be bound by any single theory, the long chain branch can increase viscosity at low shear rates, thereby negatively affecting cycle times during the manufacture of lids and closures, such as during the molding process by compression. Long chain branching can be determined using 13C NMR methods and can be quantitatively assessed using the method disclosed by Randall in Rev. Macromol. Chem. Phys. C29 (2 and 3), p. 285.
[0143] In one embodiment of the invention, the polyethylene composition will contain less than 0.3 long chain branches per 1000 carbon atoms. In another embodiment of the invention, the polyethylene composition will contain less than 0.01 long chain branches per 1000 carbon atoms.
[0144] In an embodiment of the invention, the polyethylene composition (defined as above) is prepared by contacting ethylene and at least one alpha-olefin with a polymerization catalyst under solution phase polymerization conditions in at least two polymerization reactors (for an example of solution phase polymerization conditions see for example US Pat. No. 6,372,864; 6,984,695 and US Order No. 20060247373A1 which are incorporated herein by reference).
[0145] In an embodiment of the invention, the polyethylene composition is prepared by contacting at least one single-site polymerization catalyst system (comprising at least one single-site catalyst and at least one activator) with ethylene and at least at least one comonomer (for example, a C3-C8 alpha-olefin) under solution polymerization conditions in at least two polymerization reactors.
[0146] In an embodiment of the invention, a group 4 single site catalyst system, comprising a single site catalyst and an activator, is used in a solution phase double reactor system to prepare a polyethylene composition by polymerization of ethylene in the presence of an alpha-olefin comonomer.
[0147] In an embodiment of the invention, a group 4 single site catalyst system, comprising a single site catalyst and an activator, is used in a solution phase double reactor system to prepare a polyethylene composition by polymerization of ethylene in the presence of 1-octene.
[0148] In an embodiment of the invention, a group 4 phosphinimine catalyst system, comprising a phosphinimine catalyst and an activator, is used in a solution phase double reactor system to prepare a polyethylene composition by polymerization ethylene in the presence of an alpha-olefin comonomer.
[0149] In an embodiment of the invention, a group 4 phosphinimine catalyst system, comprising a phosphinimine catalyst and an activator, is used in a solution phase double reactor system to prepare a polyethylene composition by polymerization ethylene in the presence of 1-octene.
[0150] In an embodiment of the invention, a dual solution phase reactor system comprises two solution phase reactors connected in series.
[0151] In an embodiment of the invention, a polymerization process for preparing the polyethylene composition comprises contacting at least one single-site polymerization catalyst system (comprising at least one single-site catalyst and at least one activator) with ethylene and at least one alpha-olefin comonomer under solution polymerization conditions in at least two polymerization reactors.
[0152] In an embodiment of the invention, a polymerization process for preparing the polyethylene composition comprises contacting at least one single site polymerization catalyst system with ethylene and at least one alpha-olefin comonomer under polymerization conditions. solution in a first reactor and a second reactor configured in series.
[0153] In one embodiment of the invention, a polymerization process for preparing the polyethylene composition comprises contacting at least one single-site polymerization catalyst system with ethylene and at least one alpha-olefin comonomer under polymerization conditions. solution in a first reactor and a second reactor configured in series, with at least one alpha-olefin comonomer being fed exclusively to the first reactor.
[0154] The production of the polyethylene composition of the present invention will typically include an extrusion or composition step. Such steps are well known in the art.
[0155] The polyethylene composition may further comprise polymeric components in addition to the first and second ethylene polymers. Such polymeric components include polymers manufactured in situ or polymers added to the polymeric composition during an extrusion or composition step.
[0156] Optionally, additives can be added to the polyethylene composition. Additives can be added to the polyethylene composition during an extrusion or composition step, but other suitable known methods will be apparent to a person skilled in the art. Additives can be added as is or as part of a separate polymeric component (i.e., not the first or second ethylene polymers described above) added during an extrusion or composition step. Suitable additives are known in the art and include but are not limited to antioxidants, phosphites and phosphonites, nitrones, antacids, UV light stabilizers, UV absorbers, metal deactivators, dyes, fillers and reinforcing agents, organic or inorganic nano materials -scale, antistatic agents, lubricating agents such as calcium stearates, slip additives such as erucimide, and nucleating agents (including nucleators, pigments or any other chemicals that may provide a nucleating effect to the polyethylene composition). Additives that can be optionally added are typically added in an amount of up to 20 weight percent (weight percent).
[0157] One or more nucleating agents can be introduced into the polyethylene composition by mixing a mixture of the polymer, usually in powder or pellet form, with the nucleating agent, which can be used alone or in the form of a concentrate containing other additives such as stabilizers, pigments, antistatic agents, UV stabilizers and fillers. This must be a material that is moistened or absorbed by the polymer, which is insoluble in the polymer and has a higher melting point than that of the polymer, and this must be homogeneously dispersible in the melting of polymer as thin in shape as possible (1 to 10μm). Compounds known to have a nucleating capacity for polyolefins include salts of aliphatic monobasic or dibasic acids or arylalkyl acids, such as sodium succinate or aluminum phenylacetate; and alkali metal or aluminum salts of aromatic or alicyclic carboxylic acids such as sodium β-naphttoate. Another compound known to have a nucleating capacity is sodium benzoate. The effectiveness of the nucleation can be monitored microscopically by observing the degree of reduction in size of the spherulites in which the crystallites are aggregated.
[0158] In one embodiment of the invention, the polyethylene compositions described above are used in forming molded articles. For example, articles formed by compression molding and injection molding are considered. Such items include, for example, caps, screw caps, and bottle closures. However, a person skilled in the art will easily appreciate that the compositions described above can also be used for other applications such as but not limited to film applications, injection blow molding, blow molding and sheet extrusion.
[0159] In one embodiment of the invention, a closure (or cap) is a screw cap for a bottle.
[0160] The covers and closures of the present invention can be manufactured according to any known method, including for example injection molding and compression molding techniques that are well known to those skilled in the art. Consequently, in an embodiment of the invention a closure (or cap) comprising the polyethylene composition (defined above) is prepared with a process comprising at least one compression molding step and / or at least one injection molding step.
[0161] The lids and closures (including single-piece or multiple-piece variants) of the invention comprise the polyethylene composition described above and have very good dimensional stability, good organoleptic properties, good toughness, as well as reasonable ESCR values. Consequently, the closures and caps of the present invention are well suited for sealing bottles containing drinking water, and other foodstuffs, including but not limited to liquids that are non-pressurized. The closures and lids are especially suitable for sealing bottles containing drinking water or non-carbonated drinks (for example, juice).
[0162] The invention is further illustrated by the following non-limiting examples. EXAMPLES
[0163] Melting indices, I2, I5, I6 and I21 for the polyethylene composition were measured according to ASTM D1238 (when conducted at 190 ° C, using a weight of 2.16 kg, one of 5 kg, one of 6.48 kg and 21 kg respectively).
[0164] Mn, Mw and Mz (g / mol) were determined by high temperature gel permeation chromatography with differential refractive index detection using universal calibration (for example, ASTM -D6474-99). GPC data was obtained using an instrument sold under the trade name “Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140 ° C. The samples were prepared by dissolving the polymer in this solvent and were conducted without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% for the numerical average molecular weight ("Mn") and 5.0% for the weighted average molecular weight ("Mw"). The molecular weight distribution (MWD) is the weighted average molecular weight divided by the numerical average molecular weight, MW / Mn. The average molecular weight distribution z is Mz / Mn. Polymer sample solutions (1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and spinning on a wheel for 4 hours at 150 ° C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were subjected to chromatography at 140 ° C in a PL 220 high temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the columns from oxidative degradation. The injection volume of the sample was 200 mL. The raw data were processed using the Cirrus GPC software. The columns were calibrated with polystyrene standards of narrow distribution. The molecular weights of polystyrene were converted to molecular weights of polyethylene using the Mark-Houwink equation, as described in the ASTM D6474 standard test method.
[0165] Primary melting peak (° C), melting heat (J / g) and crystallinity (%) were determined using differential scanning calorimetry (DSC) as follows: the instrument was first calibrated with indium; after calibration, a polymeric specimen is equilibrated at 0 ° C and then the temperature has been increased to 200 ° C at a heating rate of 10 ° C / min; the fusion was then maintained isothermally at 200 ° C for five minutes; the melt was then cooled to 0 ° C at a cooling rate of 10 ° C / min and maintained at 0 ° C for five minutes; the specimen was then heated to 200 ° C at a heating rate of 10 ° C / min. DSC Tm, heat of fusion and crystallinity are reported from the 2nd heating cycle.
[0166] The short chain branching frequency (SCB per 1000 carbon atoms) of the polyethylene composition was determined by Fourier Transform Infrared Spectroscopy (FTIR) as per the ASTM D6645-01 method. A Magna-IR Thermo-Nicolet 750 Spectrophotometer equipped with OMNIC software version 7.2a was used for the measurements. Unsaturation in the polyethylene composition was also determined by Fourier Transformed Infrared Spectroscopy (FTIR) as well as by ASTM D3124-98. The comonomer content can also be measured using 13C NMR techniques as discussed in Randall, Rev. Macromol. Chem. Phys., C29 (2 & 3), p 285; Pat. No. 5,292,845 and WO 2005/121239.
[0167] The density of the polyethylene composition (g / cm3) was measured according to ASTM D792.
[0168] The content of hexane extractables has been determined according to ASTM D5227.
[0169] Shear viscosity was measured using a Kayeness WinKARS Capillary Rheometer (model # D5052M-115). For the shear viscosity at lower shear rates, a mold having a mold diameter of 0.06 inches (1.52 mm) and L / D ratio of 20 and an entry angle of 180 degrees was used. For shear viscosity at higher shear rates, a mold having a mold diameter of 0.012 inches (0.30 mm) and an L / D ratio of 20 was used. The Processability Indicator: The “processability indicator” as used in the present invention is defined as: Processability indicator = 100 / n (105 s-1, 240 ° C); where n is the shear viscosity measured at 105 1 / s at 240 ° C.
[0170] To determine CDBI (50), a solubility distribution curve is first generated for the polyethylene composition. This is accomplished using data acquired from the TREF technique. This solubility distribution curve is a batch of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a cumulative distribution curve of fraction by weight versus comonomer content, from which the CDBI (50) is determined by establishing the weight percentage of a copolymer sample that has a comonomer content within 50% of the median comonomer content on each side of the median (See WO 93/03093 and U.S. Pat. No. 5,376,439). The CDBI (25) is determined by establishing the percentage by weight of a copolymer sample that has a comonomer content within 25% of the median comonomer content on each side of the median.
[0171] The specific temperature rise elution fractionation (TREF) method used here was as follows. Polymer samples (50 to 150 mg) were introduced into the reactor vessel of a TREF crystallization unit (Polymer ChARTM). The reactor vessel was filled with 20 to 40 ml of 1,2,4-trichlorobenzene (TCB), and heated to the desired dissolution temperature (for example, 150 ° C) for 1 to 3 hours. The solution (0.5 to 1.5 ml) was then loaded onto the TREF column filled with stainless steel beads. After equilibration at a given stabilization temperature (eg 110 ° C) for 30 to 45 minutes, the polymer solution was allowed to crystallize with a temperature drop from the stabilization temperature to 30 ° C (0.1 or 0, 2 oC / minute). After equilibration at 30 ° C for 30 minutes, the crystallized sample was eluted with TCB (0.5 or 0.75 mL / minute) with a temperature rise of 30 ° C to stabilization temperature (0.25 or 1 , 0 oC / minute). The TREF column was cleaned at the end of the run for 30 minutes at the dissolving temperature. The data were processed using the Polymer ChAR software, Excel spreadsheet and TREF software developed internally.
[0172] High temperature GPC equipped with an in-line FTIR detector (GPC-FTIR) was used to measure the comonomer content as a function of molecular weight.
[0173] Molded plates of the polyethylene compositions were tested according to the following ASTM methods: Environmental Stress Crack Resistance (ESCR) of Strip Bent in Condition B in 100% IGEPAL at 50 ° C, ASTM D1693; notched Izod impact properties, ASTM D256; Flexural Properties, ASTM D 790; tensile properties, ASTM D 638; Vicat softening point, ASTM D 1525; thermal deflection temperature, ASTM D 648.
[0174] Dynamic mechanical analyzes were performed with a rheometer, that is, Rheometrics Dynamic Spectrometer (RDS-II) or Rheometrics SR5 or ATS Stresstech, on samples molded by compression under a nitrogen atmosphere at 190 ° C, using cone and plate geometry 25 mm in diameter. The oscillatory shear experiments were carried out within the linear viscoelastic range of effort (10% of effort) at frequencies from 0.05 to 100 rad / s. The values of storage modulus (G '), loss modulus (G ”), complex modulus (G *) and complex viscosity (n *) were obtained as a function of frequency. The same rheological data can also be obtained using a parallel plate geometry of 25 mm in diameter at 190 ° C under a nitrogen atmosphere. Dimensional Stability Test (DST): The dimensional stability of the polyethylene compositions was determined as follows: A 150-tonx12-Oz Cincinnati Milacron injection molding machine (Hydradamp 150T 12oz PC-111, serial # 4001 A21 / 79 - 38 ) with a 2 inch (50.8 mm) thread was used to produce parts according to the conditions listed in table 1. The mold was an ASTM test mold, which makes tensile test specimens with an overall length of 1 .30 inches (33.02 mm), an overall width of 0.75 inches (19.05 mm), and a thickness of 0.12 inches (3.05 mm); tensile test specimens with an overall length of 1.375 inches (34.92 mm), an overall width of 0.375 inches (9.52 mm), and a thickness of 0.12 inches (3.05 mm); tensile test specimens with an overall length of 2.5 inches (63.5 mm), an overall width of 0.375 inches (9.52 mm), and a thickness of 0.12 inches (3.05 mm); flexural module bars with a length of 5 inches (127 mm), a width of 0.50 inches (12.7 mm), and a thickness of 0.12 inches (3.05 mm) or 0.75 inches (19 , 05 mm), and a round impact disk with a diameter of 2 inches (50.8 mm) and a thickness of 0.12 inches (3.05 mm). Immediately after molding, the injection-molded disc was removed from the channel (note: an injection-molded disc with a diameter of 2 inches (50.8 mm) and a thickness of 0.12 inches (3.05 mm) for measurements in the present invention). The diameters both in the machine direction (or inflow) (MD) and in the direction of transverse flow (TD) are then measured at room temperature (23 ± 2 ° C) after 1, 24 and 48 h of molding. Contraction at time t is defined as the percentage change in dimension at measurement time from the original mold dimensions: Contraction percentage = (Mold dimension - Specimen dimension at time t) x 100 / Mold dimension
[0175] Thus, the contraction of MD is the contraction measured in the disc in the direction of flow, and contraction in the transverse direction (TD) is the contraction measured in the direction of the transverse flow. Here, isotropic contraction is defined as equal contraction both in the direction of flow (inflow) and in the transverse direction. Differential contraction is defined as the contraction of TD minus the contraction of MD (an indication of the planarity or flatness of the part or the extent of distortion of the part). The smaller the difference, the better the planarity of the part. A TD / MD contraction ratio, the TD contraction divided by the MD contraction, can also be used as a measure of the extent of the isotropic contraction (the closer it is to the unit, the better the planarity of the part). The molding parameters used are summarized in table 1. TABLE 1


[0176] Examples of the polyethylene compositions were produced in a double reactor solution polymerization process in which the contents of the first reactor flow into the second reactor. This series "double reactor" process produces a blend of polyethylene "in situ" (ie the polyethylene composition). Note that when a series reactor configuration is used, unreacted ethylene monomer, and unreacted alpha-olefin comonomer present in the first reactor will flow into the second downstream reactor for further polymerization.
[0177] In the present inventive examples, although no comonomer is fed directly to the second downstream reactor, an ethylene copolymer is nevertheless formed in the second reactor due to the significant presence of unreacted 1-octene flows from the first reactor to the second reactor where it is copolymerized with ethylene. Each reactor is sufficiently agitated to provide conditions in which the components are well mixed. The volume of the first reactor was 12 liters and the volume of the second reactor was 22 liters. These are the scales of the pilot plant. The first reactor was operated at a pressure of 10500 to 35000 kPa and the second reactor was operated at a lower pressure to facilitate the continuous flow from the first reactor to the second. The solvent used was methylpentane. The process operates using continuous supply currents. The catalyst used in the double reactor solution process experiments was a phosphinimine catalyst, which was a titanium complex having a phosphinimine ligand (for example, (tert-butyl) 3P = N), a cyclopentadienide ligand (for example , Cp) and two activatable ligands, such as, but not limited to, chloride ligands (note: "activatable ligands" are removed, for example by electrophilic abstraction using a cocatalyst or activator to generate an active metal center). A boron-based co-catalyst (for example, Ph3CB (C6F5) 4) was used in approximately stoichiometric amounts in relation to the titanium complex. Commercially available methylaluminoxane (MAO) was included as a decontaminant in an Al: Ti of about 40: 1. In addition, 2,6-di-tert-butylhydroxy-4-ethylbenzene was added to decontaminate the free trimethylaluminum within the MAO in an Al: OH ratio of about 0.5: 1.
[0178] Comparative polyethylene compositions (Comparative Examples 1 to 3) are manufactured using a single site phosphinimine catalyst in a dual reactor solution process in which the entire comonomer is fed to the second reactor.
[0179] Comparative polyethylene composition (Comparative Example 4) is an injection molding grade that is believed to be an ethylene homopolymer made with a traditional polymerization catalyst (eg a Ziegler-Natta polymerization catalyst) and that is commercially available from Ineos as J60-800-178.
[0180] Comparative polyethylene composition (Comparative Example 5) is an injection molding grade polyethylene homopolymer, commercially available resin from NOVA Chemicals as IG-454-A.
[0181] Comparative polyethylene compositions (Comparative Examples 6, 7 and 8) are manufactured using a single-site phosphinimine catalyst in a dual reactor solution process according to Pat. No. 8,022,143 and CA Application No. 2,752,407. Comparative Resin 6 has a density of 0.952 g / cm3, a high load I21 melt index of 71 g / 10 min and an I21 / I2 melt index ratio of 48.5. Comparative Resin 7 has a density of 0.952 g / cm3, a high load I21 melting index of 71 g / 10 min and an I21 / I2 melting index ratio of 55. Comparative Resin 8 has a density of 0.953 g / cm3, a high load I21 melt index of 80.2 g / 10 min and an I21 / I2 melt ratio ratio of 64.4.
[0182] Inventive polyethylene compositions (Inventive Examples 1 to 6) are manufactured using a single site phosphinimine catalyst in a dual reactor solution process as described above and have an ESCR in B100 condition greater than 3.5 hours and an SCB1 / SCB2 ratio greater than 1.0. These inventive examples also have an Mz value of less than 300,000.
[0183] The polymerization conditions used to manufacture the inventive compositions are given in table 2.
[0184] The properties of the inventive polyethylene composition and comparative properties are described in tables 3.
[0185] The calculated properties for the first ethylene copolymer and the second ethylene copolymer for selected comparative and inventive polyethylene compositions are provided in table 4 (see “Copolymerization Reactor Modeling” below for methods).
[0186] The properties of compressed plates manufactured from comparative and inventive polyethylene compositions are given in Table 5.
[0187] Information on dimensional stability for inventive and comparative resins is provided in table 6. Copolymerization Reactor Modeling
[0188] For multi-component polyethylene polymers (or bimodal resins) with very low comonomer content, it may be difficult to safely estimate the short chain branching (and subsequently density of the polyethylene resin by combining other information) of each component polymeric by mathematical deconvolution of GPC-FTIR data, as was done for example in Pat. No. 8,022,143. In contrast, the Mw, Mn, Mz, Mw / Mn and the thousand-carbon short chain branch (SCB / 1000C) of the first and second copolymers were calculated here, using a reactor model simulation using the input conditions that were used for conditions conducted by a real pilot scale (for references on relevant reactor modeling methods, see “Copolimerization” by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements, volume 3, chapter 2 , page 17, Elsevier, 1996 and “Copolymerization of Olefins in a Series of Continuous Stirred-Tank Slurry-Reactors using Heterogeneous Ziegler-Natta and Metallocene Catalysts. I. General Dynamic Mathemacial Model” by JBP Soares and AE Hamielec in Polymer Reaction Engineering, 4 (2 & 3), p153, 1996.) This type of model is considered reliable for estimating the comonomer content (for example, 1-octene) even at low comonomer incorporation levels, since ethylene conversion, flow Ethylene inlet and comonomer inlet flow can be obtained directly from experimental conditions and because the reactive ratio (see below) can be safely estimated for the catalyst system used in the present invention. For clarity, the "monomer" or "monomer 1" represents ethylene, while the terms "comonomer" or "monomer 2" represent 1-octene.
[0189] The model takes in the flow of several reactive species (for example, catalyst, monomer such as ethylene, comonomer such as 1-octene, hydrogen, and solvent) going to each reactor, the temperature (in each reactor), and the conversion of the monomer (in each reactor), and calculates the properties of the polymer (of the polymer manufactured in each reactor, ie the first and second ethylene copolymers) using a terminal kinetic model for connected continuously stirred tank reactors (CSTRs) in series. The “terminal kinetic model” assumes that kinetics depend on the monomer unit within the polymer chain in which the active catalyst site is located (see “Copolimerization” by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements, volume 3, Chapter 2, page 17, Elsevier, 1996). In the model, copolymer chains are considered to be of reasonably large molecular weight to ensure that the monomer / comonomer unit insertion statistic in the active catalyst center is valid and that monomers / comonomers consumed in pathways except propagation are negligible. This is known as the “long chain” approach.
[0190] The terminal kinetic model for polymerization includes reaction rate equations for activation, initiation, propagation, chain transfer, and deactivation pathways. This model solves the conservation equations in steady state (for example, total mass balance and heat balance) for the reactive fluid comprising the reactive species identified above.
[0191] The total mass balance for a generic CSTR with a given number of inputs and outputs is provided by:
where m & i represents the mass flow rate of individual currents with the index i indicating the input and output currents.
[0192] Equation (1) can be further expanded to show individual species and reactions:
where Mi is the average molar weight of the fluid inlet or outlet (i), xij is the mass fraction of species j in stream i, pmix is the molar density of the reactor mixture, V is the reactor volume, Rj is the reaction rate for species j, which has units of kmol / m3s.
[0193] The total heat balance is resolved for an adiabatic reactor and is provided by: (3) 0 = (∑ miΔHi + qRxV + W - Q) i where, mi is the mass flow rate of current i (inlet or output), ΔHi is the difference in enthalpy of current i versus a reference state, qRx is the heat released by the reaction (s), V is the reactor volume, W is the working input (ie agitator ), Q is the heat input / loss.
[0194] The catalyst concentration input for each reactor is adjusted to compare to the experimentally determined ethylene conversion and reactor temperature values in order to solve the equations of the kinetic model (for example, propagation rates, heat balance and mass balance).
[0195] The H2 concentration input for each reactor can be similarly adjusted so that the calculated molecular weight distribution of a polymer manufactured in both reactors (and consequently the molecular weight of the polymer manufactured in each reactor) is compared if the one that is observed experimentally.
[0196] The degree of polymerization (DPN) for a polymerization reaction is given by the ratio of the rate of chain propagation reactions to the rate of chain transfer / termination reactions:
where kp12 is the propagation rate constant for adding monomer 2 to a growing polymer chain ending with monomer 1, [m1] is the molar concentration of monomer 1 (ethylene) in the reactor, [m2] is the molar concentration of monomer 2 (1-octene) in the reactor, ktm12 the termination rate constant for chain transfer to monomer 2 for a growing chain ending with monomer 1, kts1 is the rate constant for spontaneous chain termination for a chain ending with monomer 1, ktH1 is the rate constant for the hydrogen terminating chain for a chain ending with monomer 1. Φ1 and Φ2 and the fraction of catalyst sites occupied by a chain ending with monomer 1 or monomer 2 respectively.
[0197] The numerical average molecular weight (Mn) for a polymer follows the degree of polymerization and the molecular weight of a monomer unit. From the numerical average molecular weight of the polymer in each reactor, and assuming a Flory distribution for a single site catalyst, the molecular weight distribution is determined for the polymer formed in each reactor: (5) w (n) = T2 en-Tn where T =, ew (n) is the weight fraction of polymer having a chain length n.
[0198] The Flory distribution can be transformed into the common log sized GPC trace by applying:
d log (M) DPN 2 chain length n (n = MW / 28 where 28 is the molecular weight of the polymer segment corresponding to a C2H4 unit) and DPN is the degree of polymerization as calculated by Equation (4). From the Flory model, the Mw and Mz of the polymer manufactured in each reactor are: Mw = 2 x Mn and Mz = 1.5 x Mw.
[0199] The global molecular weight distribution over both reactors is simply the sum of the polymer molecular weight distribution manufactured in each reactor, and where each Flory distribution is multiplied by the weight fraction of polymer manufactured in each reactor:
where dW / dlog (MW) is the global molecular weight distribution function, WR1 and WR2 are the weight fraction of polymer manufactured in each reactor, DPN1 and DPN2 is the average chain length of the polymer manufactured in each reactor (ie , DPN1 = MnR1 / 28). The weight fraction of material manufactured in each reactor is determined from the knowledge of the mass flow of monomer and comonomer in each reactor together with the knowledge of the conversions to monomer and comonomer in each reactor.
[0200] The moments of the molecular weight distribution (or the molecular weight distribution of polymer manufactured in each reactor) can be calculated using equations 8a, 8b and 8c (a Flory Model is considered above, but the generic formula below applies other model distributions as well):

[0201] The comonomer content in the polymeric product (in each reactor) can also be calculated using the terminal kinetic model and long-chain approximations discussed above (see A. Hamielec, J. MacGregor, and A. Penlidis. Comprehensive Polymer Science and Supplements, volume 3, Copolimerization chapter, page 17, Elsevier, 1996).
[0202] For a given catalyst system, the incorporation of the comonomer (eg, 1-octene) is a function of the conversion of the monomer (eg, ethylene), the ratio of comonomer to monomer in the reactor (/) and the ratio of reactivity of monomer 1 (for example, ethylene) on monomer 2 (for example, 1-octene): r1 = kp11 / kp12.
[0203] For a CSTR, the molar ratio of ethylene to comonomer in the polymer (Y) can be estimated by knowing the reactivity ratio r1 of the catalyst system and knowing the conversion of ethylene in the reactor (Qm1). A quadratic equation can be derived using the May and Lewis equation for instantaneous comonomer incorporation (see “Copolimerization” by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements, volume 3, Chapter 2, page 17, Elsevier, 1996) and solving the mass balance around the reaction. The molar ratio of ethylene to 1-octene in the polymer is the negative root of the following quadratic equation:
where Y is the molar ratio of ethylene to 1-octene in the polymer, Y is the mass flow ratio of 1-octene to ethylene going to the reactor, r1 is the reactivity ratio of monomer 1 to monomer 2 for the catalyst (r1 = kp11 / kp12) and Qm1 is the partial conversion of ethylene monomer.
[0204] The branching frequency can then be calculated by knowing the molar ratio of monomer 1 to monomer 2 in the polymer:
where Y, is the molar ratio of monomer 1 (ethylene) to monomer 2 (1-octene) bi-polymer, and BF is the branching frequency (branches per 1000 carbon atoms).
[0205] The global branching frequency distribution (BFD) of the ethylene composition can be calculated by knowing the molecular weight distribution and the weight fraction of polymer manufactured in each reactor, and the average branching frequency (BF) of the ethylene copolymer manufactured in each reactor. The fraction of polymer manufactured in each reactor can be calculated from the experimental mass flows and conversion of monomer and comonomer in each reactor. The branching frequency distribution function is obtained by calculating the average branching content for each molecular weight value of the global molecular weight distribution function made from the two Flory distributions:
where BFMW is the branch in molecular weight (MW), WR1 and WR2 are the fraction by weight of polymer manufactured in Reactor 1 and Reactor 2, BFR1 and BFR2 are the average branch frequency of polymer manufactured in R1 and R2 (from Equations 9 and 10), FR1 (MWR1) and FR2 (MWR2) are the Flory distribution function of Reactor 1 and Reactor 2.
[0206] The overall branching frequency of the polyethylene composition is provided by the weighted average of the branching frequency of the polymer manufactured in each reactor: (12) BFavg = W1BF1 + W2BF2 where, BFavg is the average branching frequency for the total polymer ( for example, the polyethylene composition), W1 and W2 are the weight fraction of material manufactured in each reactor, BF1 and BF2 are the branching frequency of material manufactured in each reactor (for example, the branching frequency of the first and second copolymers ethylene).
[0207] For the polymer obtained in each reactor, the key resin parameters that are obtained from the kinetic model described above are the molecular weights Mn, Mw and Mz, the molecular weight distributions MW / Mn and Mz / Mw and the frequency of branching (SCB / 1000 Cs). With this information in hand, a component density (or composition) model and a component fusion index (or composition), I2, the model was used according to the following equations, which were empirically determined, to calculate the density and I2 melt index of each of the first and second ethylene copolymers:
where, BF is the branching frequency,
Fusion index, I2 (MI):

[0208] Consequently, the models above were used to estimate the frequency of branching, fraction by weight (or percentage by weight), melting index and density of the components of the polyethylene composition, which were formed in each of reactor 1 and 2 (this is the first and second ethylene copolymers). Table 2

TABLE 3



Table 4


TABLE 5



TABLE 6



[0209] As can be seen from the data provided in Tables 3 to 6 and Figures 1 to 3, the inventive polyethylene compositions have very good dimensional stability, are easy to process (for example, they have good injection capacity when manufacturing injection molded part), show good organoleptic properties and impact resistance and have useful ESCR for applications such as water bottle closures. For example, Figure 1 shows that compared to Comparative Examples 1, 2, 4 (J60-800-178) and 5 (IG454-A), inventive compositions 1 to 5 have an improved balance of processability and ESCR. Also, as shown in Figure 2, inventive compositions 1 to 5 have a better balance of processability and impact resistance when compared to comparative resins 1, 2, 4 (J60-800-178) and 5 (IG454-A). The processability comparison is made on the basis of a “processability indicator” which in the present invention is defined as 100 / na 105 s-1 (240 ° C), where n is the Shear Viscosity (n) at 105 s-1 (240 ° C, Pa-s) as defined above.
[0210] Figure 3 shows that inventive compositions 1 and 2 have better dimensional stability (the isotropy indicator in contraction of TD / MD) than a polypropylene homopolymer having a melt flow rate of 35 g / 10 min (tested at 230 ° C under 2.16 kg). The inventive compositions 1 and 2 have dimensional stability comparable or better than Comparative Examples 4 (J60-800-178) and 5 (IG454-A).
[0211] Table 6 shows that inventive polyethylene compositions 1 to 6 generally have better dimensional stability than comparative resins 4 to 8. Compare for example the compositions inv. 1, 2, 3, 4, 5 and 6 that have a TD contraction - MD contraction of 0.05, 0.15, 0, -0.06, 0.02, and -0.05 respectively with resins comp. 4, 5, 6, 7, and 8 that have a TD contraction - MD contraction of 0.14, 0.38, -0.19, -0.40, -0.28 respectively. Also compare the TD / MD contraction ratio (the isotropy indicator) for the compositions inv. 1, 2, 3, 4, 5 and 6 at 1.03, 1.09, 1, 0.97, 1.09 and 0.97 respectively, which are all reasonably close to 1, with the TD / contraction ratio MD (the isotropy indicator) for compositions comp. 4, 5, 6, 7, and 8 which are 1.08, 1.29, 0.90, 0.82, and 0.87 respectively.
[0212] Figure 4 compares the distribution amplitude index of the composition CDBI (50) of inventive example 1 with Comparative Example 2 as determined by elevation fractionation in temperature elution (TREF). Comparative Example 2 shows three peaks in the TREF profile and has a CDBI (50) of 45.2 weight percent (weight percent). Inventive example 1 shows a single dominant peak in the TREF profile and has a CDBI (50) greater than 70% by weight. Consequently, inventive example 1 has a more uniform distribution of the composition, which is considered to increase the toughness of the polymer (for example, impact resistance).
[0213] In addition, inventive resin 1, incidentally, all inventive compositions have relatively high CDBI (25) values (see Table 3). Compare for example the TREF analysis of the inventive resin 1 (CDBI (25) = 59.5%) with comparative resin 2 (CDBI (25) = 29.4%) as shown in Figure 4. Also see the data in the table 3 where inventive resins 1 to 6 all have a CDBI (25) greater than 59% by weight, while comparative resins 1, 2, 4 and 5 all have CDBI values (25) of less than about 54% in weight. In fact, comparative resins 1 and 2 have CDBI (25) values of less than 35% by weight.
[0214] The polyethylene compositions of the present invention can be used in drinking water, juice, hot fill applications or other non-pressurized closures and closures. INDUSTRIAL APPLICABILITY
[0215] The invention provides polyethylene compositions that are suitable for compression molding or injection molding applications. Polyethylene compositions are particularly useful for the commercial manufacture of bottle caps and closures, especially bottles containing non-pressurized liquids.

权利要求:
Claims (52)
[0001]
1. Bottle closure, CHARACTERIZED by the fact that it comprises a polyethylene composition, the polyethylene composition comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melting index, from 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) of at least 3.5 h.
[0002]
2. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a contraction ratio of transverse direction / machine direction from 0.90 to 1.15 when measured according to the Dimensional Stability Test (STD).
[0003]
3. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) from 3.5 to 15 h.
[0004]
4. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has an I2 melting index, greater than 5.0 to less than 20 g / 10 min.
[0005]
5. Closure, according to claim 1, CHARACTERIZED by the fact that the first and second ethylene copolymers are made by polymerizing ethylene and an alpha olefin in the presence of a single site catalyst.
[0006]
6. Closure according to claim 1, CHARACTERIZED by the fact that the density of the second ethylene copolymer is less than 0.030 g / cm3 higher than the density of the first ethylene copolymer.
[0007]
7. Closure, according to claim 1, CHARACTERIZED by the fact that the first ethylene copolymer has an I2 melting index, from 0.1 to 3.0 g / 10 min.
[0008]
8. Closure, according to claim 1, CHARACTERIZED by the fact that the second ethylene copolymer has an I2 melting index, from 100 to 5000 g / 10 min.
[0009]
9. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has an I2 melting index, from 6 to 12 g / 10 min.
[0010]
10. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a bimodal molecular weight distribution as determined by gel permeation chromatography.
[0011]
11. Closure, according to claim 1, CHARACTERIZED by the fact that the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of chain branches short per thousand carbon atoms in the second ethylene copolymer (SCB2) is at least 1.5.
[0012]
12. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a molecular weight distribution Mw / Mn, from 3.5 to 6.
[0013]
13. Closure, according to claim 1, CHARACTERIZED by the fact that the first ethylene copolymer has a density of 0.936 to 0.952 g / cm3.
[0014]
14. Closure according to claim 1, CHARACTERIZED by the fact that the second ethylene copolymer has a density of less than 0.965 g / cm3.
[0015]
15. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a density of 0.952 to 0.960 g / cm3.
[0016]
16. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition does not have long chain branching.
[0017]
17. Closure, according to claim 1, CHARACTERIZED by the fact that the first and second ethylene copolymers have an Mw / Mn of less than 2.5.
[0018]
18. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a composition distribution amplitude index (CDBI (50)) greater than 65% by weight.
[0019]
19. Closure, according to claim 1, CHARACTERIZED by the fact that the first and second ethylene copolymers each have a composition distribution amplitude index (CDBI (50)) greater than 65% by weight.
[0020]
20. Closure, according to claim 1, CHARACTERIZED by the fact that the polyethylene composition comprises: from 25 to 60% by weight of the first ethylene copolymer; and from 75 to 40% by weight of the second ethylene copolymer.
[0021]
21. Closure according to claim 1, CHARACTERIZED by the fact that the polyethylene composition has a comonomer content of less than 0.5 mol% as determined by 13C NMR.
[0022]
22. Closure according to claim 1, CHARACTERIZED by the fact that the polyethylene composition further comprises a nucleating agent.
[0023]
23. Closure, according to claim 1, CHARACTERIZED by the fact that the first and second ethylene copolymers are ethylene and 1-octene copolymers.
[0024]
24. Closure, according to claim 1, CHARACTERIZED by the fact that it is manufactured by compression molding or injection molding.
[0025]
25. Closure, according to claim 1, CHARACTERIZED by the fact that it is a screw cap.
[0026]
26. Closure according to claim 1, CHARACTERIZED by the fact that the polyethylene composition is prepared by contacting ethylene and an alpha-olefin with a single site polymerization catalyst under solution polymerization conditions in at least two reactors polymerization.
[0027]
27. Process for preparing a bottle closure, CHARACTERIZED by the fact that it comprises at least one compression molding or injection molding step and wherein the closure comprises a polyethylene composition, the polyethylene composition comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melt index of 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) of at least 3.5 h.
[0028]
28. Process for preparing a polyethylene composition, the polyethylene composition comprising: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melting index of 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 3.0; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) of at least 3.5 h; the process CHARACTERIZED by the fact that it comprises contacting at least one single site polymerization catalyst system with ethylene and at least one alpha-olefin under solution polymerization conditions in at least two polymerization reactors.
[0029]
29. Process according to claim 28, CHARACTERIZED by the fact that the at least two polymerization reactors comprise a first reactor and a second reactor configured in series.
[0030]
30. Process according to claim 29, CHARACTERIZED by the fact that at least one alpha-olefin is fed exclusively to the first reactor.
[0031]
31. Polyethylene composition, CHARACTERIZED by the fact that it comprises: (1) 10 to 70% by weight of a first ethylene copolymer having an I2 melting index of 0.1 to 10 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; and a density of 0.930 to 0.960 g / cm3; and (2) 90 to 30% by weight of a second ethylene copolymer having an I2 melt index of 50 to 10,000 g / 10 min; a molecular weight distribution Mw / Mn of less than 2.5; and a density higher than the density of the first ethylene copolymer, but less than 0.966 g / cm3; wherein the density of the second ethylene copolymer is less than 0.037 g / cm3 higher than the density of the first ethylene copolymer; the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) is greater than 1.0; and wherein the polyethylene composition has a molecular weight distribution Mw / Mn, from 2 to 7; a density of at least 0.950 g / cm3; a high load melt index I21, from 150 to 400 g / 10 min; an average molecular weight Z MZ, of less than 300,000; a melt flow rate I21 / I2, from 22 to 50; a voltage exponent of less than 1.40; and a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) of at least 3.5 h.
[0032]
32. Composition of polyethylene, according to claim 31, CHARACTERIZED by the fact that it has a Condition B resistance to cracking by environmental stress, ESCR, (100% IGEPAL) from 3.5 to 15 h.
[0033]
33. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has an I2 melting index, greater than 5.0 to less than 20 g / 10 min.
[0034]
34. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the first and second ethylene copolymers are made by polymerizing ethylene and an alpha olefin in the presence of a single site catalyst.
[0035]
35. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the density of the second ethylene copolymer is less than 0.030 g / cm3 higher than the density of the first ethylene copolymer.
[0036]
36. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the first ethylene copolymer has an I2 melting index of 0.1 to 3.0 g / 10 min.
[0037]
37. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the second ethylene copolymer has an I2 melting index, from 100 to 5000 g / 10 min.
[0038]
38. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has an I2 melting index of 6 to 12 g / 10 min.
[0039]
39. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a bimodal molecular weight distribution as determined by gel permeation chromatography.
[0040]
40. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the ratio (SCB1 / SCB2) of the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) to the number of branches short chain per thousand carbon atoms in the second ethylene copolymer (SCB2) is at least 1.5.
[0041]
41. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a molecular weight distribution Mw / Mn, from 3.5 to 6.
[0042]
42. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the first ethylene copolymer has a density of 0.936 to 0.952 g / cm3.
[0043]
43. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the second ethylene copolymer has a density of less than 0.965 g / cm3.
[0044]
44. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a density of 0.952 to 0.960 g / cm3.
[0045]
45. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has no long chain branching.
[0046]
46. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a distribution amplitude index of the composition CDBI (50) greater than 65% by weight.
[0047]
47. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the first and second ethylene copolymers each have a distribution amplitude index of the composition CDBI (50) greater than 65% by weight.
[0048]
48. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it comprises: from 25 to 60% by weight of the first ethylene copolymer; and from 75 to 40% by weight of the second ethylene copolymer.
[0049]
49. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a comonomer content of less than 0.5 mol% as determined by 13C NMR.
[0050]
50. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it further comprises a nucleating agent.
[0051]
51. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that the first and second ethylene copolymers are copolymers of ethylene and 1-octene.
[0052]
52. Polyethylene composition according to claim 31, CHARACTERIZED by the fact that it has a contraction ratio of transverse direction / machine direction from 0.90 to 1.15 when measured according to the Dimensional Stability Test (STD) ).

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US9963529B1|2017-04-19|2018-05-08|Nova ChemicalsS.A.|Multi reactor solution polymerization|

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CA3022700A1|2017-11-27|2019-05-27|Nova Chemicals Corporation|Bottle closure assembly comprising a polyethylene composition having good dimensional stability|

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CA3022996A1|2017-12-04|2019-06-04|Nova Chemicals Corporation|Bottle closure assembly comprising a polyethylene composition|

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CN113272339A|2018-11-29|2021-08-17|博里利斯股份公司|Polymer production process and polymer|

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CA3026098A1|2018-12-03|2020-06-03|Nova Chemicals Corporation|Narrow polyethylene homopolymer compositions having good barrier properties|

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CA3026095A1|2018-12-03|2020-06-03|Nova Chemicals Corporation|Polyethylene homopolymer compositions having good barrier properties|

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CA3028157A1|2018-12-20|2020-06-20|Nova Chemicals Corporation|Polyethylene copolymer compositions and their barrier properties|

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CA3028148A1|2018-12-20|2020-06-20|Nova Chemicals Corporation|Polyethylene copolymer compositions and articles with barrier properties|

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CA3032082A1|2019-01-31|2020-07-31|Nova Chemicals Corporation|Polyethylene compositions and articles with good barrier properties|

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WO2021144615A1|2020-01-17|2021-07-22|Nova ChemicalsS.A.|Polyethylene copolymer compositions and articles with barrier properties|

法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2021-02-17| B09A| Decision: intention to grant|

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2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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CA2798854A|CA2798854C|2012-12-14|2012-12-14|Polyethylene compositions having high dimensional stability and excellent processability for caps and closures|

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CA2798854|2012-12-14|

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PCT/CA2013/000896|WO2014089670A1|2012-12-14|2013-10-22|Polyethylene compositions having high dimensional stability and excellent processability for caps and closures|

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