POLYMER BASED ON ETHYLENE, COMPOSITION AND ARTICLE

专利摘要:
ethylene-based polymer, composition and article the invention provides an ethylene-based polymer comprising the following properties: (a) a "weight fraction (w) of molecular weight greater than 10 (6) g / mol, based on weight total polymer, and determined by gpc (abs) "which satisfies the following relationship: w <a + b (i2), where a = 0.090, and b = -4.00 x 10- (3) (min / dg); (b) a g 'value that satisfies the following relationship: g' (greater than equal) c + d log (i2), where c = 162 pa, and d = -90.0 pa / log (dg / min); (c) a melt index (i2) of 1 to 20 dg / min; and (d) extractable with chloroform which has a maximum average mw (conv) less than or equal to 4,000 g / mol.
公开号:BR112014012268B1
申请号:R112014012268-7
申请日:2012-11-20
公开日:2020-09-29
发明作者:Teresa P. Karjala；Otto J. Berbee；Cornelis F. J. Den Doelder；Stefan Hinrichs
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

Historic
[0001] Low molecular weight low density polyethylene (LDPEs) with high molecular weight fractions are desired for good processability (line speed, bubble stability, narrowing, etc.) in pure form, or in mixtures with linear low density polyethylene or with other polymers. Wide MWD LDPE constitutes a range of polymeric molecules including low and high molecular weight polymer molecules. In general, the extractable fraction in such polymers increases with an increase in the fraction of low molecular weight molecules, and also increases by increasing the frequency of short chain branching in the low molecular weight molecules. There is typically a trade-off between the MWD's breadth and the withdrawable level. The wide MWD can assist in areas such as LDPE processability during process operations such as extrusion at lower pressures or better bubble stability when making an expanded film. The extractable level is an important parameter for food packaging applications, and low extractables are desirable, since high levels of extractables typically lead to the formation of smoke and / or matrix encrustation during LDPE processing. Additionally, LDPE can be used in food contact applications, and if extractable levels are too high, LDPE will not meet the limits of the Food and Drug Administration (FDA) (US Federal Food and Pharmaceuticals Agency) for applications with or without cooking, thus restricting the use of LDPE in some applications.
[0002] Wide MWD LDPES can be prepared in different types of reactors, such as autoclaves or tubular reactors with different residence time distributions. Due to the wider distribution of residence time of an autoclave reactor, it is much easier to prepare a larger MWD with a fraction of ultra high molecular weight polymer in this type of reactor. However, the wide MWD of an autoclave product does not result in a high molecular weight fraction that can adversely affect properties, such as film optics. Wide MWD LDPEs are more difficult to achieve in a tubular reactor due to the continuous flow behavior. In a tubular reactor, more extreme process conditions, such as high temperature, low pressure, and / or higher level of conversion, etc., must be applied to obtain a wide MWD. These extreme process conditions typically lead to more extractables; however, MWD is free of extremely high molecular weight fractions as observed in polymers based on a wide MWD autoclave. There is a need to reduce the levels of extractables in very wide MWD tubular products by changing the extraction capacity of the low molecular weight fraction in the polymer, as evidenced by the analysis of the extracted low molecular weight fraction.
[0003] International publication No. WO 2006/094723 discloses a process for the preparation of an ethylene copolymer and a copolymerizable monomer with ethylene. Polymerization takes place in a tubular reactor at a maximum temperature between 290 ° C and 350 ° C. The comonomer is a bifunctional or more functional (meth) acrylate, and the comonomer is used in an amount between 0.008 mol% and 0.200 mol%, in relation to the amount of ethylene copolymer. Bifunctional or more functional (meth) acrylate is capable of acting as a crosslinking agent.
[0004] European patent EP 0928797B1 discloses an ethylene homopolymer or copolymer having a density between 0.923 and 0.935 g / cm3, and a molecular weight distribution Mw / Mn between 3 and 10, and comprising 0.10 at 0.50% by weight of units derived from a compound containing carbonyl group, based on the total weight of the homopolymer or copolymer.
[0005] U.S. Patent No. 3,334,081 discloses a continuous process for the production of ethylene polymers carried out in a tubular reactor by means of which the polymer is obtained at a higher conversion rate. In one embodiment, this patent discloses a continuous process for polymerizing ethylene in a tubular reactor at a pressure of at least about 15,000 psig and at a temperature of about 90 ° C to about 350 ° C, in the presence of an initiator via free radicals.
[0006] US patent No. 3,657,212 discloses the production of ethylene homopolymers having a specific density, by polymerization of ethylene, under the action of organic peroxides and oxygen as polymerization initiators generating free radicals, and polymerization modifiers, at elevated temperature and superatmospheric pressure, in a tubular reactor having two successive reaction zones. A mixture of ethylene, polymerization initiator, and polymerization modifier is introduced continuously at the beginning of each reaction zone. Ethylene homopolymers have a wide molecular weight distribution, but are said to be practically devoid of very high molecular weight constituents.
[0007] Additional polymerizations and / or resins are described in: US Patent Nos. 2,153,553, 2,897,183, 2,396,791, 3,917,577, 4,287,262, 6,569,962, 6,844,408, and 6,949. 611; US publications No. 2007/0225445, 2003/0114607, US2009 / 0234082; in international publications No. WO 2012/044504, WO 2011/075465, WO 2008/112373, WO 2006/096504, and WO 2007/110127; in GB1101763, GB1196183; in DD120200, DD276598A3; in DE2017945; in EP0069806A1; CA2541180; EP1777238B1; EP0792318B1; EP2123707A1; and in J. Bosch, "The Introduction of Tubular LDPE to the Extrusion Coating Market and the Specifics of the Product", 12th European PLAP TAPPI conference, 2009, pages 1-20.
[0008] The two-zone tubular reactor systems commonly used in the above technique lead to polymers either with very narrow MWD or with very high extractable levels. Achieving broad MWD resins with such reactor systems typically requires extremely high maximum temperatures and / or low reactor inlet pressures, and both lead to the formation of lower molecular weight material with increased short chain branching, which leads to and high extractables. Thus, conventional tubular polymerization processes can produce polymers of MWD relatively wide, but with high levels of extractables. As discussed above, the need remains to reduce levels of extractables in tubular products of very wide MWD. These and other needs have been met by the following invention. Summary of the invention
[0009] The invention provides an ethylene-based polymer comprising the following properties: (A) a "weight fraction (w) of molecular weight greater than 106 g / mol, based on the total weight of the polymer, and determined by GPC ( abs) "which satisfies the following relationship: w <A + B (I2), where A = 0.090, and B = -4.00 x 10 (min / dg); (B) a G 'value that satisfies the following relationship: G'> C + D log (I2), where C = 162 Pa, and D = - 90.0 Pa / log (dg / min); (C) a melting index (I2) of 1 to 20 dg / min; and (D) extractable with chloroform which has a maximum mean Mw (conv) less than or equal to 4,000 g / mol. Brief description of the figures
[0010] Figure 1 is a schematic diagram of a polymerization flow scheme;
[0011] Figure 2 is a schematic diagram of a polymerization flow scheme;
[0012] Figure 3 shows GPC chromatograms of inventive LDPE (IE 4) and comparative LDPE (PT7007) polymers; and
[0013] Figure 4 shows the distribution of four quadrants in the GPC chromatogram for the inventive chloroform extract for LDPE (IE 3). Detailed Description
[0014] As discussed above, the invention provides an ethylene-based polymer comprising the following properties: (A) a "weight fraction (w) of molecular weight greater than 106 g / mol, based on the total weight of the polymer, and determined by GPC (abs) "which satisfies the following relationship: w <A + B (I2), where A = 0, 090, and B = -4.00 x 10" 3 (min / dg); (B) a G 'value that satisfies the following relationship: G'> C + D log (I2), where C = 162 Pa, and D = -90.0 Pa / log (dg / min); (C) a melting index (I2) of 1 to 20 dg / min; and (D) extractable with chloroform which has a maximum mean Mw (conv) less than or equal to 4,000 g / mol.
[0015] The ethylene-based polymer may comprise a combination of two or more embodiments described herein.
[0016] When used here, the G 'value noted above is G' for G "= 500 Pa (at 170 ° C).
[0017] In an incorporation, the extractable with chloroform has a maximum Mw (conv) less than or equal to 3,900 g / mol. The extractable with chloroform is determined by the standard test method described here.
[0018] In an incorporation, the extractable with chloroform has a maximum Mw (conv) less than or equal to 3,700 g / mol.
[0019] In an incorporation, the ethylene-based polymer has an Mw (abs) that satisfies the following relationships: (I) Mw (abs) <E + F.log (l2), where E = 3.50 x 105 g / mol, and F = -1.20 x 105 (g / mol) / log (dg / min); and (II) Mw (abs)> G + H.log (I2), where G = 2.00 x 105 g / mol, and H = -1.20 x 105 (g / mol) / log (dg / min ).
[0020] In an incorporation, the ethylene-based polymer has a "Mw (conv) cioroform_Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in the MWD of the extractable with chloroform" which is less than or equal to 8,400 g / mol. Mw (conv) refers to the molecular weight.
[0021] In an incorporation, the ethylene-based polymer has a "Mw (conv) cioroform_Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in the MWD of the extractable with chloroform" which is less than or equal to 8,000 g / mol.
[0022] In an incorporation, the ethylene-based polymer has a "Mw (conv) chloroform_Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in the MWD of the extractable with chloroform" which is less than or equal to 7,600 g / mol.
[0023] In an incorporation, the ethylene-based polymer has an extractable with hexane that has a maximum Mw (conv) less than or equal to 2,300 g / mol, or less than or equal to 2,200 g / mol.
[0024] In an incorporation, the ethylene-based polymer has a "Mw (conv) hexane-Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in the MWD of the extractable with chloroform" which is less than or equal to 4,200 g / mol, or less than or equal to 4,000 g / mol. In an embodiment, the hexane extractable comprises a polymer comprising oxygen-containing terminal groups, derived from a non-olefinic chain transfer agent (CTA) system, in an amount greater than "0.5 terminal group" per 1000 carbon atoms, preferably greater than or equal to "0.75 terminal group" per 1000 carbon atoms, more preferably greater than or equal to "1.0 terminal group" per 1000 carbon atoms. In a further embodiment, the CTA system is selected from the following: a ketone, an aldehyde, an ester, an alcohol, or combinations thereof, preferably a ketone, an aldehyde, an alcohol, or combinations thereof, more preferably a ketone, an aldehyde, or combinations thereof. In an additional incorporation, the CTA system is selected from the following: propanal (propionic aldehyde), methyl ethyl ketone, acetone, ethanal (acetic aldehyde), propanol, an alkyl acetate, isopropanol, or combinations thereof.
[0025] In an incorporation, the extractable with chloroform comprises terminal groups containing oxygen, derived from a non-olefinic CTA system, in an amount greater than "0.5 terminal group" per 1000 carbon atoms, preferably greater than or equal to "0, 75 "terminal group" per 1000 carbon atoms, more preferably greater than or equal to "1.0 terminal group" per 100 carbon atoms. In a further embodiment, the CTA system is selected from the following: a ketone, an aldehyde, an ester, an alcohol, or combinations thereof, preferably a ketone, an aldehyde, an alcohol, or combinations thereof, more preferably a ketone, an aldehyde, or combinations thereof. In an additional embodiment, the CTA system is selected from the following: propanal (propionic aldehyde), methyl ethyl ketone, acetone, ethanal (acetic aldehyde), propanol, an alkyl acetate, isopropanol, n-butane, isobutane, or combinations thereof . In another embodiment, the CTA system is selected from the following: propanal (propionic aldehyde), methyl ethyl ketone, acetone, ethanal (acetic aldehyde), propanol, an alkyl acetate, isopropanol, or combinations thereof.
[0026] In an incorporation, the extractable with chloroform comprises a polymer that comprises vinyl end groups in an amount less than "1.0 vinyl group" per 1000 carbon atoms. In a further embodiment, the extractable with chloroform comprises a polymer comprising vinyl end groups in an amount less than "0.8 vinyl group" per 1000 carbon atoms. In a further embodiment, the extractable with chloroform comprises a polymer comprising vinyl end groups in an amount less than "0.8 vinyl group" per 1000 carbon atoms. In a further embodiment, the extractable with chloroform comprises a polymer comprising vinyl end groups in an amount less than "0.6 vinyl group" per 1000 carbon atoms.
[0027] In an incorporation, the extractable with hexane comprises a polymer comprising vinyl end groups in an amount less than "1.0 vinyl group" per 1000 carbon atoms. In an additional embodiment, the hexane extractable comprises a polymer comprising vinyl end groups in an amount less than "0.8 vinyl group" per 1000 carbon atoms. In a further embodiment, the hexane extractable comprises a polymer comprising vinyl end groups in an amount less than "0.8 vinyl group" per 1000 carbon atoms. In a further embodiment, the hexane extractable comprises a polymer comprising vinyl end groups in an amount less than "0.6 vinyl group" per 1000 carbon atoms.
[0028] In an incorporation, the ethylene-based polymer, according to any of the previous incorporations, has a density greater than or equal to 0.919 g / cm3.
[0029] In an embodiment, the ethylene-based polymer has a density of 0.916 to 0.930 g / cm3.
[0030] In an embodiment, the ethylene-based polymer has a density of 0.918 to 0.930 g / cm3.
[0031] In an embodiment, the ethylene-based polymer comprises less than 5% by weight of the comonomer, based on the weight of the polymer. In a further embodiment, the ethylene-based polymer comprises less than 2% by weight of the comonomer, based on the weight of the polymer. In a further embodiment, the ethylene-based polymer comprises less than 1% by weight of the comonomer, based on the weight of the polymer (% by weight = weight percent).
[0032] An inventive ethylene-based polymer may comprise a combination of two or more embodiments described herein.
[0033] In an embodiment, the ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based interpolymer.
[0034] In an embodiment, the ethylene-based polymer is selected from a polyethylene homopolymer or from an ethylene-based copolymer; and the comonomer of the ethylene-based copolymer is selected from vinyl acetate, alkyl acrylate, carbon monoxide (CO), acrylic acid, a comonomer containing carboxylic acid, a monoolefin, a diolefin, or polyene. In a further embodiment, the comonomer is present in an amount of 0.5 to 10% by weight of the comonomer, based on the weight of copolymer.
[0035] In an embodiment, the ethylene-based polymer is a polyethylene homopolymer.
[0036] In an embodiment, the ethylene-based polymer is an ethylene-based copolymer; and the comonomer of the ethylene-based copolymer is selected from vinyl acetate, alkyl acrylate, carbon monoxide (CO), acrylic acid, a comonomer containing carboxylic acid, a monoolefin, a diolefin, or polyene. In an additional incorporation, the comonomer is selected from vinyl acetate, alkyl acrylate, acrylic acid, mono-olefin, or diolefin.
[0037] In an embodiment, the comonomer is present in an amount of 0.5 to 10% by weight of the comonomer, based on the weight of the copolymer.
[0038] In an incorporation, the ethylene-based polymer has an I2 1.5 g / 10 min.
[0039] In an incorporation, the ethylene-based polymer has an I2 2.0 g / 10 min.
[0040] In an incorporation, the ethylene-based polymer has an I2> 2.5 g / 10 min.
[0041] In an incorporation, the ethylene-based polymer has an I2 3.0 g / 10 min.
[0042] In an incorporation, the ethylene-based polymer has an I2
[0043] 18 g / 10 min. In an embodiment, the ethylene-based polymer has an I2 <
[0044] 15 g / 10 min. In an embodiment, the ethylene-based polymer has an I2 <
[0045] 10 g / 10 min. In one embodiment, the ethylene-based polymer has a G '> 90 Pa. In a further embodiment, the ethylene-based polymer has a G'> 100 Pa.
[0046] An inventive ethylene-based polymer may comprise a combination of two or more embodiments described herein.
[0047] The invention also provides a composition comprising an inventive ethylene-based polymer.
[0048] In an embodiment, the composition comprises yet another polymer based on ethylene.
[0049] An inventive composition may comprise a combination of two or more embodiments described herein.
[0050] The invention also provides an article comprising at least one component formed by an inventive composition.
[0051] In an embodiment, the article is a film.
[0052] In an embodiment, the article is a coating.
[0053] An inventive article may comprise a combination of two or more embodiments described herein. Polymerizations
[0054] For a polymerization process initiated by free radicals at high pressure, two basic types of reactors are known. The first type is a stirred autoclave container having one or more reaction zones (autoclave reactor). The second type is a jacketed tube that has one or more reaction zones (tubular reactor).
[0055] The pressure in each autoclave or tubular reactor zone of the process is typically 100 to 400 MPa, more typically 120 to 360 MPa, and even more typically 150 to 320 MPa.
[0056] The polymerization temperature in each tubular reactor zone of the process is typically 100 to 400 ° C, more typically 130 to 360 ° C, and even more typically 140 to 340 ° C.
[0057] The polymerization temperature in each autoclave reactor zone of the process is typically 150 to 300 ° C, more typically 165 to 290 ° C, and even more typically 180 to 280 ° C. A person skilled in the art understands that the temperatures in the autoclave are considerably lower and less differentiated than those in the tubular reactor, and thus, typically more favorable extractable levels are observed in polymers produced in autoclave-based reactor systems.
[0058] The high pressure process of the present invention used to produce polyethylene homopolymers, copolymers or interpolymers having advantageous properties found in accordance with the invention, is preferably carried out in a tubular reactor having at least three reaction zones. Initiators
[0059] The process of the present invention is a polymerization process via free radicals. The type of free radical initiator to be used in the present process is not critical, but preferably one of the applied initiators must allow operation at high temperature in the range of 300 ° C to 350 ° C. Free radical initiators that are generally used include organic peroxides, such as percetal peresters, peroxy ketones, percarbonates and multifunctional cyclic peroxides. These organic peroxy initiators are used in conventional amounts, typically from 0.005 to 0.2% by weight, based on the weight of polymerizable monomers. Typically, peroxides are injected as solutions diluted in an appropriate solvent, for example, a hydrocarbon solvent.
[0060] Other suitable initiators include azodicarboxylic esters, azodicarboxylic dinitriles and derivatives of 1,2,2-tetramethylethane, and other components capable of forming free radicals in the desired range of operating temperatures.
[0061] In an embodiment, an initiator is added in at least one polymerization enhancement zone, and the initiator has a "half-life temperature in one second" greater than 225 ° C, preferably greater than 260 ° C . In an additional embodiment, such initiators are used at a maximum polymerization temperature of 320 ° C to 350 ° C. In a further embodiment, the initiator comprises at least one peroxide group incorporated in a ring structure.
[0062] Examples of such initiators include, but are not limited to, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane) and TRIGONOX 311 (3,3, 5,7,7-pentamethyl-1,2,4-trioxepano), both obtainable from Akzo Nobel and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5 -tetroxonan) obtainable from United Initiators. See also international publications WO 02/14379 and WO 01/68723. Chain Transfer Agent (CTA)
[0063] Chain transfer agents (CTAs) or telogens are used to control the melt index in a polymerization process. Chain transfer involves terminating growing polymeric chains thus limiting the final molecular weight of the polymeric material. Typically, chain transfer agents are hydrogen atom donors that will react with a growing polymer chain and stop the chain polymerization reaction. These agents can be of many different types, from saturated or unsaturated hydrocarbons to aldehydes, ketones or alcohols. By controlling the concentration of the selected chain transfer agent, one can control the length of the polymeric chains, and consequently the molecular weight, for example, the numerical average molecular weight, Mn. In the same way, the melt flow index (MFI or I2) of a polymer, which relates to Mn, is controlled.
The chain transfer agents used in the process of this invention include, but are not limited to, naphthenic hydrocarbons, aliphatic hydrocarbons, such as, for example, pentane, hexane, cyclohexane, n-butane, and isobutane; ketones such as acetone, diethyl ketone or diamyl ketone; aldehydes such as formaldehyde or acetic aldehyde; and saturated aliphatic alcohols such as methanol, ethanol, propanol or butanol.
[0065] In an embodiment, the ethylene-based polymer is polymerized in the presence of a saturated hydrocarbon comprising four or more carbon atoms.
[0066] An additional way of influencing the melting index includes the development and control, in ethylene recycling streams, of newly arrived ethylene impurities, such as methane and ethane, peroxide dissociation products, such as terciobutane, acetone, etc. ., and / or component solvents used to dilute the initiators. These ethylene impurities, peroxide dissociation products, and / or diluting component solvents can act as chain transfer agents. Polymers
[0067] In one embodiment, the ethylene-based polymers of this invention have a density of 0.914 to 0.930 g / cm3, more typically from 0.916 to 0.930 g / cm3 and even more typically from 0.918 to 0.926 g / cm3. In one embodiment, the ethylene-based polymers of this invention have a melting index (I2) of 1 to 20 g / 10 min, more typically 1 to 15 g / 10 min and even more typically 1 to 10 g / 10 min at 190 ° C / 2.16 kg.
[0068] Ethylene based polymers include LDPE homopolymer, and high pressure copolymers, including ethylene / vinyl acetate (EVA), ethylene / ethyl acrylate (EEA), ethylene / butyl acrylate (EBA), ethylene copolymers / acrylic acid (EAA), ethylene / vinyl silane (EVS), ethylene / vinyl trimethyl silane (EVTMS), and other copolymers prepared with "silane-containing" comonomers, and ethylene / carbon monoxide (ECO) copolymer. Other suitable comonomers are described in Ehrlich, P.; Mortimer, G.A .; Adv. Polymer Science; Fundamentals of Free-radical Polymerization of Ethylene; volume 7, pp. 386-448 (1970). Monomer and comonomers
[0069] When used in the present description and in the claims, the term ethylene interpolymer refers to polymers of ethylene and one or more comonomers. Suitable comonomers to be used in the ethylene polymers of the present invention include, but are not limited to, ethylenically unsaturated monomers and especially C3-20Z alpha olefins, polyolene, carbon monoxide, vinyl acetate, and C2 alkyl acrylates -6 • Mixtures
[0070] The inventive polymers can be mixed with one or more other polymers, such as, but not limited to, linear low density polyethylene (LLDPE) or LDPE; copolymers of ethylene with one or more alpha-olefins, such as, but not limited to, propylene, butene-1, pentene-1, 4-methyl-pentendo-1, hexene-1 and octene-1; high density polyethylene (HDPE), such as HDPE of HD 940-970 grades obtainable from The Dow Chemical Company. The amount of inventive polymer in the mixture can vary widely, but typically it is 10 to 90 weight percent, or 15 to 85 weight percent, or 20 to 80 weight percent, based on the weight of the polymers in the mix. Additions
[0071] One or more additives can be added in a composition comprising an inventive polymer. Suitable additives include stabilizers; fillers, such as organic or inorganic particles including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel mesh or wire, and nylon cord or polyester, nano particles, clays, etc .; and tackifying agents or thinning oils, including paraffinic and naphthenic oils. applications
[0072] An inventive composition can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles including, for example, films; molded articles, such as blow-molded, injection-molded, or rotational molded articles; foams; wire and cable coatings, extrusion coatings, and woven or non-woven fabrics. Definitions
[0073] Unless stated otherwise, implicit in the contest, or customary in the technique, all parts and percentages are based on weight, and all testing methods are current as of the filing date of this disclosure.
[0074] When used herein, the term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products of the composition materials.
[0075] When used, the terms "mixture" and "polymeric mixture" mean an intimate physical mixture (that is, without reaction) of two or more polymers. A mixture may or may not be miscible (not separated into phases at the molecular level). A mixture may or may not be separated into phases. A mixture may or may not contain domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Mixing can be carried out by physically mixing the two or more polymers at the macroscopic level (for example, melted mixed composition or resins) or at the microscopic level (for example, simultaneous formation within the same reactor).
[0076] The term "polymer" refers to a compound prepared by polymerizing monomers of either the same or different types. Thus, the generic term polymer encompasses the term "homopolymer" (which refers to polymers prepared from only one type of monomer with the understanding that traces of impurities can be incorporated into the polymeric structure), and the term "interpolymer" defined below .
[0077] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (which refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
[0078] The term "ethylene-based polymer" or "ethylene-polymer" refers to a polymer comprising a majority of polymerized ethylene, based on the weight of the polymer and, optionally, can comprise at least one comonomer.
[0079] The term "ethylene-based interpolymer" or "ethylene-interpolymer" refers to a polymer comprising a majority of polymerized ethylene, based on the weight of the interpolymer, and comprising at least one comonomer.
[0080] The term "ethylene-based copolymer" or "ethylene copolymer" refers to a polymer comprising a majority amount of polymerized ethylene, based on the weight of the copolymer and, only one comonomer (thus, only two types monomers).
[0081] When used herein, the terms "autoclave-based products" or "autoclave-based polymers" refer to polymers prepared in autoclave, autoclave / autoclave, or reactor system comprising an autoclave and a tubular reactor.
[0082] The term "CTA system" includes a single CTA or a mixture of CTAs added to the polymerization process, typically to control the melt index. A CTA system includes a component capable of transferring a hydrogen atom to a growing polymer molecule, which can then initiate a new polymer chain. In a preferred embodiment, each CTA system comprises a single type of CTA.
[0083] When used herein, the term "non-olefinic CTA system" refers to types of CTA devoid of carbon-carbon double bonds and carbon-carbon triple bonds, such as, for example, isobutane, ethanol, isopropanol, acetone, propane, and others.
[0084] When used herein, the term "oxygen-containing terminal groups derived from a non-olefinic CTA system" refers to one or more polymer terminal groups, each comprising at least one oxygen atom, and which is derived from a non-olefinic CTA system comprising at least one oxygen atom, or derived from a non-olefinic peroxide dissociation product.
[0085] The terms "comprising", "including", "having", and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. In order to avoid any doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant, or additional compound, whether polymeric or not, unless otherwise stated. On the other hand, the term "essentially consisting of" excludes any other component, step or procedure from the scope of any subsequent mention, except those that are not essential for operability. The term "consisting of" excludes any component, step or procedure not specifically related or described. Testing methods
[0086] Density: Samples are prepared for density measurement according to ASTM D 1928. The polymeric samples are pressed at 190 ° C and 207 MPa (30,000 psi) for three minutes, and then at 21 ° C and 207 MPa for one minute. Measurements are performed within one hour of sample pressing using ASTM D792, Method B.
[0087] melting index: The melting index, or I2, (g / 10 min or dg / min) is measured according to ASTM D 1238, condition 190 ° C / 2.16 kg.
[0088] Triple detector gel permeation chromatography (TDGPC): High temperature TDGPC analysis is performed on a GPCV2000 ALLIANCE instrument (Waters Corp.) adjusted to 145 ° C. The flow rate for the GPC is 1 mL / min. The injection volume is 218.5 | 1L. The column set consists of four Mixed-A columns (20 µm particles; 7.5 x 300 mm; Polymer Laboratories Ltd.).
[0089] Detection is achieved using a PolymerChar IR4 detector, equipped with a CH sensor; a Dawn DSP multi-angle light scattering (MALS) detector from Wyatt Technology (Wyatt Technology Corp. Santa Barbara, CA, USA), equipped with a 30 mW ion-argon laser operating at À = 488 nm; and a viscosity detector of three Waters capillaries. The MALS detector is calibrated by measuring the spreading intensity of the TCB solvent. The photodiodes are normalized by injecting SEM 1483, a high density polyethylene with a weight average molecular weight (Mw) of 32,100 g / mol and a polydispersion (molecular weight distribution, Mw / Mn) of 1.11. A specific increment of refractive index (dn / dc) of -0.104 mL / mg is used for polyethylene in 1,2,4-trichlorobenzene (TCB).
[0090] The conventional GPC is calibrated with 20 narrow MWD polystyrene (PS) standards (Polymer Laboratories Ltd.) with molecular weights in the range of 580 - 7,500,000 g / mol. The maximum molecular weights of polystyrene standards are converted to molecular weights of polyethylene using the following equation: Mpolethylene = AX (MpOü styrene) with A = 0.39 and B = 1. The value of A is determined using a polyethylene homopolymer high density linear (HDPE) with 115,000 g / mol Mw. The HDPE reference material is also used to calibrate the IR detector and viscometer assuming 100% mass recovery and an intrinsic viscosity of 1.873 dL / g.
[0091] 1,2,4-Trichlorobenzene grade "analyzed by Baker" distilled (JT Baker, Deventer, Netherlands) containing 200 ppm 2,6-ditherciobutyl-4-methyl-phenol (Merck, Hohenbrunn, Germany) as the solvent for sample preparation, as well as for the TDGPC experiment. HDPE SEM 1483 is obtained from the U.S. National Institute of Standards and Technology (Gaithersburg, MD, USA).
[0092] LDPE solutions are prepared by dissolving the samples with gentle agitation for three hours at 160 ° C. PS standards are dissolved in the same conditions for 30 minutes. The sample concentration is 1.5 mg / ml, and the polystyrene concentration is 0.2 mg / ml.
[0093] The MALS detector measures the scattered signal of polymers or particles in a sample at different scattering angles θ. The basic light scattering equation (from M. Anderson, B. Wittgren, KG Wahlund, Anal. Chem. 75, 4279 (2003)) can be written as follows:
where Rθ is Rayleigh's ratio of excess, K is an optical constant, which, among other things, depends on the specific increment of refractive index (dn / dc), c is the concentration of the solute, M is the molecular weight, Rg is the radius of rotation, and À is the wavelength of the incident light. The calculation of the molecular weight and radius of rotation of the light scattering data requires extrapolation to zero angle (see also PJ Wyatt, Anal. Chem. Acta 272, 1 (1993)). This is done by plotting (Kc / Rθ) 1/2 as a function of sen2 (θ / 2) on the so-called Debye graph. The molecular weight can be calculated from the intersection with the ordinate, and the radius of rotation of the initial slope of the curve. The second virial coefficient is considered negligible. Intrinsic viscosity numbers are calculated for both concentration and viscosity detector signals by taking the specific viscosity ratio and concentration in each elution slice.
[0094] ASTRA 4.72 software (Wyatt Technology Corp.) is used to collect the signals from the IR detector, viscometer, and MALS detector, and perform the calculations.
[0095] The calculated molecular weights are obtained, for example, the absolute weight average molecular weight Mw (abs), and the absolute molecular weight distribution (for example, Mw (abs) / Mn (abs)) using a constant of scattering of light derived from one or more of the aforementioned polyethylene standards and a refractive index concentration coefficient, dn / dc, of 0.104. Generally, the mass detector response and the light scattering constant should be determined from a linear pattern with an excess molecular weight of about 50,000 Dalton. Viscometer calibration can be performed using the methods described by the manufacturer, or alternatively, using the published values of appropriate linear standards such as Standard Reference Materials (SRM) 1475a, 1482a, 1483, or 1484a. It is assumed that the chromatographic concentrations are low enough to eliminate addressing the effects of the 2nd viral coefficient (effects of concentration on molecular weight).
[0096] The MWD (abs) curve obtained from TDGPC is summarized with three characteristic parameters: the absolute weight average molecular weight Ww (abs), the numerical absolute average molecular weight Mn (abs), ew, where w is defined as " weight ratio of molecular weight greater than 106 g / mol, based on the total polymer weight, and determined by GPC (abs) ".
[0097] Figure 3 shows the MWD (abs) for Comparative Example PT7007 and for Inventive Example 4. In addition, the vertical line, shown in this figure, indicates the lower integration limit to determine "w". Thus, "w" is effectively the area under the curve to the right of this vertical line.
[0098] In the form of an equation, the parameters are determined as follows. The numerical integration of the "log M" and "dw / dlog M" table is typically done with the trapezoidal rule:
Conventional gel permeation chromatography (GPC)
[0099] Conventional molecular weight and molecular weight distribution data were obtained from a high temperature gel permeation chromatography system (Model Pl-220 from Polymer Laboratories Inc., now Agilent). The column and carousel compartments were operated at 140 ° C. Three 10 µm Mixed-B (Agilent) columns with 1,2,4-trichlorobenzene (TCB) were used. The polymer extract samples were prepared at a concentration of "2 mg / mL" in solvent TCB, weighing the samples and adding the calculated amount of TCB via a dosimeter. The samples were dissolved in TCB at 160 ° C for one hour. The solvent used to prepare the samples contained "200 ppm" of the antioxidant butylated hydroxy-toluene (BHT). The injection volume used was "200 | 1L" and the flow rate was 1.0 mL / min.
[0100] The GPC column set was calibrated with twenty-one polystyrene standards of narrow molecular weight distribution with maximum molecular weight ranging from 580 to 8,400,000 g / mol (Agilent). The maximum molecular weights of polystyrene standards have been converted to molecular weights of polyethylene using the following equation: Mpolethylene = A (Mpolystyrene) B where M is the molecular weight, A has a value of 0.4316 and B is equal to 1.0 (T. Williams and IM Ward, Polymer Letters, vol. 6, pp. 621-624 (1968)). A third ordθm purct ci-justur polynomial was used and the logarithmic molecular weight dθ calibration data as a function of elution volume. Calculations of equivalent molecular weight of polyethylene were performed using the equations shown below:
where Wfi is the weight fraction of the i-th component and Mi is the molecular weight of the i-th component. Determination of log Mw greater than 3.5
[0101] The chromatogram was converted into a molecular weight distribution (MWD) graph of the weight fraction of the measured sample (Wf) against the molecular weight on a logarithmic scale (log M). The numerical average molecular weight, weight average molecular weight and average molecular weight z were calculated according to the equations:
where Wfi is the weight fraction of the i-th component and Mj. is the molecular weight of the i-th component.
[0102] The weight fraction of a component with a molecular weight greater than a given logarithmic molecular weight (such as log M> 3.5) was calculated using the following equation:
where Wfj is the weight fraction of the j-th component and Mj is the molecular weight of the j-th component with the logarithm of the molecular weight greater than a given value (such as log M> 3.5). Wfi is defined above. GPC quadrant method
[0103] For a normalized GPC curve subtracted from the baseline, two n-spatial vectors, wi and log Mi, are defined, where n is the number of data points. The vectors w ± and log Mi are, respectively, the normalized area and the logarithm of the molecular weight for the i-th slice of the GPC curve. The values of any element for log M ± are determined by the elution volume of the i-th slice, and the value of any element of Wi is determined by the i-th slice area, after subtracting the baseline, divided by the area total of all slices. The data points are together close enough in time that the area of each slice can be approximated by a rectangle whose height is determined (after baseline subtraction) by the mass detector response, and whose width is determined by the sampling frequency .
[0104] The normalized GPC curve is divided by weight into four equal sequential parts (four equal parts determined from the area under the log of the MED curve), or quartiles, and the antilogarithm of the average molecular weight logarithm is calculated for each quartile . For each quartile, Mj, where j is the quartile number, the antilogarithm of the average logarithm of molecular weight is calculated as follows:

[0105] The values of aj and bj are chosen as the first slice and the last slice of the j-th quartile.
[0106] Two additional calculations are: the global antilogarithm of the average molecular weight logarithm, Mgiobai, and a ratio. That ratio, Mrazão, is defined as the antilogarithm of the average logarithm of molecular weight of the first 50 percent of the curve, divided by the antilogarithm of the average logarithm of the second 50 percent of the curve. An example of the four quadrants for Example 3 (inventive) is shown in Figure 4 (representative figure).
G 'rheological
[0107] The sample used in the measurement of G was prepared from a compression molded plate. A piece of thin aluminum foil was placed on a backplate, and a template or template was placed on top of the backplate. Approximately 12 g of resin was placed in the mold, and a second piece of thin aluminum foil was placed on the resin and mold. Then, a second counterplate was placed on top of the thin aluminum foil. The entire set was placed in a compression molding press, which was operated under the following conditions: 3 min at 150 ° C, and pressure of 10 bar, followed by 1 min at 150 ° C and 150 bar, followed by a rapid cooling of "1.5 min" until room temperature and 150 bar. A 25 mm disk of the compression-molded plate was stamped. The thickness of this disc was approximately 2.0 mm.
[0108] The rheology measure was performed to determine G'in a nitrogen environment, at 170 ° C, and a 10% deformation. The stamped disc was placed between the two "25 mm" parallel plates in an ARES-1 rheometer oven (Rheometrics SC), which was preheated for at least 30 minutes at 170 ° C, and the gap of the "25 parallel plates" mm "was slowly reduced to 1.65 mm. Then the sample remained exactly 5 minutes in these conditions. Then, the oven was opened, the excess sample was carefully trimmed around the edge of the plates, and the oven was closed. The storage module and the loss module were measured via a small amplitude oscillatory shear according to a descending frequency scan of 100 to 0.1 rad / s (when able to obtain a G 'value less than 500 Pa in 0.1 rad / s), or from 100 to 0.01 rad / s. For each frequency sweep, 10 points (spaced logarithmically) per ten frequency were used.
[0109] The data were plotted (G '(Y-axis) against G "(X-axis)) on a log-log scale. The Y-axis scale covered the range of 10 to 1000 Pa, while the scale of X-axis covered the range from 100 to 1000 Pa. Orchestrator software was used to select data in the region where G "was between 200 and 800 Pa (or using at least 4 data points). The data were fitted to a polynomial model of log using an adjustment equation Y = Cl + C2 ln (x). Using the Orchestrator software, G 'in G "equal to 500 Pa was determined by interpolation.
[0110] In some cases, G '(in G "of 500 Pa) was determined from test temperatures of 150 ° C and 190 ° C. The value at 170 ° C was calculated from a linear interpolation the values at these two temperatures. Standard method for extracting with hexane
[0111] Polymer pellets (2.2 g of pellets pressed into a film from the polymerization and pelletizing process without further modification) were pressed in a Carver press, with a thickness of 3.0-4.0 millipinches. The pellets were pressed at 190 ° C, for three minutes, at 3,000 pounds, and then at 190 ° C, for three minutes, at 40,000 pounds. Gloves without residue ("PIP * CleanTeam * Cotton Lisle Inspection Gloves", lot number: 97-501) were heated in order not to contaminate the films with residual oils from the operator's hands. The films were cut into "1 inch x 1 inch" squares, and weighed. Sufficient film samples were used, such that "2.5 g" of film samples were used for each extraction. Then, the films were extracted for two hours, in a hexane container containing about 1000 mL of hexane, at "(49.5 ± 0.5) ° C" in a heated water bath. The hexane used was an isomeric mixture of "hexanes" (for example, Hexanes (Optima), Fisher Chemical, high purity mobile phase for HPLC and / or extraction solvent for GC applications, minimum 99.9% per GC) . After two hours, the films were removed, rinsed in clean hexane, initially dried with nitrogen and then further dried in a vacuum oven ((80 ± 5) ° C) in full vacuum (ISOTEMP vacuum oven, model 281A at approximately 30 inches) Hg) for two hours. Then, the films were placed in a desiccator, and allowed to cool to room temperature for a minimum of one hour. Then, the films were weighed again, and the amount of mass loss due to extraction in hexane was calculated. Method for collecting soluble fraction of extractables with hexane for GPC and nuclear magnetic resonance (NMR)
[0112] The above method was used for "extractable with standard hexane". For analytical calculations, and preparation of soluble fraction for GPC test, "2.5 g" of film was used. To prepare the soluble fraction for NMR, "7.5 g" of film was used.
[0113] The remaining hexane, including the hexane used for rinsing, was reduced to collect the soluble fraction. Distillation, rotary evaporation or the like can be used to remove solvent. Hexane was reduced until 100-150 ml of solution remained. The remaining hexane was then transferred to a pre-weighed evaporation dish. The evaporation plate was slightly heated in nitrogen until it dried. Once evaporated to dryness, the dish was then transferred to a vacuum oven at room temperature for at least 12 hours. Then, the weight of the residue was calculated to determine the percentage of extractable with hexane. The remaining residue was then analyzed by GPC and NMR. Standard method for extractable in chloroform
[0114] For extraction in chloroform, an automatic extraction system Avanti 2050 from FOSS SOXTEC with control unit 2050 and motor unit 2050 was used. Chloroform with a purity of at least 99% was used (JT Baker code 7386 or equivalent) . We weighed 6-8 g of pellets (from the polymerization and pelletization process without further modification; 25-45 pellets per gram) in a crucible; 180 ml of solvent (chloroform) was added, and the sample boiled at a fixed temperature of 180 ° C, for a boiling time of 3.5 hours. The pellets were submerged in the boiling solvent during the boiling period. After the boiling stage, a 3.5 hour rinsing stage was used. The rinse solvent was chloroform. The samples were raised above the surface of the boiling solvent, which condensed and flowed back to the crucible; in the meantime, the pellet sample was rinsed at a rate of about 180 drops per minute. After the rinsing step, the solvent chloroform in the crucible was partially recovered by the instrument for further use. The remaining solvent was evaporated in the crucible, and the polymer extract was retained and measured. Method for collecting soluble fraction of extractables in chloroform by GPC and nuclear magnetic resonance (NMR).
[0115] An automatic Avanti 2050 extraction from FOSS SOXTEC was used as discussed above for the standardized chloroform extraction method. This procedure was used on three film samples. These three extracts from each procedure were combined, and then analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) (for terminal groups / unsaturation by NMR of H and branching structure by NMR of C). Nuclear magnetic resonance (NMR) (extractable) - 1H NMR for terminal groups / unsaturation Sample preparation
[0116] Samples were prepared by adding approximately "100 mg of extracted polymer sample" to "3.25 g of tetrachloroethane-d2 with Cr (AcAc) 3 0.001M" in a 10 mm NMR tube 1001-7 "by NORELL The samples were purged by bubbling N2 through the solvent, via a pipette inserted into the tube, for approximately five minutes, to prevent oxidation, then the samples were capped, sealed with TEFLON tape, and left to soak at room temperature for one day. to another, to facilitate sample dissolution.The samples were kept in an N2 purge box during storage, before and after preparation, to minimize exposure to O2.The samples were heated and swirled to 115 ° C to ensure homogeneity before analysis . Data acquisition parameters
[0117] 1H NMR was performed on a Bruker 400 MHz AVANCE spectrometer, equipped with a Bruker double DUL high temperature cryogenic probe, and at a sample temperature of 120 ° C. Two experiments were performed to obtain spectra, a control spectrum to quantify the total extracted polymer protons, and a double pre-saturation experiment, which suppressed the intense peaks of the polymeric main chain and allowed high sensitivity spectra for quantifying the groups. terminals. Control was performed with a ZG pulse, a6 scans, 10,000 Hz SWH, 1.64 s AQ, 14 s Di. The double pre-saturation experiment was performed with a modified pulse sequence, lclprf2.zzl, TD 32768, 100 scans, DS 4, 10,000 Hz SWH, 1.64 s AQ, 1 s Di, 13 s Di3 . Data analysis: 1H NMR calculations for unsaturated groups per 1000 C
[0118] 1. As discussed above, two experiments were performed to obtain spectra, a control spectrum to quantify the total extracted polymer protons, and a double pre-saturation experiment, which suppressed the intense peaks of the main polymer chain and allowed high sensitivity spectra to quantify unsaturation.
[0119] 2. The residual 1H signal, in TCE-d2 (at 6.0 ppm), was integrated, and adjusted to a value of 100, and the integral of 3 to -0.5 ppm was used as the range signals for all the polymer extracted in the control experiment. For the pre-saturation experiment, the TCE signal was also adjusted to 100, and the corresponding integrals for unsaturation were obtained (vinylene at about 5.40 to 5.60 ppm, tri-substituted unsaturation at about 5.16 to 5 , 35 ppm, vinyl about 4.95 to 5.15 ppm, and vinylidene about 4.70 to 4.90 ppm).
[0120] 3. In the pre-saturation experiment spectrum, the regions for cis- and trans-vinylene, tri-substituted, vinyl, and vinylidene were integrated.
[0121] 4. The integral of the entire polymer of the control experiment was divided by two to obtain a value representing X thousand carbons (for example, if the polymer integral = 28,000, this represents 14,000 carbon, and X = 14) .
[0122] 5. Each integral of an unsaturated group was divided by the corresponding number of contributing protons for that integral, and this represented the moles of each type of unsaturation per X thousand carbons.
[0123] 6. The moles of each type of unsaturation have been divided by X to the moles of unsaturated groups per 1000 moles of carbon. Experimental (NMR from C to SCB (short chain branch)
[0124] Sample preparation: The soluble fraction, for example, "hexane-soluble fraction" samples for C NMR were prepared by adding a small amount of concentrated Cr (AcAc) 3 solution to the previously prepared 1H sample tubes (To the sample tube that was prepared and analyzed for 1H NMR, a small amount of Cr was added in solvent to prepare the correct Cr concentration for the 13C NMR analysis).
[0125] This was done by adding approximately "0.25 g of tetrachloroethane-d2 containing 0.116 g of Cr (AcAc) 3 per g of solution" to a final concentration of Cr (AcAc) 3 0.025M. The samples were homogenized by heating the tube and its contents to 150 ° C, using a heating block and torch. Each sample was inspected visually to ensure homogeneity before analysis.
[0126] Samples with polar groups originating from polar CTAs, such as propanal (propionic aldehyde), methyl ethyl ketone (MEK), acetone, or isopropanol, were prepared by adding previously prepared C sample tubes (as discussed above) "0.2 g of DMSO-d6 with 0.025M Cr (AcAc) 3", and the samples were mixed again. This allowed observation of the acetone and propanal (propionic aldehyde) ketone chain ends incorporated via chain transfer. Each sample was inspected visually to ensure homogeneity before analysis.
[0127] Data acquisition parameters: Data were collected using a Bruker 400 MHz spectrometer, equipped with a Bruker double DUL high temperature cryogenic probe. Data was acquired using 1280 to 2560 transients per data file, a 6 s pulse repetition delay, 90 degree turn angle, and reverse discontinuous decoupling with a sample temperature of 120 ° C. All measurements were made on a sample without rotation in locked mode. The samples were allowed to stay in thermal equilibrium for seven minutes before data acquisition. Chemical shifts of 13C NMR were referenced internally to the EEE triad at 30.0 ppm. Calculations - LDPE short chain branching
[0128] LDPE contains many types of branches; for example, 1,3-diethyl, the ethyl branches on a quaternary carbon, C4, C5, and if butene or propylene is used, isolated C2 (butene) branches or Ci (methyl, propylene) branches are observed. All branching levels were determined by integrating the spectrum from about 40 ppm to 5 ppm, and adjusting the integral value to 1000, then integrating the peaks associated with each type of branching, as shown in Table A below. The peak integrals then represent the number of each type of branch per 1000 C in the extracted polymer. In Table A, the last column describes the carbon associated with each range of integrals. Table A: Type of branch and integral ranges of 13C NMR used for quantification.
Quantification of carbonyls
[0129] Polar terminal groups resulting from propionic aldehyde (PA) or acetone (such as CTA or peroxide dissociation products) are quantified in a very similar way to the branch discussed above, with the full spectrum integral adjusted to 1000 C from extracted polymer. For PA, the peak is integrated at about 24.3 ppm. These represent the backbone carbon at the beta position relative to the carbonyl at the end of the ethyl ketone chain. For acetone, the peak is integrated at about 44.2 ppm, which represents the alpha carbon in relation to the carbonyl at the end of the methyl ketone chain. Therefore, the integrals represent carbonyls / 1000 C. Experimental Example 1
[0130] Polymerization was carried out in a tubular reactor with three reaction zones. In each reaction zone, pressurized water was used to cool and / or heat the reagent medium, circulating this water through the reactor jacket. The inlet pressure was 2,100 bar, and the pressure drop across the tubular reactor system was about 300 bar. Each reaction zone had an entrance and an exit. Each input stream consisted of the output stream from the previous reactor zone and / or an ethylene rich feed stream added. Ethylene was supplied according to a specification, traces of acetylene (maximum 5 molar ppm) in ethylene. Thus, the maximum potential amount of acetylene incorporated in the polymer is less than or equal to 166 molar ppm, based on the total moles of monomer units in the ethylene-based polymer (see conversion level in Table 3). Unconverted ethylene and other gaseous components at the reactor outlet were recycled through high pressure and low pressure recycles, and were compressed and distributed through blowers, primary and hyper (secondary) compressors, according to the flow diagram shown in Figure 1. Organic peroxides (see Table 3) were fed in each reaction zone. Propionic aldehyde (PA) was used as a chain transfer agent, and it was present at each reaction zone entrance and originated from low pressure and high pressure recycling flows (# 13 and # 15), as well as from current # 6 and / or current # 7 of CTA formation recently injected. In this example, the weight ratio between the # 7 and # 6 "CTA formation" streams was 0.25.
[0131] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reagent medium was cooled with the aid of pressurized water. At the exit of reaction zone 1, the reagent medium was additionally cooled by injecting a feed stream (# 20) rich in ethylene, cold and new, and the reaction was restarted by feeding an organic peroxide. This process was repeated at the end of the second reaction zone to allow additional polymerization in the third reaction zone. The polymer was extruded and pelleted (about 30 pellets per gram), using a single-screw extruder at a melting temperature around 230-250 ° C. The weight ratio of currents rich in ethylene for the three reaction zones was 1.00: 0.75: 0.25. Each of the R2 and R3 values was 0.45. R-values are calculated in accordance with U.S. provisional patent application No. 61/548996 (international patent application PCT / US12 / 059469). Rn (n = reaction zone number, n> l) is the ratio of "fraction of new ethylene feed mass to the first reaction zone (RZ1)" to "fraction of new ethylene feed mass for the n-th reaction zone (RZn) "is (Rn = RZl / RZn). The internal process speed was approximately 12.5, 9, and 11 m / s for Ia, 2 a and 3, respectively, the reaction zone. Additional information can be found in Tables 2 and 3. Example 2
[0132] Polymerization was carried out in a tubular reactor with three reaction zones, as previously discussed. All process conditions are the same as in Example 1, except that the initiator composition has been changed. In this example, additional TETMP, as described in Table 1, was used as a primer. The value of each of R2 and R3 was 0.46. Comparative Example A
[0133] Polymerization was carried out in a tubular reactor with three reaction zones, as previously discussed. Unconverted ethylene, and other gaseous components at the reactor outlet, were recycled through high pressure and low pressure recycling currents, and were compressed and distributed through the blower, primary and hyper (secondary) compressors according to the scheme. flow 2 shown in Figure 2.
[0134] In each reaction zone, polymerization with organic peroxides started as described in Example 2. After reaching the first peak temperature in reaction zone 1, the reagent medium was cooled with pressurized water. At the exit of the first reaction zone, the reagent medium was additionally cooled by injecting a feed stream (# 20) rich in ethylene, cold and new, and the reaction was restarted by feeding an organic peroxide in the reaction zone. This process was repeated at the end of the second reaction zone to allow additional polymerization in the third reaction zone. Peak temperatures were 330/319/306 ° C, respectively.
[0135] The weight ratio of currents rich in ethylene for the three reaction zones was 1.00: 0.75: 0.25. As a chain transfer agent, propylene was used, and it was present in each reactor inlet originating from the low and high pressure recycling flows (# 13 and # 15), as well as from the # 6 and / or # 7 chain of formation of recently injected CTA. The propylene supplied contained traces of propadiene and methyl acetylene (maximum sum of 5 molar ppm) in propylene. Thus, the maximum potential amount of propadiene and / or methylacetylene incorporated in the polymer is much less than 1 molar ppm.
[0136] In this comparative example, the weight ratio of CTA formation currents # 6 and # 7 was 1.00. Due to the higher peak temperature conditions, CTA consumption was significantly reduced compared to Example 1. The values R2 and R3 were each 2.22. Additional information can be found in Tables 2 and 3. Example 4
[0137] Polymerization was carried out according to the description of Example A, with the following changes. The last peak temperature was increased to 310 ° C, the CTA was acetone, and the melt index was decreased to 32.5 dg / min. The R2 and R3 values were each 2.21.
[0138] Example 3 was polymerized as discussed for Example 4 above, with the following changes noted in Tables 2 and 3. Table 1: Initiators
Table 2 Pressure and temperature conditions
Table 3: Additional process information (PA = propanal)
* When R2 and R3 are each greater than 1, the flow scheme in Figure 2 was used. When R2 and R3 are each less than 1, the flow scheme in Figure 1 was used.
[0139] Inventive Examples (IE) and Comparative Examples (EC) are listed in Table 4. The properties of GPC and other properties are listed in Tables 5-11. The results in the analysis of terminal groups are listed in Table 12. The representative TDGPC profiles are shown in Figure 3 (whole polymer) and a conventional GPC profile is shown in Figure 4 (extract Table4: Characterization data of inventive and comparative polymer
* Commercial polymers ** CE: Comparative Example; IE = Inventive Example; AC: autoclave base; tub X-link: reticulated tubular; tub: tubular. *** Old LDPE 160G from Dow. s) "170 ° C data" and interpolated from 150 ° C and 190 ° C data. t) Obtainable from The Dow Chemical Company. u) Propylene - CTA analyzed (by 13C NMR). v) Standard hexane extraction method w) Standard chloroform extraction method x) "Collect fraction of soluble hexane" by GPC. Table 5: Inventive and comparative polymer: corrected claim limits for I2
a) Mw (abs) <E + Fxlog (I2), where E = 3.50 x 10b g / mol, and F = -1.20 x 10b (g / mol) / log (dg / min). b) Mw (abs)> G + Hxlog (I2), where G = 2.00 x 105 g / mol, and H = -1.20 x 105 (g / mol) / log (dg / min). c) G '> C + Dlog (I2), where C = 162 Pa, and D = -90.0 Pa / log (dg / min). d) w <A + B (I2), where A = 0.090, and B = -4.00 x 10 “3 (min / dg). Table 6: Results of extractable in chloroform (moments of molecular weights of conventional GPC)
Table 7 - Chloroform extractable results (data from conventional GPC)
* See Figure 4 for representative GPC profile. Table 8: Results of extractable in chloroform (weight fraction of a polymer less than a given log molecular weight in g / mol)
Table 9: Results of extractable in hexane (moments of molecular weights of conventional GPC)
Table 10: Results of extractable in hexane (conventional GPC quadrant data)
Table 11: Results of extractable in hexane (weight fraction of a polymer less than a log molecular weight in g / mol)
Table 12: Hexane extraction results (terminal groups)
* ND = not detectable ** Derived from CTA terminal group and peroxide dissociation products incorporated in the polymer as a terminal group.
[140] The comparative products based on the wide MWD autoclave had measured Mw (abs) / Mn (Abs) values above 20, and weight fraction values (w) around 0.99, while the measured values of G 'were comparable to those of Inventive Example 4. Inventive Example 4 had a measured Mw (abs) / Mn (Abs) value of 11, and a "w" value around 0.02. The great difference in product design between the inventive polymer and the autoclave-based polymer was demonstrated in Figure 3, which shows a higher molecular weight fraction for the autoclave-based product. Thus the autoclave product had an ultra high molecular weight fraction, and this fraction did not significantly increase G 'compared to G' values for the inventive polymers prepared using a tubular reactor. Also, as discussed above, the ultra high molecular weight fractions in autoclave based polymers will contribute to the deterioration of optical properties in film applications.
[141] Inventive Examples 1 and 2 had acceptable G 'values and excellent levels of extractables in hexane and chloroform. The levels of extractables (in hexane and chloroform) approached the values of the wide MWD polymers based on autoclave, and also the levels of extractables in hexane must obey the strict limit of contact with food of EDA less than or equal to 2,6 % by weight of hexane extractable for packaged product cooking applications ("Polyethylene for Use in Articles that Contact Food Except for Articles Used in Packing or Holding Food During Cooking" in "Olefin Polymers" Code of Federal Regulations, Title 21, Pt 1520.77; (d) (3) (ii) Option 2, 177.1520 (c) paragraph 2.2 (2001)) and must also satisfy 5.5% by weight of extractable in hexane for applications without cooking ("Polyethylene for Use in Articles that Contact Food Except for Articles Used in Packing or Holding Food During Cooking "in" Olefin Polymers "Code of Federal Regulations, Title 21, Pt. 1520.77; (d) (3) (ii) Option 2, 177.1520 (c) paragraph 2.2 (2001)).
[142] Comparative Example A and Inventive Example 3 showed good performance of G '; however, the levels of extractables were strongly influenced by the choice of CTA. Comparative Example A, prepared with propylene, showed increased extractable level in hexane and significantly increased extractable level in chloroform when compared to Inventive Example 3.
[143] Inventive Examples 3 and 4 showed that the extractable level was not significantly affected by decreasing the melt index from 5.4 to 3.5; however, the lower melting index is favorable for a higher G 'value.
[144] The comparative LDPE 160C showed satisfactory G 'performance, although the resin design was not balanced, as shown by the high Mw value (abs) and the unfavorable high levels of extractables in hexane and chloroform. The comparative SABIC nExCoat 5 showed good performance of G ', but increased extractable level in hexane (against other autoclave-based polymers) and very high levels of extractables in chloroform.
[145] The extractable fraction analysis focused on the extract composition, expressed by MWD parameters, and the presence of functional groups, such as short chain branches, and CTA derived terminal groups. The extract consisted mainly of low molecular weight polymer molecules; however, it can be seen that, especially in the lower MWD quadrant of the extract, other process raw materials, such as peroxide thinners, solvent and compressor lubrication oil may be present. Therefore, the extraction capacity is preferably evaluated considering the "weight average molecular weight" and the quadrant with the maximum molecular weight. The analysis data on extractables in chloroform are summarized in Tables 6 to 8. Figure 4 showed the limits of the data quadrants presented in Tables 7 to 8 for Inventive Example 3.
[146] Trends and data for hexane extractables are given in Tables 9 to 11. Similar trends were observed for hexane extractables as observed for chloroform extractables. The use of propylene increased the amount of extract (see Table 4), as well as promoted the extraction of higher molecular weight polymer molecules (see Tables 9-11).
[147] The level of functional groups in the hexane extracts was analyzed by NMR, as shown in Table 12. The following data have been reported: methyl number (Cl) per 1000C (methyl originated from propylene copolymerization, when using propylene as CTA); number of short chain branches (SCB) per 1000C (short chain branches is the sum of methyl, ethyl, butyl and pentyl branches and will include propyl when using pentene-1 as CTA); number of carbons per average SCB (methyl contains 1 carbon, ethyl contains 2 carbons, etc.); number of carbons present in short chain branches per 1000C (this number is calculated by multiplying the number of SCBs by 1000 C with the number of atoms per average SCB); vinyl for 1000 C (double bond at the end of a normal chain); total unsaturation by 1000 C (sum of all vinyl, trans-vinyl and vinylidene unsaturations; these unsaturations influence the molecular weight or fusion index, and must be balanced by more or less contribution from the added CTA).
[148] It is known that polymers with a higher level of short chain branching (lower polymer density) and / or lower molecular weight will have higher levels of extractables, and will extract molecules of higher molecular weights. When comparing the SCB parameters of the SABIC nExCoat 5 sample with the Inventive Examples, a higher level of SCBs or a greater number of C in the ZSCB would be expected in the hexane extract for the SABIC nExCoat sample; however, despite the extraction of higher molecular weight molecules in the SABIC nExCoat sample, it was found that the level of SCBs in this extract was similar to the level in the Inventive Examples, and the number of carbons in the ZSCB in the extract for the SABIC sample was lower (see Table 12). The average length of the short chain branches is shorter due to the presence of methyl branches, in addition to the standardized ethyl, butyl and pentyl branches. The only parameters in the extract from the SABIC sample that differed were vinyl, total unsaturation and carbonyl level. Surprisingly, it was found that, despite the low frequency of vinyls and carbonyls in the sample extract, in general, levels of unsaturation and / or carbonyl have a strong impact on the maximum molecular weight that has been extracted. From the data analyzed, it was found that for a given SCB level, the maximum molecular weight level extracted can be reduced by decreasing the level of unsaturation and / or increasing the level of carbonyl. This decrease in the maximum molecular weight level extracted will positively affect (increase) the amount of extract (extractable level) of a polymer. The differences in the level of extractables in chloroform and hexane for a given polymer can be explained by the different affinities of solvent chloroform and hexane in relation to unsaturation and / or carbonyl functionality.
[149] In summary, to achieve broad MWD resins with extractable lows, and extracts of lower molecular weight, polymerization conditions need to be carefully selected and balanced. Important process parameters include maximum polymerization temperatures, reactor pressure, and the type, level and distribution of the chain transfer agent.

权利要求:
Claims (15)
[0001]
1. Polymer based on ethylene, characterized by the fact that it comprises the following properties: (A) a "weight fraction (w) of molecular weight greater than 106 g / mol, based on the total weight of the polymer, and determined by GPC (abs ) "which satisfies the following relationship: w <A + B (I2), where A = 0.090, and B = —4.00 x 10 3 (min / dg); (B) a G 'value that satisfies the following relationship: G'> C + D log (I2), where C = 162 Pa, and D = -90.0 Pa / log (dg / min), where the measure of rheology to determine G 'is done in a nitrogen environment, at 170 ° C, and a 10% deformation, and G' is determined at G "= 500 Pa; (C) a melting index (I2) of 1 to 20 dg / min and (D) extractable with chloroform which has a maximum mean Mw (conv) less than or equal to 4,000 g / mol.
[0002]
2. Ethylene-based polymer, according to claim 1, characterized by the fact that it still has an Mw (abs) that satisfies the following relationships: (I) Mw (abs) <E + F.log (I2), where E = 3.50 x 105 g / mol, and F = - 1.20 x 105 (g / mol) / log (dg / min); and (II) Mw (abs)> G + H.log (I2), where G = 2.00 x 105 g / mol, and H = - 1.20 x 105 (g / mol) / log (dg / min ).
[0003]
3. Ethylene-based polymer according to either of claims 1 or 2, characterized by the fact that it has a "Mw (conv) chioroform-Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in MWD of extractable with chloroform "which is less than or equal to 8,400 g / mol.
[0004]
4. Ethylene-based polymer, according to any one of claims 1 to 3, characterized by the fact that it has an extractable with hexane that has a maximum Mw (conv) less than or equal to 2,300 g / mol.
[0005]
5. Ethylene-based polymer, according to any of claims 1 to 4, characterized by the fact that it has a "Mw (conv) hexane_Q4 of the maximum molecular weight fraction of 25% (fourth quadrant (Ml)) in the MWD of the extractable with chloroform "which is less than or equal to 4,200 g / mol.
[0006]
6. Ethylene-based polymer according to any one of claims 1 to 5, characterized by the fact that the extractable with hexane comprises a polymer comprising terminal groups containing oxygen, derived from a non-olefinic CTA system, in an amount greater than " 0.5 terminal group "per 1000 carbon atoms.
[0007]
7. Ethylene-based polymer according to claim 6, characterized by the fact that the CTA system is selected from the following: a ketone, an aldehyde, an ester, an alcohol, or combinations thereof.
[0008]
8. Ethylene-based polymer according to claim 7, characterized by the fact that the CTA system is selected from the following: propanal (propionic aldehyde), methyl ethyl ketone, acetone, ethanal (acetic aldehyde), propanol, an acetate alkyl, isopropanol, or combinations thereof.
[0009]
9. Ethylene-based polymer according to any one of claims 1 to 8, characterized by the fact that the extractable with chloroform comprises a polymer comprising terminal groups containing oxygen, derived from a non-olefinic CTA system, in an amount greater than " 0.5 terminal group "per 1000 carbon atoms.
[0010]
10. Ethylene-based polymer according to claim 9, characterized by the fact that the CTA system is selected from the following: a ketone, an aldehyde, an ester, an alcohol, or combinations thereof.
[0011]
11. Ethylene-based polymer according to any one of claims 1 to 10, characterized in that the extractable with chloroform comprises a polymer comprising vinyl end groups in an amount less than "1.0 vinyl group" per 1000 carbon atoms .
[0012]
12. Ethylene-based polymer according to any one of claims 1 to 11, characterized in that the hexane extractable comprises a polymer comprising vinyl end groups in an amount less than "1.0 vinyl group" per 1000 carbon atoms .
[0013]
13. Ethylene-based polymer according to any one of claims 1 to 12, characterized by the fact that it has a density greater than or equal to 0.919 g / cm3.
[0014]
14. Composition, characterized by the fact that it comprises the ethylene-based polymer, as defined by any of claims 1 to 13.
[0015]
15. Article, characterized by the fact that it comprises at least one component formed by the composition, as defined by claim 14.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-07-07| B09A| Decision: intention to grant|

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2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/11/2012, 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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US201161563186P| true| 2011-11-23|2011-11-23|

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US201161563190P| true| 2011-11-23|2011-11-23|

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PCT/US2012/066102|WO2013078224A1|2011-11-23|2012-11-20|Low density ethylene-based polymers with extracts at lower molecular weights|

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