sealing composition, method of making a sealing composition, sealing layer, article and method of fo

专利摘要:
SEALING COMPOSITION, METHOD OF PRODUCING A SEALING COMPOSITION, SEALING LAYER, ARTICLE AND METHOD OF FORMING AN ARTICLE The present invention is a sealing composition, method of producing it, articles made therefrom, and methods of forming such articles. The sealant composition in accordance with the present invention comprises: (a) from 70 to 99.5 percent by weight of an ethylene/(Alpha)-olefin interpolymer composition, based on the total weight of the sealant composition, being that said ethylene/(Alpha)-olefin interpolymer composition comprises an ethylene/(Alpha)-olefin interpolymer, and wherein the ethylene/(Alpha)-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0. 02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/(Alpha)-olefin interpolymer composition, said propylene/(Alpha)-olefin interpolymer composition comprising a propylene/( Alpha)-olefin or a propylene/ethylene/butene terpolymer, said propylene/(Alpha)-olefin copolymer having a (...).
公开号:BR112012005698B1
申请号:R112012005698-0
申请日:2011-10-26
公开日:2021-05-25
发明作者:Mehmet Demirors；Rongjuan Cong；Cristina Serrat；Gagan Saini；Michael Rutkowske
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

field of invention
[001] The present invention relates to a sealing composition, method for its production, articles made with it, and method to form such articles. Invention history
[002] The use of polyethylene compositions in sealant applications is generally known. Any conventional method, such as a gas phase process, a slurry process, a solution process or a high pressure process, can be employed to produce such polyethylene compositions.
[003] Several polymerization techniques using different catalytic systems have been employed to produce such polyethylene compositions suitable for sealant applications.
[004] Despite research efforts to develop sealing compositions, there is still a need for a sealing composition that has lower heat seal and hot tack initiation temperatures, while at the same time it provides increased heat seal and heat setting resistance. Additionally, there is a need for a method to produce such a sealing composition that has lower heat seal and heat set initiation temperatures, while at the same time providing increased heat seal and heat seal resistance. Invention Summary
[005] The present invention is a sealing composition, method for its production, articles made with it, and method for forming such articles.
[006] The sealant composition according to the present invention comprises: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, wherein said ethylene/α-olefin interpolymer composition comprises an ethylene/α-olefin interpolymer, and the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches ( LCB) per 1000C; (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, wherein said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melt in the range of 2 Joules/g to 50 Joules/g and a DSC melting point in the range of 25oC to 110oC.
[007] In an alternative embodiment, the present invention further provides a method for producing a sealant composition comprising the steps of (1) selecting an ethylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, said The ethylene/α-olefin interpolymer composition comprises an ethylene/α-olefin interpolymer, and the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB ) by 1000C; (2) select a propylene/α-olefin interpolymer composition, wherein said propylene/α-olefin interpolymer composition comprises a propylene/α-olefin copolymer, and wherein said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/g to 50 Joules/gram, and a DSC melting point in the range of 25oC to 110oC; (3) mixing said ethylene/α-olefin interpolymer composition and said propylene/α-olefin interpolymer composition; (4) thereby forming a sealant composition comprising from 70 to 99.5 percent by weight of said ethylene/α-olefin interpolymer composition and from 0.5 to 30 percent by weight of said propylene/α interpolymer composition -olefin.
[008] In another alternative embodiment, the present invention also provides a sealing layer comprising a sealing composition comprising: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based in the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, wherein the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0. 02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, wherein said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/gram to 50 Joules/gram, and a DSC melting point in the range from 25oC to 110oC.
[009] In another alternative embodiment, the present invention further provides an article comprising: (1) at least one sealing layer comprising a sealing composition comprising (a) from 70 to 99.5 percent by weight of an interpolymer composition of ethylene/α-olefin, based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Constant of Comonomer Distribution (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and branching frequency long-chain in the range of 0.02 to 3 long-chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, and being that said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melting in the range of 2 Joules/gram to 50 Joules/gram, and a DSC melting point at range from 25oC to 110oC; and (2) at least one substrate layer.
[010] In another alternative embodiment, the present invention further comprises a method for forming an article comprising the steps of: (1) selecting a sealant composition comprising: (a) from 70 to 99.5 percent by weight of a composition of ethylene/α-olefin interpolymer, based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, wherein the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and frequency of long-chain branching in the range of 0.02 to 3 long-chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, and being that said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melting in the range of 2 Joules/gram to 50 Joules/gram, and a DSC melting point at range from 25oC to 110oC; and (2) selecting at least one substrate layer; (3) applying said sealant composition to at least one surface of said at least one substrate layer; (4) thus forming at least one sealing layer associated with at least one surface of said at least one substrate layer.
[011] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therewith, and a method for making such articles, in accordance with any of the preceding embodiments, except that the composition The sealer has a heat seal resistance measured in lbs of force in a three-layer film structure equal to or greater than [((0.7053(T))-(47.521)], where T is the heat seal temperature in the range of 68 at 74oC, where the heat seal resistance is measured using a W Kopp heat seal instrument at a temperature in the range of 68oC to 74oC.
[012] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therewith, and a method for making such articles, in accordance with any of the preceding embodiments, except that the composition The sealer has a heat seal resistance measured in lbs of force in a three-layer film structure equal to or greater than [((0.6322(T))-(41.0429)], where T is the heat seal temperature in the range from 65 to 72oC, where the heat seal resistance is measured using the W Kopp heat seal instrument at a temperature in the range of 65oC to 72oC.
[013] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therewith, and a method for making such articles, in accordance with any of the preceding embodiments, except that the composition sealer has a hot setting strength resistance (N) in a three-layer film structure equal to or greater than [((46 4 -3 3 -1 2 .1540) (10 )(T))+((1, 2797)(10 )(T))-((1.4144)(10 )(T))+ ((6.7463)(T))-117.390], where T is the temperature of the hot setting test in oC in the range of 50 to 105oC, and the hot setting is measured using an Enepay hot setting instrument at a temperature in the range of 50 to 105oC.
[014] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therefrom, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin comprises less than 120 units of total unsaturation/1,000,000C.
[015] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therefrom, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer ethylene/α-olefin has a zero shear viscosity ratio (ZSVR) in the range of greater than 2.1; for example, more than 2.3 or, alternatively, more than 2.5; or alternatively, from 2.5 to 7.0.
[016] In an alternative embodiment, the present invention provides a sealant composition, method for its production, a sealant layer, articles made therewith, and method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin has a trisubstituted unsaturation in the range of less than 20 units/1,000,000C.
[017] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therefrom, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin has vinylene unsaturation in the range of less than 20 units/1,000,000C.
[018] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therewith, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin has a molecular weight distribution (Mw/Mn) in the range of 2.0 to 5.0.
[019] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therewith, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin has a melt flow ratio (I10/I2) in the range of 5 to 15.
[020] In an alternative embodiment, the present invention provides a sealing composition, a method for its production, a sealing layer, articles made therefrom, and a method for making such articles, according to any of the preceding embodiments, except that the interpolymer of ethylene/α-olefin has a crystallinity in the range of less than 80 percent; for example, less than 75 percent, or alternatively less than 65 percent, or alternatively less than 55 percent, measured via DSC. Brief description of the drawings
[021] For the purpose of illustrating the invention, a representative form is shown in the drawings; it is understood, however, that the present invention is not restricted to the precise arrangements and means shown.
[022] Figures 1-20 illustrate Formulas 1-20, respectively;
[023] Figure 21 is a graph illustrating the integration limits for unsaturation, where the dashed line means that the position may be slightly different depending on the sample/catalyst.
[024] Figure 22 illustrates the pulse sequences modified for unsaturation with the Bruker AVANCE 400 MHz spectrometer;
[025] Figure 23 is a graph illustrating the relationship between the heat setting force (N) per inch of sealing temperature and the hot setting temperature (oC) of the sealing compositions of the invention and comparatives; and
[026] Figure 24 is a graph illustrating the relationship between the thermal seal resistance (lbf) per inch of seal temperature and the thermal seal (oC) of the compositions of the invention and comparatives. Detailed description of the invention
[027] The present invention is a sealing composition, method for its production, articles made with it, and method for forming such articles. The sealant composition according to the present invention comprises: a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, said composition of ethylene/α-olefin interpolymer comprises an ethylene/α-olefin interpolymer, and wherein the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, wherein said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melt in the range of 2 Joules/g to 50 Joules/g and a DSC melting point in the range of 25oC to 110oC.
[028] In one embodiment, the sealant composition has a heat seal strength measured in lbs of force in a three-layer film structure equal to or greater than [((0.7053(T))-(47,521)], where T is heat seal temperature in the range of 68 to 74oC, where the heat seal resistance is measured using a W Kopp heat seal instrument at a temperature in the range of 68oC to 74oC.
[029] In an alternative embodiment, the sealant composition has a thermal seal strength measured in lbs of force in a three-layer film structure equal to or greater than [((0.6322(T))-(41.0429)], where T is the heat seal temperature in the range of 65 to 72oC, where the heat seal resistance is measured using the W Kopp heat seal instrument at a temperature in the range of 65oC to 72oC.
[030] In another alternative embodiment, the sealing composition has a resistance to hot setting force (N) in a three-layer film structure equal to or greater than [((-4,1540)(10-6)(T4) )+((1.2797)(10-3)(T3))-((1.4144)(10-1) (T2))+((6.7463)(T))-117.390], where T it is hot setting test temperature in oC in the range of 50 to 105oC, where the hot setting resistance is measured by Enepay instrument at a temperature in the range of 50 to 105oC.
[031] The sealing composition can further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The sealant composition can contain any amounts of such additives. The sealant composition can, for example, comprise from about 0 to about 20 percent of the combined weight of such additives, based on the weight of the sealant composition and one or more additives. Ethylene/α-Olefin Interpolymer Composition
[032] The ethylene/α-olefin interpolymer composition according to the present invention comprises at least one ethylene/α-olefin interpolymer. The ethylene/α-olefin interpolymer according to the present invention has a density in the range of 0.875 to 0.963 g/cm3. All individual values and subranges from 0.875 to 0.963 g/cm3 are included and described here; for example, the density can be from a lower limit of 0.875, 0.880, 0.885, or 0.900 g/cm3 to an upper limit of 0.963, 0.960, 0.955, 0.950, 0.925, 0.920, 0.915, 0.910 or 0.905 g/cm3. For example, the ethylene/α-olefin interpolymer can have a density in the range of 0.875 to 0.960/cm3; or alternatively, the ethylene/α-olefin interpolymer can have a density in the range of 0.905 to 0.963 g/cm3; or alternatively, the ethylene/α-olefin interpolymer can have a density in the range of 0.875 to 0.920 g/cm3; or alternatively, the ethylene/α-olefin interpolymer may have a density in the range of 0.875 to 0.910 g/cm3; or alternatively, the ethylene/α-olefin interpolymer can have a density in the range of 0.875 to 0.905 g/cm3; or alternatively, the ethylene/α-olefin interpolymer can have a density in the range of 0.875 to 0.902 g/cm3; or alternatively, the ethylene/α-olefin interpolymer can have a density in the range of 0.875 to 0.900 g/cm 3 .
[033] The ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range of 15 to 250. In one embodiment, the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range from 30 to 250. In another embodiment, the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range from 80 to 150. In another embodiment, the ethylene/α-olefin interpolymer has a Constant of Comonomer Distribution (CDC) in the range of 30 to 50.
[034] The ethylene/α-olefin interpolymer has a long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; for example, 0.05 to 3 long chain branches (LCB) per 1000C, or alternatively, 0.5 to 3 long chain branches (LCB) per 1000C.
[035] The ethylene/α-olefin interpolymer has a crystallinity in the range of less than 80 percent; for example, less than 75 percent, or alternatively less than 65 percent, or alternatively less than 55 percent, measured via DSC.
[036] The ethylene/α-olefin interpolymer, according to the present invention, has a molecular weight distribution (Mw/Mn) (measured according to the conventional GPC method) in the range greater than 2.0. All individual values and subranges greater than 2 are included and described here; for example, the ethylene/α-olefin interpolymer can have a molecular weight distribution (Mw/Mn) in the range of more than 2 and less than 5; or alternatively, the ethylene/α-olefin interpolymer may have a molecular weight distribution (Mw/Mn) in the range of more than 2 and less than 4.
[037] The ethylene/alpha-olefin interpolymer of the invention has a molecular weight (Mw) in the range of equal to or greater than 50,000 g/mol, for example, in the range of 50,000 to 220,000 g/mole.
[038] The ethylene/α-olefin interpolymer, according to the present invention, has a melt index (I2) in the range of 0.2 to 20g/10 minutes. All individual values and subranges from 0.2 to 20g/10 minutes are included and described here; for example, the melt index (I2) can range from a lower limit of 0.2, 0.5, 0.6, 0.8 or 0.9g/10 minutes, to a maximum limit of 0.9, 1 , 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 10, 15 or 20g/10 minutes. For example, the ethylene/α-olefin interpolymer can have a melt index (I2) in the range of 0.5 to 15g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer may have a melt index (I 2 ) in the range of 0.5 to 10g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer can have a melt index (I 2 ) in the range of 0.5 to 5g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer may have a melt index (I 2 ) in the range of 0.5 to 4g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer can have a melt index (I 2 ) in the range of 0.5 to 3g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer may have a melt index (I 2 ) in the range of 0.5 to 2g/10 minutes; or alternatively, the ethylene/α-olefin interpolymer may have a melt index (I 2 ) in the range of 0.5 to 1g/10 minutes.
[039] In one embodiment, the ethylene/α-olefin interpolymer, according to the present invention, has a melt flow ratio (I10/I2) in the range from 5 to 15. All individual values and subranges from 5 to 15 are included and described herein; for example, the melt flow ratio (I10/I2) can range from a low limit of 5, 5.5, 6 or 6.5 to a high limit of 8, 10, 12, 14 or 15. For example, the ethylene/α-olefin interpolymer can have a melt flow ratio (I10/I2) in the range of 5 to 14; or alternatively, the ethylene/α-olefin interpolymer may have a melt flow ratio (I10/I2) in the range of 5 to 12; or alternatively, the ethylene/α-olefin interpolymer may have a melt flow ratio (I10/I2) in the range of 6 to 12; or alternatively, the ethylene/α-olefin interpolymer can have a melt flow ratio (I10/I2) in the range of 7 to 14.
[040] In one embodiment, the ethylene/α-olefin interpolymer has less than 120 units of total unsaturation/1,000,000C. All individual values and sub-ranges less than 120 units of total unsaturation/1,000,000C are included and described herein; for example, the ethylene/α-olefin interpolymer can have less than 100 units of total unsaturation/1,000,000C; or alternatively, less than 50 units of total unsaturation/1,000,000C; or alternatively, less than 20 units of total unsaturation/1,000,000C.
[041] Ethylene/α-olefin interpolymer has a zero shear viscosity ratio (ZSVR) in the range equal to or greater than 2.1; for example, equal to or greater than 2.3, or alternatively, equal to or greater than 2.5; or alternatively, from 2.1 to 7.0; or alternatively, from 2.3 to 7.0; or alternatively, from 2.5 to 7.0.
[042] In one embodiment, the ethylene/α-olefin interpolymer may further comprise at least 0.01 part by weight of metal residues and/or metal oxide residues remaining from the catalytic system comprising a metal complex of a polyvalent aryloxyether per a million parts of ethylene/α-olefin interpolymer. Metal residues and/or metal oxide residues remaining from the catalytic system comprising a metal complex of a polyvalent aryloxyether in the ethylene/α-olefin interpolymer can be measured by X-ray fluorescence (XRF), calibrated according to standards of reference.
[043] The ethylene/alpha-olefin interpolymer may comprise less than 20 percent by weight of units derived from one or more α-olefin comonomers. All individual values and subranges less than 18 percent by weight are included and described herein; for example, the ethylene/alpha-olefin interpolymer may comprise less than 15 percent by weight of units derived from one or more alpha-olefin comonomers; or, alternatively, the ethylene/alpha-olefin interpolymer may comprise less than 10 percent by weight of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/α-olefin interpolymer can comprise from 1 to 20 percent by weight of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/alpha-olefin interpolymer of the invention may comprise from 1 to 10 percent by weight of units derived from one or more α-olefin comonomers.
[044] The ethylene/α-olefin interpolymer may comprise less than 10 mole percent of units derived from one or more α-olefin comonomers. All individual values and subranges of less than 10 mole percent are included and described herein; for example, the ethylene/alpha-olefin interpolymer can comprise less than 7 mole percent of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/alpha-olefin interpolymer may comprise less than 4 mole percent of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/alpha-olefin interpolymer may comprise less than 3 mole percent of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/alpha-olefin interpolymer can comprise from 0.5 to 10 mole percent of units derived from one or more α-olefin comonomers; or alternatively, the ethylene/alpha-olefin interpolymer can comprise from 0.5 to 3 mole percent of units derived from one or more α-olefin comonomers.
[045] α-Olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers can preferably have from 3 to 10 carbon atoms, and more preferably from 3 to 8 carbon atoms. Representative α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1- pentene. The one or more α-olefin comonomers may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene; or alternatively, from the group consisting of 1-hexene and 1-octene.
[046] The ethylene/alpha-olefin interpolymer may comprise at least 80 percent by weight of ethylene-derived units. All values and subranges of at least 80 percent by weight are included and described herein; for example, the ethylene/alpha-olefin interpolymer can comprise at least 82 percent by weight of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer may comprise at least 85 weight percent ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer may comprise at least 90 percent by weight of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer may comprise from 80 to 99 weight percent ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer may comprise from 90 to 99 weight percent ethylene-derived units.
[047] The ethylene/alpha-olefin interpolymer may comprise at least 90 mole percent of ethylene-derived units. All individual values and subranges of at least 90 mole percent are included and described herein; for example, the ethylene/alpha-olefin interpolymer can comprise at least 93 mole percent of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer can comprise at least 96 mole percent of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer can comprise at least 97 mole percent of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer may comprise from 90 to 99.5 mole percent of ethylene-derived units; or alternatively, the ethylene/alpha-olefin interpolymer can comprise from 97 to 99.5 mole percent of ethylene-derived units.
[048] Any conventional polymerization processes can be employed to produce the ethylene/alpha-olefin interpolymers. Such conventional polymerization processes include, but are not restricted to solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors , isothermal reactors, gas phase fluidized bed reactors, stirred tank reactors, batch reactors in parallel, in series and/or any combinations thereof.
[049] The ethylene/alpha-olefin interpolymer can, for example, be produced through the solution phase polymerization process, using one or more loop reactors, isothermal reactors and their combinations.
[050] In general, solution phase polymerization processes occur in one or more well stirred reactors, such as one or more loop reactors or one or more spherical isothermal reactors at a temperature in the range of 150 to 300oC; for example, from 160 to 190oC, and at pressures in the range of 300 to 1000 psi; for example, from 400 to 750 psi. The residence time of the solution phase polymerization process typically ranges from 2 to 30 minutes; for example, 10 to 20 minutes. Ethylene, solvent, catalytic system, for example a catalytic system comprising a metal complex of a polyvalent aryloxyether, described in more detail in the present invention, optionally one or more cocatalysts, and optionally one or more comonomers are fed continuously to one or more reactors . Representative solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of ethylene/alpha-olefin interpolymer and solvent is then removed from the reactor and the ethylene/α-olefin interpolymer is isolated. The solvent is typically recovered through a solvent recovery unit, ie heat exchangers and vapor-liquid separator drum, and is then recycled back to the polymerization system.
[051] In one embodiment, ethylene/alpha-olefin interpolymers can be produced through solution polymerization in a dual reactor system, for example a double loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalytic system comprising a metal complex of a polyvalent aryloxyether in at least one reactor, where said metal complex of a polyvalent aryloxyether corresponds to the formula:
where M3 is Ti, Hf or Zr, preferably Zr;
[052] Ar4 is, independently at each occurrence, a substituted C9-20 aryl group, where the substituents, independently at each occurrence, are selected from the group consisting of alkyl groups; cycloalkyl; and aryl; and derivatives thereof substituted with halo, trihydrocarbylsilyl and halohydrocarbyl, provided that at least one substituent is devoid of coplanarity with the aryl group to which it is attached;
[053] T4 is, independently at each occurrence, a C2-20 alkylene, cycloalkylene or cycloalkenylene group, or an inertly substituted derivative thereof; 21
[054] R is, independently at each occurrence, hydrogen, halo group, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino of up to 50 atoms not counting hydrogen;
[055] R3 is, independently in each occurrence, hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino with up to 50 atoms not counting hydrogen, or two R3 groups on the same arylene ring together or a group R3 and R21 in the same or on a different arylene ring together form a divalent linking group attached to the arylene group at two positions or join two different arylene rings; and
[056] RD is, independently in each occurrence, halo or hydrocarbyl or trihydrocarbylsilyl group with up to 20 atoms not containing hydrogen, or 2 RD groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group. Additionally, one or more cocatalysts can be present.
[057] In another embodiment, ethylene/alpha-olefin interpolymers can be produced via solution polymerization in a simple reactor system, for example, a single loop reactor system, where ethylene is optionally one or more α -olefins are polymerized in the presence of a catalytic system comprising a metal complex of a polyvalent aryloxyether in the single loop reactor system, where said metal complex of a polyvalent aryloxyether corresponds to the formula:
where M3 is Ti, Hf or Zr, preferably Zr; Ar4 is, independently at each occurrence, a substituted C9-20 aryl group, where the substituents, independently at each occurrence, are selected from the group consisting of alkyl groups; cycloalkyl; and aryl; and derivatives thereof substituted with halo, trihydrocarbylsilyl and halohydrocarbyl, provided that at least one substituent is devoid of coplanarity with the aryl group to which it is attached;
[058] T4 is, independently at each occurrence, a C2-20 alkylene, cycloalkylene or cycloalkenylene group, or an inertly substituted derivative thereof;
[059] R21 is, independently in each occurrence, hydrogen, halo group, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino with up to 50 atoms not counting hydrogen;
[060] R3 is, independently in each occurrence, hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino with up to 50 atoms not counting hydrogen, or two R3 groups on the same arylene ring together or a group R3 and R21 in the same or on a different arylene ring together form a divalent linking group attached to the arylene group at two positions or join two different arylene rings; and
[061] RD is, independently in each occurrence, halo or hydrocarbyl or trihydrocarbylsilyl group with up to 20 atoms not containing hydrogen, or 2 RD groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group. Additionally, one or more cocatalysts can be present.
[062] Such polyvalent aryloxyether metal complexes and their synthesis are described in WO 2007/136496 or WO 2007/136497, incorporated herein by reference, using the synthetic procedures described in US-A-2004/0010103, incorporated herein by reference.
[063] The metal complex of a polyvalent aryloxyether can be activated to form an active catalyst composition, by combination with one or more cocatalysts, preferably a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof. Suitable cocatalysts for use include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as compatible, non-coordinating, inert ion-forming compounds. Representative suitable cocatalysts include, but are not limited to modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetracis(pentafluorophenyl)borate(1-)amine (RIBS-2), triethyl aluminum (TEA), and combinations thereof.
[064] In another embodiment, the ethylene/alpha-olefin interpolymers described above can be produced through solution polymerization in a dual reactor system, for example a double loop reactor system, where ethylene and optionally one or plus α-olefins, are polymerized in the presence of one or more catalytic systems. Such ethylene/alpha-olefin interpolymers are commercially available under the name ELITE™ from The Dow Chemical Company.
[065] In another embodiment, the ethylene/alpha-olefin interpolymers described above can be produced via solution polymerization in a simple reactor system, for example, a single loop reactor system, where ethylene is optionally one or more α-olefins are polymerized in the presence of one or more catalytic systems. Such ethylene/alpha-olefin interpolymers are commercially available under the name AFFINITYTM and are distributed by The Dow Chemical Company.
[066] The ethylene/alpha-olefin interpolymer composition may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene/alpha-olefin interpolymer composition can contain any amounts of additives. The ethylene/alpha-olefin interpolymer composition can comprise from about 0 to about 20 percent combined weight of such additives, based on the weight of the ethylene/alpha-olefin interpolymer composition and the one or more additives. Propylene/α-olefin Interpolymer Composition
[067] The propylene/α-olefin interpolymer composition comprises a propylene/alpha-olefin copolymer and/or a propylene/ethylene/butene terpolymer, and may optionally further comprise one or more polymers, for example a polypropylene of random copolymer (RCP). In a particular embodiment, the propylene/alpha-olefin copolymer is characterized by having substantially isotactic propylene sequences. "Substantially isotactic propylene sequences" means that the sequences have an isotactic triad (mm) measured by 13 C NMR of greater than about 0.85; alternatively, greater than about 0.90; alternatively, greater than about 0.92; and alternatively, greater than about 0.93. Isotactic triads are well known in the prior art, and described, for example, in U.S. Patent No. 5,504,172 and International Publication No. WO 00/01745, which refer to the isotactic sequence in terms of a triadic unit in the molecular chain of copolymer determined by 13C NMR spectra.
[068] The propylene/alpha-olefin copolymer can have a melt flow rate in the range of 0.1 to 500g/10 minutes, measured in accordance with ASTM D-1238 (at 230oC/2.16 kg). All individual values and subranges from 0.1 to 500g/10 minutes are included and described here; for example, the melt flow rate can range from a low limit of 0.1g/10 minutes, 0.2g/10 minutes or 0.5g/10 minutes to a maximum limit of 500g/10 minutes, 200g/10 minutes , 100g/10 minutes or 25g/10 minutes. For example, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 0.1 to 200g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 100g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 50g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 0.5 to 50g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 1 to 50g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 1 to 40g/10 minutes; or alternatively, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 1 to 30g/10 minutes.
[069] The propylene/alpha-olefin copolymer has a crystallinity in the range of at least 1 percent by weight (a heat of fusion of at least 2 Joules/gram) to 30 percent by weight (a heat of fusion of less than 50 Joules/gram). All individual values and subranges from 1 percent by weight (a heat of fusion of at least 2 Joules/gram) to 30 percent by weight (a heat of fusion of less than 50 Joules/gram) are included and described herein; for example, crystallinity can range from a lower limit of 1 percent by weight (a heat of fusion of at least 2 Joules/gram), 2.5 percent (a heat of fusion of at least 4 Joules/gram) or 3 percent (a heat of fusion of at least 5 Joules/gram) to a maximum limit of 30 percent by weight (a heat of fusion of less than 50 Joules/gram), 24 percent by weight (a heat of fusion of less than 40 Joules/gram), 15 percent by weight (a heat of fusion of less than 24.8 Joules/gram) or 7 percent by weight (a heat of fusion of less than 11 Joules/gram). For example, the propylene/alpha-olefin copolymer can have a crystallinity in the range of at least 1 percent by weight (a heat of melt of at least 2 Joules/gram) to 24 percent by weight (a heat of melt of less than 40 Joules/gram); or alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the range of at least 1 percent by weight (a heat of melt of at least 2 Joules/gram) to 15 percent by weight (a heat of melt of less than 24.8 Joules/gram); or alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the range of at least 1 percent by weight (a heat of melt of at least 2 Joules/gram) to 7 percent by weight (a heat of melt of less than 11 Joules/gram); or alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the range of at least 1 percent by weight (a heat of melt of at least 2 Joules/gram) to 5 percent by weight (a heat of melt of less than 8.3 Joules/gram). Crystallinity is measured using the DSC method. The propylene/alpha-olefin copolymer comprises units derived from propylene and polymer units derived from one or more alpha-olefin comonomers. Representative comonomers used in the manufacture of the propylene/alpha-olefin copolymer are alpha-olefins C2, and C4 to C10; for example C2, C4, C6 and C8 alpha-olefins.
[070] The propylene/alpha-olefin copolymer comprises from 1 to 40 percent by weight of one or more alpha-olefin comonomers. All individual values and subranges from 1 to 40 percent by weight are included and described herein; for example, the comonomer content can range from a lower limit of 1 percent by weight, 3 percent by weight, 4 percent by weight, 5 percent by weight, 7 percent by weight, or 9 percent by weight. , up to a maximum of 40 percent by weight, 35 percent by weight, 30 percent by weight, 27 percent by weight, 20 percent by weight, 15 percent by weight, 12 percent by weight, or 9 percent by weight. For example, the propylene/alpha-olefin copolymer comprises from 1 to 35 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 1 to 30 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 27 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 20 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 15 percent by weight of one or more alpha-olefin comonomers.
[071] Propylene/alpha-olefin copolymer has a molecular weight distribution (MWD), defined as weight average molecular weight divided by number average molecular weight (Mw/Mn) of 3.5 or less; alternatively 3.0 or less; or in another alternative, from 1.8 to 3.0.
[072] Such propylene/alpha-olefin copolymers are also described in detail in US Pat. 6,960,635 and 6,525,157, incorporated herein by reference. Such propylene/alpha-olefin copolymers are commercially available from The Dow Chemical Company under the trade name VERSIFYTM or from ExxonMobil Chemical Company under the trade name VISTAMAXXTM.
[073] In one embodiment, the propylene/alpha-olefin copolymers are further characterized as comprising: (A) between 60 and less than 100, preferably between 80 and 99 and more preferably between 85 and 99 percent by weight of units derived from propylene, and (B) between more than zero and 40, preferably between 1 and 20, more preferably between 4 and 16, and even more preferably between 4 and 15 percent by weight of units derived from at least one of ethylene and/or of a C4-10 α-olefin; and containing an average of at least 0.001, preferably an average of at least 0.005 and more preferably an average of at least 0.01 long chain branches/1000 total carbons. The maximum number of long chain branches in the propylene/alpha-olefin copolymer is not critical, although it typically does not exceed 3 long chain branches/1000 total carbons. The term long-chain branching, as used herein in connection with propylene/alpha-olefin copolymers, refers to a chain length of at least one (1) carbon more than one short-chain branch, and branching of short chain as used herein in connection with propylene/alpha-olefin copolymers refers to a chain length of two (2) carbons less than the number of carbons in the comonomer. For example, a propylene/1-octene interpolymer has backbones with long chain branches that are at least seven (7) carbons in length, although these backbones also have short chains that are only six (6) carbons in extension. Such propylene/alpha-olefin copolymers are also described in detail in US Provisional Patent Application No. 60/988,999 and International Patent Application No. PCT/US08/08s2599, each of which is incorporated herein by reference.
[074] The propylene/alpha-olefin interpolymer composition may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The propylene/alpha-olefin interpolymer composition can contain any amounts of additives. The propylene/alpha-olefin composition can comprise from about 0 to about 20 percent of the combined weight of such additives, based on the weight of the propylene/alpha-olefin interpolymer composition and the one or more additives. Process for Producing the Sealing Composition
[075] One or more ethylene/α-olefin interpolymer compositions and one or more propylene/α-olefin interpolymer compositions, as described herein, can be mixed by any method known in the prior art, including without restriction , dry blending, and melt blending, by any suitable equipment, for example, an extruder, to produce a sealant composition of the invention. Applications of Sealing Composition for End Use
[076] The sealing compositions, according to the present invention, can be used in any sealing applications, for example, food packaging and specialty applications.
[077] In one embodiment, the present invention provides a sealing layer comprising a sealing composition comprising: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on weight total of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, and the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range from 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, wherein said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melt in the range of 2 Joules/g to 50 Joules/g and a DSC melting point in the range of 25oC to 110oC.
[078] In another alternative embodiment, the present invention provides an article comprising: (1) at least one sealing layer comprising a sealing composition comprising (a) from 70 to 99.5 percent by weight of an ethylene interpolymer composition /α-olefin, based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Constant of Comonomer distribution (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and branching frequency of long chain in the range of 0.02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, and being that said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melting in the range of 2 Joules/gram to 50 Joules/gram, and a DSC melting point at range from 25oC to 110oC; and (2) at least one substrate layer.
[079] In another alternative embodiment, the present invention further provides a method for forming an article comprising the steps of (1) selecting a sealant composition comprising: (a) from 70 to 99.5 percent by weight of an interpolymer composition of ethylene/α-olefin, based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, wherein the ethylene/α-olefin interpolymer has a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and frequency of long chain branching in the range of 0.02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer, and being that said propylene/α-olefin copolymer has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of melting in the range of 2 Joules/gram to 50 Joules/gram, and a DSC melting point at range from 25oC to 110oC; and (2) selecting at least one substrate layer; (3) applying said sealant composition to at least one surface of said at least one substrate layer; (4) thus forming at least one sealing layer associated with at least one surface of said at least one substrate layer.
[080] The sealing compositions of the present invention have been shown to improve the heat setting and heat sealing strength performance, including increasing the heat setting and heat sealing resistance, reducing the heat setting and heat setting resistance initiation temperatures. thermal sealing, and enlarging the heat setting resistance window. Examples of Sealing Composition 1 of the Invention
[081] The sealant composition 1 of the invention comprises (a) 90% by weight of an ethylene-octene interpolymer (herein designated ethylene-octene interpolymer A), marketed under the trade name ELITE TM 5500G by The Dow Chemical Company, with a density of approximately 0.9141 g/cm3, a melt index (I2), measured at 190°C, and 2.16 kg of approximately 1.5g/10 minutes, a melt flow ratio (I10/I2) of approximately 7.3; and (b) 10% by weight of a propylene-ethylene interpolymer, marketed under the trade name VERSIFYTM 2200 by The Dow Chemical Company, having a melt flow rate, measured at 230°C and 2.16 kg, of approximately 2 .0g/10 minutes. Additional properties of the ethylene-octene A interpolymer were measured and reported in Table 1. Sealing Composition 2 of the Invention
[082] The sealing composition 2 of the invention comprises (a) 90% by weight of an ethylene-octene interpolymer (herein designated ethylene-octene interpolymer B), with a density of approximately 0.9014 g/cm3, an index of melt (I2), measured at 190oC, and 2.16 kg of approximately 1.0g/10 minutes, a melt flow ratio (I10/I2) of approximately 6.5; and (b) 10% by weight of a propylene-ethylene interpolymer, marketed under the trade name VERSIFYTM 2200 by The Dow Chemical Company, having a melt flow rate, measured at 230°C and 2.16 kg, of approximately 2 .0g/10 minutes. Additional properties of the ethylene-octene B interpolymer were measured and reported in Table 1.
[083] The ethylene-octene B interpolymer was prepared through solution polymerization in a single loop reactor system, in the presence of a zirconium-based catalytic system comprising [2,2'''-[1,3-propanediylbis (oxy-KO)]bis[3",5,5"-tris(1,1-dimethylethyl)-5z-methyl[1,1Z:3Z1"-[terphenyl]-2z-olate-K']]dimethyl -, (OC-6-33)-zirconium, represented by the following formula:
Sealing Composition of the Invention 3
[084] The sealing composition of the invention 3 comprises (a) 90% by weight of an ethylene-octene interpolymer (herein designated as ethylene-octene interpolymer C), with a density of approximately 0.9029 g/cm3, an index melt (I2), measured at 190oC and 2.16kg of approximately 0.90g/10 minutes, a melt flow ratio (I10/I2) of approximately 10.7; and (b) 10% by weight of a propylene-ethylene interpolymer, commercially available under the tradename VERSIFYTM2200 from The Dow Chemical Company, having a melt flow rate, measured at 230°C and 2.16 kg, of approximately 2.0g/10 minutes. Additional properties of ethylene-octene C interpolymer were measured, and are reported in Table 1.
[085] The ethylene-octene C interpolymer was prepared through solution polymerization in a dual loop reactor system in the presence of a zirconium-based catalytic system comprising [2,2'''-[1,3-propanediylbis( oxy-KO)]bis[3",5,5"-tris(1,1-dimethylethyl)-5z-methyl [1,1Z:3Z1"-[terphenyl]-2z-olate-K']]dimethyl-, (OC-6-33)-zirconium, represented by the following formula:

[086] The polymerization conditions for ethylene-octene interpolymer C are reported in Tables 2 and 3. Referring to Tables 2 and 3, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(tallowalkyl hydrogenated)methyl, tetracis(pentafluorophenyl)borate(1-)amine. Sealing Composition 4 of the Invention
[087] The sealant composition of the invention 4 comprises (a) 90% by weight of an ethylene-octene interpolymer (herein designated as ethylene-octene interpolymer D), with a density of approximately 0.9071 g/cm3, an index melt (I2), measured at 190oC and 2.16kg of approximately 0.84g/10 minutes, a melt flow ratio (I10/I2) of approximately 7.3; and (b) 10% by weight of a propylene-ethylene interpolymer, commercially available under the tradename VERSIFYTM2200 from The Dow Chemical Company, having a melt flow rate, measured at 230°C and 2.16 kg, of approximately 2.0g/10 minutes. Additional properties of ethylene-octene D interpolymer were measured, and are reported in Table 1.
[088] The ethylene-octene D interpolymer was prepared through solution polymerization in a dual loop reactor system in the presence of a zirconium-based catalytic system comprising [2,2'''-[1,3-propanediylbis( oxy-KO)]bis[3",5,5"-tris(1,1-dimethylethyl)-5z-methyl[1,1Z:3Z1"-[terphenyl]-2z-olate-K']]dimethyl- , (OC-6-33)-zirconium, represented by the following formula:
Comparative Sealing Composition 1
[089] Comparative sealant composition 1 comprises 100% by weight of an ethylene-octene interpolymer (herein designated as ethylene-octene interpolymer A, as described above), available on the market under the trade name ELITETM 5500G distributed by The Dow Chemical Company, having a density of approximately 0.9141 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 1.5 g/10 minutes, a melt flow ratio (I10 /I2) of approximately 7.3. Additional properties of ethylene-octene A interpolymer were measured, and are reported in Table 1. Comparative Sealing Composition 2
[090] Comparative sealant composition 2 comprises 100% by weight of an ethylene-octene interpolymer (herein designated as ethylene-octene interpolymer E, as described above), available on the market under the trade name DOWLEXTM 2056 distributed by The Dow Chemical Company, having a density of approximately 0.920 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 1.0 g/10 minutes. Additional properties of ethylene-octene E interpolymer were measured, and are reported in Table 1. Comparative Sealing Composition 3
[091] The sealant composition of invention 3 comprises (a) 90% by weight of an ethylene-octene interpolymer (herein designated as ethylene-octene interpolymer E, as described above), available on the market under the trade name DOWLEXTM 2056 by The Dow Chemical Company, with a density of approximately 0.920 g/cm3, a melt index (I2), measured at 190oC and 2.16kg of approximately 1.0g/10 minutes; and (b) 10% by weight of a propylene-ethylene interpolymer, commercially available under the tradename VERSIFYTM2200 from The Dow Chemical Company, having a melt flow rate, measured at 230°C and 2.16 kg, of approximately 2.0g/10 minutes. Additional properties of ethylene-octene E interpolymer were measured, and are reported in Table 1. Comparative Sealing Composition 4
[092] Comparative sealant composition 4 comprises 100% by weight of an ethylene-octene interpolymer (referred to herein as ethylene-octene interpolymer B, as described above), having a density of approximately 0.9014 g/cm3, an index melt (I2), measured at 190oC and 2.16 kg, of approximately 1.0 g/10 minutes, a melt flow ratio (I10/I2) of approximately 6.5. Additional properties of the ethylene-octene B interpolymer were measured, and are reported in Table 1. Comparative Sealing Composition 5
[093] Comparative sealant composition 5 comprises 100% by weight of an ethylene-octene interpolymer (referred to herein as ethylene-octene interpolymer D, as described above), having a density of approximately 0.9071 g/cm3, an index melt (I2), measured at 190oC and 2.16 kg, of approximately 0.84 g/10 minutes, a melt flow ratio (I10/I2) of approximately 7.3. Additional properties of the ethylene-octene D interpolymer were measured, and are reported in Table 1. Three-Layer Films 1-4 of the Invention
[094] Three-layer films 1-4 of the invention are manufactured through a co-extrusion process. The manufacturing apparatus contains three extruders: (1) extruder 1 with a barrel diameter of 25mm; (2) extruder 2, with a barrel diameter of 30mm; and (3) extruder 3 with a barrel diameter of 25mm, each capable of making a layer of film. The average total production of all three extruders, depending on the material, is approximately 10-15 kg/h. Each extruder has a single threaded screw. The die diameter is 60mm. The maximum line starting speed is 30m/min. Extrusion conditions are reported in Tables 4-5.
[095] The three-layer film 1 of the invention comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of the sealing composition of invention 1, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[096] The three-layer film 2 of the invention comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of the sealing composition of invention 2, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[097] The three layer film 3 of the invention comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of the sealing composition of invention 3, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[098] The three-layer film 4 of the invention comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of the sealing composition of the invention 4, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[099] The three-layer films 1-4 of the invention were tested for their sealing properties, the results being reported in figures 23 and 24.
[100] The three-layer comparative films 1-4 are manufactured using a co-extrusion process. The manufacturing apparatus contains three extruders: (1) extruder 1 with a barrel diameter of 25mm; (2) extruder 2, with a barrel diameter of 30mm; and (3) extruder 3 with a barrel diameter of 25mm, each capable of making a layer of film. The average total production of all three extruders, depending on the material, is approximately 10-15 kg/h. Each extruder has a single threaded screw. The die diameter is 60mm. The maximum line starting speed is 30m/min. Extrusion conditions are reported in Tables 6-7.
[101] Comparative three-layer film 1 comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of comparative sealing composition 1, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[102] The three-layer comparative film 2 comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of comparative sealing composition 2, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[103] The three-layer comparative film 3 comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of comparative sealing composition 3, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[104] The three-layer comparative film 4 comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of comparative sealer composition 4, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[105] Comparative three-layer film 5 comprises: (1) 25 percent by weight of a coating layer, based on the total weight of the three-layer film, which was manufactured via extruder number 1, comprising Ultramid C33L01; (2) 50 percent by weight of a core layer, based on the total weight of the three-layer film, which was manufactured via extruder number 2, comprising 90 percent by weight of ATTANETM 4201 and 10 percent by weight of AMPLIFYTM GR-205, based on the total weight of the core layer; (3) 25 percent by weight of comparative sealing composition 5, as described above, based on the total weight of the three-layer film, which was manufactured via extruder number 3.
[106] The three-layer films 1-5 of the invention were tested for their sealing properties, with the results reported in figures 23 and 24.









Test Methods Test methods include the following: Density
[107] Samples that are measured for density are prepared in accordance with ASTM D-1928. Measurements are performed within one hour of sample compression using ASTM D-792, Method B. Melt Index
[108] The melt index (I2) is measured in accordance with ASTM-D 1238, Condition 190oC/2.16 kg, and is reported in grams eluted over 10 minutes. The melt index rate (I10) is measured in accordance with ASTM-D 1238, Condition 190oC/10kg, and is reported in grams eluted over 10 minutes. DSC Crystallinity
[109] Differential Scanning Calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide range of temperatures. For example, TA Instruments DSC Q1000 equipment, equipped with an RCS (refrigerated cooling system) and an autosampler, is used to perform this analysis. Each sample is melt pressed into a thin film at about 175oC; the molten sample is then air cooled to room temperature (~25oC). A 3-10mg specimen, 6mm in diameter is extracted from the cooled polymer, weighed, placed in a lightweight aluminum container (ca 50mg), and closed by compression. Analysis is then conducted to determine thermal properties.
[110] The thermal behavior of the sample is determined by raising and lowering the temperature of the sample to create a profile of thermal flux versus temperature. First, the sample is quickly heated to 180oC and kept isothermal for 3 minutes to remove the thermal history. The sample is then cooled to -40oC at a cooling rate of 10oC/minute and kept isothermal at -40oC for 3 minutes. The sample is then heated to 150oC (this is the "second heat" increase) at a heating rate of 10oC/minute. Cooling and second heating curves are recorded. The cooling curve is analyzed by establishing baseline parameters from the start of crystallization at -20oC. The heating curve is analyzed by establishing baseline parameters from -20oC until the end of melting. The values determined are peak melting temperature (Tm), peak crystallization temperature (Tc), heat of melting (Hf) (in Joules per gram), and % crystallinity calculated for samples using appropriate equation, eg for the ethylene/alpha-olefin interpolymer using Equation 1, as shown in Figure 1.
[111] The heat of fusion (Hf) and the peak fusion temperature are reported from the second heating curve. The crystallization peak temperature is determined from the cooling curve. Dynamic Mechanical Spectroscopy Frequency Scan (DMS)
[112] Fusion rheology, constant temperature frequency scans were conducted using a TA Instruments Advanced Rheometric Expansion System (ARES) rheometer equipped with 25mm parallel plates under nitrogen purge. Frequency scans were conducted at 190oC for all samples within a range of 2.0mm and a constant strain of 10%. The frequency range was 0.1 to 100 radians/second. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (Gz), loss modulus (G"), and dynamic melt viscosity (n*) were analyzed. Gel Permeation Chromatography (GPC)
[113] Ethylene/alpha-olefin interpolymers were tested for their properties via GPC, according to the procedure described below. The GPC system consists of a Waters (Milford, MA) 150oC high temperature chromatograph (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) equipped with a differential refractometer on -board (RI). Additional detectors may include a Polymer ChAR IR4 infrared detector (Valencia, Spain), Precision Detectors (Amherst, MA) Model 2040 2-Angle Laser Light Scattering Detector (Amherst, MA), and a Viscotek 150R 4-capillary solution viscometer ( Houston, TX). A GPC system with the last two independent detectors and at least one of the first detectors is sometimes referred to as "3D-GPC", while the term "GPC" alone generally refers to conventional GPC. Depending on the sample, the 15 degree angle or the 90 degree angle of the light scattering detector is used for calculation purposes. Data collection is conducted using Viscotek TriSEC software, Version 3, and a 4-channel Viscotek DM400 Data Manager. The system is also equipped with an online solvent degassing device from Polymer Laboratories (shropshire, UK). Suitable GPC columns at high temperature can be used, such as Shodex HT803 columns of 13 microns and 30 cm in length or Polymer Labs 30 cm load columns with 20 micron mixed pore size (MixA LS, Polymer Labs). The sample carousel compartment at 140oC and the column compartment is operated at 150oC. Samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent contain 200 ppm butylated hydroxytoluene (BHT). The two solvents are sparged with nitrogen. Polyethylene samples are gently shaken at 160oC for four hours. The injection volume is 200 microliters. The flow rate across the entire GPC is adjusted to 1 ml/minute.
[114] The GPC column assembly is calibrated prior to running the Examples by running twenty-one polystyrene standards with narrow molecular weight distribution. The molecular weight (MW) of the standards ranges from 580 to 8,400,000 grams per mole, and the standards are contained in six "cocktail" blends. Each master blend has at least a dozen separations between individual molecular weights. Standard blends are purchased from Polymer Laboratories (Shropshite, UK). Polystyrene standards are prepared at 0.025g in 50ml solvent for molecular weights equal to or greater than 1,000,000 grams per mol and 0.05g in 50ml solvent for molecular weights less than 1,000,000 grams per mol. Polystyrene standards were dissolved at 80oC with gentle agitation for 30 minutes. Narrow standard blends are run first and in descending order of higher molecular weight component to minimize degradation. Polystyrene standard peak molecular weights are converted to Mw of polyethylene using the Mark-Houwink K equation and values (sometimes referred to as α) mentioned later for polystyrene and polyethylene. See the Examples section for a demonstration of this procedure. With 3D-GPC, the weight average molecular weight ("Mw,Abs") and intrinsic viscosity are also independently obtained from narrow polyethylene standards using the same conditions mentioned above. These linear polyethylene narrow standards can be obtained from Polymer Laboratories (Shropshire, UK; Part Nos. PL2650-0101 and PL2650-0102). The systematic method for determining multidetector offsets is conducted in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym., chapter 12 (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., chapter 13 (1992)), optimizing the triple detector log results (Mw and intrinsic viscosity) ) of Dow 1683 wide distribution polystyrene (American Polymer Standards Corp.; Mentor, OH) or its equivalent against the narrow standard column calibration results of the Narrow Polystyrene Standards Calibration Curve. Molecular weight data relating to the determination of detector volume displacement are obtained in a manner consistent with that published by Zimm (Zimm, BH, J.Chem.Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil) , P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight is obtained from the mass detector area and mass detector constant derived from an appropriate linear homopolymer polyethylene, or one of the polyethylene standards. The calculated molecular weights are obtained using a light scattering constant derived from one or more polyethylene standards mentioned and a refractive index concentration coefficient, dn/dc, of 0.104. Generally, the mass detector response and light scattering constant should be determined from a linear standard with a molecular weight greater than about 50,000 daltons. Calibration of the viscometer can be performed using the methods described by the manufacturer or, alternatively, using published values of linear standards such as Standard Reference Materials (SRM) 1475a, 1482a, 1483 or 1484a. Chromatographic concentrations are considered low enough to eliminate the effects of the second virial coefficient (effects of concentration on molecular weight).
[115] The index (gz) for the sample polymer is determined by first calibrating the light scattering, viscosity, and concentration detectors described in the Gel Permeation Chromatography method above with homopolymer polyethylene SRM 1475a (or equivalent reference). The light scattering and displacements of the viscometer detector are determined relative to the concentration detector as described in the calibration. Baselines are subtracted from the light scattering, viscometer, and concentration schedules and the integration windows are then adjusted, making sure to integrate all low molecular weight retention volume ranges into the light scattering and viscometer chromatograms that indicate the presence of detectable polymer from the refractive index chromatogram. A linear homopolymer polyethylene is used to establish the Mark-Houwink (MH) linear reference line by injecting a broad molecular weight polyethylene reference such as standard SRM1475a, calculating the data file, and recording the intrinsic viscosity (IV) and molecular weight (Mw), each derived from the light scattering and viscosity detectors respectively, and the concentration as determined from the detector mass constant RI for each chromatographic portion is repeated to obtain a line of Mark-Houwink sample. Note that for some samples, the lower molecular weights, intrinsic viscosity and molecular weight data may need to be extrapolated so that the measured molecular weight and intrinsic viscosity asymptotically approximate a linear homopolymer GPC calibration curve. For this purpose, many highly branched ethylene-based polymer samples require that the linear reference line be shifted slightly to account for the short chain branching contribution before proceeding with the calculation of the long chain branching index (g') .
[116] A g-prime (gi') is calculated for each chromatographic portion of the branched sample (i) and measuring the molecular weight (Mi) according to Equation 2, as shown in Figure 2, where the calculation uses the linear reference,j to the equivalent molecular weight, Mj, in the linear reference sample. In other words, sample portion IV (i) and reference portion IV (j) have the same molecular weight (Mi = Mj). For simplicity, the linear reference,j portions are calculated from a fifth-order polynomial fit of the Mark-Houwink reference graph. The IV, or gi', ratio is only obtained at molecular weights greater than 3,500, due to the signal-to-noise limitations of light scattering data. The number of branches along the sample polymer (Bn) in each data portion (i) can be determined using Equation 3, as shown in Figure 3, assuming an epsilon viscosity shielding factor of 0. 75.
[117] Finally, the average amount of LCBf per 1000 carbons in the polymer in all portions (i) can be determined using Equation 4, as shown in Figure 4. Branching Index gpcBR through 3D-GPC
[118] In the 3D-GPC configuration, polyethylene and polystyrene standards can be used to measure the Mark-Houwing constants, K and α, independently for each of the two polymer types, polystyrene and polyethylene. These can be used to refine the equivalent molecular weights of Williams and Ward polyethylene in applying the following methods.
[119] The gpcBR branching index is determined first by calibrating the light scattering, viscosity, and concentration detectors as described above. Baselines are then subtracted from the light scattering, viscometer, and concentration chromatograms. The integration windows are then adjusted to ensure integration of the entire low molecular weight retention volume range into the light scattering and viscometer chromatograms that indicate the presence of detectable polymer from the refractive index chromatogram. Linear polyethylene standards are then used to establish Mark-Houwink polyethylene and polystyrene constants as described above. When obtaining the constants, the two values are used to construct two conventional linear reference calibrations ("cc") for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution volume, as shown in Equations 5 and 6, Figures 5 and 6, respectively.
[120] The gpcBR branching index is a robust method for characterizing long-chain branching. See Yau, Wallace W., "Examples of Using 3D-GPC - TREF for Polyolefin Characterization", Macromol. Symp., 2007, 257, 29-45. The index bypasses the 3D-GPC portion-by-portion calculations traditionally used in determining gz values and branch frequency calculations in favor of total polymer detector areas and scalar area products. From the 3D-GPC data, the Mw in mass of the sample can be obtained through the light scattering detector (LS) using the peak area method. The method avoids the portion-by-portion relationship of light scattering detector signal to concentration detector signal required in gz determination.
[121] The area calculation in Equation 7, shown in Figure 7, offers more accuracy since, as a global sample area, it is much less sensitive to variation caused by detector noise and GPC adjustments at integration limits and baseline. Most importantly, the peak area calculation is not affected by deviations in detector volume. Similarly, high precision sample intrinsic viscosity (IV) is obtained by the area method shown in Equation 8, as shown in Figure 8, where DPi means the differential pressure signal monitored directly from the online viscometer.
[122] To determine the gpcBR branching index, the light scattering elution area for the sample polymer is used to determine the molecular weight of the sample. The viscosity detector elution area for the sample polymer is used to determine the intrinsic viscosity (IV or [n]) of the sample.
[123] Initially, the molecular weight and intrinsic viscosity for a linear polyethylene standard sample, such as SRM1475a or an equivalent, are determined using conventional calibrations for both molecular weight and intrinsic viscosity as a function of volume of elution, for Equations 9 and 10, as shown in Figures 9 and 10, respectively.
[124] Equation 11, as shown in Figure 11, is used to determine the branching index gpcBR, where [n]cc is the intrinsic viscosity of the conventional calibration, Mw is the measured weight average molecular weight, and Mw,cc is the weight average molecular weight of the conventional calibration. The Mw through light scattering (LS) using Equation 7, as shown in Equation 7, is commonly called absolute Mw; whereas the Mw,cc of Equation 9, as shown in Figure 9, using the molecular weight calibration curve via conventional GPC is often called the polymer chain Mw. All statistical values with the subscript "cc" are determined using their respective elution volumes, the corresponding conventional calibration as described above, and the concentration (Ci) derived from the response mass of the detector. Unsubscribed values are measured values based on mass detector areas, LALLS, and viscometer areas. The KPE value is iteratively adjusted until the linear reference sample has a measured gpcBR value of zero. For example, the final values of α and Log K for the determination of gpcBR in this specific case are 0.725 and -3.355, respectively, for polyethylene and 0.722 and -3.933 for polystyrene, respectively.
[125] Once the K and α values are determined, the procedure is repeated using the branched samples. The branched samples are analyzed using the final Mark-Houwink constants as the best "cc" calibration values and applying Equations 7-11, as shown in Figures 7-11, respectively.
[126] The interpretation of gpcBR is straightforward. For linear polymers, the gpcBR calculated from Equation 11, as shown in Figure 11, will be close to zero since the values measured by LS and viscosimetry will be close to the conventional calibration standard. For branched polymers, gpcBR will be greater than zero, especially with high levels of LCB, as the measured polymer Mw will be greater than the calculated Mw,cc and the calculated IVcc will be greater than the Intrinsic Viscosity (IV) of the measured polymer. In fact, the value of gpcBR represents the fractional change IV due to the effect of molecular size shrinkage as a result of polymer branching. A gpcBR value of 0.5 or 2.0 would mean an IV molecular size shrinkage effect at the 50% and 200% level, respectively, versus a linear polymer molecule of equivalent weight.
[127] For these specific Examples, the advantage of using gpcBR compared to g' index and branch frequency calculations is due to the higher accuracy of gpcBR. All parameters used in determining the gpcBR index are obtained with good precision and are not adversely affected by the low response of the 3D-GPC detector with high molecular weight concentration detector. Errors in detector volume alignment do not affect the accuracy of gpcBR index determination. In other specific cases, other methods for determining Mw moments may be preferable to the aforementioned technique. CEF method
[128] Comonomer distribution analysis is conducted with Crystallization Elution Fractionation (CED) (PolymerChar in Spain) (B Monrabal et al., Macromol. Symp. 257, 71-79 (2007)). Ortho-dichlorobenzene (ODCB) with 600ppm antioxidant butylated hydroxytoluene (BHT) is used as a solvent. Sample preparation is performed with an automatic sampler at 160oC for 2 hours under shaking at 4mg/ml (unless otherwise specified). The injection volume is 300μl. The temperature profile of CEF is crystallization at 3oC/min from 110oC to 30oC, thermal equilibrium at 30oC for 5 minutes, elution at 3oC/min from 30oC to 140oC. The flow rate during crystallization is 0.052 ml/min. The flow rate during elution is 0.50 ml/min. Data is collected on the basis of one data point/second.
[129] The CEF column is loaded by The Dow Chemical Company with 125 μm+/-6% glass beads (MO-SCI Specialty Products) with 1/8" stainless steel tubing. The glass beads are acid washed by the MO-SCI Specialty by request from The Dow Chemical Company Column volume is 2.0 ml Column temperature calibration is conducted using a 1475a linear polyethylene mixture as per NIST Standard Reference Material (1.0mg /ml) and Eicosan (2mg/ml) in ODCB. The temperature is calibrated by adjusting the heating elution rate so that the 1475a NIST linear polyethylene has a peak temperature of 101.0oC and Eicosan a peak temperature of 30 ,0oC CEF column resolution is calculated with a mixture of linear polyethylene 1475a NIST (1.0mg/ml) and hexacontane (Fluka, purum, > 97.0%, 1mg/ml) A line separation is obtained. of hexacontane and 1475a NIST polyethylene base. The area of hexacontane (from 35.0 to 67.0oC) relative to the area of 1475a NIST of 67.0 at 110.0oC it is 50 to 50, and the amount of soluble fraction below 35.0oC is <1.8% by weight. The CEF column resolution is defined in equation 12, as shown in Figure 12, where the column resolution is 6.0. CDC method
[130] The comonomer distribution constant (CDC) is calculated from the comonomer distribution profile through CEF. CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Shape Factor, multiplying by 100, as shown in Equation 13, Figure 13.
[131] Comonomer distribution index means the weight fraction of polymer chains with the comonomer content ranging from 0.5 of the median comonomer content (Cmedian) and 1.5 of Cmedian from 35.0 to 119.0oC. Comonomer Distribution Shape Factor is defined as a ratio of the half-width of the comonomer distribution profile divided by the standard deviation of the peak temperature comonomer distribution profile (Tp).
[132] CDC is calculated from the comonomer distribution profile through CEF, and CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Format Factor, multiplying by 100 as shown in Equation 13, Figure 13, where comonomer distribution index means the total weight fraction of polymer chains with comonomer content ranging from 0.5 of the median comonomer content (Cmedian) and 1.5 of Cmedian from 35.0 to 119, 0oC, where the Comonomer Distribution Shape Factor is defined as the ratio of the half-width of the comonomer distribution profile divided by the standard deviation of the peak temperature comonomer distribution profile (Tp).
[133] The CDC is calculated according to the following steps: (A) obtain a weight fraction at each temperature (T) (wT(T)) from 35.0oC to 119.0oC with a gradual temperature increase of 0.200 oC of CEF according to Equation 14, as shown in Figure 14; (B) calculate the median temperature (Tmedian) at the cumulative weight fraction of 0.500 according to Equation 15, as shown in Figure 15; (C) calculate the corresponding median comonomer content in mol % (Cmedian) at the median temperature (Tmedian) using the comonomer content calibration curve according to Equation 16, as shown in Figure 16; (D) construct a comonomer content calibration curve using a series of reference materials with known amount of comonomer content, ie, eleven reference materials with narrow comonomer distribution (monomodal comonomer distribution in CEF of 35.0 at 119.0oC) with weight average Mw from 35,000 to 115,000 (measured via conventional GPC) at a comonomer content ranging from 0.0 mol% to 7.0 mole % are analyzed with CEF under the same experimental conditions specified in the experimental sections of CEF; (E) calculate the comonomer content calibration using a peak temperature (Tp) of each reference material and its comonomer content. Calibration is calculated from each reference material as shown in Formula 16, Figure 16, where R2 is the correlation constant; (F) Calculate the Comonomer Distribution Index from the total weight fraction with a comonomer content ranging from 0.5*Cmedian to 1.5*Cmedian, and if Tmedian is greater than 98.0C, the Index of Comonomer Distribution is set to 0.95; (G) Obtain the maximum peak height of the CEF comonomer distribution profile by searching each data point for the highest peak from 35.0oC to 119.0oC (if the two peaks are identical then the highest temperature peak will be selected low); half width is defined as the temperature difference between the front temperature and the rear temperature at half the maximum peak height, the front temperature at half the maximum peak is fetched forward from 35.0oC, while the rear temperature at half the maximum peak is fetched backwards from 119.0oC, in the case of a well-defined bimodal distribution, in which the difference in peak temperatures is equal to or greater than 1.1 times the sum of the half width of each peak , the half-width of the ethylene-based polymer composition of the invention is calculated as the arithmetic mean of the half-width of each peak; and (H) calculate the temperature standard deviation (Stdev) according to Equation 17, as shown in Figure 17. Zero Shear Viscosity Method via Fluency Test
[134] Zero-shear viscosities are obtained through creep tests that are conducted in an AR-G2 tension-controlled rheometer (TA Instruments; New Castle, Del) using 25mm diameter parallel plates at 190oC. The rheometer oven is set at the test temperature for at least 30 minutes before zeroing the accessories. At the test temperature, the compression molded sample disc is inserted between the plates and allowed to reach equilibrium for 5 minutes. The top plate is then lowered to 50μm above the desired test space (1.5mm). Any superfluous material is trimmed and the top plate lowered into the desired space. Measurements are performed under nitrogen purge at a flow rate of 5L/min. The default fluency period is set to 2 hours.
[135] A constant low shear stress of 20 Pa is applied to all samples to ensure that the steady state shear rate is low enough to be in the Newtonian region. The resulting steady-state shear rates are on the order of 10-3s-1 for the samples in this study. Steady state is determined by taking linear regression for all data in the last 10% time window of the log(J(t)) vs. graph. log(t), where J(t) is the creep curve and t is the creep time. If the linear regression curve is greater than 0.97, the steady state is considered reached and the fluency test stopped. In all cases in this study, the curve meets the criterion within 30 minutes. The steady-state shear rate is determined from the linear regression curve of all data points in the last 10% time window of the ε vs. graph. t, where ε is the deformation. Zero shear viscosity is determined from the ratio of applied stress to steady state shear rate.
[136] To determine if the sample degrades during the creep test, a small amplitude oscillatory shear test is conducted before and after the creep test on the same specimen at 0.1 to 100 rad/s. The complex viscosity values of the two tests are compared. If the difference in viscosity values at 0.1 rad/s is greater than 5%, the sample is considered to have degraded during the creep test, and the result is discarded. Zero Shear Viscosity Ratio
[137] The zero shear viscosity ratio (ZSVR) is defined as the ratio of the zero shear viscosity (ZSV) of the polymer of the invention to the ZSV of a linear polyethylene material at equivalent weight average molecular weight (Mw-gpc) as shown in Equation 18, Figure 18.
[138] The value n0 (in Pa.s) is obtained from the creep test at 190oC via the method described above. It is known that the linear polyethylene ZSV n0L has a force law dependence on its Mw when the Mw is above the critical molecular weight Mc. An example of such a relationship is described in Karjala et al. (Annual Technical Conference - Society of Plastics Engineers (2008), 66a, 887-891) as shown in Equation 19, Figure 19, to calculate the ZSVR values. With reference to Equation 19, as shown in Figure 19, the Mw-gpc (g/mol) value is determined using the GPC method, as defined immediately above. Determination of Mw-gpc
[139] To obtain Mw-gpc values, the chromatographic system consists of Polymer Laboratories Model PL-210 or Model PL-220. Column and carousel compartments are operated at 140oC. Three 10-μm Mixed-B columns from Polymer Laboratories are used with a 1,2,4-trichlorobenzene solvent. Samples are prepared at a concentration of 0.1g polymer in 50ml solvent. The solvent used to prepare the samples contains 200ppm of the antioxidant butylated hydroxytoluene (BHT). Samples were prepared by gently shaking for 4 hours at 160oC. The injection volume used is 100 microliters and the flow rate is 1.0 ml/min. Calibration of the GPC column assembly is performed with twenty-one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories. Polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 20, as shown in Figure 20.
[140] Referring to Equation 20, as shown in Figure 20, M is the molecular weight, A has a value of 0.4316, and B is equal to 1.0. A third-order polynomial function is determined to construct the logarithmic molecular weight calibration as a function of the injection volume. Polyethylene equivalent molecular weight calculations are conducted using Viscotek TriSEC version 3.0 software. The accuracy of the weight average molecular weight ΔMw is excellent at <2.6%. 1H NMR Method
[141] 3.26g of concentrated solution is added to 0.133g of polyolefin sample in 10mm NMR tube. The concentrated solution is a mixture of tetrachloroethane-d2 (TCE) and perchlorethylene (50:50, w:w) with 0.001M Cr3+. The solution in the tube is purged with N2 for 5 minutes to reduce the amount of oxygen. The capped sample tube is left at room temperature overnight to swell the polymer sample. The sample is dissolved at 110oC with stirring. The samples are free from additives that may contribute to unsaturation, such as glidants such as erucamide.
[142] The 1H NMR is conducted with a 10mm cryoprobe at 120oC on the Bruker AVANCE 400 MHz spectrometer.
[143] Two experiments are performed to obtain unsaturation: the double pre-saturation control experiments.
[144] For the control experiment, data is processed with the exponential window function with LB=1 Hz, and baseline corrected from 7 to -2 ppm. The TCE residual 1H signal is set to 100, the Itotal integral from -0.5 to 3ppm is used as the total polymer signal in the control experiment. The number of CH2 group in the polymer is calculated as follows: NCH2 = Itotal/2
[145] For the double presaturation experiment, data is processed with the exponential window function with LB=1 Hz, baseline corrected from 6.6 to 4.5 ppm. The TCE residual 1H signal is set to 100, the corresponding integrals for unsaturation (Ivinylidene, Ytrisubstituted, Ivinyl and Ivinylidene were integrated based on the region shown in Figure 21. The unsaturation unit number for vinylene, trisubstituted, vinyl is calculated. and vinylidene: Nvinylene=Ivinylene/2 Ntrisubstituted=Itrisubstituted Nvinyl=Ivinyl/2 Nvinylidene=Ivinylidene/2
[146] The unsaturation unit/1,000,000 carbons is calculated as follows: Nvinylene /1,000,000C = (Nvi nylene /NCH2)*1,000,000 Ntrisubstituted/1,000,000C = (Ntrisubstituted/NCH2)*1,000,000 Nvinyl / 1,000,000C = (Nvinylidene/NCH2)*1,000,000 Nvinylidene/1,000,000C = (Nvinylidene/NCH2)*1,000,000
[147] The requirement for NMR analysis of unsaturation includes: quantitation level of 0.47 ± 0.02/1,000,000 carbons to Vd2 with 200 scans (data acquisition in less than 1 hour including time to run the experiment control) with 3.9% by weight of sample (for Vd2 structure, see Macromolecules, vol.38, 6988, 2005), 10mm high temperature cryoprobe. The quantization level is defined as the signal-to-noise ratio of 10.
[148] The chemical shift reference is set at 6.0 ppm for the 1H residual proton signal of TCT-d2. Control is conducted with pulse ZG, TD 32768, NS4, DS 12, SWH 10,000 Hz, AQ 1.64s, D1 14s. The dual presaturation experiment is conducted with a modified pulse sequence, 01P 1.354 ppm, O2P, 0.960 ppm, PL9 57 db, PL21 70 db, TD 32768, NS 200, DS 4, SWH 10,000 Hz, AQ 1.64s , D1 s1, D13 13s. Pulse sequences modified for unsaturation with Bruker AVANCE 400 MHz spectrometer are shown in Figure 22. Hot tack
[149] Film heat setting measurements are performed using commercial Enepay testing machines in accordance with ASTM F-1921 (Method B). Prior to testing, samples are conditioned for at least 40 hours at 23oC and 50% relative humidity in accordance with ASTM D-618 (Procedure A). The hot set test simulates filling the material into a pouch or bag before the seal has a chance to cool completely.
[150] Sheets in the dimensions of 8.5" by 14" are cut from the film, with the longest dimension in the machine direction. Strips 1" wide and 14" long are cut from the film [samples need only be long enough to hold]. Tests are conducted on these samples over a range of temperatures and the results reported as the maximum load as a function of temperature. Typical temperature steps are 5oC or 10oC with 6 replicates run at each temperature. The parameters used in the test are as follows:
[151] Test specimen width: 25.4 mm (1.0") - Sealing pressure: 0.275 N/mm2 - Sealing exposure time: 0.5s - Delay time: 0.1s - Peeling speed : 200mms/s
[152] Enepay machines do 0.5" seals. Data is reported as a hot set curve where the Average Hot Set Force (N) is plotted as a function of temperature, as shown in Figure 23. The temperature The hot setting initiation temperature is the temperature required to achieve a preset Minimum Hot Set Strength. This strength is typically in the 1-2N range, but varies depending on the specific application. The final hot setting strength is the peak on the hot set curve. The Hot Set Range is the temperature range in which the seal resistance exceeds the Minimum Hot Set Strength.
[153] Thermal seal measurements on the film are conducted on a commercial tensile testing machine in accordance with ASTM F-88 (Technique A). The heat seal test is a gauge of the strength of seals (seal strength) in flexible barrier materials. This is done by measuring the force required to separate a strip of test material containing the seal and identifying the specimen's failure mode. Sealing strength is relevant in relation to opening strength and package integrity.
[154] Prior to cutting, films are conditioned for a minimum of 40 hours at 23oC (±2oC) and 50% (±5%) relative humidity in accordance with ASTM D-618 (procedure A). The sheets are then cut from the film in the machine direction to a length of approximately 11" and a width of approximately 8.5". The sheets are thermally sealed in the machine direction on a Kopp Heat Sealer in a temperature range under the following conditions:
[155] Sealing pressure: 0.275 N/mm2 - Sealing exposure time: 0.5s
[156] The temperature range is approximately given by the Hot Set Range (ie the temperature range in which at least a minimum hot set seal is obtained and before the firing temperature).
[157] Sealed sheets are conditioned for a minimum of 3 hours at 23oC (±2oC) and 50% (±5%) relative humidity before cutting into 1" wide strips. These strips are then conditioned for a minimum of 24 hours at 23oC (±2oC) and 50% (±5%) relative humidity before testing.
[158] For testing, the strips are placed in the grips of a tensile testing machine with an initial separation of 2" mm and pulled at a grip separation rate of 10 inches/min at 23oC (±2oC) and 50 % (±5%) relative humidity Strips are tested unsupported Six test replicates are conducted for each sealing temperature.
[159] Data are reported as maximum force at failure, average peel force (as shown in Figure 24), and failure mode.
[160] The present invention may be embodied in other ways without departing from the spirit and essential attributes thereof, and, consequently, reference should be made to the attached claims, in place of the aforementioned report, as indicative of the scope of the invention.

权利要求:
Claims (15)
[0001]
1. Sealing composition, characterized in that it comprises: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on the total weight of the sealing composition, said composition of ethylene/α-olefin interpolymer comprises an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in a range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, said propylene/α-olefin interpolymer composition comprising a copolymer of propylene/α-olefin or a propylene/ethylene/butene terpolymer, said propylene/α-olefin copolymer having a crystallinity in the range of 1 weight percent to 30 weight percent, a heat of fusion in the range from 2 Joules/g to 50 Joules/g and a DSC melting point in the range of 25oC to 110oC.
[0002]
2. Method for producing a sealant composition, characterized in that it comprises the steps of: - selecting an ethylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, said ethylene/α interpolymer composition -olefin comprises an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/ cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; and - selecting a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer or a propylene/ethylene/butene terpolymer, wherein said copolymer of propylene/α-olefin has a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/g to 50 Joules/gram, and a DSC melting point in the range of 25oC to 110oC; - mixing said ethylene/α-olefin interpolymer composition and said propylene/α-olefin interpolymer composition; thereby forming a sealant composition comprising from 70 to 99.5 percent by weight of said ethylene/α-olefin interpolymer composition and from 0.5 to 30 percent by weight of said propylene/α-olefin interpolymer composition.
[0003]
3. Sealing layer, characterized in that it comprises a sealing composition comprising: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on the total weight of the sealing composition, being that said ethylene/α-olefin interpolymer composition comprises an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches ( LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer or a terpolymer of propylene/ethylene/butene, said propylene/α-olefin copolymer having a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/g to 50 Joules/g , and a DSC melting point in the range of 25oC to 110oC.
[0004]
4. An article, characterized in that it comprises: (a) at least one sealing layer comprising a sealing composition comprising: (b) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC ) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0.02 to 3 long chain branches (LCB) per 1000C; and (c) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer or a terpolymer of propylene/ethylene/butene, said propylene/α-olefin copolymer having a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/gram to 50 Joules/ gram and a DSC melting point in the range of 25oC to 110oC; and - at least one substrate layer.
[0005]
5. Method for forming an article, characterized in that it comprises the steps of: - selecting a sealant composition comprising: (a) from 70 to 99.5 percent by weight of an ethylene/α-olefin interpolymer composition, with based on the total weight of the sealant composition, said ethylene/α-olefin interpolymer composition comprising an ethylene/α-olefin interpolymer, the ethylene/α-olefin interpolymer having a Comonomer Distribution Constant (CDC) in the range of 15 to 250, and a density in the range of 0.875 to 0.963 g/cm3, a melt index (I2) in the range of 0.2 to 20g/10 minutes, and long chain branching frequency in the range of 0 .02 to 3 long chain branches (LCB) per 1000C; and (b) from 0.5 to 30 percent by weight of a propylene/α-olefin interpolymer composition, said propylene/α-olefin interpolymer composition comprising a propylene/α-olefin copolymer or a terpolymer of propylene/ethylene/butene, said propylene/α-olefin copolymer having a crystallinity in the range of 1 percent by weight to 30 percent by weight, a heat of fusion in the range of 2 Joules/gram to 50 Joules/ gram, and a DSC melting point in the range of 25oC to 110oC; - select at least one substrate layer; - applying said sealing composition to at least one surface of said at least one substrate layer; - thus forming at least one sealing layer associated with at least one surface of said at least one substrate layer.
[0006]
6. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to the respective independent claims 1, 2, 3, 4 or 5, characterized in that the ethylene/α interpolymer -olefin comprises less than 120 units of total unsaturation/1,000,000C.
[0007]
7. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to each respective independent claim 1, 2, 3, 4 or 5 or claim 6, characterized in that a said sealing composition having a heat seal resistance measured in pounds/strength in a three-layer film structure equal to or greater than [((0.7053(T))-(47.521)], where T is the heat seal temperature in the range 68 to 74oC, where the heat seal resistance is measured using a W Kopp heat seal instrument at a temperature in the range of 68oC to 74oC.
[0008]
8. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to each respective independent claim 1, 2, 3, 4 or 5 or claim 6, characterized in that a said sealant composition having a heat seal resistance measured in pounds/strength in a three-layer film structure equal to or greater than [((0.6322(T))-(41.0429)], where T is the heat seal temperature in the range of 65 to 72oC, where the heat seal resistance is measured using the W Kopp heat seal instrument at a temperature in the range of 65oC to 72oC.
[0009]
9. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 8, characterized in that said sealing composition having a resistance to hot setting force (N of force) in a three-layer film structure equal to or greater than [((-4,1540)(10-6)(T4))+((1.2797) )(10-3)(T3))- ((1.4144)(10-1)(T2))+((6.7463)(T))-117.390], where T is the temperature of the grip test at hot temperature in oC in the range of 50 to 105oC, and the hot setting resistance is measured using an Enepay instrument at a temperature in the range of 50 to 105oC.
[0010]
10. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 9, characterized in that said ethylene/α-olefin interpolymer having a zero shear viscosity ratio (ZSVR) in the range of greater than 2.1 to 7.0.
[0011]
11. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 10, characterized in that said ethylene/α-olefin interpolymer having a trisubstituted unsaturation in the range of less than 20 units/1,000,000C.
[0012]
A sealing composition, method of making a sealing composition, sealing layer, article or method of forming an article, according to each respective independent claim 1, 2, 3, 4 or 5 or any one of claims 6 to 11, characterized in that said ethylene/α-olefin interpolymer has a vinylene unsaturation in the range of less than 20 units/1,000,000C.
[0013]
13. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 12, characterized in that said ethylene/α-olefin interpolymer having a molecular weight distribution (Mw/Mn) in the range of 2.0 to 5.0.
[0014]
14. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 13, characterized in that said ethylene/α-olefin interpolymer having a melt flow ratio (I10/I2) in the range of 5 to 15.
[0015]
15. Sealing composition, method of producing a sealing composition, sealing layer, article or method of forming an article, according to any one of claims 1, 2, 3, 4 or 5 or 6 to 14, characterized in that said ethylene/α-olefin interpolymer having a crystallinity in the range of less than 80 percent as measured by DSC.

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法律状态:
2020-10-20| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-10-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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US40938910P| true| 2010-11-02|2010-11-02|

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US61/409,389|2010-11-02|

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PCT/US2011/057780|WO2012061168A1|2010-11-02|2011-10-26|A sealant composition, method of producing the same|

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