• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    POLYOLEFIN COMPOSITION SUITABLE FOR PACKAGING, FILM, SHEET AND PACKAGING DEVICE APPLICATIONS The present invention provides a polyolefin composition suitable for applications in packaging, film, multilayer structures and packaging devices made therefrom. The polyolefin composition according to the present invention comprises: an ethylene/(Alpha)-olefin interpolymer composition comprising (a) from 50 to 75 weight percent of a first ethylene/(Alpha)-olefin copolymer fraction having a density in the range of 0.894 to 0.908 g/cm3, a melt index (I2) in the range of 0.2 to 1 g/10 min, and (b) from 25 to 50 percent by weight of a second fraction of ethylene/(Alpha)-olefin copolymer, said ethylene/(Alpha)-olefin interpolymer composition having a density in the range of 0.910 to 0.924 g/cm3, a melt index (I2) in the range of 0. 5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR) in the range of 1.15 to 2.5, a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight ( Mw/Mn) in the range of 2.0 to 4.0, and tg ? (delta) at 0.1 radian/second and 190°C in the range of 6 to 43.
    公开号:BR112015015172B1
    申请号:R112015015172-8
    申请日:2013-12-27
    公开日:2021-04-20
    发明作者:Mehmet Demirors；David T. Gillespie；Mridula Kapur；Pradeep Jain；Philip Fontaine；Douglas S. Ginger；Mustafa Bilgen
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    field of invention
    [0001] The present invention relates to a polyolefin composition suitable for packaging applications, and a method to produce the same. Invention history
    [0002] In general, it is known to use polyolefin compositions in packaging applications. To produce such polyolefin compositions, any conventional method can be employed.
    [0003] To produce such polyolefin compositions suitable for packaging applications, various polymerization techniques using different catalytic systems have been employed.
    [0004] Despite research efforts in the development of compositions suitable for packaging applications, there is still a need for compositions suitable for packaging applications having a good balance of processability as well as improved mechanical properties. Additionally, there is a need for a method to produce such compositions suitable for packaging applications having a good balance of processability as well as improved mechanical properties. Invention Summary
    [0005] The present invention provides a polyolefin composition suitable for applications in packaging, film, multilayer structures and packaging devices made with the same.
    [0006] In one embodiment, the present invention provides a polyolefin composition suitable for packaging applications comprising: an ethylene/α-olefin interpolymer composition comprising (a) from 50 to 75 weight percent of a first copolymer fraction of ethylene/α-olefin having a density in the range of 0.894 to 0.908 g/cm3, a melt index (I2) in the range of 0.2 to 1 g/10 min, and (b) of 25 to 50 percent by weight of a second ethylene/α-olefin copolymer fraction, said ethylene/α-olefin interpolymer composition having a density in the range of 0.910 to 0.924 g/cm3, a melt index (I2) in the range of 0 .5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR) in the range of 1.15 to 2.5, a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) in the range of 2.0 to 4.0, and tg δ (delta) in 0.1 radian/second and 190°C in the range of 6 to 43, with said composition of i The ethylene/α-olefin interpolymer has at least 2 peaks in the elution profile via the crystallization elution fractionation (CEF) procedure, each peak comprising at least 25 percent by weight of the total area of the elution profile, wherein the separation of the 2 peak positions are in the range of 20 to 40°C, with a larger elution temperature peak being at an elution temperature greater than 90°C, and a smaller elution temperature peak being at a temperature of elution in the range of 50 to 80°C, and where the elution temperature peak width greater by 10 percent of peak height is less than 9°C, and the elution temperature peak width being smaller by 50 percent peak height is less than 8°C, and the elution temperature peak width is less than 10 percent peak height is less than 25°C. Brief description of the figures
    [0007] For the purpose of illustrating the invention, an exemplary form is shown in the drawings; however, it is understood that this invention is not limited to the precise arrangements and instruments shown.
    [0008] Figure 1 illustrates the elution profile via fractionation elution with crystallization (CEF) procedure for Inventive Example 1, Comparative Example 1 and Comparative Example 2. Detailed description of the invention
    [0009] The present invention provides a polyolefin composition suitable for applications in packaging, film, multilayer structures and packaging devices made with the same.
    In one embodiment, the present invention provides a polyolefin composition suitable for packaging applications comprising: an ethylene/α-olefin interpolymer composition comprising (a) from 50 to 75 weight percent of a first copolymer fraction of ethylene/α-olefin having a density in the range of 0.894 to 0.908 g/cm3, a melt index (I2) in the range of 0.2 to 1 g/10 min, and (b) of 25 to 50 percent by weight of a second ethylene/α-olefin copolymer fraction, said ethylene/α-olefin interpolymer composition having a density in the range of 0.910 to 0.924 g/cm3, a melt index (I2) in the range of 0 .5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR) in the range of 1.15 to 2.5, a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) in the range of 2.0 to 4.0, and tg δ (delta) in 0.1 radian/second and 190°C in the range of 6 to 43, with said composition of i The ethylene/α-olefin interpolymer has at least 2 peaks in the elution profile via the crystallization elution fractionation (CEF) procedure, each peak comprising at least 25 percent by weight of the total area of the elution profile, wherein the separation of the 2 peak positions are in the range of 20 to 40°C, with a larger elution temperature peak being at an elution temperature greater than 90°C, and a smaller elution temperature peak being at a temperature of elution in the range of 50 to 80°C, and where the elution temperature peak width greater by 10 percent of peak height is less than 9°C, and the elution temperature peak width being smaller by 50 percent peak height is less than 8°C, and the elution temperature peak width is less than 10 percent peak height is less than 25°C.
    The polyolefin composition may comprise further components such as one or more other polymers. For example, the polyolefin composition can further comprise one or more ethylene polymers, or one or more propylene-based polymers, or combinations thereof.
    [0012] In one embodiment, one or more ethylene/α-olefin interpolymer compositions and one or more propylene/α-olefin interpolymer compositions described herein may be mixed via any method known to a person of ordinary skill in the art including, but not limited to, dry mixing, and melt mixing via any suitable equipment, for example, an extruder, to produce the inventive packaging composition.
    [0013] The polyolefin composition may further comprise additional components such as one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleants, processing aids, pigments, tackifiers, flame retardants, antimicrobial agents, agents odor reducers, fungicides, and combinations thereof. The polyolefin composition can contain from about 0.01 to about 10 percent of the combined weight of such additives, based on the weight of the ethylene-based polymer composition including such additives. Ethylene/α-olefin interpolymer composition
    [0014] The ethylene/α-olefin interpolymer composition comprises (a) from 50 to 75 percent by weight of a first ethylene/α-olefin copolymer fraction having a density in the range of 0.894 to 0.908 g/cm3, a melt index (I2) in the range of from 0.2 to 1 g/10 min, and (b) from 25 to 50 percent by weight of a second ethylene/α-olefin copolymer fraction, said composition of ethylene/α-olefin interpolymer has a density in the range of 0.910 to 0.924 g/cm3, a melt index (I2) in the range of 0.5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR ) in the range of 1.15 to 2.5, a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) in the range of 2.0 to 4.0, and tg δ (delta) at 0.1 radian/second and 190°C in the range of 6 to 43, with said ethylene/α-olefin interpolymer composition having at least 2 peaks in the elution profile via the elution fractionation procedure crystallized action (CEF), with each peak comprising at least 25 percent by weight of the total area of the elution profile, and the separation of the 2 peak positions are in the range of 20 to 40°C, with a peak temperature of The largest elution is at an elution temperature greater than 90°C, and a smaller elution temperature peak is at an elution temperature in the range of 50 to 80°C, and the width of the elution temperature peak is greater in 10 percent peak height is less than 9°C, and where the elution temperature peak width is less than 50 percent peak height is less than 8°C, and where the peak temperature width lower elution at 10 percent peak height is less than 25°C.
    [0015] The ethylene/α-olefin interpolymer composition comprises (a) an amount less than or equal to 100 percent, for example, at least 70 percent, or at least 80 percent, or at least 90 percent of ethylene-derived units; and (b) less than 30 percent, for example, less than 25 percent, or less than 20 percent, or less than 10 percent of units derived from one or more α-olefin comonomers. The term "ethylene/α-olefin interpolymer composition" refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least a comonomer.
    [0016] Typically, α-olefin comonomers have an amount of carbon atoms less than or equal to 20. For example, α-olefin comonomers may preferably have from 3 to 10 carbon atoms, and more preferably from 3 to 8 carbon atoms. Exemplary 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. For example, the one or more α-olefin comonomers can 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.
    [0017] The ethylene/α-olefin interpolymer composition is characterized by having a comonomer distribution constant (CDC) in the range of 50 to 500, for example, from 100 to 450, or from 150 to 450, or from 190 to 450, or from 100 to 400.
    [0018] The ethylene/α-olefin interpolymer composition is characterized by having a zero shear viscosity ratio (ZSVR) in the range of 1.15 to 2.5, for example, from 1.15 to 2.0 , from 1.2 to 2.0, or alternatively from 1.2 to 1.8.
    [0019] The ethylene/α-olefin interpolymer composition is characterized by having a tg δ (delta) at 0.1 radian/second, determined at 190°C, in the range of 6 to 43, for example, 6 to 40, from 6 to 35, from 6 to 30, from 10 to 40, from 10 to 35, or from 10 to 30.
    [0020] The ethylene/α-olefin interpolymer composition has a density of from 0.910 to 0.924 g/cm3, for example, from 0.912 to 0.920 g/cm3. For example, the density can be from a lower limit of 0.910, 0.912, or 0.914 g/cm3 to an upper limit of 0.924, 0.922, or 0.920 g/cm3.
    [0021] The first ethylene/α-olefin copolymer fraction has a density of 0.864 to 0.908 g/cm3, for example 0.896 to 0.906 g/cm3. For example, the density can be from a lower limit of 0.894, 0.896, 0.898, 0.900 g/cm3 to an upper limit of 0.908, 0.906, 0.904, or 0.902 g/cm3.
    [0022] The second ethylene/α-olefin copolymer fraction has a density in the range of 0.940 to 0.955 g/cm3, for example, from 0.943 to 0.953 g/cm3. For example, the density can be from a lower limit of 0.940, 0.943, or 0.945 g/cm3 to an upper limit of 0.955, 0.953, 0.952, or 0.951 g/cm3. The density of the second ethylene/α-olefin copolymer fraction can be approximated based on the density of a polymer prepared in a single reactor under the same polymerization conditions as the second ethylene/α-olefin copolymer fraction in the absence of the first copolymer fraction of ethylene/α-olefin.
    [0023] The ethylene/α-olefin interpolymer composition has a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) in the range of 2.0 to 4.0. For example, the molecular weight distribution (Mw/Mn) can be from a lower limit of 2.0, 2.1, or 2.2 to an upper limit of 2.6, 2.8, 3.0, 3 .5, or 4.0.
    [0024] The first ethylene/α-olefin copolymer fraction has a molecular weight distribution (Mw/Mn) in the range of 1.5 to 3.5, for example, from 2 to 3. For example, the distribution of molecular weight (Mw/Mn) can be from a lower limit of 1.5, 1.7, 2.0, 2.1, or 2.2 to an upper limit of 2.5, 2.6, 2.8 , 3.0, or 3.5.
    [0025] The second ethylene/α-olefin copolymer fraction has a molecular weight distribution (Mw/Mn) in the range of 1.5 to 3.0, for example, from 2 to 3. For example, the distribution of molecular weight (Mw/Mn) can be from a lower limit of 1.5, 1.7, 2.0, 2.1, or 2.2 to an upper limit of 2.5, 2.6, 2.8 , or 3.0.
    [0026] The ethylene/α-olefin interpolymer composition has a melt index (I2) (at 190°C/2.16 kg) in the range of 0.5 to 2.5 g/10 min, for example, 0.5 to 2.0 g/10 min, or 0.5 to 1.5 g/10 min, or 0.5 to 1.0 g/10 min. For example, the melt index (I2) (at 190°C/2.16 kg) can be from a lower limit of 0.5, 0.6, or 0.7 g/10 min to an upper limit of 0 0.9, 1.0, 1.2, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.5 g/10 min.
    [0027] The first ethylene/α-olefin copolymer fraction has a melt index (I2) (at 190°C/2.16 kg) in the range of 0.1 to 0.8 g/10 min, for example , from 0.2 to 0.6 g/10 min, or from 0.3 to 0.5 g/10 min, or from 0.3 to 0.4g/10 min.
    [0028] The ethylene/α-olefin interpolymer composition has vinyl unsaturation less than 0.15, for example, less than 0.1, or less than 0.05 vinyl per thousand carbon atoms present in the main chain of the composition of ethylene-based polymer.
    [0029] The ethylene/α-olefin interpolymer composition has normalized intrinsic Elmendorf breaking strength greater than 375 g/milliinch, for example, greater than 400 g/milliinch or 425 g/milliinch.
    [0030] The ethylene/α-olefin interpolymer composition may further comprise additional components such as one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleants, processing aids, pigments, primary antioxidants, secondary antioxidants, UV stabilizers, nonsticks, slip agents, tackifiers, flame retardants, antimicrobial agents, odor reducing agents, fungicides, and combinations thereof. The ethylene/α-olefin interpolymer composition can contain from about 0.1 to about 10 percent combined by weight of such additives, based on the weight of the ethylene-based polymer composition including such additives.
    [0031] In one embodiment, the ethylene/α-olefin interpolymer composition has at least 2 peaks in the elution profile via the crystallization elution fractionation (CEF) procedure, each peak comprising at least 25 percent by weight of the total area of the elution profile, with the separation of the 2 peak positions being in the range of 20 to 40°C, with a larger elution temperature peak being at an elution temperature greater than 90°C, and with a peak of the lower elution temperature is at an elution temperature in the range of 50 to 80°C, and the width of the elution temperature peak greater by 10 percent of the peak height is less than 9°C, and where the width of the smallest elution temperature peak at 50 percent peak height is less than 8°C, and the width of the smallest elution temperature peak at 10 percent peak height is less than 25°C.
    [0032] To produce the ethylene/α-olefin interpolymer composition any conventional polymerization process can be employed. Such conventional polymerization processes include, but are not limited to, a solution polymerization process, using one or more conventional reactors, e.g., continuous reactors, isothermal reactors, stirred tank reactors, batch reactors in parallel, in series, and /or any combinations thereof.
    [0033] The ethylene/α-olefin interpolymer composition can be produced, for example, via a solution polymerization process using one or more continuous reactors, isothermal reactors, and combinations thereof.
    [0034] In general, the solution polymerization process takes place in one or more well-mixed reactors such as one or more continuous isothermal reactors or one or more adiabatic reactors at a temperature in the range of 115 to 250°C, for example, 115 at 250°C, and at pressures in the range 300 to 1000 psi, eg 400 to 750 psi. In an incorporation in a double reactor, the temperature in the first reactor is in the range of 115 to 190°C, for example, from 115 to 150°C, and the temperature of the second reactor is in the range of 150 to 200°C, for example, from 170 to 195°C. In another embodiment in a single reactor, the temperature in the reactor is in the range of 115-190°C, for example, 115-150°C. Residence time in the solution polymerization process is typically in the range of 2 to 30 minutes, for example 10 to 20 minutes. Ethylene, solvent, hydrogen, one or more catalytic systems, optionally one or more cocatalysts, and optionally, one or more comonomers are continuously fed into one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the trade name ISOPAR E from ExxonMobil Chemical Company, Houston, Texas. Then, the resulting mixture of ethylene/α-olefin interpolymer and solvent is removed from the reactor and the ethylene/α-olefin interpolymer is isolated. Typically, the solvent is recovered via a solvent recovery unit, ie, heat exchangers and liquid-vapour separator drum, and then recycled back to the polymerization system.
    [0035] In one embodiment, the ethylene/α-olefin interpolymer composition can be produced via solution polymerization in a two reactor system, e.g. a two continuous reactor system, in which ethylene and optionally one or more α polymerize. -olefins in the presence of one or more catalytic systems. Additionally, one or more cocatalysts may be present.
    [0036] In another embodiment, ethylene/α-olefin interpolymers can be produced via solution polymerization in a single reactor system, e.g., a single continuous reactor system, in which ethylene and optionally one or more α polymerize. -olefins in the presence of one or more catalytic systems.
    [0037] An exemplary catalytic system suitable for producing the first ethylene/α-olefin interpolymer may be a catalytic system comprising a component procatalyst comprising a binder-metal complex of formula (IA):
    in which: M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; en is an integer from 0 to 3, and when n is 0 (zero), X is absent; and each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs join to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and en are chosen such that the binder-metal complex of formula (IA) is overall neutral; and each Z is independently O, S, N(C1-C40 hydrocarbyl) or P(C1-C40 hydrocarbyl). The ZLZ fragment is comprised of formula (II):
    R1-16 are selected from the group consisting of C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, NN CC CCC(R)2, OR, SR , NO2, CN, CF3, RS(O)-, RS(O)2-, (R)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)- , (RC)2NC(O)-, halogen atom, hydrogen atom, and combinations thereof.
    [0038] Optionally, two or more R groups (from R9-13 or R4-8) can combine into ring structures, with such ring structures having from 3 to 50 ring carbon atoms excluding any hydrogen atoms.
    [0039] Each of the groups aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N(R)-, (RC)2NC(O)-, hydrocarbylene, and heterohydrocarbylene is independently unsubstituted or substituted with one or more RS substituents; and each RS is a halogen atom, polyfluor substitution, perfluor substitution, unsubstituted C1-C18 alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-, RS (O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)-, or R2NC(O)-, or two of the R2 join to form an unsubstituted C1-C18 alkylene group, each R is independently an unsubstituted C1-C18 alkyl group.
    [0040] In one embodiment, the suitable catalytic system for producing the first ethylene/α-olefin interpolymer may be a catalytic system comprising dimethyl bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5 -(methyl)phenyl)-2-phenoxy-methyl)-methylene-1,2-cyclohexanediyl-hafnium (IV), represented by the following formula:

    [0041] An exemplary catalytic system suitable for producing the second ethylene/α-olefin interpolymer may be a catalytic system comprising a component procatalyst comprising a binder-metal complex of formula (IB):
    in which: M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; en is an integer from 0 to 3, and when n is 0 (zero), X is absent; and each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs join to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and en are chosen such that the binder-metal complex of formula (IB) is overall neutral; and each Z is independently O, S, N(C1-C40 hydrocarbyl) or P(C1-C40 hydrocarbyl); and L is C3-C40 hydrocarbylene or C3-C40 heterohydrocarbylene, the C3-C40 hydrocarbylene having a moiety comprising a linker main chain of 3 to 10 carbon atoms connecting the Z atoms in formula (IB) ( to which L is attached) and the C3-C40 heterohydrocarbylene has a moiety comprising a linker main chain of 3 to 10 carbon atoms connecting the Z atoms in formula (IB), each of the 3 to 10 atoms of the C3-C40 heterohydrocarbylene linker backbone is independently a carbon atom or a heteroatom, each heteroatom being independently O, S, S(O), S(O)2, Si(RC)2, Ge (RC)2, P(RP), or N(RN), where each RC is independently C1-C30 hydrocarbyl, each RP is C1-C30 hydrocarbyl, and each RN is C1-C30 hydrocarbyl or absent ; and R1, R16, or both comprise formula (III),
    and, preferably, R1 and R16 are the same; and R1-24 are selected from the group consisting of C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, CC CCCC OR, SR, NO2, CN, CF3, RS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, RCOC(O)-, RCC(O)N(R) -, (RC)2NC(O)-, halogen atom, hydrogen atom, and combinations thereof. When R22 is H, then R19 is C1-C40 hydrocarbyl, C1CC heterohydrocarbyl CPN CC 40, Si(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2 , CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N(R)- , (RC)2NC(O)-, or halogen atom; and when R19 is H, then R22 is C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, SC CPN CC i(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2, CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N( R)-, (RC)2NC(O)-, or halogen atom; and preferably, R22 and R19 are both C1-C40 hydrocarbyl, C1CC heterohydrocarbyl CPN CC 40, Si(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2 , CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N(R)- , (RC)2NC(O)- or halogen atom; and when R8 is H, then R9 is C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, SC CPN CC i(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2, CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N( R)-, (RC)2NC(O)-, or halogen atom; and when R9 is H, then R8 is C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, SC CPN CC i(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2, CN, CF3, R CC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N (R)-, (RC)2NC(O)-, or halogen atom; and preferably R8 and R9 are both C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, SC CPN CC i(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR , NO2, CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C=N-, RC(O)O-, R OC(O)-, RC(O)N(R )-, (RC)2NC(O)-, or halogen atom; and optionally two or more R groups (from R9-13 or R4-8) can combine into ring structures, with such ring structures having from 3 to 50 ring carbon atoms excluding any hydrogen atoms. Each of the groups aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, NN C CC CCC (R)2, OR, SR, RS(O)-, RS (O)2-, (R)2C=N-, RC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, hydrocarbylene, and heterohydrocarbylene is independently unsubstituted or substituted with one or more RS substituents; and each RS is a halogen atom, polyfluor substitution, perfluor substitution, unsubstituted C1-C18 alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-, RS (O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)-, or R2NC(O)-, or two of the R2 join to form an unsubstituted C1C18 alkylene group, each R is independently an unsubstituted C1-C18 alkyl group. Optionally two or more R groups (from R20-24) can combine into ring structures, with such ring structures having from 3 to 50 ring atoms excluding any hydrogen atoms.
    [0042] In one embodiment, the catalytic system suitable for producing the second ethylene/α-olefin interpolymer may be a second catalytic system comprising dimethyl ((3-(2,7-ditertiobutyl-9H-carbazol-9-yl)-2 '-(3-((3'-(2,7-ditertiobutyl-9H-carbazol-9-yl)-5-fluoro-2'-hydroxy-3-methyl-5'-(2,4,4-trimethyl) -pentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2 - yl)-[1,1'-biphenyl]-2-yl)oxy)hafnium (IV), represented by the following formula:
    component cocatalyst
    [0043] The catalytic systems described above can be made catalytically active by contacting or combining them with an activating cocatalyst or using an activation technique such as those known in the art for use with metal-based olefin polymerization reactions. Suitable activating cocatalysts for use herein include alkyl aluminum compounds, polymeric or oligomeric aluminoxanes (also known as alumoxanes), neutral Lewis acids, and non-coordinating, non-polymeric ion-forming compounds (including the use of such compounds under oxidizing conditions) . A proper activation technique is bulk electrolysis. Combinations of one or more of the prior art and activation catalysts are also contemplated. The term "alkyl aluminum" means a monoalkyl aluminum dihydride or monoalkyl aluminum dihalide, a dialkyl aluminum hydride or a dialkyl aluminum halide, or a trialkyl aluminum. Aluminoxanes and their preparations are disclosed, for example, in U.S. Patent No. 6,103,657. Examples of preferred polymeric or oligomeric aluminoxanes are: methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.
    Exemplary Lewis acid activating cocatalysts are compounds of Group 13 metals containing 1 to 3 hydrocarbyl substituents as described herein. In some embodiments, they are composed of exemplary Group 13 metals: aluminum compounds substituted by tri(hydrocarbyl), or tri(hydrocarbyl) boron. In some other embodiments, exemplary tri(hydrocarbyl), or tri(hydrocarbyl)-boron aluminum compounds are: tri(C1-C10 alkyl)aluminum or tri(C6-C18 alkyl)boron compounds and halogenated derivatives (including perhalogenates) thereof. In some other embodiments, exemplary Group 13 metal compounds are tris(phenyl substituted with fluoro)boranes, in other embodiments, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is a C1-C20 hydrocarbyl borate (eg, trityl tetrafluoroborate) or a tri(C1-C20 hydrocarbyl)ammonium tetra(C1-C20 hydrocarbyl) borane (eg, bis(octadecyl)methyl aluminum tetrakis(pentafluorophenyl)borane). When used herein, the term "ammonium" means a nitrogen cation that is one (hydrocarbyl of C1-C20)4N+, one (hydrocarbyl of C1-C20)3N(H)+, one (hydrocarbyl of C1-C20)2N( H)2+, a (C1-C20 hydrocarbyl)N(H)3+, or N(H)4+, with each C1-C20 hydrocarbyl being the same or different.
    [0045] Exemplary combinations of neutral Lewis acid activating cocatalysts include mixtures comprising a combination of a tri(C1-C4 alkyl) aluminum and a tri(C6-C18 aryl) boron, especially a tris(pentafluor-phenyl)borane . Other exemplary embodiments are combinations of such mixtures of neutral Lewis acids with a polymeric or oligomeric aluminoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluor-phenyl)borane, with a polymeric or oligomeric aluminoxane. Exemplary incorporations of mole numbers of (binder-metal complex):(tris(pentafluor-phenyl-borane):(aluminoxane) [eg, (binder-metal complex of Group 4): (tris(pentafluor-phenyl-) borane):(aluminoxane)] are from 1:1:1 to 1:10:30; other embodiments are from 1:1:1.5 to 1:5:10.
    [0046] Many activating cocatalysts and activation techniques have been previously taught with respect to different ligand-metal complexes in the following US Patent Nos: 5,064,802, 5,153,157, 5,296,433, 5,321,106, 5,350,723, 5,425,872, 5,625,087, 5,721,185, 5,783,512, 5,883,204, 5,919,983, 6,696,379, and 7,163,907. Examples of suitable hydrocarbyloxides are disclosed in U.S. Patent No. 5,296,433. Examples of suitable Bronsted acid salts for addition polymerization catalysts are disclosed in U.S. Patent Nos. 5,064,802, 5,919,983, and 5,783,512. Examples of suitable salts of a cationic oxidizing agent and a compatible, non-coordinating anion as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent No. 5,321,106. Examples of carbene salts suitable as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent No. 5,350,723. Examples of silyl salts suitable as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent No. 5,625,087. Examples of suitable complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are disclosed in U.S. Patent No. 5,296,433. Some of these catalysts are also described in an excerpt of US 6,515,155 B1 beginning at column 50, line 39 to column 56, line 55, only this section of which is incorporated herein by reference.
    [0047] In some embodiments, the catalytic systems described above can be activated to form an active catalytic composition by combination with one or more cocatalysts such as 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, inert, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluor-phenyl)borate(1-)amine (RIBS-2), triethyl aluminum (TEA) , and any combinations thereof.
    [0048] In some embodiments, one or more of the above activating cocatalysts are used in combination with each other. An especially preferred combination is a mixture of an aluminum tri(C 1 -C 4 hydrocarbyl), tri(C 1 -C 4 hydrocarbyl) borane, or an ammonium borate with a polymeric or oligomeric aluminoxane. End-use applications of polyolefin composition
    [0049] The polyolefin compositions according to the present invention can be used in any food, consumer and industrial packaging applications such as construction film, heavy duty transport bags, protective film, agricultural and waste management films, which require high film dart properties, perforation and/or tear strength.
    Polyolefin compositions according to the present invention can be molded into a film, sheet, or multilayer structure. Typically, such multilayer structures comprise one or more layers or sheets of films comprising the inventive polyolefin compositions. The multilayer structure can further comprise one or more layers comprising one or more polyamides, one or more polyesters, one or more polyolefins, and combinations thereof.
    [0051] The inventive polyolefin compositions according to the present invention are characterized by two or more of the following: (a) having an A dart impact of at least 1000 g, measured according to ASTM D1709, when said polyolefin composition is cast in a one-layer expanded film having a thickness of 1 milliinch; (b) having a dart B impact of at least 400 g, measured in accordance with ASTM D1709, when said polyolefin composition is cast into a one-layer expanded film having a thickness of 1 milliinch; and/or (c) have an Elmendorf standard breaking strength in the machine direction of at least 250 g/milliinch, measured in accordance with ASTM D1922, when said polyolefin composition is cast into an expanded one-layer film having a thickness of 1 milliinch.
    [0052] The polyolefin composition according to the present invention may further comprise from 5 to 20 percent by weight of low density polyethylene (LDPE), and in which the dart A impact is greater than 275 g, preferably greater than 300 g measured in accordance with ASTM D1709, when said polyolefin composition is cast into a one-layer expanded film having a thickness of 1 milliinch. Examples
    [0053] The following examples illustrate the present invention, but are not intended to limit the scope of the invention. Inventive Polyolefin Composition 1
    [0054] The inventive polyolefin composition 1 (IPC-1) comprises an ethylene/octene interpolymer having a density of approximately 0.919 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0.96 g/10 min, a melt flow ratio (I10/I2) of approximately 6.3. Additional properties of IPC-1 were measured, and they are reported in Table 2.
    [0055] IPC-1 was prepared via solution polymerization in a system of two continuous reactors in the presence of a first catalytic system, described below, in the first reactor and a second catalytic system, described below, in the second reactor.
    [0056] The first catalytic system comprises dimethyl bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy-methyl)-methylene-1,2 -cyclohexanediylhafnium (IV), represented by the following formula:

    [0057] The second catalytic system comprises dimethyl ((3-(2,7-ditertiobutyl-9H-carbazol-9-yl)-2'-(3-((3'-(2,7-ditertiobutyl-9H-carbazole) -9-yl) -5-fluoro-2'-hydroxy-3-methyl-5'-(2,4,4-trimethyl-pentan-2-yl) -[1,1'-biphenyl]-2-yl )oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)hafnium (IV), represented by the following formula:

    [0058] The polymerization conditions for IPC-1 are reported in Table 1. Referring to Table 1, MMAO is modified methyl aluminoxane, and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluor-phenyl) borate (1-)amine, used as cocatalysts. Inventive Polyolefin Composition 2
    [0059] The inventive polyolefin composition 2 (IPC-2) comprises an ethylene/octene interpolymer having a density of approximately 0.918 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0.74 g/10 min, a melt flow ratio (I10/I2) of approximately 6.1. Additional properties of IPC-2 were measured, and they are reported in Table 2.
    [0060] IPC-2 was prepared via solution polymerization in a system of two continuous reactors in the presence of a first catalytic system, described below, in the first reactor and a second catalytic system, described below, in the second reactor.
    [0061] The first catalytic system comprises dimethyl bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy-methyl)-methylene-1,2 -cyclohexanediylhafnium (IV), represented by the following formula:

    [0062] The second catalytic system comprises dimethyl ((3-(2,7-ditertiobutyl-9H-carbazol-9-yl)-2'-(3-((3'-(2,7-ditertiobutyl-9H-carbazole) -9-yl) -5-fluoro-2'-hydroxy-3-methyl-5'-(2,4,4-trimethyl-pentan-2-yl) -[1,1'-biphenyl]-2-yl )oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)hafnium (IV), represented by the following formula:

    [0063] The polymerization conditions for IPC-1 are reported in Table 1. Referring to Table 1, MMAO is modified methyl aluminoxane, and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluor-phenyl) borate (1-)amine, used as cocatalysts. Inventive polyolefin composition 3
    [0064] The inventive polyolefin composition 3 (IPC-3) comprises an ethylene/octene interpolymer having a density of approximately 0.918 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0.68 g/10 min, a melt flow ratio (I10/I2) of approximately 6.8. Additional properties of IPC-2 were measured, and they are reported in Table 2.
    [0065] IPC-3 was prepared via solution polymerization in a system of two continuous reactors in the presence of a first catalytic system, described below, in the first reactor and a second catalytic system, described below, in the second reactor.
    [0066] The first catalytic system comprises dimethyl bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy-methyl)-methylene-1,2 -cyclohexanediylhafnium (IV), represented by the following formula:

    [0067] The second catalytic system comprises dimethyl ((3-(2,7-ditertiobutyl-9H-carbazol-9-yl)-2'-(3-((3'-(2,7-ditertiobutyl-9H-carbazole) -9-yl) -5-fluoro-2'-hydroxy-3-methyl-5'-(2,4,4-trimethyl-pentan-2-yl) -[1,1'-biphenyl]-2-yl )oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)hafnium (IV), represented by the following formula:

    [0068] The polymerization conditions for IPC-1 are reported in Table 1. Referring to Table 1, MMAO is modified methyl aluminoxane, and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluor-phenyl) borate (1-)amine, used as cocatalysts. Comparative polyolefin composition 1
    [0069] Comparative polyolefin composition 1 (CPC-1) comprises an ethylene/octene interpolymer having a density of approximately 0.917 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0.9 g/10 min, a melt flow ratio (I10/I2) of approximately 8.4. Additional properties of CPC-1 are reported in Table 2. CPC-1 was prepared via solution polymerization in a continuous two reactor system. Comparative polyolefin composition 2
    [0070] Comparative polyolefin composition 2 (CPC-2) comprises an ethylene/hexene interpolymer having a density of approximately 0.919 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0.94 g/10 min, a melt flow ratio (I10/I2) of approximately 5.6. Additional properties of CPC-1 are reported in Table 2. CPC-2 was prepared via gas phase polymerization in a single fluidized bed reactor system. Table 1



    1N.D.= not determined Note: Among unsaturation species values determined by 1H NMR, cells marked as “not detected” mean that unsaturation was not detected at a detection limit of 0.001/1000 carbons. Expanded one-layer films
    Expanded one-layer films were produced from inventive polyolefin compositions 1-3 and comparative polyolefin compositions 1-2, in one-layer films 1-3 (IMF 1-3) and comparative one-layer films 1 -2 (CMF 1-2), respectively, via a standard Egan Davis extruder, equipped with a 3.5 inch inner diameter semi-grooved barrel and 30/1 L/D ratio, a barrier spindle, and a ring of Alpine air. The extrusion line has an 8 inch die with internal bubble cooling. The extrusion line also has a film thickness gauge analyzer. The manufacturing conditions were: film thickness maintained at 0.0254 mm (1 milliinch); explosion ratio (BUR) 2.5; 90 milli-inch array span; and 30-inch freezing line height (FLH). Additional film fabrication conditions are given in Table 3. Additional film properties are reported in Table 5. Table 3
    Expanded one-layer films
    Expanded one-layer films were produced from inventive polyolefin compositions 1-3 and comparative polyolefin compositions 1-2, which are further blended with low density polyethylene (LDPE), into one-layer films 1a-3a (IMF 1a-3a) and comparative single layer films 1a-2a (CMF 1a-2a), respectively, via a standard Egan Davis extruder, equipped with a semi-grooved drum with a 3.5 inch inner diameter and L/D ratio 30/1, a barrier spindle, and an Alpine air ring. The extrusion line has an 8 inch die with internal bubble cooling. The extrusion line also has a film thickness gauge analyzer. The manufacturing conditions were: film thickness maintained at 0.0254 mm (1 milliinch); explosion ratio (BUR) 2.5; 90 milli-inch array span; and 30-inch freezing line height (FLH). Additional film fabrication conditions are given in Table 4. LDPE comprised 20 percent of the total composition. LDPE had a melt index (I 2 ) of 2 g/10 min, and density of 0.919 g/cm 3 . Additional film properties are reported in Table 6. Table 4
    Table 5
    MD= machine direction Table 6
    MD= machine direction Co-extruded multilayer films
    [0073] Co-extruded multi-layer expanded films were fabricated on a Hosokawa Alpine 7-layer expanded film extrusion machine based on the formulation components reported in Table 7. This extrusion machine consists of seven semi-grooved feed extruders from Hosokawa. 50mm, 30:1 L/D using barrier spindles and a 7.87 inch coextrusion die. The matrix is equipped with internal bubble cooling.
    [0074] The manufacturing conditions were: film thickness maintained at 4.5 milliinch; explosion ratio (BUR) 1.71; 78.7 milli-inch array span; and 35-inch freezing line height (FLH). Additional film manufacturing conditions are given in Table 8. The coextruded multilayer film properties are reported in Table 9. The properties of bags manufactured with the coextruded multilayer films are reported in Table 10. Table 7
    LLDPE= linear low density polyethylene= inventive or comparative resin. LDPE=low density polyethylene having I2 melt index of 0.25 g/10 min, and density of 0.920 g/cm3. HDPE=high density polyethylene having I2 melt index of 0.8 g/10 min, and density of 0.961 g/cm3. Table 8

    [0075] The physical properties of the coextruded multilayer films manufactured with the comparative and inventive samples are reported in Table 9. Table 9
    MD=machine direction
    Bags with a holding capacity of fifty pounds were made with the inventive coextruded multilayer film and with the comparative resin film. The bags were loaded, sealed and subjected to the bag drop test. The results of the drop test are reported in Table 10. Table 10
    Test Methods
    [0077] Test methods include the following: Density
    To measure density, samples were prepared in accordance with ASTM D4703. Density measurements were carried out within one hour after pressing the sample, using method B of ASTN D792. fusion index
    [0079] The melt index (I2) is measured according to ASTM D1238, Condition 190°C/2.16 kg, and the result is reported in grams eluted over 10 minutes. The melt flow rate (I10) is measured in accordance with ASTM D-1238, Condition 190°C/10 kg, and the result is reported in grams eluted over 10 minutes. Differential Scanning Calorimetry (DSC)
    [0080] Differential scanning calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, the model Q1000 DSC from TA Instruments equipped with an RSC (Refrigerated Cooling System) and an autosampler module to perform this analysis. During testing, a nitrogen purge gas flow of 50 mL/min is used. Each sample is compressed melted into a thin film at about 175°C; the molten sample is then air cooled to room temperature (~25°C). A 3-10 mg sample of the cooled material is cut into a 6 mm diameter disk, weighed, placed in a lightweight aluminum pan (approximately 50 mg), and crimped shut. Then, the analysis is performed to determine its thermal properties.
    [0081] The thermal behavior of the sample is determined by changing the temperature of the sample up and down to create a heat flux versus temperature profile. First, the sample is rapidly heated to 180°C and held in an isothermal state for 3 minutes to remove any previous thermal history. The sample is then cooled to -40°C at a cooling rate of 10°C/min and held at -40°C for 3 minutes. The sample is then heated to 150°C (this is the “second heat” ramp) at a heating rate of 10°C/min. The cooling and second heating curves are recorded. The cooling curve is analyzed by adjusting baseline extreme points from the start of crystallization at -20°C. The heating curve is analyzed by adjusting baseline endpoints from -20°C to the end of melting. The values determined are the maximum melting temperature (Tm), the maximum crystallization temperature (Tc), the melting heat (Hf) (in J/g), and the crystallization heat (in J/g).
    [0082] The heat of fusion (Hf) and the maximum fusion temperature are reported from the second heating curve. The maximum crystallization temperature and the crystallization heat are determined from the cooling curve. Dynamic-mechanical spectroscopy (DMS) frequency scanning
    [0083] The samples were compression molded in circular plates 25 mm in diameter by 3 mm thick at 177°C for 5 minutes at a pressure of 10 MPa in air. Afterwards, the sample was removed from the press and placed on the bench to cool.
    Constant temperature frequency scans and melt rheology were performed using a TA Instruments ARES controlled strain rheometer equipped with 25 mm parallel plates in a nitrogen purge. Frequency scans were performed at 190°C for all samples within a range of 2.0 mm and a constant strain of 10%. The frequency range was 0.1 to 100 radians/second. The voltage response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G”), complex modulus (G*), dynamic complex viscosity (n*) were calculated ), and tg δ or tg delta. Conventional Gel Permeation Chromatography (GPC)
    [0085] The GPC system consists of a Model 210 or Model 220 instrument from Polymer Laboratories equipped with a concentration by refractive index (RI) detector. Column and carousel compartments are operated at 140°C. Three 10 µm Mixed-B columns from Polymer Laboratories are used with the solvent 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 g polymer in 50 ml solvent. The solvent used to prepare the samples contains 200 ppm of the antioxidant butylated hydroxy toluene (BHT). Samples are gently shaken at 160°C for four hours. The injection volume is 200 μL and the flow rate is 1 mL/min. The GPC column set is calibrated with twenty-one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories.
    [0086] The maximum molecular weights of polystyrene standards (MPS) are converted to polyethylene molecular weights (MPE) using Equation 1. The equation is described in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968): MPE = A x (MPS)B (Equation 1) where A has the value 0.4316 and B is equal to 1.0.
    [0087] A third order polynomial is determined to construct the logarithmic molecular weight calibration as a function of the elution volume.
    [0088] Calculations of polyethylene equivalent molecular weights were performed using PolymerChar's “GPC One” software. Numerical average molecular weight (Mn), weight average molecular weight (Mw), and z average molecular weight (Mz) were calculated by feeding the computer with the GPC results in equations 2 to 4:
    where RIi and MPE,i are, respectively, the concentration detector baseline corrected response and conventional calibrated polyethylene molecular for the i-th slice of the paired concentration response, elution volume dataset. The precision of the weight average molecular weight ΔMw is less than 2.6%.
    [0089] MWD is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
    [0090] The GPC column set is calibrated prior to running the Examples by operating 21 polystyrene standards of narrow molecular weight distribution. The molecular weight (Mw) of the standards ranges from 580 to 8,400,000 g/mol, and the standards are contained in 6 “cocktail” blends. Each mixture of standards has at least a dozen separations between individual molecular weights. Standard blends are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared in 0.025 g in 50 mL solvent for molecular weights greater than or equal to 1,000,000 g/mol and 0.05 g in 50 mL solvent for molecular weights less than 1,000,000 g/mol. Polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. Narrow standard blends are used first and in order to lower maximum molecular weight component to minimize degradation. CEF method
    Comonomer distribution analysis is performed using the crystallization elution fractionation (CEF) method (PolymerChar, Spain) (see B. Monrabal et al., Macromol. Symp. 257, 71-79 (2007) ). As a solvent, ortho-dichlorobenzene (ODBC) is used with 600 ppm of the antioxidant butylated hydroxytoluene (BHT). Sample preparation is carried out with an automatic feeding system at 160°C for 2 hours with vibration at 4 mg/mL (unless otherwise specified). The injection volume is 300 μL. The CEF temperature profile is: crystallization at 3°C/min from 110°C to 30°C, thermal equilibrium at 30°C for 5 minutes, elution at 3°C /min from 30°C to 140°C. The flow rate during crystallization is 0.052 ml/min. The flow rate during elution is 0.50 ml/min. Data is collected at one data point/second.
    [0092] The CEF column is filled with glass beads at 125 μm ± 6% (MO-SCI Specialty Products) with 1/8-inch steel tube. Glass beads are acid washed by MO-SCI Specialty on request from The Dow Chemical Company. Column volume is 2.06 ml. Column temperature calibration is performed using a linear polyethylene mixture of NIST 1475a standard reference material (1.0 mg/mL) and eicosan (2 mg/mL) in ODCB. The temperature is calibrated by adjusting the heat elution rate so that NIST 1475a linear polyethylene has a maximum temperature of 101.0°C, and eicosan has a maximum temperature of 30.0°C. Column resolution of CEF is calculated with a mixture of linear polyethylene NIST 1475a (1.0 mg/ml) and hexacontane (Fluka, purity >97.0%, 1 mg/ml). A baseline separation of hexacontane and NIST 1475a polyethylene is achieved. The area of hexacontane (from 35.0 to 67.0°C) for the area of NIST 1475a (from 67.0 to 110°C) is 50 to 50, the amount of soluble fraction below 35.0°C is less than 1.8% by weight. Column resolution of CEF is defined in Equation 1, where the column resolution is 6.0.
    Determination of half height and one tenth height of the CEF elution profile
    [0093] The CEF instrument is calibrated according to the CEF method described here, and the relative IR detector signal is plotted as a function of temperature. A single baseline is subtracted from the IR measurement signal to create an elution-relative mass profile plot starting and ending at zero relative mass at their minimum and maximum elution temperatures (typically between 25°C and 110°C Ç). For convenience, this graph (Figure 1) is plotted as a normalized quantity with an area equivalent to 100. In the elution-relative mass profile graph, peaks representing an area of at least 25% of the total integrated signal between 35°C and 110°C are designated. Any peaks that do not return to baseline by at least 10% of the elution height-relative mass (connected by more than 10% height at their minimum point), are defined as a single peak (no deconvolution or similar numerical methods are used to mathematically separate complicated peaks). Then, each separate peak is measured for width in °C at 50% of the maximum peak height on the elution profile-mass graph. Then, each separate peak is measured for width in °C at 10% of the maximum peak height on the elution profile-mass graph. CDC method
    [0094] The comonomer distribution constant (CDC) is calculated from the comonomer distribution profile by CEF. CDC is defined as the comonomer distribution index divided by the comonomer distribution form factor by multiplying by 100, as shown in Equation 1. Equation 1

    [0095] The comonomer distribution index means the total weight fraction of polymeric chains with the comonomer content ranging between 0.5 of the average comonomer content (Caverage) and 1.5 of Caverage from 35.0 to 119.0° Ç. Comonomer distribution form factor is defined as a ratio of the comonomer distribution profile half-width divided by the maximum temperature comonomer distribution profile standard deviation (Tp).
    [0096] CDC is calculated from the comonomer distribution profile by CEF, and CDC is defined as the comonomer distribution index divided by the comonomer distribution form factor by multiplying by 100 as shown in Equation 1, and being that the comonomer distribution index means the total weight fraction of polymeric chains with the comonomer content ranging between 0.5 of the average comonomer content (Caverage) and 1.5 of Cmedium from 35.0 to 119.0°C, and where the comonomer distribution profile is defined as a ratio of the half-width of the comonomer distribution profile divided by the maximum temperature (Tp) comonomer distribution profile standard deviation.
    [0097] CDC is calculated according to the following steps: (A) Obtain a weight fraction at each temperature (T) (wT(T)) from 35.0 to 119.0°C with an increase in the temperature step of 0.2°C of CEF according to Equation 2.
    (B) Calculate the mean temperature (Tmean) in cumulative weight fraction of 0.500 according to Equation 3.
    (C) Calculate the corresponding mean comonomer content in mole % (Cmean) at the mean temperature (Tmean) using the comonomer content calibration curve according to Equation 4. Equation 4.
    (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 to 119.0°C) with weight average molecular weight (Mw) of 35,000 to 115,000 (measured via conventional GPC) at a comonomer content ranging from 0.0% mol to 7.0 mol% with CEF under the same conditions specified in experimental sections of CEF. (E) Calculate comonomer content calibration using the maximum temperature (Tp) of each reference material and its comonomer content; the calibration of each reference material is calculated as shown in Equation 4 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*Cmedium to 1.5*Cmedium, and if Tmean is greater than 98.0°C, define -á the comonomer distribution index as 0.95. (G) Obtain maximum peak height from comonomer distribution profile by CEF by searching each data point for the maximum peak of 35.0°C to 119.0°C (if two peaks are identical, then it will be selected the smallest peak temperature); 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 sought forward of 35.0°C, while the rear temperature is searched behind 119.0°C, in the case of a well-defined bimodal distribution where the difference between the maximum temperatures is greater than or equal to 1.1 times the sum of the half width of each peak; the half-width of the inventive ethylene-based polymer composition is calculated as the arithmetic mean of the half-width of each peak.
    [0098] (H) Calculate the standard deviation of temperature (Stdev) according to Equation 5.
    Flow zero shear viscosity method
    [0099] Zero shear viscosities are obtained via creep tests which are performed in an AR-G2 tension controlled rheometer (TA Instruments, New Castle, Del) using 25 mm diameter parallel plates at 190°C. Set rheometer oven to test temperature for at least 30 minutes before zeroing fixtures. At the test temperature, a compression-molded sample disc is inserted between the plates and allowed to reach equilibrium for 5 minutes. Then, the top plate is lowered to 50 μm above the desired test gap (1.5 mm). Any superfluous material is trimmed and the top plate is lowered to the desired gap. Measurements are made in nitrogen purge at a flow rate of 5 L/min. Preset creep time is set to 2 hours.
    [0100] 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. In this study, the resulting steady-state shear rates for the samples are on the order of 10-3 s-1. The steady state is determined by considering a linear regression for all data in the time window of at least 10% of the log (J(t)) versus log (t) graph, where J(t) is creep conformity and t is the fluency time. If the slope of the linear regression is greater than 0.97, it will be considered that the steady state has been reached, and then the fluency test will be interrupted. In all cases in this study, the slope meets the criterion within 30 minutes. The steady-state shear rate is determined from the slope of the linear regression of all data points in the time window of at least 10% of the graph of ε against t, where ε is strain. Viscosity at zero shear is determined from the ratio of the applied stress to the steady state shear ratio.
    [0101] In order to determine if the sample degrades during the creep test, a small amplitude oscillatory shear test is performed before and after the creep test on the same specimen from 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 (ZSVR)
    [0102] Zero shear viscosity ratio (ZSVR) is defined as the zero shear viscosity ratio (ZSV) of the inventive polymer to the ZSV of a linear polyethylene material at the following equivalent weight average molecular weight:

    [0103] The ZSV value is obtained from the creep test at 190°C via the method described above. The Mw-gpc value is determined by the conventional GPC method (Equation 3 in the description of the conventional GPC method). The correlation between linear polyethylene ZSV and its Mw-gpc was established based on a series of linear polyethylene reference materials. A description of the ZSV-Mw relationship can be found in ANTEC: Karjala, Teresa P., Sammler, Robert L., Mangnus, Marc A., Hazlitt, Lonnie G., Johnson, Mark S., Hagen, Charles M. Jr. ., Huang, Joe WL, Reichek, Kenneth N., “Detection of low levels of long-chain branching in polyolefins”, Annual Technical Conference - Society of Plastics Engineers (2008), 66a, 887-891. 1H NMR Method
    [0104] 3.26 g of stock solution are added to 0.133 g of polyolefin sample in 10 mm NMR tube. The stock solution is a mixture of tetrachloroethane-d2 (TCE) and perchlorethylene (50:50, w:w) with Cr3+ 0.001M. 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 polymeric sample. The sample is dissolved at 110°C with vibration. The samples are free of additives that can contribute to unsaturation, for example glidants such as erucamide.
    [0105] 1H NMR is performed with a 10 mm cryogenic probe at 120°C on an AVANCE 400 MHz Bruker spectrometer.
    [0106] Two experiments are performed to obtain the unsaturation: the control experiments and the double pre-saturation.
    [0107] For the control experiment, data is processed with exponential window function with LB= 1 Hz, baseline was corrected from 7 to -2 ppm. The residual 1H TCE signal is adjusted to 100, Itotal from -0.5 to 3 ppm is used as the whole polymer signal in the control experiment. The number of CH2 group, NCH2 in the polymer is calculated as follows: NCH2= Itotal/2 (Equation 1)
    [0108] For the double pre-saturation experiment, the data are processed with exponential window function with LB = 1 Hz, baseline was corrected from 6.6 to 4.5 ppm. The residual 1H signal of TCE is adjusted to 100, the corresponding integrals for unsaturations (Ivinylene, Itrisubstituted, Ivinyl and Ivinylidene) were integrated based on the region shown in Figure 6. Calculate the unsaturation unit number for vinylene, trisubstituted, vinyl and vinylidene:

    [0109] The unit of unsaturation/1,000 carbons is calculated as follows:

    [0110] The chemical shift reference is set at 6.0 ppm for the 1H residual proton signal of TCT-d2. Control is carried out with pulse ZG, TD 32768, NS 4, DS 12, SWH 10,000 Hz, AQ 1.64 s, D1 14 s. The double presaturation experiment is performed with a modified pulse sequence, O1P 1.354 ppm, O2P 0.960 ppm, PL9 57db, PL21 70db, TD 32768, NS 200, DS 4, SWH 10,000 Hz, AQ 1.64 s, D1 1 s, D13 13 s. The modified pulse sequences for desaturation with Bruker's AVANCE 400 MHz spectrometer are shown below in Figure 7. 13C NMR method
    [0111] Samples were prepared by adding approximately 2.74 g of a 50/50 mixture of tetrachloroethane-d2/ortho-dichlorobenzene containing 0.025M Cr(AcAc)3 to 0.2 g of sample in a 10 mm Norell NMR tube 1001-7. Oxygen was manually removed by purging tubes with N2 using a Pasteur pipette for 1 minute. The samples were dissolved and homogenized by heating the tube and its contents to ~150 °C using a heating block with minimal use of a torch. Each sample was visually inspected to ensure homogeneity. Samples were thoroughly mixed immediately prior to analysis, and were not allowed to cool prior to insertion into the heated NMR probe. This is necessary to ensure that the sample is homogeneous and representative of the whole. Data were collected using a Bruker 400 MHz spectrometer equipped with a Bruker cryogenic probe. Data were acquired using 160 scans, a 6 s pulse repetition delay with a sample temperature of 120°C. All measurements are performed on non-rotating specimens in locked mode. Samples were thermally equilibrated for 7 minutes prior to data acquisition. Chemical shifts were mentioned internally as an EEE triad at 30 ppm. Cast strength measurement
    [0112] The melt strength was measured on a Rheotens Model 71.97 melt strength analyzer. The melt was produced in a Rheotester 2000 Gottfert capillary rheometer with a 30/2 flat die at a shear rate of 38.2 s-1. The rheometer drum (diameter: 12 mm) was loaded in less than one minute. A 10 minute delay was allowed for proper melting. The compensation speed of the Rheotens wheels varied, with a constant acceleration of 2.4 mm/s2. The tension in the stretched line was monitored over time, until the line was broken. Steady-state force and burst velocity were reported. Intrinsic Elmendorf Disruption
    [0113] The Elmendorf tear test determines the average force to propagate tear through a specified length of plastic film or soft sheet after tear has been initiated, using an Elmendorf-type tear analyzer.
    [0114] The intrinsic rupture of the sample is measured by ASTM D1922 in compression molded plates. Plates are molded in accordance with Annex 1 of Procedure C of ASTM D4703 (Controlled Cooling at 15°C/min). The final thickness of the intrinsic rupture samples is targeted to be in the 10 to 12 milliinch range. Details of ASTM D1922 are given in the following section. Before testing, the thickness of the specimen in the center of the plate is measured. A total of 15 specimens are tested per resin sample and the average breaking strength and average thickness are reported. Average breaking strength is normalized to average thickness. Extruded one-layer and multi-layer expanded film tests
    [0115] The following expanded film properties of one layer and extruded multilayers were measured. Total fogging by ASTM D1003
    [0116] Samples to measure internal haze and global (total) haze are obtained and prepared in accordance with ASTM D1003. Internal haze was achieved via refractive index combination using mineral oil on both sides of the films. For the test, HAZEGUARD PLUS (BYK-Gardner, USA, Columbia, MD) is used. Surface haze is determined as the difference between total haze and internal haze. Total haze is reported as the mean of five measurements. Type B Elmendorf break in MD (machine direction) and CD (cross direction) per ASTM D1922
    [0117] The Elmendorf tear test determines the average force to propagate tear through a specified length of plastic film or soft sheet after tear has been initiated, using an Elmendorf-type tear analyzer.
    [0118] After film production from the sample to be tested, the film is conditioned for at least 40 hours at 23°C (+/- 2°C) and 50% relative humidity (RH) (+/- 5 %) by ASTM standards. Test conditions are 23°C (+/- 2°C) and 50% relative humidity (RH) (+/- 5%) per ASTM standards.
    [0119] The force in grams required to propagate rupture through a specimen film or sheet is measured using a precisely calibrated pendulum device. In the test, acting by gravity, the pendulum swings through an arc, breaking the specimen from a pre-cut slot. The specimen is held on one side by the pendulum and on the other side by a stationary member. Energy loss by the pendulum is indicated by an arrow or an electronic scale. The scale indication is a function of the force required to break (tear) the specimen.
    [0120] The sample specimen geometry used in the Elmendorf rupture test is “constant radius geometry” as specified in ASTM D1922. Typically, the test is performed on specimens that have been cut in both the MD and CD directions of the film. Before testing, the thickness of the film specimen at the center of the sample is measured. A total of 15 specimens are tested per film direction and the average breaking strength and average thickness are reported. Average breaking strength is normalized to average thickness. 2% Modulus of Elasticity in MD and CD by ASTM D882
    [0121] The modulus of elasticity in MD (machine direction) and CD (cross direction) of film was determined by ASTM D882. The reported modulus of elasticity value is the average of five measurements. Internal method of drilling
    [0122] The puncture test determines the resistance of a film to puncture by a probe at a standard low rate, at a single test speed.
    [0123] The internal drill test is based on ASTM D5748.
    [0124] After film production, it is conditioned for at least 40 hours at 23°C (+/- 2°C) and relative humidity (RH) of 50% (+/- 5%) by ASTM standards. Test conditions are 23°C (+/- 2°C) and 50% relative humidity (RH) (+/- 5%) per ASTM standards.
    [0125] Perforation is measured on a tensile testing machine. Square specimens are cut from a sheet to a size of 6 inches by 6 inches. The specimen is stapled to a 4 inch diameter circular specimen clamp and a drill probe is pressed into the center of the stapled film at a piston speed of 10 inches/minute.
    [0126] The internal test method follows ASTM D5748 with one modification. It deviates from the ASTM D5748 method in that the probe used is a 0.5 inch diameter polished steel ball on a 0.25 inch support rod (instead of the pear shaped probe 0. 75 inch specified in D5748).
    [0127] There is a maximum travel length of 7.7 inches to prevent damage to the test facility. There is no length between repairs; before testing the probe is as close as possible, but not touching the specimen.
    [0128] A single thickness measurement is made at the center of the specimen. For each specimen, the maximum force, breaking force, penetration distance and energy to break are determined. A total of five specimens are tested to determine an average perforation value. After each specimen, the drilling probe is cleaned using a tissue. Dart Drop by ASTM D1709
    [0129] The drop dart on film test determines the energy that causes the plastic film to fail under specified impact conditions by a free-fall dart. The test result is the energy, expressed in terms of the missile's weight falling from a specified height, that would result in a failure of 50% of the test specimens tested.
    [0130] After producing the film, it is conditioned for at least 40 hours at 23°C (+/- 2°C) and relative humidity (RH) of 50% (+/- 5%) by ASTM standards. Test conditions are 23°C (+/- 2°C) and 50% relative humidity (RH) (+/- 5%) per ASTM standards.
    [0131] The test result is reported either by Method A, which uses a 1.5" diameter dart head and 26" drop height, or by Method B, which uses a 2" dart head of diameter and drop height of 60”. Measure the thickness of the sample at the center of the sample and then staple the sample to an annular fastener having an inside diameter of 5 inches. The dart is loaded above the center of the sample and released by a pneumatic or electromagnetic mechanism.
    [0132] The test is performed according to the “ladder” method. If the sample fails, a new sample will be tested with the dart weight reduced by a known and fixed amount. If the sample does not fail, a new sample will be tested with the weight of the dart increased by a known amount. After 20 specimens have been tested, the number of failures is determined. If the number is 10 then the test is complete. If the number is less than 10, then the test will continue until 10 failures are recorded. If the number is greater than 10, testing will continue until the total of non-fails is 10. The dart drop resistance is determined from this data by ASTM D1709 and expressed in grams that the dart drop impact is Type A or Type B. In some cases, the drop impact strength of the dart in the sample may be between A and B. In these cases it is not possible to obtain a quantitative dart value. bag drop test
    [0133] Five full 50-pound bags, made of 4.5 milli-inch thick co-extruded film, fall from a height of 2.4 meters (8 feet). Each bag drops three times using the following protocol: (1) Side drop of bag; (2) Fall with the bottom of the bag; (3) Drop with the face of the bag.
    [0134] After each drop, bags are inspected for any sign of failure. Test results are reported as (1) the total number of bags that passed, and (2) the total number of bags that failed the drop test.
    权利要求:
    Claims (8)
    [0001]
    1. Polyolefin composition suitable for packaging applications, characterized in that it comprises: an ethylene/α-olefin interpolymer composition comprising (a) from 50 to 75 weight percent of a first ethylene/α-copolymer fraction olefin having a density in the range of 0.894 to 0.908 g/cm3, measured in accordance with ASTM D792, Method B, a melt index (I2) in the range of 0.2 to 1 g/10 minutes as measured in accordance with ASTM D1238 , condition at 190°C/2.16 kg, and (b) from 25 to 50 percent by weight of a second ethylene/α-olefin copolymer fraction, said ethylene/α-olefin interpolymer composition having a density in the range of 0.910 to 0.924 g/cm3, measured in accordance with ASTM D792, Method B, a melt index (I2) in the range of 0.5 to 2 g/10 minutes as measured in accordance with ASTM D1238, condition 190°C/2.16 kg, a zero shear viscosity ratio (ZSVR) in the range of 1.15 to 2.5, a molecular weight distribution, expressed as the mo weight ratio weight average molecular weight for numerical average molecular weight (Mw/Mn) in the range of 2.0 to 4.0, and tg δ (delta) in 0.1 radian/second and 190°C in the range of 6 to 43, where said ethylene/α-olefin interpolymer composition has at least 2 peaks in the elution profile via the crystallization elution fractionation (CEF) procedure, each peak comprising at least 25 weight percent of the total area of the elution profile. elution, where the separation of the 2 peak positions are in the range of 20 to 40°C, with a larger elution temperature peak being at an elution temperature greater than 90°C, and an elution temperature peak the smallest is at an elution temperature in the range of 50 to 80°C, and where the elution temperature peak width greater at 50 percent peak height is less than 4°C, and where the peak width of elution temperature greater at 10 percent peak height is less than 9°C, and the elution temperature peak width being me nor at 50 percent peak height is less than 8°C, and the elution temperature peak width being smaller at 10 percent peak height is less than 25°C.
    [0002]
    2. Polyolefin composition according to claim 1, wherein said ethylene/α-olefin interpolymer composition is characterized by having one or more of the following: (a) a vinyl unsaturation of less than 0.1 vinyl per thousand carbon atoms present in the backbone of the ethylene/α-olefin interpolymer composition; and/or (b) a tg δ (delta) at 0.1 radian/second, determined at 190°C, in the range of 6 to 43; and/or (c) CDC in the range of 50 to 500.
    [0003]
    3. Polyolefin composition according to claim 1, characterized in that it further comprises one or more ethylene polymers, or one or more propylene-based polymers, or combinations thereof.
    [0004]
    4. Film, characterized in that it comprises the polyolefin composition, as defined by claim 1.
    [0005]
    5. Sheet, characterized in that it comprises the polyolefin composition, as defined by claim 1.
    [0006]
    6. The polyolefin composition of claim 1, wherein said polyolefin composition is characterized by having at least two of the following: (a) a dart A impact of at least 1000 g measured in accordance with ASTM D1709 , when said polyolefin composition is cast into an expanded monolayer film having a thickness of 1 milliinch; (b) a dart B impact of at least 400 g measured in accordance with ASTM D1709, when said polyolefin composition is cast into an expanded monolayer film having a thickness of 1 milliinch; and/or (c) Elmendorf breaking strength in the standard machine direction of at least 250 g/milliinch, measured in accordance with ASTM D1922, when said polyolefin composition is cast into an expanded monolayer film having a thickness of 1 milliinch.
    [0007]
    7. Polyolefin composition according to claim 6, characterized in that it further comprises from 5 to 20 percent by weight of low density polyethylene (LDPE), and the dart impact A being greater than 275 g, preferably greater than 300 g measured in accordance with ASTM D1709, when said polyolefin composition is cast into an expanded monolayer film having a thickness of 25.4 µm (1 milliinch).
    [0008]
    8. Packaging device, characterized in that it comprises the film as defined by claim 4 or the sheet as defined by claim 5.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015015172B1|2021-04-20|polyolefin composition suitable for packaging, film, foil and packaging device applications
    BR112015007853B1|2021-06-01|POLYOLEFIN COMPOSITION, SEALING COMPOSITION, FILM, MULTILAYER STRUCTURE AND PACKAGING DEVICE
    CN106470838B|2019-05-17|Casting films with improved toughness
    BR112014031191B1|2021-08-24|POLYETHYLENE MIXTURE COMPOSITION SUITABLE FOR BLOW FILM AND BLOW FILM
    KR20170023955A|2017-03-06|Ethylene-based polymer composition for films with improved toughness
    ES2453115T3|2014-04-04|A composition suitable for a stretch cover, a method for the production of it and articles made from it
    BR112015005490B1|2021-05-18|film structure
    US20140255674A1|2014-09-11|Multi-layered shrink films
    ES2632549T3|2017-09-14|Ethylene / alpha-olefin interpolymer composition
    ES2758928T3|2020-05-07|1-Butene / alpha-olefin copolymer and composition containing it
    US10308736B2|2019-06-04|Polyethylene polymers and articles made therefrom
    ES2572557T3|2016-06-01|A composition-mixture of polyethylene suitable for blown films, and films prepared therefrom
    BR112016005685B1|2021-05-25|polymer blend composition, injection molded article, film, sheet, tape, multilayer structure, and article
    BR112019026262A2|2020-06-30|polyethylene laminates for use in flexible packaging materials
    CN108699267A|2018-10-23|Ventilated membrane and the method for preparing the ventilated membrane
    EP3772415A1|2021-02-10|Multilayer films comprising polyethylene and barrier layers and methods of producing the same
    US20200171809A1|2020-06-04|Low temperature multilayer shrink films, and methods of making thereof
    BR112019010350A2|2019-08-27|ethylene / alpha-olefin interpolymer compositions
    BR112020005201A2|2020-09-15|modified polyethylene compositions and method for producing the same
    CA3146305A1|2021-02-11|Multilayer films that include at least five layers and methods of producing the same
    WO2021026139A1|2021-02-11|Multilayer films that include at least five layers and methods of producing the same
    BR112020003952A2|2020-09-08|thermoformed film compositions with enhanced toughness after thermoforming processes
    CN114222782A|2022-03-22|Polyethylene composition
    BR112017003299B1|2021-11-30|ETHYLENE COPOLYMER, POLYMER COMPOSITIONS AND COMBINED POLYMER COMPOSITION COMPRISING SAID ETHYLENE COPOLYMER AND ARTICLE, SINGLE-LAYER FILM, MULTI-LAYER FILM AND PACKAGING ARTICLE COMPRISING SAID POLYMER COMPOSITION
    BR112019015332A2|2020-03-10|MULTIPLE LAYER MOVIES WITH TUNING TENSION HARDENING
    同族专利:
    公开号 | 公开日
    EP2938643A1|2015-11-04|
    CN104870489A|2015-08-26|
    CN104870488A|2015-08-26|
    KR20150100852A|2015-09-02|
    EP2938647B1|2017-06-07|
    JP2016503109A|2016-02-01|
    CN104870490B|2017-08-15|
    US9751998B2|2017-09-05|
    KR20150100694A|2015-09-02|
    JP2016505694A|2016-02-25|
    ES2665586T3|2018-04-26|
    EP2938643B1|2018-01-31|
    US20150148490A1|2015-05-28|
    JP6393693B2|2018-09-19|
    US9102819B2|2015-08-11|
    US9631059B2|2017-04-25|
    CN104870490A|2015-08-26|
    US20160194464A1|2016-07-07|
    SG11201503581PA|2015-06-29|
    EP2938647A1|2015-11-04|
    US20180009958A1|2018-01-11|
    SG11201505081RA|2015-07-30|
    SG11201505074PA|2015-07-30|
    JP6364023B2|2018-07-25|
    WO2014105411A1|2014-07-03|
    CN104870488B|2017-05-17|
    EP2938646B1|2017-05-10|
    BR112015015167A2|2017-07-11|
    WO2014106017A1|2014-07-03|
    CN104870489B|2018-03-09|
    US20150344681A1|2015-12-03|
    US9115275B2|2015-08-25|
    ES2634639T3|2017-09-28|
    EP2938646A1|2015-11-04|
    KR102077365B1|2020-04-07|
    BR112015015167B1|2021-05-11|
    US10214622B2|2019-02-26|
    WO2014106052A1|2014-07-03|
    KR20200062369A|2020-06-03|
    JP2016503103A|2016-02-01|
    US20150291713A1|2015-10-15|
    KR102077364B1|2020-04-02|
    ES2630378T3|2017-08-21|
    JP6294350B2|2018-03-14|
    US20150148491A1|2015-05-28|
    AR094336A1|2015-07-29|
    BR112015015394A2|2017-07-11|
    BR112015015172A2|2017-07-11|
    KR20150100851A|2015-09-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1069848A|1965-05-17|1967-05-24|Imp Chemical Imdustries Ltd|Process for the polymerisation of vinyl chloride|
    US5153157A|1987-01-30|1992-10-06|Exxon Chemical Patents Inc.|Catalyst system of enhanced productivity|
    US7163907B1|1987-01-30|2007-01-16|Exxonmobil Chemical Patents Inc.|Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization|
    US5064802A|1989-09-14|1991-11-12|The Dow Chemical Company|Metal complex compounds|
    JP2545006B2|1990-07-03|1996-10-16|ザダウケミカルカンパニー|Addition polymerization catalyst|
    US5721185A|1991-06-24|1998-02-24|The Dow Chemical Company|Homogeneous olefin polymerization catalyst by abstraction with lewis acids|
    US5296433A|1992-04-14|1994-03-22|Minnesota Mining And Manufacturing Company|Trisborane complexes and catalysts derived therefrom|
    US5350723A|1992-05-15|1994-09-27|The Dow Chemical Company|Process for preparation of monocyclopentadienyl metal complex compounds and method of use|
    US5372682A|1993-06-24|1994-12-13|The Dow Chemical Company|Electrochemical preparation of addition polymerization catalysts|
    US5631069A|1994-05-09|1997-05-20|The Dow Chemical Company|Medium modulus molded material comprising substantially linear polyethlene and fabrication method|
    US5625087A|1994-09-12|1997-04-29|The Dow Chemical Company|Silylium cationic polymerization activators for metallocene complexes|
    US6506866B2|1994-11-17|2003-01-14|Dow Global Technologies Inc.|Ethylene copolymer compositions|
    EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|
    KR20000005027A|1996-03-27|2000-01-25|그레이스 스티븐 에스.|Solution polymerization process with dispersed catalyst activator|
    CA2253804C|1996-05-02|2005-07-26|Lyondell Petrochemical Company|Catalyst system containing reaction product of liquid silicone and polyamine|
    US5783512A|1996-12-18|1998-07-21|The Dow Chemical Company|Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same|
    US6103657A|1997-07-02|2000-08-15|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst for the production of olefin polymers|
    US6696379B1|1997-09-19|2004-02-24|The Dow Chemical Company|Supported modified alumoxane catalyst activator|
    US6323285B1|1998-01-09|2001-11-27|The Dow Chemical Company|Heteromorphic polymer compositions|
    US5936058A|1998-05-15|1999-08-10|Exxon Chemical Patents, Inc.|Impact modified thermoplastic polymer blends|
    JP2000159829A|1998-11-27|2000-06-13|Tosoh Corp|Catalyst for olefin polymerization and production of polyolefin using same|
    AU1773901A|1999-12-10|2001-06-18|Dow Chemical Company, The|Substituted group 4 metal complexes, catalysts and olefin polymerization process|
    US6897276B2|2002-04-24|2005-05-24|Symyx Technologies, Inc.|Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom|
    US7060848B2|2002-04-24|2006-06-13|Symyx Technologies, Inc.|Bridged bi-aromatic catalysts, complexes, and methods of using the same|
    US7396878B2|2002-10-01|2008-07-08|Exxonmobil Chemical Patents Inc.|Polyethylene compositions for injection molding|
    WO2004072176A2|2003-02-04|2004-08-26|Dow Global Technologies Inc.|Film layers made from polymer blends|
    GB0317012D0|2003-07-21|2003-08-27|Borealis Tech Oy|Injection moulding polymer|
    AR048104A1|2004-03-17|2006-03-29|Dow Global Technologies Inc|CATALYZING COMPOSITION THAT INCLUDES A LINK AGENT FOR THE FORMATION OF OLEFIN'S TOP COPOLYMERS IN MULTIPLE BLOCKS|
    EP1674523A1|2004-12-22|2006-06-28|Total Petrochemicals Research Feluy|Caps and closures|
    EP1674490A1|2004-12-23|2006-06-28|Borealis Technology Oy|Copolymer|
    WO2007136495A2|2006-05-17|2007-11-29|Dow Global Technologies Inc.|High efficiency solution polymerization process|
    JP5330414B2|2008-02-29|2013-10-30|ダウグローバルテクノロジーズエルエルシー|Oriented film containing ethylene / α-olefin block interpolymer|
    CA2629576C|2008-04-21|2016-01-05|Nova Chemicals Corporation|Closures for bottles|
    CN104169312A|2012-02-22|2014-11-26|埃克森美孚化学专利公司|Vinyl-terminated macromonomer oligomerization|
    US8372930B2|2008-06-20|2013-02-12|Exxonmobil Chemical Patents Inc.|High vinyl terminated propylene based oligomers|
    WO2010061630A1|2008-11-28|2010-06-03|三菱レイヨン株式会社|Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body|
    US8101685B2|2008-12-15|2012-01-24|Exxonmobil Chemical Patents Inc.|Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom|
    US8106127B2|2008-12-15|2012-01-31|Exxonmobil Chemical Patents Inc.|Heterogeneous in-reactor polymer blends|
    US20110003940A1|2009-07-01|2011-01-06|Dow Global Technologies Inc.|Ethylene-based polymer compositions for use as a blend component in shrinkage film applications|
    EP2473538B1|2009-08-31|2017-07-26|Dow Global Technologies LLC|Catalyst and process for polymerizing an olefin and polyolefin prepared thereby|
    US8716400B2|2009-10-02|2014-05-06|Dow Global Technologies Llc|Block composites and impact modified compositions|
    US8802774B2|2009-10-02|2014-08-12|Dow Global Technologies Llc|Block composites and impact modified compositions|
    US20110172354A1|2010-01-04|2011-07-14|Dow Global Technologies Inc.|Ethylene-based polymer compositions for use in fiber applications|
    SG2014006266A|2010-02-19|2014-03-28|Dow Global Technologies Llc|Process for polymerizing an olefin monomer and catalyst therefor|
    CN103038281B|2010-03-02|2015-11-25|陶氏环球技术有限责任公司|Based on the polymer composition of ethene|
    WO2011146044A1|2010-05-17|2011-11-24|Dow Global Technologies Llc|Process for selectively polymerizing ethylene and catalyst therefor|
    US8609794B2|2010-05-17|2013-12-17|Dow Global Technologies, Llc.|Process for selectively polymerizing ethylene and catalyst therefor|
    KR20130089165A|2010-07-06|2013-08-09|티코나 게엠베하|Ultra-high molecular weight polyethylene, its production and use|
    EP2609123B1|2010-08-25|2017-12-13|Dow Global Technologies LLC|Process for polymerizing a polymerizable olefin and catalyst therefor|
    WO2012061168A1|2010-11-02|2012-05-10|Dow Global Technologies Llc|A sealant composition, method of producing the same|
    US20120116034A1|2010-11-08|2012-05-10|Dow Global Technologies, Inc.|Solution polymerization process and procatalyst carrier systems useful therein|
    SG190985A1|2010-12-03|2013-07-31|Dow Global Technologies Llc|Processes to prepare ethylene-based polymer compositions|
    KR101989206B1|2011-12-20|2019-09-24|다우 글로벌 테크놀로지스 엘엘씨|Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same|
    EP2797962B1|2011-12-29|2015-11-18|Dow Global Technologies LLC|Process for producing low molecular weight ethylene- and alpha-olefin-based materials|
    EP2797963B1|2011-12-29|2019-07-03|Dow Global Technologies LLC|Hyperbranched olefin oil-based dielectric fluid|
    WO2014062329A1|2012-10-18|2014-04-24|Dow Global Technologies Llc|Oleic and medium chain length triglyceride based, low viscosity, high flash point dielectric fluids|
    ES2731574T3|2012-12-27|2019-11-18|Dow Global Technologies Llc|A polymerization process to produce ethylene-based polymers|
    KR20150100844A|2012-12-27|2015-09-02|다우 글로벌 테크놀로지스 엘엘씨|An ethylene based polymer|
    SG10201705090XA|2012-12-27|2017-07-28|Dow Global Technologies Llc|An ethylene based polymer|
    JP6393693B2|2012-12-27|2018-09-19|ダウ グローバル テクノロジーズ エルエルシー|Catalytic system for olefin polymerization.|
    US9527940B2|2012-12-27|2016-12-27|Dow Global Technologies Llc|Polymerization process for producing ethylene based polymers|
    US9534070B2|2013-01-18|2017-01-03|Dow Global Technologies Llc|Polymerization processes for high molecular weight polymers|
    MX2015016913A|2013-06-28|2016-04-04|Dow Global Technologies Llc|Hyperbranched ethylene-based oligomers.|
    SG11201510689SA|2013-06-28|2016-01-28|Dow Global Technologies Llc|Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts|
    US10072172B2|2013-09-25|2018-09-11|Mitsubishi Chemical Corporation|Flexible vinyl chloride resin composition, molded product, electric wire coating material, and coated electric wire|
    JP6327471B2|2013-09-25|2018-05-23|三菱ケミカル株式会社|Wire covering material and covered wire|KR101632818B1|2012-01-24|2016-06-22|토탈 리서치 앤드 테크놀로지 펠루이|Method for processing polyethylene|
    SG10201703271QA|2012-10-09|2017-07-28|Dow Global Technologies Llc|Sealant Composition|
    US9527940B2|2012-12-27|2016-12-27|Dow Global Technologies Llc|Polymerization process for producing ethylene based polymers|
    JP6393693B2|2012-12-27|2018-09-19|ダウ グローバル テクノロジーズ エルエルシー|Catalytic system for olefin polymerization.|
    ES2731574T3|2012-12-27|2019-11-18|Dow Global Technologies Llc|A polymerization process to produce ethylene-based polymers|
    US9534070B2|2013-01-18|2017-01-03|Dow Global Technologies Llc|Polymerization processes for high molecular weight polymers|
    SG11201510689SA|2013-06-28|2016-01-28|Dow Global Technologies Llc|Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts|
    EP3053954A4|2013-10-30|2017-07-05|LG Chem, Ltd.|Olefin resin|
    US20170152377A1|2014-06-26|2017-06-01|Dow Global Technologies Llc|Breathable films and articles incorporating same|
    US20170129230A1|2014-06-26|2017-05-11|Dow Global Technologies Llc|Cast films with improved toughness|
    EP3160740A1|2014-06-26|2017-05-03|Dow Global Technologies LLC|Blown films with improved toughness|
    US10519260B2|2014-06-30|2019-12-31|Dow Global Technologies Llc|Polymerizations for olefin-based polymers|
    EP3161022A1|2014-06-30|2017-05-03|Dow Global Technologies LLC|Ethylene-based polymers|
    US9975975B2|2014-07-24|2018-05-22|Dow Global Technologies Llc|Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers|
    WO2016109429A1|2014-12-31|2016-07-07|Dow Global Technologies Llc|A polyolefin composition and method of producing the same|
    EP3317312B1|2015-06-30|2020-06-10|Dow Global Technologies LLC|A polymerization process for producing ethylene based polymers|
    CN107787336B|2015-06-30|2021-05-28|陶氏环球技术有限责任公司|Polymerization process for preparing ethylene-based polymers|
    CN107923883B|2015-08-28|2021-02-12|陶氏环球技术有限责任公司|Chromatography of polymers with reduced co-crystallization|
    WO2017058858A1|2015-09-30|2017-04-06|Dow Global Technologies Llc|A polymerization process for producing ethylene based polymers|
    WO2017058910A1|2015-09-30|2017-04-06|Dow Global Technologies Llc|Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same|
    WO2017058981A1|2015-09-30|2017-04-06|Dow Global Technologies Llc|Procatalyst and polymerization process using the same|
    WO2017139096A1|2016-02-12|2017-08-17|Dow Global Technologies Llc|Cast films, and articles made therefrom|
    ES2691556T3|2016-03-02|2018-11-27|Dow Global Technologies Llc|A composition of an ethylene / alpha-olefin copolymer, and articles comprising the same|
    ES2703602T3|2016-03-03|2019-03-11|Dow Global Technologies Llc|Polyethylene composition, method for manufacturing it, and films made from it|
    WO2017173074A1|2016-03-31|2017-10-05|Dow Global Technologies Llc|An olefin polymerization catalyst|
    US10221260B2|2016-07-29|2019-03-05|Exxonmobil Chemical Patents Inc.|Phenolate transition metal complexes, production and use thereof|
    WO2018022279A1|2016-07-29|2018-02-01|Exxonmobil Chemical Patents Inc.|Phenolate transition metal complexes, production and use thereof|
    SG11201900653RA|2016-07-29|2019-02-27|Dow Global Technologies Llc|Silyl-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization|
    BR112019006150A2|2016-09-30|2019-06-18|Dow Global Technologies Llc|capped multiple or double head compositions useful for chain transfer and process for preparing same|
    WO2018064553A1|2016-09-30|2018-04-05|Dow Global Technologies Llc|Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same|
    EP3519474A1|2016-09-30|2019-08-07|Dow Global Technologies LLC|Process for preparing multi- or dual-headed compositions useful for chain shuttling|
    CN110023353A|2016-12-16|2019-07-16|陶氏环球技术有限责任公司|Ethylene/alpha-olefin interpolymers composition|
    US11149102B2|2017-03-10|2021-10-19|Sumitomo Chemical Company, Limited|Film|
    CN110582518A|2017-03-15|2019-12-17|陶氏环球技术有限责任公司|Catalyst system for forming multi-block copolymers|
    US20210122840A1|2017-03-15|2021-04-29|Dow Global Technologies Llc|Catalyst system for multi-block copolymer formation|
    SG11201908306TA|2017-03-15|2019-10-30|Dow Global Technologies Llc|Catalyst system for multi-block copolymer formation|
    US20200247918A1|2017-03-15|2020-08-06|Dow Global Technologies Llc|Catalyst system for multi-block copolymer formation|
    WO2018170208A1|2017-03-15|2018-09-20|Dow Global Technologies Llc|Catalyst system for multi-block copolymer formation|
    JP2020512462A|2017-03-31|2020-04-23|ダウ グローバル テクノロジーズ エルエルシー|Bis-biphenyl-phenoxy catalyst for olefin polymerization|
    EP3601387A1|2017-03-31|2020-02-05|Dow Global Technologies LLC|Germanium-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization|
    US10442921B2|2017-04-19|2019-10-15|Nova ChemicalsS.A.|Means for increasing the molecular weight and decreasing the density employing mixed homogeneous catalyst formulations|
    US10442920B2|2017-04-19|2019-10-15|Nova ChemicalsS.A.|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|
    CN108864338B|2017-05-12|2020-11-10|中国石油化工股份有限公司|Catalyst composition for olefin polymerization and olefin polymerization method|
    US20180370201A1|2017-06-22|2018-12-27|Liqui-Box Corporation|Bag-In-Box Film For Packaging Refrigerated Liquids|
    US11242415B2|2017-09-29|2022-02-08|Dow Global Technologies Llc|Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility|
    EP3688042A1|2017-09-29|2020-08-05|Dow Global Technologies LLC|Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility|
    BR112020005407A2|2017-09-29|2020-09-29|Dow Global Technologies Llc|bis-phenyl-phenoxy polyolefin catalysts with a methylenethialalkylsilicon binder in the metal for enhanced solubility|
    US10903435B2|2017-10-18|2021-01-26|Dongwoo Fine-Chem Co., Ltd.|Flexible display device|
    US10683376B2|2017-11-07|2020-06-16|Nova ChemicalsS.A.|Manufacturing ethylene interpolymer products at higher production rate|
    US10995166B2|2017-11-07|2021-05-04|Nova ChemicalsS.A.|Ethylene interpolymer products and films|
    WO2019123028A1|2017-12-21|2019-06-27|사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디|Metal-ligand complex, catalyst composition comprising same for ethylene-based polymerization, and method for preparing ethylene-based polymer by using same|
    CN111448200A|2017-12-29|2020-07-24|陶氏环球技术有限责任公司|Dual head organoaluminum compositions|
    US20200332045A1|2017-12-29|2020-10-22|Dow Global Technologies Llc|Capped dual-headed organoaluminum compositions|
    US20210002315A1|2018-03-19|2021-01-07|Dow Global Technologies Llc|Silicon-terminated organo-metal compounds and processes for preparing the same|
    CA3101628A1|2018-03-19|2019-09-26|Dow Silicones Corporation|Hot melt adhesive composition containing a polyolefin - polydiorganoosiloxane copolymer and methods for the preparation and use thereof|
    WO2019182988A1|2018-03-19|2019-09-26|Dow Global Technologies Llc|Silicon-terminated organo-metal compounds and processes for preparing the same|
    CN111918904A|2018-03-19|2020-11-10|美国陶氏有机硅公司|Polyolefin-polydiorganosiloxane block copolymers and methods of synthesizing the same|
    US20200407600A1|2018-03-19|2020-12-31|Dow Silicones Corporation|Hot melt adhesive compositions containing polyolefin-polydiorganosiloxane copolymers and methods for the preparation and use thereof|
    CN112074547A|2018-03-19|2020-12-11|陶氏环球技术有限责任公司|Method for functionalizing organometallic compounds with silane-based functionalizing agents and silane-functionalized compounds prepared thereby|
    US20210017311A1|2018-03-19|2021-01-21|Dow Silicones Corporation|Silicon-terminated telechelic polyolefin compositions and processes for preparing the same|
    JP2021516709A|2018-03-19|2021-07-08|ダウ シリコーンズ コーポレーション|Polyolefin-polydiorganosiloxane block copolymers and hydrolysis reaction methods for their synthesis|
    US11066494B2|2018-09-20|2021-07-20|Exxonmobil Chemical Patents Inc.|Amine bridged anilide phenolate catalyst compounds|
    JP2022502527A|2018-10-05|2022-01-11|ダウ グローバル テクノロジーズ エルエルシー|Dielectric reinforced polyethylene formulation|
    AR117125A1|2018-11-20|2021-07-14|Dow Global Technologies Llc|MANUFACTURING METHOD OF CURLED FIBERS AND NON-WOVEN BANDS HAVING SUCH FIBERS|
    AR117108A1|2018-11-20|2021-07-14|Dow Global Technologies Llc|WAVY MULTICOMPONENT FIBERS|
    WO2020140058A1|2018-12-28|2020-07-02|Dow Global Technologies Llc|Telechelic polyolefins and processes for preparing the same|
    SG11202107067RA|2018-12-28|2021-07-29|Dow Global Technologies Llc|Organometallic chain transfer agents|
    JP2022516118A|2018-12-28|2022-02-24|ダウ グローバル テクノロジーズ エルエルシー|Curable composition containing unsaturated polyolefin|
    BR112021012786A2|2018-12-28|2021-09-14|Dow Global Technologies Llc|CURABLE FORMULATION|
    US10882987B2|2019-01-09|2021-01-05|Nova ChemicalsS.A.|Ethylene interpolymer products having intermediate branching|
    US11046843B2|2019-07-29|2021-06-29|Nova ChemicalsS.A.|Ethylene copolymers and films with excellent sealing properties|
    WO2021084416A1|2019-11-01|2021-05-06|Nova ChemicalsS.A.|Linear high-density polyethylene with high toughness and high escr|
    WO2021091959A1|2019-11-04|2021-05-14|Dow Global Technologies Llc|Titanium biphenylphenol polymerization catalysts|
    WO2021091983A1|2019-11-04|2021-05-14|Dow Global Technologies Llc|Biphenylphenol polymerization catalysts|
    WO2021127150A1|2019-12-19|2021-06-24|Dow Global Technologies Llc|Gas-phase biphenylphenol polymerization catalysts|
    WO2021133613A1|2019-12-26|2021-07-01|Dow Global Technologies Llc|Process for the production of polymer compositions with excellent processability|
    WO2021138073A1|2019-12-30|2021-07-08|Dow Global Technologies Llc|Process for preparing an alpha-substituted acrylate|
    WO2021138075A1|2019-12-30|2021-07-08|Dow Global Technologies Llc|Process for preparing an alpha-substituted acrylate|
    WO2021155168A1|2020-01-31|2021-08-05|Dow Global Technologies Llc|Polymerization processes that include group iii and lanthanide bis-phenyl-phenoxy metal-ligand complexes and chain transfer agents|
    WO2021155158A1|2020-01-31|2021-08-05|Dow Global Technologies Llc|Group iii and lanthanide bis-phenyl-phenoxy metal-ligand complexes|
    WO2021202294A1|2020-03-31|2021-10-07|Dow Global Technologies Llc|POLYMERIZATION OF C6-C14 a-OLEFIN MONOMERS AND POLYMERS THEREOF|
    WO2021202302A1|2020-03-31|2021-10-07|Dow Global Technologies Llc|Drag reducing agent|
    WO2021243213A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Catalyst systems and processes for producing polyethylene using the same|
    WO2021242792A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated post-metallocene catalysts|
    WO2021243145A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Chemically converted catalysts|
    WO2021242801A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated hybrid catalysts|
    WO2021242800A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated post-metallocene catalysts|
    WO2022015370A1|2020-07-17|2022-01-20|Dow Global Technologies Llc|Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes|
    WO2022015369A1|2020-07-17|2022-01-20|Dow Global Technologies Llc|Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes|
    WO2022015368A1|2020-07-17|2022-01-20|Dow Global Technologies Llc|Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261746151P| true| 2012-12-27|2012-12-27|
    US61/746,151|2012-12-27|
    PCT/US2013/077936|WO2014106017A1|2012-12-27|2013-12-27|A polyolefin composition|
    [返回顶部]