POLYMER COMPOSITION, FILM AND RETORT BAG

专利摘要:
polymeric composition, film and autoclave bag a polymeric composition is disclosed herein. the polymeric composition includes: (a) a propylene-based polymer; (b) an ethylene/(alpha)-olefin copolymer; (c) a block composite comprising: (i) a crystalline polymer based on propylene; (ii) an ethylene/(alpha)-olefin polymer; and (iii) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-(alpha)olefin block. the polymeric composition provides improved thermal seals when formed into film, film layer, or flexible containers such as an autoclave bag.
公开号:BR112013007274B1
申请号:R112013007274-1
申请日:2011-09-29
公开日:2021-08-10
发明作者:Wenbin Liang；Kim L. Walton；Gary R. Marchand
申请人:Dow Global Technologies Ll；
IPC主号:

专利说明:

Historic
[0001] Plastic films find utility in a wide variety of packaging applications such as bags, containers, cups, pouches, tubes, and trays. Often, laminates, single-layer films, and multi-layer films having a heat-sealable layer are used in “form, fill, and seal” (FFS) machines. FFS machines create a continuous stream of film packages, the packages capable of being closed by film-to-film seals.
[0002] Film-to-film heat seal closures are formed by placing the film between heat seal jaws that apply pressure and also apply heat above the seal start temperature of the film. Prepared heat seal closures are often the strongest after the seal has cooled to room temperature. In order to increase production capacity, packages are filled with product before the thermal seal has time to cool completely. Consequently, it is necessary for the heat seal closure to provide sufficient strength very quickly without the need to cool the package to room temperature. Otherwise, the heat seal closure will be compromised resulting in rejected product, disposal, and increased expense.
[0003] In addition, films used in autoclave packaging need to form thermal seals that can withstand the high temperature required for sterilization. Typically, autoclave packages are exposed to temperatures greater than 121°C, or greater than 130°C, for an extended period of time in order to sterilize the contents inside.
[0004] Therefore, the art recognizes the continuing need to develop improved films for FFS applications. In particular, there is a need for films having a low heat seal onset temperature and strong thermal tack resistance over a wide temperature range in order to increase the production efficiency of packaging procedures such as FFS procedures. There is still a need for films having high temperature seal strength in addition to the aforementioned film properties. summary
[0005] The present disclosure provides a polymeric composition and films produced with it. When formed into a film (or film layer), the present polymer composition exhibits (I) low heat seal onset temperature, (II) strong hot tack resistance over a wide temperature window, and (III) high tack resistance the hot. In addition, the composite film of the present polymer composition has high temperature sealing strength suitable for use as an autoclave package film.
[0006] The present disclosure provides a polymeric composition. In one embodiment, a polymeric composition is provided including: (A) a propylene-based polymer; (B) an ethylene/α-olefin polymer; (C) a block composite comprising: (I) a crystalline polymer based on propylene; (II) an ethylene/α-olefin polymer; and (III) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-olefin block.
[0007] In one embodiment, the polymer composition includes at least 50 percent by weight, based on the sum weight of (A) and (B) of the ethylene/α-olefin copolymer.
[0008] The present disclosure provides a film. In one embodiment, a film is provided which includes at least one layer formed of a polymeric composition comprising: (A) a propylene-based polymer; (B) an ethylene/α-olefin polymer; (C) a block composite comprising: (I) a crystalline polymer based on propylene; (II) an ethylene/α-olefin polymer; and (III) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-olefin block.
[0009] In an embodiment, the film includes a second layer. The second layer is composed of an olefin-based polymer.
[0010] The present disclosure provides an article. In one embodiment, a retort bag is provided that includes a first layer, a second layer, and an optional third layer. The first layer is composed of a polymeric composition comprising: (A) a propylene-based polymer; (B) an ethylene/α-olefin polymer; (C) a block composite comprising: (I) a crystalline polymer based on propylene; (II) an ethylene/α-olefin polymer; and (III) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-olefin block.
[0011] In an embodiment, the second layer can be composed of an olefin-based polymer.
[0012] An advantage of the present disclosure is an improved polymeric composition that provides improved heat seal properties when formed into a film or film layer such as low heat seal start temperature and/or strong hot tack resistance over a wide range. temperature window, and/or high hot tack resistance.
[0013] An advantage of the present disclosure is an improved film for heat seal applications. Brief description of the drawings
[0014] Figure 1 is a plan view of a retort pouch according to an embodiment of the present disclosure;
[0015] Figure 2 is a side elevational view of a multilayer film according to an embodiment of the present disclosure;
[0016] Figure 3 is a side elevational view of a multilayer film according to an embodiment of the present disclosure;
[0017] Figure 4 is a graph showing hot tack strength and temperature for comparative samples and embodiments of the present disclosure;
[0018] Figure 5 is a graph showing hot tack temperature window for comparative samples and embodiments of the present disclosure;
[0019] Figure 6 is a graph comparing hot tack temperature window and component (A) to component (B) ratios for comparative samples and embodiments of the present disclosure;
[0020] Figure 7 is a graph showing hot tack onset temperature and component (A) to component (B) ratios for comparative samples and embodiments of the present disclosure;
[0021] Figure 8 is a graph showing thermal seal resistance and temperature for comparative samples and embodiments of the present disclosure;
[0022] Figure 9 is a graph showing coefficients of friction for comparative samples and embodiments of the present disclosure;
[0023] Figure 10 is a graph showing hot tack strength at 150°C for comparative samples and embodiments of the present disclosure; and
[0024] Figure 11 is a graph showing clarity for comparative samples and embodiments of the present disclosure. Detailed Description
[0025] The present disclosure provides a polymeric composition. In one embodiment, a polymeric composition is provided which includes: (A) a propylene-based polymer; (B) an ethylene/α-olefin copolymer; (C) a block composite comprising: (I) a crystalline polymer based on propylene; (II) an ethylene/α-olefin polymer; and (III) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-olefin block.
[0026] Optionally, the polymer composition may include (D) an olefin-based polymer and/or (E) additives. In one embodiment, the polymer composition contains at least 50 percent by weight of component (B), based on the sum weight of components (A) and (B).
[0027] In another embodiment, the polymer composition contains from 1% by weight to 50% by weight of component (A), at least 50% by weight, or at least 50% by weight to 95% by weight of component (B) , and 1% by weight to 30% by weight of component (C). Weight percentages are based on the total weight of the composition. It is understood that the amount of each component (A)-(E) can be adjusted to produce 100% of a polymeric composition. (A) Propylene-based polymer
[0028] The polymer composition contains a propylene-based polymer, component (A). The propylene-based polymer can be a homopolymer of propylene or a propylene/α-olefin interpolymer. In one embodiment, the propylene-based polymer is a homopolymer of propylene. Propylene homopolymer has a density of 0.88 g/cm3 to 0.92 g/cm3, and/or a melt flow rate of 1.0 g/10 min to 3.0 g/10 min, and/ or a melting point (Tm) greater than 130°C to 170°C. A non-limiting example of a suitable propylene homopolymer is H110-02N obtainable from The Dow Chemical Company, Midland, Michigan.
[0029] In one embodiment, the propylene-based polymer is a propylene/α-olefin interpolymer. For the purposes of this disclosure, ethylene is considered to be an α-olefin. Non-limiting examples of suitable comonomer include ethylene, C4-20 α-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene , 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene; C4-20 diolefins such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; C8-40 vinyl aromatics including styrene, o-, m-, and p-vinyl styrene, divinylbenzene, vinyl biphenyl, vinyl naphthalene; and halogen substituted C8-40 vinyl aromatics such as chlorine styrene and fluorine styrene. The α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane.
[0030] In one embodiment, the propylene/α-olefin interpolymer is a random propylene/ethylene copolymer. The propylene/ethylene random copolymer contains from 1% by weight to 10% by weight of ethylene-derived units (based on the total weight of the propylene/ethylene copolymer). The propylene/ethylene copolymer has a density of 0.88 g/cm3 to 0.92 g/cm3, and/or a melt flow rate (MFR) of 1.0 g/10 min to 10 g/10 min , and or a melting temperature (Tm) greater than 130°C to 170°C. A non-limiting example of a random propylene/ethylene copolymer is DS6D81 obtainable from The Dow Chemical Company, Midland, Michigan.
[0031] In one embodiment, the propylene-based polymer has a molecular weight distribution (MWD) greater than 4.0. In a further embodiment, the propylene-based polymer is a propylene/ethylene copolymer with a MWD greater than 4.0.
[0032] The propylene-based polymer may comprise two or more embodiments disclosed herein. (B) Ethylene/α-olefin copolymer
[0033] The present polymer composition contains an ethylene/α-olefin copolymer, component (B). The comonomer can be an α-olefin such as a linear, branched or cyclic C3-20 α-olefin. Non-limiting examples of suitable C3-20 α-olefins include propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene , 1-hexadecene, and 1-octadecene. The α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. While not being α-olefins in the classical sense of the term, for the purposes of this disclosure certain cyclic olefins, such as norbornene and related olefins, particularly 5-ethylidene-2-norbornene, are α-olefins and may be used in place of some or of all α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methyl-styrene, etc.) are α-olefins for the purposes of this disclosure. Illustrative ethylene polymers include copolymers of ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/propylene/butene, ethylene/butene/1-octene, ethylene/propylene/diene monomer (EPDM) and ethylene/ butene/styrene. Copolymers can be random or block.
[0034] In one embodiment, the ethylene/α-olefin copolymer is a homogeneously branched ethylene/α-olefin interpolymer (EXXACT obtainable from ExxonMobil Corporation, Irving, Texas and TAFMER from Mitsui), or an ethylene/α-olefin interpolymer substantially linear (AFFINITY and ENGAGE obtainable from The Dow Chemical Company, Midland, Michigan).
In one embodiment, the ethylene/α-olefin polymer has a melt index of 0.5 g/10 min, or 1.0 g/10 min to 25 g/10 min or 15 g/10 min.
[0036] In one embodiment, the ethylene/α-olefin polymer is a substantially linear ethylene/α-olefin polymer. A substantially linear ethylene/α-olefin interpolymer (SLEP) is a homogeneously branched polymer and is described in US Patent Nos. 5,272,236, 5,278,272, 6,054,544, 6,335,410 and 6,723,810 each. incorporated herein by reference. Substantially linear ethylene/α-olefin interpolymers have long chain branching. The long-chain branches have the same comonomer distribution as the polymeric backbone, and can be approximately the same length as the length of the polymeric backbone. Typically, "substantially linear" refers to a polymer that is substituted, on average, with "0.01 long chain branches per 1000 carbons" to "3 long chain branches per 1000 carbons". The length of a long-chain branch is greater than the carbon length of a short-chain branch formed by incorporating a comonomer into the polymer backbone.
[0037] Some polymers can be substituted with 0.01 long chain branch per 1000 total carbons to 3 long chain branches per 1000 total carbons, more preferably from 0.05 long chain branch per 1000 total carbons to 2 long chain branches per 1000 total carbons long chain branch per 1000 total carbons, and especially from 0.3 long chain branch per 1000 total carbons to 1 long chain branch per 1000 total carbons.
Substantially linear ethylene/α-olefin interpolymers form a unique class of homogeneously branched ethylene polymers. They differ substantially from the well-known class of conventional homogeneously branched linear ethylene/α-olefin interpolymers, as discussed above, and, furthermore, they are not in the same class as heterogeneous "Ziegler-Natta catalyst polymerized" linear ethylene polymers conventional (e.g., ultra low density polyethylene (ULDPE), linear low density polyethylene (LLDPE) or high density polyethylene (HLDPE), prepared, for example, using the technique disclosed by Anderson et al. ° 4,076,698); nor are they in the same class as high-pressure, free radical-initiated, highly branched polyethylene such as, for example, low-density polyethylene (LDPE), ethylene/acrylic acid (EAA) copolymers, and ethylene/vinyl acetate copolymers (EVE).
The homogeneously branched substantially linear ethylene/α-olefin interpolymers useful in the invention have excellent processability, although they have a relatively narrow molecular weight distribution. Surprisingly, the melt flow ratio (I10/I2) according to ASTM D 1238, of substantially linear ethylene interpolymers can vary widely, and essentially independently of the molecular weight distribution (Mw/Mn or MWD). This surprising behavior is contrary to that of conventional homogeneously branched linear ethylene interpolymers, such as those described, for example, by Elston in US 3,645,992, and conventional heterogeneously branched "Ziegler-Natta polymerized" linear polyethylene interpolymers such as those described by Anderson et al., in US 4,076,698. Unlike substantially linear ethylene interpolymers, linear ethylene interpolymers (either homogeneously or heterogeneously branched) have rheological properties such that, as the molecular weight distribution increases, the I10/I2 value also increases.
Long-chain branching can be determined using 13C nuclear magnetic resonance spectroscopy (13C NMR), and can be quantified using the Randall method (Rev. Micromol. Chem. Phys., 1989, C29 (2&3) ), pages 285297), the disclosure of which is incorporated herein by reference. Two other methods are gel permeation chromatography, coupled with a low-angle laser light scattering detector (GPC-LALLS), and gel permeation chromatography, coupled with a differential viscosimetric detector (GPC-DV). The use of these techniques for detecting long-chain branching, and the underlying theories, are well documented in the literature. See, for example, Zimm B.H. and Stockmayer, W.H., J. Chem. Phys., 17, 1301 (1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991), pages 103-112.
[0041] In one embodiment, SLEP has a density less than or equal to 0.91 g/cm3, or from 0.885 g/cm3 to 0.89 g/cm3, or 0.905 g/cm3. SLEP has a melt index of 0.5 g/10 min to 2 g/10 min, and/or a melting temperature of 95°C to 105°C. A non-limiting example of a suitable SLEP is AFFINITY PL 1880 obtainable from The Dow Chemical Company, Midland, Michigan.
[0042] As used herein, the "sum-weight" is the combined weight of component (A) plus the weight of component (B). The sum-weight is a measure to evaluate component (A) with respect to component (B) and vice versa. In other words, the sum-weight excludes component (C). In one embodiment, the sum weight contains greater than 50% by weight, or greater than 50% by weight to 95% by weight of component (B) (the ethylene/α-olefin copolymer).
[0043] The ethylene-based polymer may comprise two or more embodiments disclosed herein. (C) Composite in blocks
[0044] The present polymer composition contains a composite in blocks. The block composite includes: (I) a crystalline polymer based on propylene; (II) an ethylene/α-olefin polymer; and (III) a block copolymer comprising a propylene-based crystalline block and an ethylene/α-olefin block.
[0045] The term "block copolymer" or "segmented copolymer" refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear fashion, that is, a polymer comprising units chemically differentiated that bond end-to-end with respect to polymerized ethylenic functionality, rather than pendant or grafted. In an embodiment, the blocks differ in the amount or type of comonomer incorporated in each of them, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long-chain branching or hyperbranching, homogeneity, or any other chemical or physical property. The block copolymers of the present disclosure are characterized by unique polymer polydispersion (PDI or Mw/Mn) distributions, block length distribution, and/or block number distribution due, in a preferred embodiment, to the effect of the exchange agents in combination with catalysts.
[0046] A "block composite" is a new polymer comprising a soft copolymer, a hard copolymer and a block copolymer having a soft segment and a hard segment, the hard segment of the block copolymer having the same polymer composition hard in the block composite and the soft segment of the block copolymer has the same composition as the soft copolymer of the block composite. The block copolymer can be linear or branched. More specifically, when produced in a continuous process, the block composite desirably has a PDI of 1.7 to 15, or 1.8 to 3.5, or 1.8 to 2.2, or 1.8 to 2.1. When produced in a batch or semi-batch process, the composite block has a PDI from 1.0 to 2.9, or from 1.3 to 2.5, or from 1.4 to 2.0, or from 1, 4 to 1.8.
"Hard" segments refer to very crystalline blocks of polymerized units in which the monomer is present in an amount greater than 95 percent by weight, and preferably greater than 98 percent by weight. In other words, the comonomer content in the hard segments is less than 5 percent by weight, and preferably less than 2 percent by weight. In some embodiments, the hard segments comprise all or substantially all of the propylene units. On the other hand, "soft" segments refer to amorphous, substantially amorphous or elastomeric blocks of polymerized units in which the comonomer content is greater than 10 mol%. Block Composite Index
[0048] The present examples (Tables 3 and 4) show that the insoluble fractions contain an appreciable amount of ethylene that would otherwise not be present if the polymer were simply a mixture of iPP homopolymer and EP copolymer. To explain this “extra ethylene”, a mass balance calculation can be performed to estimate a composite block index of the amount of xylene soluble and insoluble fractions and the percentage by weight of ethylene present in each of the fractions.
[0049] A sum of the percentage by weight of ethylene of each fraction according to equation 1 results in an overall percentage by weight of ethylene (in the polymer). This mass balance equation can also be used to quantify the amount of each component in a binary mixture or extended to a ternary mixture or n-component mixture.

[0050] Applying equations 2 to 4, it is calculated the amount of soft block (providing the source of extra ethylene) present in the insoluble fraction. By substituting the % by weight of C2 from the insoluble fraction in the left member of equation 2, one can calculate the % by weight of hard iPP and the % by weight of soft EP using equations 3 and 4. Note that the % by weight of ethylene in the EP mole is adjusted to equal the % by weight of ethylene in the xylene-soluble fraction. The % by weight of ethylene in the iPP block is set to zero or if otherwise known from its DSC melting point or other measure of composition, the value can be put in its place.

[0051] After explaining the "additional" ethylene present in the insoluble fraction, the only way to have an EP copolymer present in the insoluble fraction, the EP polymer chain must be connected to an iPP polymer block (or else it would have been extracted in the xylene-insoluble fraction). Therefore, when the iPP block crystallizes, it prevents the EP block from solubilizing.
[0052] To estimate the composite index in blocks, the relative amount of each block must be taken into account. To approximate this, the ratio of soft EP to hard iPP is used. The ratio of the soft EP polymer to the hard iPP polymer can be calculated using Equation 2 of the mass balance of the total ethylene measured in the polymer. Alternatively, it can also be estimated from a mass balance of monomer and comonomer consumption during polymerization. Table 3 refers to the estimated ratio of iPP and EP present in the diblock copolymer for all experiments. The weight fraction of hard iPP and the weight fraction of soft EP are calculated using Equation 2 and it is assumed that the hard iPP does not contain any xylene. The % by weight of ethylene of the EP mole is the amount of ethylene present in the fraction soluble in xylene.
[0053] For example, if a block composite of the invention (C) composed of iPP (C)(I), EP (C)(II) and iPP/EP diblock (C)(III) contains a total of 47 % by weight of C2 and is prepared under conditions to produce a soft EP polymer with 67% by weight of C2 and an iPP homopolymer containing zero ethylene, the amount of soft EP and hard iPP will respectively be 70% in weight and 30% by weight (calculated using Equations 3 and 4). If the percentage of EP is 70% by weight and that of iPP is 30% by weight, the relative ratio of the EP:iPP blocks can be expressed as 2.33:1.
[0054] Hence, if someone skilled in the art performs a xylene extraction of the polymer and recovers 40% by weight of insoluble and 60% by weight of soluble, this will be an unexpected result and this would lead to the conclusion that a block copolymer fraction inventive was present. If the ethylene content of the insoluble fraction is subsequently measured to be 25% by weight of C2, Equations 2 to 4 can be solved to explain this additional ethylene and will result in 37.3% by weight of soft EP polymer and 62 .7% by weight of hard iPP polymer.
[0055] Since the insoluble fraction contains 37.3% by weight of EP copolymer, it can be bonded to an additional 16% by weight of iPP polymer, based on the EP:iPP block ratio of 2. 33:1. This brings the estimated amount of diblocks in the insoluble fraction to be 53.3% by weight. For the whole (unfractionated) polymer, the composition is described as being 21.3% by weight iPP/EP diblocks, 18.7% by weight iPP polymer, and 60% by weight EP polymer. . Since the compositions of these polymers are new, the term "block composite index" (or "BCI") is defined herein as equal to the weight percentage of diblock divided by 100% (i.e., weight fraction). The composite index value in diblocks can range from 0 to 1, where 1 would equal 100% inventive diblocks and zero would be a material such as a random copolymer or traditional blend. For the example described above, the block composite index for the block composite is 0.213. For the insoluble fraction, the BCI is 0.533, and for the soluble fraction the BCI is zero.
[0056] Depending on the estimates made of the total polymer composition and the error in the analytical measurements that are used to calculate the composition of the hard and soft blocks, an error between 5 and 10% is possible in the computed value of the composite block index. Such estimates include the % by weight of C2 in the hard iPP block measured from DSC melting point, NMR analysis, or process condition; the average % by weight of C2 in the soft block estimated from the composition of the xylene solubles, either by NMR, or by soft block DSC melting point (if detected). But overall, the block composite index calculation reasonably explains the unexpected amount of "additional" ethylene present in the insoluble fraction, the only way to have an EP copolymer present in the insoluble fraction, the EP polymer chain must be bonded to a polymer block of iPP (or else s would have been extracted in the xylene-soluble fraction).
[0057] The block composite polymers of the present disclosure are prepared by a process comprising contacting an addition polymerizable monomer or blending monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a chain exchange agent, said process being characterized by formation of at least part of the growing polymer chains under different process conditions in two or bad reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under continuous polymerization conditions.
[0058] In one embodiment, the block composite comprises a fraction of the block polymer that has a very likely distribution of block lengths. Preferred polymers in accordance with the present disclosure are block copolymers containing 2 or 3 blocks or segments. In a polymer containing three or more segments (i.e. blocks separated by a distinguishable block) each may be the same or chemically different and generally characterized by a distribution of properties. In a process to prepare polymers, exchange agent is used as a way to extend the half life of a polymer chain such that a substantial fraction of the polymer chains exit at least the first reactor of a series of multiple reactors or the first zone in a multizone reactor operating substantially under continuous flow conditions in the form of polymer terminated with a chain exchange agent, and the polymer chain experiences different polymerization conditions in the polymerization zone or in the next reactor. Different polymerization conditions in the respective reactors or zones include the use of different monomers, comonomer, or monomer/comonomer ratios, different polymerization temperatures, pressures or partial pressures of various monomers, different catalysts, different monomer gradients, or any other difference that leads to the formation of a distinguishable polymeric segment. Thus, at least a portion of the polymer comprises two, three or more, preferably two or three intermolecularly arranged differentiated polymeric segments.
[0059] The following mathematical treatment of the resulting polymers is based on theoretically derived parameters believed to apply and demonstrate that, especially in two or more steady states, continuous reactors or zones connected in series, having different polymerization conditions to which they are exposed the growing polymer, the block lengths of polymer being formed in each reactor or zone will conform to a most likely distribution derived as follows, in which pi (π) is the probability of polymer propagation in a reactor with respect to sequences of catalyst blocks i. The theoretical treatment is based on standard methods and hypotheses known in the art and used in predicting the effects of polymerization kinetics on molecular architecture, including the use of reaction rate expressions of masses that are not affected by block lengths. or chains, and the hypothesis that polymer chain growth completes in a very short time interval compared to the average reactor residence time. Such methods have previously been disclosed in W.H. Hamielec and J.F. MacGregor, "Polymer Reaction Engineering", K.H. Reichert and W. Geisler, Eds., Hanser, Munich, 1983. Furthermore, it is assumed that each incidence of the chain exchange reaction in a given reactor results in the formation of a single polymeric block, while the transfer of the polymer terminated by chain exchange agent to a different reactor or zone and exposure to different polymerization conditions results in the formation of a different block. For catalyst i, the fraction of sequences of length n being produced in the reactor is given by Xi[n], where n is an integer from 1 to infinity representing the total number of monomeric units in the block. Xi[n]=(1-pi)pi(n-1) very likely distribution of block lengths Ni= 1/1-pi numeric average block length
[0060] If more than one catalyst is present in a reactor or zone, each catalyst will have a propagation probability (pi) and therefore will have a single average block length and distribution for polymer being made in that reactor or zone. In a most preferred embodiment, the propagation probability is defined as:
where Rp[i]= local rate of monomer consumption per catalyst i, (mol/L/time); Rt[i]= total chain transfer rate and termination for catalyst i, (mol/L/time); and Rs[i]= local chain transfer rate with inactive polymer (mol/L/time).
[0061] For a given reactor, the polymer propagation rate, Rp[i], is defined using an apparent rate constant, kpi, multiplied by a total concentration of monomers, [M], and multiplied by the local concentration of catalyst i, [Ci] as follows:

[0062] Chain transfer, termination, and exchange rate are determined as a function of chain transfer to hydrogen (H2), beta hydride elimination, and chain transfer to chain exchange agent (CSA). The quantities [H2] and [CSA] are molar concentrations and each heat k subscript is a rate constant for the reactor or zone:

[0063] Inactive polymer chains are created when a polymer portion transfers to a CSA and all reacting CSA portions are each supposed to be paired with an inactive polymer chain. The catalyst inactive polymer chain transfer rate i is given as follows, where [CSAf] is the feed concentration of CSA, and the amount ([CSAf]-[CSA]) represents the concentration of inactive polymer chains :

[0064] As a result of the above theoretical treatment, it can be seen that the overall block length distribution of the resulting block copolymer is the sum of the block length distribution given previously by Xi[n], influenced by the rate of production of local polymer for catalyst i. This means that a polymer prepared in at least two different polymer-forming conditions will have at least two distinguishable blocks or segments, each having a most likely block length distribution.
Suitable catalysts and catalyst precursors for producing the composite in blocks (C) include metal complexes such as disclosed in WO2005/090426, in particular those disclosed beginning on page 20, line 30 to page 53, line 20, which here it is incorporated by reference. Suitable catalysts are also disclosed in US 2006/0199930, US 2007/0167578, US 2008/0311812, US 7,355,089, or WO 2009/012215, which are incorporated herein by reference with respect to catalysts. Suitable cocatalysts are those disclosed in WO 2005/090426, in particular those disclosed at page 19, line 21 to page 20, line 12, which are incorporated herein by reference. Particularly preferred chain exchange agents are dialkyl zinc compounds.
[0066] The block polymers of the block composite comprise in polymerized form propylene and ethylene and/or one or more C4-20 α-olefin comonomers, and/or one or more additional copolymerizable comonomers or they comprise 4-methyl- 1-pentene and ethylene and/or one or more C4-20 α-olefin comonomers, or they comprise 1-butene and ethylene, propylene and/or one or more C5-20 α-olefin comonomers and/or a or more additional copolymerizable comonomer. Additional suitable comonomers are selected from diolefins, cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, and vinylidene aromatic compounds.
[0067] One can measure the comonomer content in the resulting block composite polymers using any appropriate technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. It is most desirable that some or all polymeric blocks comprise amorphous or relatively amorphous polymers such as copolymers of propylene, 1-butene or 4-methyl-1-pentene and a comonomer, especially random copolymers of propylene, 1-butene or 4-methyl -1-pentene with ethylene, and any remaining polymeric blocks (hard segments), if any, predominantly comprise propylene, 1-butene or 4-methyl-1-pentene in polymerized form. Preferably such segments are very crystalline or stereospecific polypropylene, polybutene or poly(4-methyl-1-pentene), especially isotactic homopolymers.
[0068] More preferably still, the block copolymers of the present disclosure comprise from 10 to 90 percent of crystalline or relatively hard segments and from 90 to 10 percent of amorphous or relatively amorphous segments (soft segments), preferably from 20 to 80 per cent. percent crystalline or relatively hard segments and 80 to 20 percent amorphous or relatively amorphous segments (soft segments), most preferably 30 to 70 percent crystalline or relatively hard segments, and 70 to 30 percent amorphous or relatively hard segments or relatively amorphous (soft segments). Within the soft segments, the mole percent of comonomer may range from 10 to 90 mole percent, preferably from 20 to 80 mole percent, most preferably from 33 to 75 mole percent. In the case where the comonomer is ethylene, preferably it is present in an amount of from 10 mole percent to 90 mole percent, more preferably from 20 mole percent to 80 mole percent, and most preferably from 33 mole percent to 75 mole percent molar. Preferably, the copolymers comprise hard segments that are from 90 mole percent to 100 mole percent propylene. The segments may be more than 90 mole percent, preferably more than 93 mole percent and more preferably more than 95 mole percent propylene, and most preferably more than 98 mole percent propylene. Such hard segments have corresponding melting points with values greater than or equal to 80°C, preferably greater than or equal to 100°C, more preferably greater than or equal to 115°C, and most preferably greater than or equal to 120°C. Preferably, the block copolymers of the present disclosure comprise from 10 to 90 percent crystalline or relatively hard segments and from 90 to 10 percent amorphous or relatively amorphous segments (soft segments). Within the soft segments, the mole percentage of comonomer can range from 5 to 90 mole percent, preferably from 10 to 60 mole percent. In the case where the comonomer is ethylene, preferably it is present in an amount from 10% by weight to 75% by weight, more preferably from 30% by weight to 70% by weight. Preferably, the copolymers comprise hard segments which are from 80% by weight to 100% by weight of propylene. The segments can be more than 90% by weight, preferably more than 95% by weight and more preferably more than 98% by weight propylene.
[0069] The block composite polymers of the present disclosure can be differentiated from conventional random copolymers, physical polymer blends, and from block copolymers prepared via sequential addition of monomers. Block composites can be distinguished from random copolymers by characteristics such as higher melting temperatures for a comparable amount of comonomer, block index and block composite index, as described below; of a physical blend by characteristics such as block index, composite block index, better tensile strength, improved fracture toughness, finer morphology, improved optics, and higher impact strength at lower temperature; of block copolymers prepared by sequential addition of monomers by molecular weight distribution, rheology, shear decrease, rheology ratio, and because there is block polydispersion.
[0070] In some embodiments, the block composites of the present disclosure have a composite block index (BCI), defined below, that is greater than zero but less than about 0.4 or from about 0.1 to about 0.3. In other embodiments, BCI is greater than about 0.4 and up to about 1.0. Additionally, the BCI can range from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments, the BCI is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, of about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, BCI is in the range of from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from about from 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
[0071] Other desirable compositions according to the present disclosure are elastomeric block copolymers of propylene, 1-butene or 4-methyl-1-pentene with ethylene, and optionally one or more α-olefins or diene monomers. Preferred α-olefins for use in this embodiment of the present disclosure are designated by the formula CH2=CHR*, where R* is a linear or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene (when copolymerized with propylene), and 1-octene. Suitable dienes for use in the preparation of such polymers, especially multiblock EPDM-type polymers include conjugated and unconjugated, straight or branched chain, cyclic or polycyclic dienes containing from 4 to 20 carbon atoms. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene. The resulting product may comprise alternating isotactic homopolymer segments with elastomeric copolymer segments, prepared in place during polymerization. Preferably, the product may comprise only the elastomeric block copolymer of propylene, 1-butene or 4-methyl-1-pentene with one or more comonomers, especially ethylene.
[0072] Since diene-containing polymers contain alternating segments or blocks containing greater or lesser amounts of diene (including no amount) and α-olefin (including none), the total amount of diene and α-olefin can be reduced without loss of subsequent polymeric properties. That is, as diene and α-olefin monomers are preferentially incorporated into a block type of polymer rather than uniformly or randomly throughout the polymer, they are used more efficiently and subsequently the crosslink density of the polymer can be better controlled . Such crosslinkable elastomers and cured products have advantageous properties, including greater tensile strength and better elastic recovery.
[0073] In one embodiment, the block composite has a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 35,000 to about 1,000,000 and more preferably from 50,000 to about 300,000, preferably from 50,000 to about 200,000. The composite in blocks (C) is disclosed in co-pending U.S. Patent Application No. 61/248,160 filed October 2, 2009, the entire contents of which are incorporated herein by reference. Crystalline Block Composite
[0074] The block composite (C) can be a crystalline block composite. The term "crystalline block composite" (CBC) refers to a new polymer comprising a crystalline ethylene-based polymer (CEP), a crystalline alpha-olefin-based polymer (CAOP), and a block copolymer having a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB), with the CEB of the block copolymer having essentially the same composition as the CEP of the block composite and the CAOB of the block copolymer having essentially the same composition of the CAOP of the composite in blocks. Block copolymers can be linear or branched. More specifically, each of the respective block segments may contain long chain branches of similar composition as the respective block, but the block copolymer segment is substantially linear as opposed to containing grafted or branched blocks. When produced in a continuous process, the crystalline block composites desirably have PDI from 1.7 to 15, preferably from 1.8 to 5, more preferably from 1.8 to 3.5, and most preferably from 1.8 to 2.5.
[0075] CAOB refers to very crystalline blocks of polymerized alpha-olefin units in which the monomer is present in an amount greater than 90 mol%, preferably greater than 93 mol%, more preferably greater than 95 mol percent, and preferably greater than 96 mole percent. In other words, the comonomer content in CAOBs is less than 10 mole percent, and preferably less than 7 mole percent, and more preferably less than 5 mole percent, and most preferably less than 4 mole percent. Such CAOBs have corresponding melting points that are greater than or equal to 80°C, preferably greater than or equal to 100°C, more preferably greater than or equal to 115°C, and most preferably greater than or equal to 120°C. In some embodiments, the CAOB comprises all or substantially all of the propylene units. On the other hand, CEB refers to blocks of polymerized ethylene units in which the comonomer content is less than or equal to 10 mol%, preferably between 0 mol% and 10 mol%, more preferably between 0 mol% and 7 mol% and most preferably between 0 mol% and 5 mol%. Such CEB has corresponding melting points which preferably are greater than or equal to 75°C, more preferably greater than or equal to 90°C, and most preferably greater than or equal to 100°C.
[0076] Preferably, the crystalline block composite polymers of the present disclosure comprise from 0.5 to 94% by weight of CEP, from 0.5 to 94% by weight of CAOP and from 5 to 99% by weight of copolymer in blocks. More preferably, the crystalline block composite polymers comprise from 0.5 to 79% by weight of CEP, from 0.5 to 79% by weight of CAOP and from 20 to 99% by weight of block copolymer and more preferably, from 0.5 to 49% by weight of CEP, from 0.5 to 49% by weight of CAOP and from 50 to 99% by weight of block copolymer.
[0077] Preferably, the block copolymers of the present disclosure comprise from 5 to 95% by weight of crystalline ethylene blocks (CEP) and from 95 to 5 percent by weight of crystalline alpha-olefin blocks (CAOB). They may comprise from 10 wt% to 90 wt% CEB and from 90 wt% to 10 wt% CAOB. More preferably, the block copolymers comprise from 25 to 75% by weight of CEB and from 75 to 25% by weight of CAOB, and even more preferably they comprise from 30 to 70% by weight of CEB and from 70 to 30% by weight of CAOB weight.
[0078] In some embodiments, the block composites of the present disclosure have a crystalline block composite index (CBCI), defined below, that is greater than zero but less than about 0.4 or about 0.1 to about 0.3. In other embodiments, CBCI is greater than about 0.4 and up to about 1.0. Additionally, the CBCI can range from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments, CBCI is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about from 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, CBCI is in the range of from about 0.4 to about 1.0, from about 0.5 to about 1.0, from about 0.6 to about 1.0, from about 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
[0079] Still preferably, crystalline block composites of this embodiment of the present disclosure have a weight average molecular weight (Mw) of from 1,000 to about 2,500,000, preferably from 35,000 to about 1,000,000 and more preferably from 50,000 to 500,000, from 50,000 to about 300,000, and preferably from 50,000 to about 200,000. The crystalline block composite and crystalline block composite index (CBCI) calculation is disclosed in co-pending US Patent Application No. 61/356,978 filed June 21, 2010, the entire contents of which are incorporated herein by reference .
[0080] In one embodiment, the block composite (C) includes homopolymer of isotactic crystalline propylene, or iPP (C)(I), ethylene/propylene copolymer, or EP (C)(II), and block copolymer (C )(III). The block copolymer subcomponent (C)(III) includes a diblock of formula (1) below.

[0081] The term "EP" represents a segment of polymerized ethylene and propylene monomeric units. The term "iPP" represents an isotactic propylene homopolymer segment or a substantially isotactic propylene homopolymer segment with minimal (<1%) atactic or syndiotactic defects.
[0082] In one embodiment, the composite block (C) has an ethylene content greater than 20% by weight, or greater than 30% by weight, or greater than 35% by weight. The ethylene weight percentage is based on the total weight of the block composite (C).
[0083] In an embodiment, component (C)(III) is present in an amount greater than 15% by weight, or greater than 20% by weight, or greater than 25% by weight, or greater than 30% by weight, or greater than 50% by weight to about 80% by weight, based on the total weight of component (C).
[0084] In an embodiment, the composite in blocks (component C) has a density of 0.865 to 0.90 g/cm3, or 0.897 g/cm3 and/or a melt index (I2) of 1 to 50 g/10 min.
[0085] In one embodiment, the C-block composite has a melt index of about 1, or about 2, or about 3, or about 4, or about 5, or about 6 at about 40, or at about 35, or at about 20, or at about 15, or at about 13 g/10 min.
[0086] In one embodiment, the C-block composite has I10/I2 of about 6, or about 7, or about 8 to about 20, or about 19, or about 17, or a about 17, or about 15, or about 13, or about 12, or about 11. D. Olefin-Based Polymer
[0087] The present polymer composition may optionally include an olefin-based polymer. Non-limiting examples of suitable olefin-based polymers include propylene-based polymer and ethylene-based polymer. Non-limiting examples of suitable ethylene-based polymer include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), HDPE, homogeneously branched polyethylene (non-limiting examples include polymers sold under the EXXACT trade name from ExxonMobil and with Mitsui's TAFMER tradename), substantially linear ethylene polymer (non-limiting examples include polymers sold under the tradenames AFFINITY and ENGAGE of The Dow Chemical Company), functionalized olefin-based polymer, and any combination thereof.
[0088] In one embodiment, the olefin-based polymer may include a functionalized olefin-based polymer. Non-limiting examples of suitable functionalized olefin-based polymers include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene/acrylic acid copolymer, ethylene/methacrylate copolymer, and any combination thereof. E. Additives
[0089] The present polymer composition may optionally comprise one or more additives. Known additives can be incorporated into the resin composition as long as they do not compromise the objectives of the disclosure. Non-limiting examples of such additives include nucleating agents, antioxidants, acid scavengers, thermal stabilizers, light stabilizers, ultraviolet light absorbers, lubricants, antistatic agents, pigments, dyes, dispersing agents, inhibitors, neutralizing agents, foaming agents, plasticizers , flow improvers, non-stick agents, slip additives, and weld strength improvers.
[0090] The aforementioned additives can be employed in any combination and each of them can be contained in the respective polymeric compositions in amounts of 0.0001 to 10 percent by weight (or any individual value or sub-range thereof) or in an amount of 0.001 to 1.0 percent by weight.
[0091] The polymer composition may comprise two or more embodiments disclosed herein. two . film
[0092] The present disclosure provides films comprising the present polymeric composition. In other words, the present polymer composition can be cast into a film. In one embodiment, a film is provided which includes: (A) from 1% by weight to 50% by weight of the propylene-based polymer; (B) at least 50% by weight of the ethylene/α-olefin polymer based on the sum weight of (A) and (B); and (C) from 1% by weight to 30% by weight of the composite block.
[0093] Optionally, the film may include olefin-based polymer (D) and/or additives (E). Components (A)-(E) may be any respective components (A)-(E) disclosed above for the polymer composition. In one embodiment, the film contains from 5% by weight to 50% by weight of component (A), at least 50% by weight to 95% by weight of component (B), and from 1% by weight to 30% by weight of component (C). Weight percentages are based on the total weight of the film. The film exhibits one, some, or all of the following properties shown in Table 1 below. Table 1 - Film Properties

[0094] To improve processing and/or make the packaging speed faster, a low coefficient of friction (COF) is desirable. The friction coefficient in Table 1 above is the film-to-film friction coefficient. A wide hot tack temperature window is advantageous for (I) lowering seal start temperatures, (II) improving seal stability at autoclave temperatures (120°C to 130°C), and (III) making faster processing speeds. A high hot tack resistance at 150°C is advantageous for autoclave applications.
[0095] Applicant has found a film with the following desirable combination of properties: low COF, wide hot tack temperature window, low hot tack onset temperature, and high hot tack resistance at high temperature.
[0096] Furthermore, the present film has desirable optical properties: low opacity and high clarity.
[0097] In one embodiment, the film of a hot tack onset temperature (HTIT) less than 80°C, or less than 75°C.
[0098] The present film may be a single layer film. The present polymer composition can be molded in one or more layers into a multilayer film. The mono/multilayer film structure can be laminated, extruded (pour/sheet), coextruded (pour/sheet), oriented (axially, biaxially, stretch structure, bubble, double bubble, trapped bubble), and combinations thereof.
[0099] In one embodiment, the present film is free from crosslinking. As used herein, a film is "cross-link free" when it has a gel content of less than 5% measured in accordance with Method A of ASTM D-2765-84.
[0100] In an embodiment, the film has a thickness of about 7.6 µm to about 127 µm (0.3 mil (milliinch) to about 5.0 mil), or about 89 µm (3 .5 thousand). (A) Multilayer film
[0101] The present disclosure provides a multilayer film. In one embodiment, a multilayer film is provided that includes a first layer, a second layer, and an optional third layer. The first layer includes: (A) from 1% by weight to 50% by weight of the propylene-based interpolymer; (B) at least 50% by weight of the ethylene/α-olefin polymer based on the sum weight of (A) and (B), and (C) from 1% by weight to 30% by weight of the block composite .
[0102] Weight percentages are based on the total weight of the first layer. Components (A), (B), and (C) can be any component (A)-(C) thereof disclosed for the present polymer composition. The first layer can include optional components (D) and (E).
[0103] In an embodiment, component (B) of the first layer is an ethylene/α-olefin polymer having a density less than or equal to 0.91 g/cm3 and/or a melt index of 0.5 g/10 min at 25 g/10 min.
[0104] In one embodiment, the first layer of component (C) of the multilayer film comprises (I) iPP, (II) ethylene/propylene copolymer, and (III) a diblock copolymer comprising a block of iPP and a block of ethylene/propylene. The density of the block composition (C) is 0.87 g/cm3, or 0.875 g/cm3 to 0.915 g/cm3, or 0.92 g/cm3.
[0105] In an embodiment, the second layer of the multilayer film is composed of an olefin-based polymer. Non-limiting examples of suitable olefin-based polymers include LLDPE, LDPE, homogeneously branched polyethylene, SLEP, HDPE, propylene-based polymer, and any combination thereof.
[0106] In one embodiment, the second layer includes from 70% by weight to 99% by weight of olefin-based polymer and from 30% by weight to 1% by weight of functionalized olefin-based polymer. Non-limiting examples of functionalized olefin-based polymers include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene/acrylic acid copolymer, ethylene/acrylate copolymer, and any combination thereof. Weight percentages are based on the total weight of the second layer.
[0107] The optional third layer includes a material selected from nylon, poly(ethylene terephthalate) (PET), polypropylene, and any combination thereof.
[0108] In one embodiment, the multilayer film is a three layer film. The first layer is a sealing layer (containing the present polymer composition), the second layer is a core layer (containing the olefin-based polymer), and the third layer is a lining layer (containing nylon, PET, and/ or polypropylene). The sealing layer is an inner layer. The second layer is a core layer. A “core layer” is a layer located between at least two other layers. In other words, the core layer is not the innermost layer or an outermost layer. The lining layer is an outermost layer.
[0109] In an embodiment, the three-layer film has a thickness of 7.6 μ m (0.3 mil), or 12.7 μ m (0.5 mil) to 127 μ m (5 mil), or of 76 μm (3 mil (milliinch)).
[0110] The present film may comprise two or more embodiments disclosed herein. 3. Articles
[0111] The present disclosure provides articles comprising at least one component formed by the present polymeric composition. In other words, the present polymer composition can be molded into articles. The present polymer composition and/or the present film can be molded into a finished article of manufacture by any of a number of conventional processes and apparatus. Illustrative processes include, but are not limited to, extrusion, calendering, injection molding, and/or compression molding. For example, articles can be prepared by injection molding, extrusion, extrusion followed by thermoforming, low pressure molding, compression molding, and the like. Non-limiting examples of suitable articles include extruded profiles (single- or multi-layered films), foams, sealing strips, belts, hoses, wire and cable coatings, tubes, flooring materials, gaskets, molded products, sheets, and parts extruded. Additional items include automotive parts (eg instrument panels and window seals), computer parts, building materials, appliances, toys, shoe components, labels and tags, paperboard such as milk cartons, sachets, bags, pouches, sealed bags or sausage and/or meat wrap, dry food packages such as for cereal, sugar, flour, etc., thermoformed multilayer films, blister packs, and pharmaceutical packaging films. (A) Retort bag
[0112] In one embodiment, the article is a flexible container containing the present polymeric composition. Referring to the drawings, and initially to Figure 1, one form of article is a retort pouch and is shown and indicated generally by reference numeral 10. As used herein, "a retort pouch" is a flexible package that can remain hermetically sealed. after exposure to temperatures of 120°C-135°C and pressure up to 500 kPa for 30-80 minutes. The retort pouch 10 includes two sheets 12A and 12B of a multilayer film, joined and sealed together at their respective peripheries by a thermal closure 14. Thermal closure 14 may extend along the entire common periphery of sheets 12A, 12B. Alternatively, thermal closure 14 may extend along a portion of the common periphery of sheets 12A, 12B and within thermal closure 14. Storage space 16 is isolated from the surrounding environment and contains the contents 18 of the retort pouch, for example, foodstuffs. Although the package is described as having two sheets 12A, 12B, it is understood that a single sheet may be used. The single sheet can be folded back on itself to form the two layers. The three unconnected edges would then be heat sealed after the contents were placed between the folded layers.
[0113] The 12A, 12B of the retort pouch 10 can be fabricated with the two-layer film structure shown in Figure 2. An outer layer 20 is further away from the packaging contents 18. In an embodiment, the outer layer corresponds to the second layer of the film described above.
[0114] A seal layer 22 is immediately adjacent to the outer layer 20. The seal layer 22 (or the innermost layer, or the retort pouch content contacting layer) is composed of the present polymer composition. The outer layer 20 and the sealing layer 22 can be directly coextruded with each other. Alternatively, an adhesive layer 24 can bond the outer layer 20 to the sealing layer 22 as shown in Figure 2. The film-to-film contact under heat and pressure of opposing sealing layers 24 forms a thermal seal 14.
[0115] In one embodiment, the retort pocket 10 is a retort pocket that is bend-free or substantially bend-free.
[0116] In one embodiment, a retort bag 100 is manufactured with a three-layer film as shown in Figure 3. The retort bag 100 is similar to the retort bag 10 except that the retort bag 100 is manufactured with a film three-layer, not with a two-layer film. Sealing layer 22 contacts layer 20. A liner layer 26 contacts layer 20. Contact between layers can be "direct" (intimate and/or immediate touch) or "indirect" (intermediate adhesive layer and/or intermediate structure between film layers). In this configuration, layer 20 (corresponding to the second layer of the film described above) becomes a core layer. Layer 26 is the outermost layer and corresponds to the third layer of the film described above.
[0117] The thicknesses of layers 22, 20, and 26 can be the same or different.
[0118] In one embodiment, the sealant layer 22 is coextruded to the core layer 20. The liner layer 26 is coextruded to the core layer 20. Each of the sealant layer 22 and the liner layer 26 is in direct and intimate contact with the layer 20. In other words, there are no intermediate layers between the sealing layer 22 and the core layer 20. Similarly, there are no intermediate layers between the liner layer 26 and the core layer 20.
[0119] In one embodiment, the retort bag 10 or the retort bag 100 includes a barrier layer.
[0120] The 10/100 retort bag is designed to withstand a maximum applied temperature in the range of 120 to 135°C (or any individual value or sub-range thereof) for 30 to 90 minutes without significant degradation.
[0121] The retort bag is used to secure, protect, or conserve non-limiting items such as food, condiments, medicines, and sterile solutions. The retort bag can be shaped like a "pillow", or a "flat bottom" or "platelet" retort bag. In "form and fill" packaging, they are formed in line by manufacturing bottom and side closures of two films joined in surface contact with each other, adding the material to be preserved, and forming the final closure for wrapping the food or other substance to be packaged, all in continuous operation. Generally speaking, the resulting retort bag is a pillow-shaped bag. Alternatively, the processor can employ prefabricated pouches having a single open end, which are filled and closed or sealed after filling. This technique is best suited for autoclave pouches in the form of a platelet. In a final step, the retort bag and its contents are normally heated to pasteurize, sterilize or cook the contents, such as by using an oven or pressurized steam in an autoclave. Definitions
[0122] All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements published and registered, by CRC Press, Inc., 2003. Likewise, any references to a Group or Groups shall be to a Group or Groups shown in this Table Periodical of the Elements using the IUPAC system to number groups. Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. For purposes of US patent practice, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with regarding disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
[0123] Any numerical range mentioned herein includes all values from the lower value to the upper value, in increments of one unit, provided there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that the quantity of a component, or a value of a compositional or physical property, such as, for example, quantity of a mixing component, softening temperature, melting index, etc., is between 1 and 100, it is intended that all individual values such as 1, 2, 3, etc., and subranges such as 1 to 20, 55 to 70, 97 to 100, etc., are expressly listed in this report. For ranges containing values that are less than one, or containing fractional numbers greater than one (eg 1.1, 1.5, etc.) a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, where appropriate. For ranges containing single-digit numbers less than ten (for example, 1 to 5), one unit is typically considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical values between the enumerated minimum value and maximum value will be considered to be expressly set forth in this patent application. In other words, any numerical range mentioned here includes any value or subrange within the stated range. Within this disclosure, numerical ranges are provided to, among other things, refer to melt index, melt flow rate, and other properties.
[0124] As used herein, the terms "blend" and "polymer blend" mean a blend of two or more polymers as well as blends of polymers with various additives. Such a mixture may or may not be miscible. Such a mixture may or may not be phased apart. Such a mixture may or may not contain one or more domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and any other method known in the art.
[0125] As used herein, the term "composition" includes a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
[0126] The term “comprising” and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. For the avoidance of doubt, all compositions claimed by the use of the term "comprising" may include any additional additive, adjuvant, or compound, polymeric or not, unless stated otherwise. In contrast, the term “consisting essentially of” excludes from the scope of any subsequent mention any other component, step or procedure, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically described or listed. Unless otherwise stated, the term “or” refers to members listed individually as well as in any combination.
[0127] As used herein, the term "ethylene-based polymer" is a polymer comprising a majority weight percentage of polymerized ethylene monomer (based on polymer weight) and optionally may comprise at least one polymerized comonomer .
[0128] “Hot tack onset temperature” (HTIT) is the temperature at which the hot tack reaches 10.16 N/cm (4 N/inch) when the seal temperature increases.
[0129] “Hot tack temperature window” or “delta T” is the temperature range in which the hot tack resistance is greater than or equal to 12.70 N/cm (5 N/inch).
[0130] The term "olefin-based polymer" is a polymer containing, in polymerized form, a majority weight percentage of an olefin, eg, ethylene or propylene, based on the weight of the polymer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.
[0131] The term "polymer" is a macromolecular compound prepared by polymerizing monomers of the same or different types. "Polymer" includes homopolymers, copolymers, terpolymers, interpolymers, and so on. The term "interpolymer" means a polymer prepared by polymerizing at least two types of monomers or comonomers. It includes, but is not limited to, copolymers (which refers to polymers prepared from two different types of monomers or comonomers), terpolymers (which refers to polymers prepared from three different types of monomers or comonomers), tetrapolymers (which refers to polymers prepared from four different types of monomers or comonomers), and the like.
[0132] As used herein, the term "propylene-based polymer" refers to a polymer comprising a majority weight percentage of polymerized propylene monomer (based on polymer weight), and optionally may comprise at least one polymerized comonomer. Clarity Test Methods
[0133] Clarity is measured in accordance with ASTM D 1746. Coefficient of friction
[0134] Coefficient of friction (COF) of coextruded films is measured between films with outer layer (sealant) moved against the outer layer (sealant) of the expanded film, measured according to ASTM D 1894 at room temperature (23°C) . A piece of film is held on a horizontal bed. Another piece of film (approximately 6.4 by 7.6 cm (2.5 by 3 inches)) is attached to the bottom of a sled, which has been placed on top of the flat film bed. A TMI monitor/slip and friction analyzer model 32-06-00 was used to measure COF. The drag speed is 14.24 cm/min (6 inches/min). The forces required to initiate relative motion and to maintain constant motion are recorded and used to obtain static friction coefficient and kinetic friction coefficient, respectively. Values are an average of 5 readings. crystallinity
[0135] Differential scanning calorimetry (DSC) is used to measure crystallinity of ethylene-based (PE) and propylene (PP)-based samples. A sample is compressed into a thin film at a temperature of 190°C. About 5 to 8 mg of film sample is weighed and placed in a DSC pan. The lid is nailed into the pan to ensure a closed atmosphere. The sample pan is placed in a DSC cell, and then heated, at a rate of approximately 10°C/min, to a temperature of 180°C for PE (230°C for PP). The sample is kept at this temperature for three minutes. The sample is then cooled at a rate of 10°C/min to -60°C for PE (-40°C for PP), and held isothermally at that temperature for 3 minutes. The sample is then heated at a rate of 10°C/min until it melts completely (second heating). The percentage of crystallinity is calculated by dividing the heat of fusion (Hf), determined by the second heating curve, by a theoretical heat of fusion of 292 J/g for PE (165 J/g for PP), and multiplying this amount by 100 (for example, % crystallinity = (Hf/292 J/g) x 100 (for PE)). Density
[0136] Density is measured according to ASTM D 792-08. Opacity
[0137] Opacity is measured according to ASTM D 1003. Thermal Seal Resistance
[0138] Heat seal resistance is measured using Enepay's MAGMA heat seal and hot tack test system. The films are sealed at specified temperatures, and allowed to cool completely to room temperature (23°C). The specimens are conditioned at 23°C and 50% relative humidity for a minimum of 24 hours before testing. Sample films with thermal closures are prepared in the Examples section below. Hot stickiness test
[0139] Sample films (prepared in the Examples section below) are measured using a MAGMA heat seal and hot tack test system from Enepay (available from Enepay Corporation, Raleigh, NC), based on ASTM F 1921, method B according to the following conditions: Table 2. Hot tack test conditions of coextruded films

[0140] Hot tack data is collected in 10°C temperature increments. Melt Flow Rate (MFR)
[0141] MFR is measured according to ASTM D 1238 test method at 230°C with a weight of 2.16 kg. Melting Index (MI)
[0142] MI is measured according to the test method of ASTM D 1238 at 190°C with a weight of 2.16 kg. Melting temperature (Tm)
[0143] Tm of polymeric samples is measured by means of differential scanning calorimetry (DSC). A sample is compressed into a thin film at a temperature of 190°C. About 5 to 8 mg of film sample is weighed and placed in a DSC pan. The lid is nailed into the pan to ensure a closed atmosphere. The sample pan is placed in a DSC cell, and then heated, at a rate of approximately 10°C/min, to a temperature of 180°C for PE (230°C for PP). The sample is kept at this temperature for three minutes. The sample is then cooled at a rate of 10°C/min to -60°C for PE (-40°C for PP), and held isothermally at that temperature for 3 minutes. The sample is then heated at a rate of 10°C/min until it melts completely (second heating). The melting point of a substance is the temperature at which the material changes from a solid to a liquid state. The melting point of a polymer is defined here as the temperature at which the heat of fusion reaches its maximum.
[0144] By way of illustration and not limitation, examples of the present disclosure will now be provided. Examples 1. Polymeric composition
[0145] The composite in blocks, component (C) described in paragraphs 82-91 of co-pending US patent application No. 61/248,160, filed October 2, 2009, is prepared, the entire contents of which are incorporated herein by reference. .
[0146] The polymerization conditions for the production of examples of composites in blocks 02, 03 and 14 are provided in Tables 3A-3D below. Table 4 shows the physical properties of the composites in blocks 02, 03 and 14 resulting.
[0147] The catalytic system includes catalyst ([[rel-2',2"'-[(1R,2R)-1,2-cyclohexanediyl bis(methylene oxy-KO)]bis[3-(9H-carbazole) -9-yl)-5-methyl [1,1'-biphenyl]-2-olate-KO]]dimethyl hafnium) and cocatalyst, a mixture of methyl di(C14-18 alkyl)ammonium salts of tetrakis(pentafluorine) borate phenyl), prepared by reacting a long-chain trialkylamine (ARMEEN™ M2HT, obtainable from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4] as substantially disclosed in USP 5,919,983, Example 2, are purchased from Boulder Scientific and used without further purification.
[0148] The catalytic system also includes CSA (diethyl zinc or DEZ) and modified methyl aluminoxane) purchased from Akzo-Nobel and used without further purification. Solvent for 100/140) obtainable from Shell through beds of sieves (SBP Chemical Company and purified 13-X moleculars before use. Table 3A. Process conditions for producing block composites, Examples 02 and 03
Table 3B. Physical properties of Examples 02 and 03 of composite in blocks
Table 3C. Process conditions for producing block composites, Example 14.
3D Table. Physical Properties of Block Composite Example 14

[0150] Each block composite of Examples 02, 03 and 14 contains: (I) crystalline isotactic propylene homopolymer (iPP); (II) ethylene/propylene polymer (EP); and (III) block copolymer (diblock) composed of iPP block and EP block.
[0151] Table 4 provides an analytical summary of the block composites of Examples 02, 03 and 14. Unless otherwise indicated, the properties in Table 4 are for the block composite (C). Table 4. Analytical summary of the block composites of Examples 02, 03 and 14.
two . Films
[0152] Components (A), (B), and (C) are dry blended prior to addition to the extruder feed hopper. The polymer composition composed of (A) propylene/α-olefin interpolymer, (B) ethylene-based polymer, and (C) block composite is extruded into film structures.
[0153] Three-layer co-extruded films are manufactured using a Colin extrusion expanded film line with three extruders. Table 5 shows the film manufacturing conditions. ULTRAMID C33L01 nylon is used as the lining layer (inside the blister). As the core layer a mixture of 90% by weight of ATTANE 4201 (a commercial grade ultra-low density ethylene/octene copolymer, obtainable from The Dow Chemical Company) and 10% by weight of AMPLIFY GR 205 (polymer) is used. of maleic anhydride grafted HDPE, available from The Dow Chemical Company). Table 6 shows the sealing layer conditions and the respective three layer film properties.
[0154] Table 5A below shows the components of the sealing layer. Table 5A. Sealing layer components
MI measured at 190°C, 2.16 kg. *MFR measured at 230°C, 2.16 kg. Table 5B. Coextruded 3-layer extrusion conditions.
Table 6. Sealing layer compositions and three-layer film properties.
Hot sticky temperature window
[0156] With specified film structure, co-extruded films prepared with the present polymer composition exhibit hot tack greater than 12.7 N/cm (5 N/in) over a temperature range of at least 40°C, or of at least 45°C, or at least 50°C (Table 6) based on ASTM F 1921, method B with a thermal contact time of 1.0 second and cooldown time of 0.1 second. Figure 6 shows the hot tack temperature window data. Hot tack onset temperature (HTIT)
[0157] The coextruded films prepared with the present polymeric composition in the sealing layer exhibit comparable or lower hot tack onset temperature, compared to the comparative samples. In general, a lower hot tack onset temperature is desirable to improve the processing and production rate of the packaging operation. Co-extruded films containing the present polymer composition in the sealing layer exhibit lower HTIT than films containing a SLEP in the sealing layer. Table 6 lists the HTIT data that is shown in Figure 7. Coefficient of friction (COF)
[0158] In general, a lower COF is desirable to improve processing and/or speed up packaging. Table 6 and Figure 9 show the COF data. Extruded films with sealing layer prepared with the present polymer composition exhibit lower COF compared to comparative samples prepared with SLEP and propylene-based polymers. Hot tack resistance at elevated temperatures
[0159] Another very useful aspect of the present examples is their hot tack resistance at elevated temperatures, such as at 150°C. Increased hot tack resistance at elevated temperatures allows for packaging and/or processing of contents at elevated temperatures, such as sterilization via boiling water or other heating mechanisms, for use in autoclave applications. As shown in Figure 10 and Table 6, hot tack values of the present examples at 150°C are greater than those of the corresponding comparative samples. optical properties
[0160] The present examples exhibit very good optical properties, as shown in Table 6 and Figure 11. The clarity values of the sealant-containing films of the comparative examples and the present examples are all above 90%.
[0161] Specifically, it is intended that the present disclosure is not limited to the embodiments and illustrations contained therein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements from different embodiments as being within the scope of the following claims.

权利要求:
Claims (15)
[0001]
1. Polymeric composition, characterized in that it comprises: (A) from 1-50% by weight, based on the sum weight of (A) and (B), of a propylene-based polymer; (B) at least 50 percent by weight, based on the sum weight of (A) and (B) of an ethylene/α-olefin copolymer having a density less than or equal to 0.91 g/cm3; and (C) from 1 to 30% by weight of a block composite comprising a soft copolymer, a hard copolymer and a block copolymer having a soft segment and a hard segment, the hard segment of the block copolymer having the The same composition of the hard polymer in the block composite and the soft segment of the block copolymer has the same composition as the soft copolymer of the block composite, with the hard segments referring to very crystalline blocks of polymerized units in which the monomer is present in an amount greater than 95% by weight, and soft segments refer to amorphous or elastomeric blocks of polymerized units in which the comonomer content is greater than 10% by weight, where: (D) the hard polymer is a crystalline polymer a propylene base; (E)) the soft polymer is an ethylene/α-olefin polymer; and (iii) the block copolymer comprises the propylene-based crystalline block and the ethylene/α-olefin block.
[0002]
2. Polymer composition according to claim 1, characterized in that the propylene-based polymer (A) is selected from the group consisting of propylene homopolymer and propylene/ethylene copolymer.
[0003]
3. Polymer composition according to any one of claims 1 or 2, characterized in that the ethylene/α-olefin copolymer (B) comprises a homogeneously branched ethylene/α-olefin copolymer.
[0004]
4. Polymer composition according to any one of claims 1 to 3, characterized in that the ethylene/α-olefin copolymer (B) comprises a linear ethylene polymer.
[0005]
5. Polymer composition according to any one of claims 1 to 4, characterized in that the ethylene/α-olefin polymer has a melt index of 0.5 g/10 min to 25 g/10 min.
[0006]
6. Polymeric composition according to any one of claims 1 to 5, characterized in that the block copolymer (C) (iii) comprises a diblock with the formula (1) below: (EP)-(iPP) (1 ) in which EP represents a segment of polymerized ethylene and propylene monomer units, and iPP represents a segment of isotactic propylene homopolymer.
[0007]
7. Polymeric composition according to any one of claims 1 to 6, characterized in that the composite in blocks (C) comprises more than 15% by weight of C (iii), based on the total weight of composite in blocks ( Ç).
[0008]
8. Polymeric composition according to any one of claims 1 to 7, characterized in that the composite in blocks (C) has a density of 0.88 g/cm3 to 0.90 g/cm3 and a melt index of 1 g/10 min to 50 g/10 min.
[0009]
9. Polymer composition according to any one of claims 1 to 8, characterized in that it comprises an olefin-based polymer.
[0010]
10. Film, characterized in that it comprises at least one layer (22) formed from the polymeric composition, as defined in any one of claims 1 to 9.
[0011]
11. Film, characterized in that it comprises: - a first layer (22) comprising the polymer composition, as defined in any one of claims 1 to 9; and - a second layer (20) comprising an olefin-based polymer.
[0012]
12. The film according to claim 11, characterized in that the second layer (20) comprises an olefin-based polymer and optionally a functionalized olefin-based polymer.
[0013]
13. Retort bag, characterized in that it comprises: - a first layer (22) comprising the polymeric composition, as defined in any one of claims 1 to 9; - a second layer (20) comprising an olefin-based polymer; and - an optional third layer (26).
[0014]
14. Retort bag according to claim 13, characterized in that the first layer (22) is a sealing layer and the second layer (20) comprises from 70% by weight to 99% by weight of a polymer base of olefin and from 30% by weight to 1% by weight of a functionalized olefin-based polymer.
[0015]
15. Retort bag according to any one of claims 13 or 14, characterized in that the third layer (26) comprises a material selected from the group consisting of nylon, poly(ethylene terephthalate) (PET), polypropylene, and combinations of the same.

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法律状态:
2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US38854210P| true| 2010-09-30|2010-09-30|

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US61/388,542|2010-09-30|

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