Patent Grant
11905397
There is a need for compositions that can be used to form films that can be used to form wrap or bags, and which do not need to be stripped off from the enclosed material (for example, polymer pellets) during the mixing of the enclosed material. As a result, the film gets incorporated and dispersed during the mixing process. The films should also possess enough stiffness and heat seal strength for proper use in industrial scale bagging lines.
Polymer compositions and/or films are described in the following references: WO2003097355, WO2011129869, WO2015004311, WO2008137285, EP1525092A1, EP3016865A1, EP2744648A1, EP717759A1, US2006005741, US20140308466, US20140363600, US20140170742, US20140170379, US20150336652, US20150282978, US20160303833, US20160136934, US20160244229, U.S. Pat. Nos. 4,918,133, 6,090,888, 6,984,442, 7,288,316, 8,663,810, 9,050,243, 9,452,593, CN104943309A (abstract), KR2000057382A (abstract), CA2269672A, CA2410483C, CA2170042A1 and JP2001505610A (abstract). However, as discussed above, there remains a need for compositions to be used in films that have good stiffness and flowability, and can be used for wrap or bags that do not need to be stripped off from the enclosed material, when mixing the enclosed material. These needs have been met by the following invention.
A composition comprising at least the following components:
Structure a, wherein R1 and R2 are each, independently, selected from hydrogen, an alkyl;
Structure b, wherein R3 and R4 are each, independently, selected from hydrogen, an alkyl;
Structure c, wherein R5 and R6 are each, independently, selected from hydrogen, an alkyl;
Structure d, wherein R7 and R8 are each, independently, selected from hydrogen, an alkyl;
wherein component A is present in an amount ≥50 wt %, based on the weight of the composition, and wherein component B is present in an amount from 5 to 12 wt %, based on the sum weight of components A and B.
Compositions have been discovered that can be used to form films that have an optimal balance of melting temperature, stiffness and seal strength. Such films can be used to form wrap or bags for polymer materials, such as EPDM pellets, and such films do not need to be stripped off from the enclosed polymer. Such films have low melting temperatures, and are incorporated and dispersed during the mixing process of the enclosed polymer. These films also possess enough stiffness and heat seal strength for proper use in industrial scale bagging lines.
As discussed above, a composition is provided, comprising at least the following components:
Structure a, wherein R1 and R2 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic), further R1 and R2 are each, independently, selected from hydrogen or a C1-C6 alkyl, or hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen;
Structure b, wherein R3 and R4 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic), further R3 and R4 are each, independently, selected from hydrogen or a C1-C6 alkyl, or hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen;
Structure c, wherein R5 and R6 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic), further R5 and R6 are each, independently, selected from hydrogen or a C1-C6 alkyl, or hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen;
Structure d, wherein R7 and R8 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic), further R7 and R8 are each, independently, selected from hydrogen or a C1-C6 alkyl, or hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen;
wherein component A is present in an amount ≥50 wt %, based on the weight of the composition, and wherein component B is present in an amount from 5 to 12 wt %, based on the sum weight of components A and B.
The composition may comprise a combination of two or more embodiments described herein. Each component of the composition may comprise a combination of two or more embodiments described herein.
In one embodiment, the cycloolefin interpolymer of component B has a Tg from 60° C. to 90° C., or from 65° C. to 90° C.
In one embodiment, the ethylene-based polymer of component A has a Tm from 70° C. to 95° C., or from 85° C. to 90° C.
In one embodiment, the ethylene-based polymer of component A has a density ≤0.900 g/cc, or ≤0.890 g/cc, or ≤0.885 g/cc, or ≤0.880 g/cc (1 cc=1 cm3).
In one embodiment, the ratio of the Tg of component B to the Tg of component A is from −1.0 to −5.0, or from −1.1 to −4.5, or from −1.1 to −4.0, or from −1.1 to −3.5, or from −1.1 to −3.0, or from −1.1 to −2.5.
In one embodiment, component B is present in an amount from 5 to 12 wt %, or from 5 to 11 wt %, or from 5 to 10 wt %, based on the sum weight of components A and B.
In one embodiment, component B is present in an amount from 5 to 12 wt %, or from 5 to 11 wt %, or from 5 to 10 wt %, based on the weight of the composition.
In one embodiment, the weight ratio of component A to component B is from 4.0 to 20.0, or from 5.0 to 20.0, or from 5.0 to 15.0, or from 7.0 to 11.0, or from 8.0 to 10.0.
In one embodiment, the ethylene-based polymer of component A is an ethylene/alpha-olefin interpolymer, or an ethylene/alpha-olefin copolymer, or an ethylene/C3-C8 α-olefin copolymer.
In one embodiment, the ethylene-based polymer of component A is an ethylene/alpha-olefin/diene interpolymer, and further an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is ENB.
In one embodiment, the ethylene-based polymer of component A is an ethylene-vinyl acetate (EVA) copolymer.
In one embodiment, component A is present in an amount ≥55 wt %, or ≥60 wt %, or ≥65 wt %, or ≥70 wt %, or ≥75 wt %, or ≥80 wt %, or ≥85 wt %, or ≥84 wt % based on the weight of the composition. In one embodiment, component A is present in an amount ≤95 wt %, or ≤94 wt %, or ≤93 wt %, or ≤92 wt %, or ≤91 wt %, or ≤90 wt %, based on the weight of the composition.
In one embodiment, the composition comprises ≥80 wt %, or ≥85 wt %, or ≥90 wt %, or ≥95 wt %, or ≥98 wt % of the sum of component A and component B, based on the weight of the composition. In one embodiment, the composition comprises ≤100 wt %, or ≤99 wt % of the sum of component A and component B, based on the weight of the composition.
In one embodiment, the composition comprises less than 1.0 wt %, or less than 0.5 wt % of a polymer comprising, in polymerized form, styrene, and optionally, one or more other comonomers.
In one embodiment, the cycloolefin interpolymer is an ethylene/bridged cyclic olefin copolymer.
In one embodiment, the at least one bridged cyclic olefin selected from the following:
Structure a, wherein R1 and R2 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic). In a further embodiment, R1 and R2 are each, independently, selected from hydrogen or a C1-C6 alkyl, and further hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen.
In one embodiment, the at least one bridged cyclic olefin selected from the following:
Structure b, wherein R3 and R4 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic). In a further embodiment, R1 and R2 are each, independently, selected from hydrogen or a C1-C6 alkyl, and further hydrogen or a C1-C5 alkyl, or hydrogen or a C 1-C4 alkyl, or hydrogen or a C 1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen.
In one embodiment, the at least one bridged cyclic olefin selected from the following:
Structure c, wherein R5 and R6 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic). In a further embodiment, R1 and R2 are each, independently, selected from hydrogen or a C1-C6 alkyl, and further hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen.
In one embodiment, the at least one bridged cyclic olefin selected from the following:
Structure d, wherein R7 and R8 are each, independently, selected from hydrogen, an alkyl (linear or branched or cyclic). In a further embodiment, R1 and R2 are each, independently, selected from hydrogen or a C1-C6 alkyl, and further hydrogen or a C1-C5 alkyl, or hydrogen or a C1-C4 alkyl, or hydrogen or a C1-C3 alkyl, or hydrogen or a C1-C2 alkyl, or hydrogen or methyl, or hydrogen.
In one embodiment, the cycloolefin interpolymer of component B comprises, in polymerized form, ethylene and only one bridged cyclic olefin selected from Structures a to d as defined herein.
In one embodiment, the composition further comprises an ethylene vinyl acetate copolymer. In a further embodiment, the ethylene vinyl acetate copolymer is present in an amount from 5 to 20 wt %, based on the weight of the composition.
In one embodiment, the composition does not contain a coupling agent, for example, an azide compound or a peroxide.
The composition may comprise one or more additional additives. Suitable additives include, but are not limited to, fillers, antioxidants, UV stabilizers, flame retardants, colorants or pigments, crosslinking agents, slip agents, antiblocks, and combinations thereof. In one embodiment, the composition comprises one or more additional additives in an amount from 0.5 to 20 wt %, or 1 to 15 wt %, or 5 to 10 wt %, based on the weight of the composition. In a further embodiment, the composition comprises a slip agent and/or an antiblock in an amount from 0.5 to 20 wt %, or 1 to 15 wt %, or 5 to 10 wt %, based on the weight of the composition.
In one embodiment, the composition further comprises a thermoplastic polymer. Such polymers include, but are not limited to, propylene-based polymers, ethylene-base polymers, and olefin multi-block interpolymers. Suitable ethylene-base polymers include, but are not limited to, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), homogeneously branched linear ethylene/α-olefin interpolymers or copolymers, and homogeneously branched substantially linear ethylene/α-olefin interpolymers or copolymers (that is homogeneously branched long chain branched ethylene/α-olefin interpolymers or copolymers).
In one embodiment, the composition has a Tm ≥80° C., or ≥81° C., or ≥82° C. In one embodiment, the composition has a Tm ≤90° C., or ≤88° C., or ≤86° C.
In one embodiment, the composition has a V0.1 (130° C.) value ≥35,000 Pa·s, or ≥40,000 Pa·s, or ≥45,000 Pa·s. In one embodiment, the composition has a V0.1 (130° C.) value ≤65,000 Pa·s, or ≤60,000 Pa·s, or ≤55,000 Pa·s.
In one embodiment, the composition has a V100 (130° C.) value from 2,800 Pa·s to 4,000 Pa·s, or from 3,000 Pa·s to 3,800 Pa·s, or from 3,200 Pa·s to 3,600 Pa·s.
In one embodiment, the composition has a V0.1/V100 (RR) value ≥10, or ≥11, or ≥12. In one embodiment, the composition has a V0.1/V100 (RR) value ≤16, or ≤15, or ≤14.
In one embodiment, the composition has an E1 value from 0.84 to 0.92, or from 0.85 to 0.91, or from 0.86 to 0.90.
In one embodiment, the composition has an E2 value from 0.92 to 0.98, or from 0.93 to 0.97, or from 0.94 to 0.96.
In one embodiment, the composition has an Ec value from 0.40 to 0.60, or from 0.41 to 0.59, or from 0.42 to 0.58.
Also is provided a film comprising at least one layer formed from the composition of any one or more embodiments described herein. In a further embodiment, the film comprising a core layer formed from a core composition comprising ≤1.0 wt %, or ≤0.5 wt %, or ≤0.2 wt %, ≤0.1 wt % of an ethylene/bridged cyclic olefin interpolymer or copolymer. In a further embodiment, the core composition does not comprise an ethylene/bridged cyclic olefin interpolymer or copolymer.
In one embodiment, the film comprises at least one additional layer, formed from a composition comprising from 1 to 12 wt % of an ethylene/bridged cyclic olefin interpolymer or copolymer, based on the weight of this composition.
Also is provided a film comprising at least three layers a/b/c, and wherein layer b is formed from a composition comprising ≤1.0 wt %, or ≤0.5 wt %, or ≤0.2 wt %, ≤0.1 wt %, or none, of an ethylene/bridged cyclic olefin interpolymer or copolymer; and wherein the layer a and/or layer c are each, independently, formed from a composition of one or more embodiments described herein.
Also is provided a film comprising at least five layers a/b/c/d/e, and wherein layer c is formed from a composition comprising ≤1.0 wt %, or ≤0.5 wt %, or ≤0.2 wt %, ≤0.1 wt %, or none, of an ethylene/bridged cyclic olefin interpolymer or copolymer; and wherein the layer a, layer b, layer d and/or layer e are each, independently, formed from a composition of one or more embodiments described herein.
Also is provided a film comprising at least six layers a/b/c/d/e/f, and wherein layer c and layer d are each, independently, formed from a composition comprising ≤1.0 wt %, or ≤0.5 wt %, or ≤0.2 wt %, ≤0.1 wt %, or none, of an ethylene/bridged cyclic olefin interpolymer or copolymer; and wherein the layer a, layer b, layer e and/or layer f are each, independently, formed from a composition of one or more embodiments described herein.
In one embodiment, a film comprising at least one layer formed from the composition of any one or more embodiments described herein has a thickness of from 0.5 to 10 mil, or from 4 to 7 mil, or from 5 to 6 mil.
Also is provided an article comprising at least one component formed from the composition of any one or more embodiments described herein.
Also is provided an article comprising at least one component formed from the film of any one or more embodiments described herein.
Definitions
Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure.
The term “composition,” as used herein, includes the material(s), which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
The term “polymer,” as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer.
The term “interpolymer,” as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
The term, “olefin-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, 50 wt % or a majority amount of olefin monomer, for example ethylene or propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The term “ethylene-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, 50 wt % or a majority weight percent of ethylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The term “ethylene-based interpolymer,” as used herein, refers to an interpolymer that comprises, in polymerized form, a 50 wt % or a majority weight percent of ethylene (based on the weight of the interpolymer), and at least one comonomer.
The term, “ethylene-based copolymer,” as used herein, refers to a copolymer that comprises, in polymerized form, 50 wt % or a majority amount of ethylene monomer (based on the weight of the copolymer), and an α-olefin, as the only two monomer types.
The term, “ethylene/α-olefin copolymer,” as used herein, refers to a copolymer that comprises, in polymerized form, 50 wt % or a majority amount of ethylene monomer (based on the weight of the copolymer), and an α-olefin, as the only two monomer types.
The term, “propylene-based polymer,” as used herein, refers to a polymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers.
The terms “comprising,” “including,” “having,” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically delineated or listed.
As one of ordinary skill in the art would understand, the term “COC” refers to a cyclic olefin copolymer.
Test Methods
Differential Scanning Calorimetry (DSC) (Component A, Component B, Composition)
Differential Scanning Calorimetry (DSC) is used to measure melting and crystallization behavior of polymers (e.g., ethylene-based (PE) polymers). In the case of compounded Bland, the sample is first melt pressed (25000 lbs for about 10 sec) into a thin film, at about 175° C., and then cooled to room temperature. About 5 to 8 mg of polymer film sample is cut with a die punch and is weighed and placed into a DSC pan. In the case of fabricated films, the sample is directly punched from the film. The lid is crimped on the pan to ensure a closed atmosphere. The sample pan is placed into a calibrated DSC cell purged with nitrogen gas, and then heated at a rate of approximately 10° C./min, to a temperature of 180° C. The sample is kept at this temperature for three minutes. Then the sample is cooled at a rate of 10° C./min to −40° C. to record the crystallization trace, and kept isothermally at that temperature for three minutes. The sample is next reheated at a rate of 10° C./min, until complete melting. Unless otherwise stated, peak melting point (Tm) is determined from the first heating curve, and corresponds to the temperature of the highest peak (intensity) in the endotherm. The crystallization temperature (Tc) is determined from the cooling curve (peak Tc). The onset end of the melting temperature can be defined as the extrapolated end of the melting curve calculated from the intersection of two lines a and b, where a is the tangent with the point of maximum slope on the secondary side of the peak and b is the extrapolation of the baseline after the melting. The Tg is measured from the second heating curve, and determined at the midpoint of the inflection transition. Some DSCs transitions are shown in
Tensile Strength and Tensile Energy to Break (MD and CD)
Tensile Strength and Tensile Energy to Break (MD and CD) were measured in accordance with ASTM D882-10 (average of five film samples in each direction; each sample “1 in×6 in” or 25 mm×150 mm). Before characterization samples were preconditioned for 40 hours at temperature from 21° C. to 25° C., and relative humidity of 50%±5. Preparation of each film is described in the experimental section below.
Density
Samples that are measured for density are prepared according to ASTM D-1928. Within one hour of sample pressing, measurement are made using ASTM D-792, Method B.
Melt Index
Melt index (I2) is measured in accordance with ASTM-D 1238, Condition 190° C./2.16 kg, and is reported in grams eluted per 10 minutes.
Dynamic Mechanical Spectroscopy (DMS)
Small angle oscillatory shear (melt DMS) was performed using a TA Instruments ARES, equipped with “25 mm parallel plates,” under a nitrogen purge. The time between sample loading, and the beginning of the test, was set to five minutes for all samples. The experiments were performed at 130° C., over a frequency range of 0.1 to 100 rad/s. The strain amplitude was adjusted, based upon the response of the samples, from 1 to 10%. The stress response was analyzed in terms of amplitude and phase, from which, the storage modulus (G′), loss modulus (G″), dynamic viscosity η*, tan delta, and phase angle were determined. The viscosities V0.1 at 130° C. and V100 at 130° C., and rheology ratio (V0.1/V100 at 130° C.; also referred to as “RR”) were recorded. Specimens for Dynamic Mechanical Spectroscopy were “25 mm diameter×3.3 mm thick” compression molded discs, formed at 180° C., and 10 MPa molding pressure, for five minutes, and then quenched between chilled platens (15-20° C.) for two minutes.
The following examples illustrate the present invention but are not intended to limit the scope of the invention. Materials are listed below. Polymers are typically stabilized with ppm amounts of one or more stabilizers.
ELVAX® 460 (hereinafter “ELVAX 460”) is an EVA, available from DuPont, with a density of 0.941 g/cc (1 cc=1 cm3), a melt index (I2) of 2.5 g/10 min, and a VA content of 18 wt % (based on the weight of the EVA).
ELVAX® 470 (hereinafter “ELVAX 470”) is an EVA, available from DuPont, with a density of 0.94 g/cc, a melt index (I2) of 0.7 g/10 min, and a VA content of 18 wt % (based on the weight of the EVA).
AMPACET 100329 is a slip agent, available from AMPACET Corp.
AMPACET 100342 is an antiblock, available from AMPACET Corp.
AMPACET 10090 is a slip agent, available from AMPACET Corp.
AMPACET 100450 is an antiblock, available from AMPACET Corp.
ALCUDIA® PA-539 (hereinafter “ALCUDIA 539”) is an EVA, available from Entec Polymers, with a density of 0.937 g/cc, a melt index (I2) of 2 g/10 min, and a VA content of 18 wt % (based on the weight of the EVA).
ALCUDIA® PA-537 (hereinafter “ALCUDIA 537”) is an EVA, available from Entec Polymers, with a density of 0.941 g/cc, a melt index (I2) of 0.7 g/10 min, and a VA content of 18 wt % (based on the weight of the EVA).
ENGAGE™ 8003 (hereinafter “ENGAGE 8003”) is an ethylene/octene copolymer, available from The Dow Chemical Company, with a density of 0.885 g/cc, a melt index (I2) of 1.0 g/10 min and a Tg of −46° C.
ENGAGE™ 8540 (hereinafter “ENGAGE 8540”) is an ethylene/octene copolymer, available from The Dow Chemical Company, with a density of 0.908 g/cc, a melt index (I2) of 1.0 g/10 min, and a Tg of -32° C.
ENGAGE™ 8100 (hereinafter “ENGAGE 8100”) is an ethylene/octene copolymer, available from The Dow Chemical Company, with a density of 0.87 g/cc, a melt index (I2) of 1.0 g/10 min and a Tg of −52° C.
NORDEL™ IP 4820 (hereinafter “NIP4820”) an EPDM, available from The Dow Chemical Company, with a density of 0.88 g/cc, a melt index (I2) of 1.0 g/10 min and a Tg of −18° C.
AFFINITY™ PF 1140G POP (hereinafter “AFFINITY 1140”) is an ethylene/octene copolymer (random), available from The Dow Chemical Company, with a density of 0.897 g/cc, a melt index (I2) of 1.6 g/10 min, and a Tg of −33° C.
AFFINITY™ VP 8770G1 POP (hereinafter “AFFINITY 8770”) is an ethylene/octene copolymer (random), available from The Dow Chemical Company, with a density of 0.885 g/cc, a melt index (I2) of 1.0 g/10 min, and a Tg of −46° C.
VERSIFY™ 2200 (hereinafter “VERSIFY 2200”) is an propylene/ethylene copolymer, available from The Dow Chemical Company, with a density of 0.876 g/cc, and a melt flow rate at 230° C. (MFR) of 2.0 g/10 min.
LDPE 132I is polyethylene homopolymer available from The Dow Chemical Company, with a density of 0.921 g/cc, and a melt index (I2) of 0.25 g/10 min.
TOPAS® 9506F-04 (hereinafter “TOPAS 9506F-04”) is a COC copolymer (ethylene and norbornene), available from Topas Advanced Polymers, with a density of 1.02 g/cc, a melt volume rate (MVR), at 230° C./2.16 kg (ISO 1133), of 6 cm3/10 min, a melt index, at 190° C./2.16 kg, of 0.9 g/10 min, and a Tg of 63° C.
TOPAS® 8007F-04 (hereinafter “TOPAS 8007F-04”) is a COC copolymer (ethylene and norbornene), available from Topas Advanced Polymers, with a density of 1.02 g/cc, a melt volume rate (MVR), at 230° C./2.16 kg (ISO 1133), of 12 cm3/10 min, a melt index, at 190° C./2.16 kg, of 1.8 g/10 min, and a Tg of 77° C.
“AB” refers to 20 wt % of Talc AB compounded with 80 wt % ENGAGE 8003.
Properties of Compositions
Rheology
To determine the melt-flow properties of polymers and the above polymer compositions, dynamic oscillatory shear measurements were conducted over a range from 0.1 rad s−1 to 100 rad s−1, at a temperature of 130° C. and 10% strain, using stainless steel, parallel plates of “25-mm diameter.” See above DMS test method. Test sample has 25 mm diameter and a thickness of 3.3 mm, on a strain-controlled rheometer, ARES/ARES-G2 by TA Instruments. The V0.1 and V100 are the viscosities at 0.1 rad s−1 and 100 rad s−1, respectively, with V0.1/V100 ratio being a measure of shear thinning characteristics. The effect of the “COC” content on the composition rheology is shown below in Tables 1-3. See also
Film Production
Inventive (Inv.) and comparative (Comp.) films are presented below. Tables 7A-7F and 8 show the compositions of each layer of each film; each weight percent is based on total weight of the respective composition used to form each film layer. Each composition used to form each film layer was prepared using a HAAKE Rheomix 3000, equipped with roller mixing blades, at a mixing speed of 40 RPM. The raw materials were dry mixed before adding to the mixer, which was preheated to 150° C. A mixing time of five minutes was used after the addition of raw materials and the securing of the ram.
Each five layer film (skin/intermediate/core/intermediate/skin) was produced on a five-layer blown film line. The blown film line was a 75 mm 5-Layer Flat Die (30/10/20/10/30), with 25 mm skin extruders and 20 mm intermediate/core extruders. The line had a Dual Lip Air Ring, ABS Gravimetric Feed, and Dual Surface Winders. Films from 0.8 mils to 6 mils thickness can be produced, with blow up ratios from 2.2 to 3.9, production rates from 9 to 27 kg/hr, and haul-off from 2.4 to 18 meter per min. The line was capable of on-line slitting and separating film layers. On-line slitting and separating film layers were performed for all examples except for Inv. F4. On-line slitting and film layer separation was not performed in Inv. F4, but instead left as a collapsed bubble. Table 6 below provides the processing conditions for the production of multilayer (5) films.
Inv. F3 and Comp. F12 were prepared on a seven layer blown film line. The remaining films were prepared on the five layer blown film line. The Alpine 7-Layer Coextrusion Blown Film Line was used to fabricate Inv. F3 and Comp. F12. This line consisted of a 7-layer coex die with inserts available in widths of 200 mm and 250 mm, a 7-50 mm 30:1 L/D grooved fed extruders utilizing barrier type screws, four component Maguire in-line blenders for each extruder, ExVis an Alpine control system, an NDC gauge thickness detection system with auto gauging, a 358° oscillating nip roll capable of speeds up to 400 fpm and film width of 60 inches, and a Pillar corona device. Table 8 below shows the compositions for each film layer and film process conditions for the production of each seven layer film. Each weight percent is based on total weight of the respective composition used to form each film layer. See also Table 9. Some additional film properties are shown in Tables 10A-10C below.
Tensile Properties
Tensile properties will be defined by the modulus of the compositions of the films. The higher the modulus, the higher the stress the composition can handle, without significant deformation. The information here reported the stress required to deform the composition 7% and 25% in the machine direction (MD). See Table 5 below.
Processing Time
Here the processing time is the time required for the compositions of the films to cool down below the transition temperature of the composition therefore recovering the typical properties of a solid-like composition. It is known that the higher the transition temperature, the faster the composition sets. It has been discovered that a temperature dependent constraint of 60° C., above which crystallization should have already taken place, was suitable for the inventive compositions. To describe the crystallization profile above this temperature, the parameter Ec was defined as the fraction of the enthalpy of crystallization above 60° C., relative to the total enthalpy of crystallization measured by DSC. The
A set of “18 wt %VA EVAs” with a peak melting temperature of 88° C. These compositions show a relatively high Tc and Ec values, indicating that more than 40% of the enthalpy of crystallization occurred well above the 60° C. constraint. An Ec of 0.4 (40%) is expected to result in acceptable processing times.
Ethylene-based polymers with melting temperatures from 75° C. to 95° C. An increase in crystallinity drives both Tc and Ec upwards (increase in Tc and Ec). This set of samples meets the Ec of 0.4. The POEs exhibiting Tm lower than 75° C., have a Tc value lower than the 60° C. constraint (Ec approaching to zero, i.e., ENGAGE 8100, 0.87 density, 1 MI), and their processing would be excessively long.
Compositions of propylene based elastomers (PBE) with POE's. Typically a PBE will have a higher modulus than a POE, and this higher modulus will increase the modulus of PBE/POE blend to that approaching EVA. However, the PBE fraction in the blend crystallizes well below the “60° C. temperature constraint,” therefore affecting the EC of the blend, and making its processing unpractical (the crystallization above 60° C. is less than 40%, Ec<0.4). It was discovered that only one of the PBE samples was able to match the 40% enthalpy of crystallization, however, as it will be shown below, this composition has unacceptable E2 value.
Compositions of POE and COC with matching transition temperatures in the 70° C. to 100° C. temperature range. In this case, the POE selected had a Tm peak of 82° C., and the COC a Tg of 77° C. Various levels of the COC where explored in the 3 to 15 wt % range. It has been discovered, as shown in the graph, these compositions preserve the crystallization behavior of the POE (EC≥0.4 and Tc peak ≥60° C.).
Dispersion
It has been discovered that that the following two temperature constraints can be used to optimize the dispersion of the polymer components of the film compositions. The two temperature dependent constraints are as follows: 1) a target temperature of 85° C., below which, it is desire the composition exhibits its DSC melting temperature peak (Tm), and 2) a target temperature of 95° C., below which, it is desire the composition exhibits its DSC onset Tm at end of melting. Above the “onset Tm, at end of melting,” the melting profile ends and returns to the DSC base line, and the composition is considered molten.
E1. Fraction of the enthalpy of melting below 85° C., relative to the total enthalpy of melting measured by DSC. See
Based on the above analyses, it has been discovered that the three efficiencies (Ec, E1, E2) are required to approach one, to minimize processing time and eliminate the presence of undispersed polymer (gels) after compounding.
Summary of Results
Complete mixing in the case of polymeric components in such formulations has been correlated with the high flowability, which results after a material transition, such as melting or glass transition. New compositions have been developed that fulfill a series of temperature dependent constraints, to provide good flowability and high stiffness at ambient temperatures, for adequate transportation of the bagged material. The good flowability allows for ready dispersion of the composition at temperatures in the range from 90° C. to 150° C., and for high hot tack, at sealing temperatures, during packaging operations (>100° C.).
It has been discovered that compositions containing an ethylene-based polymer and a cycloolefin interpolymer that have overlapping transition temperatures in the 70-100 C range have excellent processing properties, dispersion properties and tensile properties, and can be used to form films with excellent physical properties. The inventive compositions have good flowability and therefore good mixing of a final film formulation.
It has also been discovered that such compositions provides an optimization of the tensile properties, as well as processing time. The processing time is the time required for the composition to cool below its transition temperature, and therefore recover the typical properties of a solid-like material. In the case of olefin-based polymers, crystallinity is typically varied to tailor melting behavior, tensile properties, and processing time, however, the inventive compositions do not completely rely on crystallinity to have superior physical properties. For example, both tensile properties and fast processing time benefit from maximizing crystallinity, while good dispersion and fast mixing benefit from low crystallinity. It has been discovered that the inventive compositions have an optimal balance of the ethylene-based polymer (POE) and the cycloolefin interpolymer (COC) to provide an optimal balance between flowability and modulus.
This application claims the benefit of U.S. Provisional Application No. 62/549,147, filed Aug. 23, 2017.
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| PCT/US2018/047445 | 8/22/2018 | WO |
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| WO2019/040574 | 2/28/2019 | WO | A |
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| 20200255640 A1 | Aug 2020 | US |
| Number | Date | Country | |
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| 62549147 | Aug 2017 | US |
