Azeotropic and azeotrope-like compositions comprising cyclopentane and 1h,1h,2h-heptafluorocyclopentane or 2-methylpentane and 1h,1h,2h-heptafluorocyclopentane and use of the compositions as flash spinning agents

Abstract

The present invention relates to (i) an azeotropic or azeotrope-like composition comprising cyclopentane and 1H,1H,2H-heptafluorocyclopentane or comprising 2‑methylpentane and 1H,1H,2H-heptafluorocyclopentane, (ii) a spin fluid for flash spinning comprising these azeotropic or azeotrope-like compositions and a polymer, and (iii) a process for the preparation of plexifilamentary film-fibril strands of polymers using the spin fluid.

Description

[0001] TITLE

[0002] AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS COMPRISING CYCLOPENTANE AND 1 H, 1 H.2H-HEPTAFLUOROCYCLOPENTANE OR 2- METHYLPENTANE AND 1 H,1 H,2H-HEPTAFLUOROCYCLOPENTANE AND USE OF THE COMPOSITIONS AS FLASH SPINNING AGENTS

[0003] FIELD OF THE INVENTION

[0004] The present invention relates to (i) an azeotropic or azeotrope-like composition comprising cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane or comprising 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane, (ii) a spin fluid for flash spinning comprising these azeotropic or azeotrope-like compositions and a polymer and (iii) a process for the preparation of plexifilamentary film-fibril strands of polymers using the spin fluid.

[0005] BACKGROUND

[0006] Flash spinning is a process for producing fibrils that involves the following steps: (i) dissolving a polymer in a composition comprising one or more solvents (often called a spin agent), at elevated temperature and pressure to form a homogeneous solution (often called a spin fluid), (ii) reducing the pressure sufficiently below the spin fluid’s cloud point pressure (i.e., the pressure at which the spin fluid transitions from a clear solution to a cloudy, two-phase dispersion), while still maintaining sufficient pressure to prevent the spin fluid from reaching its bubble point pressure (i.e., the pressure at which the spin agent in the spin fluid begins to boil), (iii) releasing the resulting dispersion continuously through one or more orifices into a lower pressure region at or near atmospheric temperature and pressure so that the spin agent flash evaporates as it emerges from the one or more orifices, (iv) collecting the polymer which remains as a stream of fibrils, e.g., plexifilamentary fibrils, and (v) recovering the evaporated spin agent for re-use. Examples of flash spinning processes are disclosed in US 3,081,519 and US 3,227,794.

[0007] In a commercial flash spinning process, the spin agent’s solvent properties and physical properties are critical. In particular, the solvent properties of the spin agent determine whether and under what conditions fibrils are produced in the flash spinning process, and the spin agent’s physical properties impact the process for recovering and re-using the spin agent. The process for recovering spin agents typically involves a step in which the spin agent is condensed from the gas state to the liquid state. During this step, it is preferred that the composition of the spin agent remains essentially constant. This is inherent when spin agents comprise only one solvent but not when spin agents comprise two or more solvents which are often required to provide the necessary solvent properties for flash spinning the desired polymer. Accordingly, when using a spin agent that comprises two or more solvents, it is advantageous to use a composition that is azeotropic or azeotrope-like which behaves similarly to a spin agent with only one solvent. Where an azeotrope forms between two different components in the spin agent, it is beneficial if this is a positive azeotrope because the boiling point of the azeotrope is then lower than that of either individual component of the spin agent composition. This allows the low-pressure region into which flash spinning takes place (i.e., the spin-cell) to be maintained at a lower temperature without risking the spin agent composition condensing inside it. This also reduces the need for spin-cell heating and provides a more comfortable environment for operators working near the spin-cell. On the other hand, a negative azeotrope, which has a higher boiling point than that of either individual component of the spin agent composition, could require spin-cell heating which would lead to increased equipment and operating costs. When using a spin agent that comprises two or more solvents, it is further advantageous to use a spin agent composition that forms a homogeneous liquid phase at ambient temperatures and pressures, rather than a heterogeneous liquid phase where, due to low miscibility of the components of the spin agent composition, a liquid phase separation occurs. Compositions forming heterogeneous liquid phases are usually undesired since processes involving such compositions are more complex and expensive due to the liquid phase separation.

[0008] Some solvents, such as chlorinated solvents, dissolve polymers such as polyolefins at relatively low pressures, and therefore cannot be used as the only component in a spin agent composition for flash spinning. Weaker solvents such as hydrofluorocarbons can be mixed with these solvents to reduce the solvent strength of the spin agent and increase the spin fluid’s cloud point pressure such that flash spinning can be readily accomplished. WO 2016 / 200873 A1 suggests spin agent compositions of dichloromethane or dichloroethylene with 1H,6H- perfluorohexane, 1 H-perfluorohexane, or 1 H-perfluoroheptane. However, use of such linear hydrofluorocarbons in combination with chlorinated solvents results in spin agents that often exhibit undesirably high global warming potential (GWP). In view of the growing concerns regarding climate change and increasing regulatory requirements, there is a need to find suitable low GWP replacements for currently used spin agent compositions.

[0009] Other examples of commonly used solvents for polymers such as polyolefins are cyclic C5. 7 hydrocarbons, for example, cyclopentane or cyclohexane. Similar to spin agent systems based on chlorinated solvents, cyclic hydrocarbon solvents are typically blended with other components to adjust the polymer solubility to give a cloud-point pressure such that fibrils can be produced by flash spinning using a fibril-forming polymer. It is beneficial if such blended hydrocarbon-based spin agents form a homogeneous liquid phase at ambient temperature and pressure, and if they exhibit azeotropic or azeotrope- 1 ike behavior at blend ratios which are suitable for flash spinning.

[0010] US 6,793,840 suggests spin fluids comprising azeotropic and azeotrope-like compositions containing perfluorobutylethylene and a second component which may be cyclopentane. The disadvantage of this mixture is the presence of a double bond in the perfluorobutylethylene which reduces its chemical stability at high temperature and pressure.

[0011] US 6,319,970 and US 6,153,134 disclose spinning processes using a ternary azeotropic mixture of cyclopentane, trans-1 ,2-dichloroethylene and decafluoropentane. However, the cloudpoint pressure curve for common fibril-forming polymers such as, for example, polyethylene in this azeotropic mixture is not suitable for the flash spinning, so this spin agent has only limited applications.

[0012] Accordingly, there is a need for, and the present inventors have discovered azeotropic and azeotrope-like compositions of either cyclopentane or 2-methylpentane, in combination with a low GWP hydrofluorocarbon that (i) form a positive homogenous azeotrope with a boiling temperature below 60 °C, (ii) simplify the spin agent recovery and re-use process, and (iii) provide suitable cloud point pressures for flash-spinning a broad range of different polyolefins and blends / mixtures thereof.

[0013] SUMMARY OF THE INVENTION

[0014] In one embodiment, the invention is directed to an azeotropic or azeotrope-like composition comprising

[0015] (i) cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane; or

[0016] (ii) 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane.

[0017] In a further embodiment, the invention is directed to a spin fluid for flash spinning comprising (a) from 10 to 28 weight percent of a polymer, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises an azeotropic or azeotrope-like composition comprising cyclopentane and 1 H,1H,2H-heptafluorocyclopentane or comprises an azeotropic or azeotrope-like composition comprising 2-methylpentane and 1H,1 H,2H- heptafluorocyclopentane.

[0018] In a further embodiment, the invention is directed to a process for the preparation of plexifilamentary fibrils of polymer. The process comprises the steps of:

[0019] (i) generating a spin fluid comprising (a) about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid, and

[0020] (b) a spin agent, and

[0021] (ii) flash spinning the spin fluid at a pressure that is above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifilamentary films of the polymer, wherein the spin agent comprises

[0022] (1) an azeotropic or azeotrope-like composition comprising cyclopentane and 1 H,1H,2H-heptafluorocyclopentane, or

[0023] (2) an azeotropic or azeotrope-like composition comprising 2-methylpentane and 1 H , 1 H , 2 H - h eptaf I u orocycl o pe nta ne .

[0024] BRIEF DESCRIPTION OF THE FIGURES

[0025] Fig. 1 shows the calculated vapor-liquid equilibrium (VLE) for the compositions of cyclopentane and trans-1 H,1 H,2H-heptafluorocyclopentane at 40 °C.

[0026] Fig. 2 shows the cloud point pressure curve of a spin fluid comprising 24 wt% polyethylene and a spin agent of cyclopentane and 1 H,1H,2H-heptafluorocyclopentane in a 60:40 ratio by weight.

[0027] Fig. 3 shows the cloud point pressure curve of a spin fluid comprising 16 wt% polyethylene and a spin agent of cyclopentane and 1 H,1H,2H-heptafluorocyclopentane in a 65:35 ratio by weight.

[0028] Fig. 4 shows the cloud point pressure curve of a spin fluid comprising 22 wt% ethylenehexene copolymer and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight.

[0029] Fig. 5 shows the cloud point pressure curve of a spin fluid comprising 17 wt% polypropylene and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight.

[0030] Fig. 6 shows the calculated vapor-liquid equilibrium (VLE) for the compositions of 2-methylpentane and trans-1 H,1 H,2H-heptafluorocyclopentane at 40 °C.

[0031] Fig. 7 shows the cloud point pressure curve of a spin fluid comprising 20 wt% polyethylene and a spin agent of 2-methylpentane and 1 H,1H,2H-heptafluorocyclopentane in a 70:30 ratio by weight. Fig. 8 shows the cloud point pressure curve of a spin fluid comprising 18 wt% polyethylene and a spin agent of 2-methylpentane and 1 H,1H,2H-heptafluorocyclopentane in a 70:30 ratio by weight.

[0032] Fig. 9 shows the cloud point pressure curve of a spin fluid comprising 24 wt% polyethylene and a spin agent of 2-methylpentane and 1 H,1H,2H-heptafluorocyclopentane in a 60:40 ratio by weight.

[0033] Fig. 10 shows the cloud point pressure curve of a spin fluid comprising 15 wt% polypropylene and a spin agent with a composition of 2-methylpentane and 1 H,1 H,2H- heptafluorocyclopentane in a 52:48 ratio by weight.

[0034] DETAILED DESCRIPTION

[0035] Definitions and Clarification of Terms

[0036] Before addressing details of embodiments, some terms and test methods are defined or clarified. Unless otherwise mentioned, all tests were carried out without preconditioning of the samples. When average values are indicated herein, this refers to the arithmetic average.

[0037] Density is determined according to the method described in ISO 1183 (Plastics - Methods for determining the density of non-cellular plastics).

[0038] Melting temperature is determined by differential scanning calorimetry, following the guidance provided in ASTM D3418 (Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry) and ASTM Standard F2625 (Standard Test Method for Measurement of Enthalpy of Fusion, Percent Crystallinity and Melting Point of Ultra-High-Molecular weight polyethylene by means of differential scanning calorimetry). For polyethylene, heating and cooling is performed under inert gas at a rate of 10 °C / minute, heating the sample first from room temperature to 210 °C, then cooling the sample back to room temperature and subsequently heating the sample a second time to 210 °C. The melting point reported herein is the peak temperature of the endotherm of the second heating cycle. For polypropylene, the same procedure applies - where the maximum temperature is 230 °C.

[0039] The melt flow rate is determined according to the method described in ISO 1133 (Plastics - Determination of the melt mass-flow rate (MFR) and the melt volume-flow rate (MVR) of thermoplastics). The melt flow rate for polyethylene is determined at a temperature of 190 °C and using a mass of 2160 grams (2.16kg), 5000 grams (5kg) or 21 ,600 gram (21.6kg). The melt flow rate for polypropylene is determined at a temperature of 230 °C and using a mass of 2160 grams. The melt flow rates of other polyolefins are performed at different temperatures as specified in ISO 1133.

[0040] The term “polymer” is intended to embrace, without limitation, homopolymers, copolymers (such as for example, block, graft, random, and alternating copolymers), terpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and random symmetries.

[0041] The term “polyethylene” is intended to embrace not only homopolymers of ethylene, but also copolymers and terpolymers wherein at least 85% of the recurring units are ethylene units, and the comonomer unit is for example propylene, butylene, hexene or octene. One useful polyethylene is a high-density polyethylene that has a melting temperature of about 123 °C to about 140 °C, a density in the range of 0.94 to 0.98 grams per cubic centimeter (ISO 1133), and a melt flow rate (ISO 1133, 190 °C / 2160 grams) of between 0.05 g / 10min and 30 g / 10min, preferably less than 4 g / 10min, and / or a melt flow rate (ISO 1133, 190 °C / 21 ,600 grams) of between 1 g / 10min and 15 g / 10min.

[0042] The term “polypropylene” is intended to embrace not only homopolymers of propylene but also copolymers and terpolymers where at least 85% of the recurring units are propylene units. Furthermore, unless otherwise specifically limited, the term “polypropylene” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and random symmetries.

[0043] The term “polymer type” refers to the chemical class into which the polymer falls, for example, polyolefin, polyethylene, polypropylene, etc.

[0044] The term “plexifilamentary” refers to a three-dimensional integral network or web of a multitude of thin, ribbon-like, fibrils of random length and a median fibril width of less than about 25 microns. In plexifilamentary structures, the fibrils are generally coextensively aligned with the longitudinal axis of the structure, and they intermittently unite and separate at irregular intervals in various places throughout the length, width, and thickness of the structure to form a continuous three-dimensional network or web.

[0045] The terms “spin agent” or “spin agent composition” refers to a composition comprising one or more solvents and any additives that are used to initially dissolve the polymer(s) to form the spin fluid. Suitable additives include stabilizers, such as antioxidants or acid scavengers.

[0046] The term “spin fluid” refers to a solution for spinning in a flash spinning process comprising a polymer and a spin agent. The solution may also include one or more additives. The term “dew point pressure” refers to the pressure at which, at constant temperature, liquid starts condensing from a vapor, vapor mixture, or vapor-gas mixture.

[0047] The term “bubble point pressure” refers to the pressure at which, at constant temperature, a liquid, liquid mixture, or liquid-solution begins to boil.

[0048] The term “azeotropic composition” refers to a composition comprising two or more fluids wherein the bubble point pressure equals the dew point pressure. An azeotropic composition boils without change of the composition and behaves as a single substance. The azeotropic compositions described herein are determined in a temperature range of -20 °C to 100 °C and expressed in mass fractions.

[0049] The term “azeotrope-like composition” refers to a composition comprising two or more fluids which exhibit only small differences between the dew point pressure and the bubble point pressure, i.e., the dew point pressure is different by 5% or less from the bubble point pressure (both expressed in absolute pressure). An azeotrope- 1 ike composition boils without substantial change of the composition and behaves substantially as a single substance. The azeotrope-like compositions described herein are determined in a temperature range of -20 °C to 100 °C and expressed in mass fractions.

[0050] The term “cloud point pressure” refers to the pressure at which, at constant temperature, a clear single phase spin fluid transitions from a clear solution to a cloudy, two-phase dispersion. At the cloud point pressure, a clear spin fluid becomes turbid.

[0051] Atmospheric pressure means 101.325 kPa. Essentially atmospheric pressure means 101.325 kPa ± 5 %.

[0052] As used herein, the singular forms "a," "an," and "the" include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. When a range of values is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about", it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable.

[0053] Azeotropic or Azeotrope-like Compositions

[0054] Azeotropic or azeotrope-like compositions comprising cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane Provided herein are azeotropic or azeotrope- 1 ike compositions comprising cyclopentane and 1 H, 1 H,2H-heptafluorocyclopentane.

[0055] In some embodiments, the azeotropic or azeotrope- 1 ike compositions comprise from about

[0056] 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 34 kPa to about 498 kPa. In some embodiments, the azeotropic or azeotrope-like compositions comprise from about 44 to about 80 weight percent cyclopentane and from about 56 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 36.6 kPa to about 498 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about 52 to about 99 weight percent cyclopentane and from about 48 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 60 °C and at a boiling pressure of about 34 kPa to about 162 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about 57 to about 99 weight percent cyclopentane and from about 43 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 40 °C and at a boiling pressure of about 34 kPa to about 83 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about

[0057] 45 to about 74 weight percent cyclopentane and from about 55 to about 26 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 79.9 kPa to about 498 kPa.

[0058] In some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 34 kPa to about 498 kPa. In some embodiments, the azeotropic or azeotrope-like compositions consists essentially of from about 44 to about 80 weight percent cyclopentane and from about 56 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 36.6 kPa to about 498 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 52 to about 99 weight percent cyclopentane and from about 48 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope- 1 ike compositions boil at a temperature of about 20 °C to about 60 °C and at a boiling pressure of about 34 kPa to about 162 kPa. In other embodiments, the azeotropic or azeotropelike compositions consist essentially of from about 57 to about 99 weight percent cyclopentane and from about 43 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 40 °C and at a boiling pressure of about 34 kPa to about 83 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consists essentially of from about 45 to about 74 weight percent cyclopentane and from about 55 to about 26 weight percent 1 H,1H,2H-heptafluorocyclopentane. These azeotropic or azeotrope- 1 ike compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 79.9 kPa to about 498 kPa.

[0059] In some embodiments, the azeotropic or azeotrope- 1 ike compositions consist of from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 34 kPa to about 498 kPa. In some embodiments, the azeotropic or azeotrope- 1 ike compositions consists of from about 44 to about 80 weight percent cyclopentane and from about 56 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 36.6 kPa to about 498 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist of from about 52 to about 99 weight percent cyclopentane and from about 48 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 60 °C and at a boiling pressure of about 34 kPa to about 162 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist of from about 57 to about 99 weight percent cyclopentane and from about 43 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 20 °C to about 40 °C and at a boiling pressure of about 34 kPa to about 83 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consists of from about 45 to about 74 weight percent cyclopentane and from about 55 to about 26 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 79.9 kPa to about 498 kPa.

[0060] In some embodiments, the composition comprising cyclopentane and 1H,1 H,2H- heptafluorocyclopentane is azeotropic. In some embodiments, the azeotropic composition consists essentially of from about 50 to about 65 weight percent cyclopentane and from about 50 to about 35 weight percent 1 H,1H,2H-heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 38 kPa to about 498 kPa. In some embodiments, the azeotropic composition consists of from about 50 to about 65 weight percent cyclopentane and from about 50 to about 35 weight percent 1H,1 H,2H- heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about 20 °C to about 100 °C and at a boiling pressure of about 38 kPa to about 498 kPa.

[0061] In some embodiments, the azeotropic composition consists essentially of about 65.3 weight percent cyclopentane and about 34.7 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 38.0 kPa and at a boiling temperature of about 20 °C. In some embodiments, the azeotropic composition consists of about 65.3 weight percent cyclopentane and about 34.7 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 38.0 kPa and at a boiling temperature of about 20 °C.

[0062] In some embodiments, the azeotropic composition consists essentially of about 60.4 weight percent cyclopentane and about 39.6 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 82.5 kPa and at a boiling temperature of about 40 °C. In some embodiments, the azeotropic composition consists of about 60.4 weight percent cyclopentane and about 39.6 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 82.5 kPa and at a boiling temperature of about 40 °C.

[0063] In some embodiments, the azeotropic composition consists essentially of about 57.4 weight percent cyclopentane and about 42.6 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 161.7 kPa and at a boiling temperature of about 60 °C. In some embodiments, the azeotropic composition consists of about 57.4 weight percent cyclopentane and about 42.6 weight percent 1H,1H,2H-heptafluorocyclopentane at a pressure of about 161.7 kPa and at a boiling temperature of about 60 °C.

[0064] In some embodiments, the azeotropic composition consists essentially of about 50.1 weight percent cyclopentane and about 49.9 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 497.7 kPa and at a boiling temperature of about 100 °C. In some embodiments, the azeotropic composition consists of about 50.1 weight percent cyclopentane and about 49.9 weight percent 1H,1H,2H-heptafluorocyclopentane at a pressure of about 497.7 kPa and at a boiling temperature of about 100 °C.

[0065] In some embodiments, the azeotropic composition consists essentially of about 60.0 weight percent cyclopentane and about 40.0 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 101.3 kPa and at a boiling temperature of about 45.8 °C. In some embodiments, the azeotropic composition consists of about 60.0 weight percent cyclopentane and about 40.0 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 101.3 kPa and at a boiling temperature of about 45.8 °C.

[0066] Azeotropic or azeotrope-like compositions comprising 2-methy I pentane and

[0067] 1 H,1 H,2H-heptafluorocyclopentane

[0068] Provided herein are azeotropic or azeotrope-like compositions comprising 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane.

[0069] In some embodiments, the azeotropic or azeotrope- 1 ike compositions comprise from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 3 kPa to about 385 kPa. In some embodiments, the azeotropic or azeotrope-like compositions comprise from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 60 °C and at a boiling pressure of about 3 kPa to about 121 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 40 °C and at a boiling pressure of about 3 kPa to about 60 kPa. In other embodiments, the azeotropic or azeotrope- 1 ike compositions comprise from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 20 °C and at a boiling pressure of about 3 kPa to about 27 kPa. In some embodiments, the azeotropic or azeotrope-like compositions comprise from about 40 to about 65 weight percent 2-methylpentane and from about 60 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 57 kPa to about 385 kPa.

[0070] In some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 3 kPa to about 385 kPa. In some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 60 °C and at a boiling pressure of about 3 kPa to about 121 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 49 to about 82 weight percent 2- methylpentane and from about 51 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane. These azeotropic or azeotrope- 1 ike compositions boil at a temperature of about -20 °C to about 40 °C and at a boiling pressure of about 3 kPa to about 60 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1H,2H- heptafluorocyclopentane. These azeotropic or azeotrope- 1 ike compositions boil at a temperature of about -20 °C to about 20 °C and at a boiling pressure of about 3 kPa to about 27 kPa. In some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 40 to about 65 weight percent 2-methylpentane and from about 60 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 57 kPa to about 385 kPa.

[0071] In some embodiments, the azeotropic or azeotrope- 1 ike compositions consist of from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 3 kPa to about 385 kPa. In some embodiments, the azeotropic or azeotrope- 1 ike compositions consist of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 60 °C and at a boiling pressure of about 3 kPa to about 121 kPa. In other embodiments, the azeotropic or azeotrope- 1 ike compositions consists of from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 40 °C and at a boiling pressure of about 3 kPa to about 60 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consists of from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 20 °C and at a boiling pressure of about 3 kPa to about 27 kPa. In some embodiments, the azeotropic or azeotrope-like compositions consist of from about 40 to about 65 weight percent 2-methylpentane and from about 60 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about 40 °C to about 100 °C and at a boiling pressure of about 57 kPa to about 385 kPa.

[0072] In some embodiments, the composition comprising 2-methylpentane and 1H,1H,2H- heptafluorocyclopentane is azeotropic. In some embodiments, the azeotropic composition consists essentially of from about 46 to about 66 weight percent 2-methylpentane and from about 54 to about 34 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 3 kPa to about 385 kPa. In some embodiments, the azeotropic composition consists of from about 46 to about 66 weight percent 2-methylpentane and from about 54 to about 34 weight percent 1H,1 H,2H-heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 3 kPa to about 385 kPa.

[0073] In some embodiments, the azeotropic composition consists essentially of from about 52 to about 66 weight percent 2-methylpentane and from about 48 to about 34 weight percent 1 H,1 H,2H-heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 60 °C and at a boiling pressure of about 3 kPa to about 121 kPa. In some embodiments, the azeotropic composition consists of from about 52 to about 66 weight percent 2-methylpentane and from about 48 to about 34 weight percent 1 H,1H,2H- heptafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 60 °C and at a boiling pressure of about 3 kPa to about 121 kPa.

[0074] In some embodiments, the azeotropic composition consists essentially of about 65.5 weight percent 2-methylpentane and about 34.5 weight percent 1H,1 H,2H- heptafluorocyclopentane at a pressure of about 3.4 kPa and at a boiling temperature of about - 20 °C. In some embodiments, the azeotropic composition consists of about 65.5 weight percent 2-methylpentane and about 34.5 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 3.4 kPa and at a boiling temperature of about -20 °C.

[0075] In some embodiments, the azeotropic composition consists essentially of about 58.2 weight percent 2-methylpentane and about 41.8 weight percent 1H,1 H,2H- heptafluorocyclopentane at a pressure of about 26.4 kPa and at a boiling temperature of about 20 °C. In some embodiments, the azeotropic composition consists of about 58.2 weight percent 2-methylpentane and about 41.8 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 26.4 kPa and at a boiling temperature of about 20 °C.

[0076] In some embodiments, the azeotropic composition consists essentially of about 54.1 weight percent 2-methylpentane and about 45.9 weight percent 1 H,1H,2H- heptafluorocyclopentane at a pressure of about 59.6 kPa and at a boiling temperature of about 40 °C. In some embodiments, the azeotropic composition consists of about 54.1 weight percent 2-methylpentane and about 45.9 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 59.6 kPa and at a boiling temperature of about 40 °C.

[0077] In some embodiments, the azeotropic composition consists essentially of about 51.8 weight percent 2-methylpentane and about 48.2 weight percent 1 H,1H,2H- heptafluorocyclopentane at a pressure of about 120.3 kPa and at a boiling temperature of about 60 °C. In some embodiments, the azeotropic composition consists of about 51.8 weight percent 2-methylpentane and about 48.2 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 120.3 kPa and at a boiling temperature of about 60 °C.

[0078] In some embodiments, the azeotropic composition consists essentially of about 46 weight percent 2-methylpentane and about 54 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 385 kPa and at a boiling temperature of about 100 °C. In some embodiments, the azeotropic composition consists of about 46 weight percent 2-methylpentane and about 54 weight percent 1 H , 1 H,2H-heptafluorocyclopentane at a pressure of about 385 kPa and at a boiling temperature of about 100 °C.

[0079] In some embodiments, the azeotropic composition consists essentially of about 52.6 weight percent 2-methylpentane and about 47.4 weight percent 1H,1 H,2H- heptafluorocyclopentane at a pressure of about 101.3 kPa and at a boiling temperature of about 54.8 °C. In some embodiments, the azeotropic composition consists of about 52.6 weight percent 2-methylpentane and about 47.4 weight percent 1 H,1 H,2H-heptafluorocyclopentane at a pressure of about 101.3 kPa and at a boiling temperature of about 54.8 °C.

[0080] Properties of the azeotropic or azeotrope-like compositions

[0081] The compound 1 H,1H,2H-heptafluorocyclopentane has a reported GWP-100 (global warming potential over a 100-year period) of 231 (IPCC 2021 report). While no specific data is available for cyclopentane and 2-methylpentane, values reported for hydrocarbons with up to four carbon atoms show a rapid decline in GWP-100 as the number of carbon atoms increases, so it is reasonable to assume a GWP-100 of at or close to zero for these compounds. Accordingly, the azeotropic or azeotrope- 1 ike compositions combining the two compounds cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane or the two compounds 2-methylpentane and 1H,1 H,2H- heptafluorocyclopentane have a low global warming potential (GWP). In some embodiments the azeotropic or azeotrope-like compositions comprising cyclopentane and 1H,1 H,2H- heptafluorocyclopentane have a GWP-100 (global warming potential over a 100-year period) of less than about 130, in other embodiments of less than about 115, and in other embodiments of less than about 100. In some embodiments the azeotropic or azeotrope-like compositions comprising 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane have a GWP-100 (global warming potential over a 100-year period) of less than about 130, in other embodiments of less than about 120, in other embodiments of less than about 110, and in other embodiments of less than about 85.

[0082] The azeotropic or azeotrope- 1 ike compositions as described herein have the advantage of being homogeneous azeotropic or azeotrope-like compositions. For homogenous azeotropic or azeotrope-like compositions, the components of the composition at ambient temperatures and pressures form a single liquid phase. This is to be contrasted with heterogeneous azeotropic or azeotrope-like compositions, where, due to low miscibility of the components of the composition, the components of the composition undergo phase separation in the liquid phase. Phase separation is usually undesired since processes involving the composition are more complex and expensive. The homogeneous nature of the azeotropic or azeotrope-like compositions is achievable over a broad range of practical conditions including ambient pressure and temperature.

[0083] The azeotropic or azeotrope-like compositions are useful in a wide range of applications. In some embodiments, the azeotropic or azeotrope- 1 ike compositions are used as spin agents for flash spinning, in other embodiments as cleaning agents, and in other embodiments as solvents.

[0084] Spin Agents and Spin Fluids for Flash Spinning

[0085] In some embodiments, the azeotropic or azeotrope- 1 ike compositions are spin agents within spin fluids for flash spinning.

[0086] In some embodiments, the spin fluid comprises (a) from about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising cyclopentane and 1 H,1H,2H-heptafluorocyclopentane or wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising 2- methylpentane and 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin fluid comprises (a) from about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope- 1 ike composition comprising cyclopentane and 1 H,1H,2H- heptafluorocyclopentane or wherein the spin agent comprises the azeotropic or azeotrope-like composition comprising 2-methylpentane and 1H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises from about 72 to about 90 weight percent of a spin agent, based on the total amount of the spin fluid, and in other embodiments from about 76 to about 85 weight percent of a spin agent, based on the total amount of the spin fluid.

[0087] In some embodiments, the spin agent consists essentially of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1 H,2H- heptafluorocyclopentane, in other embodiments from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1H,1 H,2H-heptafluorocyclopentane, in other embodiments from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0088] In some embodiments, the spin agent consists essentially of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1H,1H,2H- heptafluorocyclopentane, in other embodiments from about 49 to about 82 weight percent 2- methylpentane and from about 51 to about 18 weight percent 1H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin agent consists essentially of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 65 to about 82 weight percent 2- methylpentane and from about 35 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0089] The spin fluid may include additives, such as antioxidants or acid scavengers in minor amounts, provided that their presence does not interfere with the azeotropic or azeotrope-like nature of the compositions of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane or 2- methylpentane and 1 H, 1 H,2H-heptafluorocyclopentane described herein. In some embodiments, the spin fluid comprises additives in an amount of about 1.5 weight percent or less of the total amount of the spin agent, and in other embodiments in an amount of about 0.1 weight percent or less of the total amount of the spin agent.

[0090] In some embodiments, the spin agent consists of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1H,2H-heptafluorocyclopentane, in other embodiments from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1H,2H- heptafluorocyclopentane.

[0091] In some embodiments, the spin agent consists of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1H,1 H,2H- heptafluorocyclopentane, in other embodiments from about 49 to about 82 weight percent 2- methylpentane and from about 51 to about 18 weight percent 1H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin agent consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0092] In some embodiments, the spin fluid comprises from about 15 to about 24 weight percent of a polymer and the spin agent consists essentially of or consists of from about 57 to about 85 weight percent cyclopentane and from about 43 to about 15 weight percent 1H,1H,2H- heptafluorocyclopentane.

[0093] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polymer and the spin agent consists essentially of or consists of from about 54 to about 75 weight percent 2-methylpentane and from about 46 to about 25 weight percent 1H,1 H,2H- heptafluorocyclopentane.

[0094] The spin fluid can be used for a broad range of different polymers and blends / mixtures thereof. In some embodiments, the polymer is one or more polyolefins.

[0095] In some embodiments, polyolefins are polyethylene (PE), polypropylene (PP), polybutene- 1 , poly(4-methyl-1 -pentene), and blends / mixtures thereof. Particularly preferred polyolefins are polyethylene (PE), in particular high-density polyethylene (HDPE), and blends / mixtures of high- density polyethylene (HDPE) and low-density polyethylene (LDPE), in particular linear low-density polyethylene (LLDPE). In some embodiments, the polyolefin is a high-density polyethylene (HDPE).

[0096] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1H,1H,2H- heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2- methylpentane and from about 42 to about 35 weight percent 1H,1H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1 H,1H,2H- heptafluorocyclopentane, or from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0097] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1 -pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1-pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1H,1H,2H- heptafluorocyclopentane, or from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0098] In some embodiments, the spin fluid comprising the azeotropic or azeotrope-like composition as described herein exhibits a cloud point pressure in the range of about 45 to about 300 bar, in other embodiments in the range of about 50 to about 300 bar, and in other embodiments in the range of about 70 to about 300 bar. In some embodiments, the spin fluid comprising the azeotropic or azeotrope- 1 ike composition as described herein exhibits a cloud point pressure in the range of about 45 to about 250 bar, in other embodiments in the range of about 50 to about 250 bar, and in other embodiments in the range of about 70 to about 250 bar. In some embodiments, the spin fluid comprising the azeotropic or azeotrope-like composition as described herein exhibits a cloud point pressure in the range of about 45 to about 200 bar, in other embodiments in the range of about 50 to about 200 bar, and in other embodiments in the range of about 70 to about 200 bar. The flash spinning process must take place at an operating pressure below the spin fluid’s cloud point pressure but above the spin fluid’s bubble point pressure. If the cloud point pressure is above about 300 bar, the flash spinning equipment must be built to withstand very high pressure which increases costs and operational constraints.

[0099] When used as a spin agent, the homogeneous azeotropic or azeotrope-like compositions have the advantage that in the spin agent recovery process, upon condensation of the spin agent, no phase separation occurs. Furthermore, the azeotropic or azeotrope-like compositions described herein result in spin fluids with a cloud point pressures at or close to the azeotrope. This then makes it easy to condense the used spin agent into a liquid with the same or substantially the same composition so that it can be re-used.

[0100] Preparation of Plexifilamentary Film-fibril Strands of Polymer

[0101] In some embodiments, there is provided a process for the preparation of plexifilamentary fibrils of polymer, wherein the process comprises the steps of:

[0102] (i) generating a spin fluid comprising

[0103] (a) about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid, and

[0104] (b) a spin agent, and (ii) flash spinning the spin fluid at a pressure that is above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifilamentary fibrils of the polymer; wherein the spin agent comprises or consists essentially of

[0105] (1) an azeotropic or azeotrope-like composition comprising cyclopentane and 1H,1 H,2H-heptafluorocyclopentane, or

[0106] (2) an azeotropic or azeotrope-like composition comprising 2-methylpentane and 1H,1 H,2H-heptafluorocyclopentane.

[0107] In some embodiments, the spin fluid comprises (a) from about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising cyclopentane and 1 H,1H,2H-heptafluorocyclopentane or wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising 2- methylpentane and 1 H,1 H,2H-heptafluorocyclopentane.

[0108] In some embodiments, the flash-spinning is performed at a pressure in the range of about 45 to about 300 bar, or in the range of about 50 to about 300 bar, or in the range of about 70 to about 300 bar. In some embodiments, the flash-spinning is performed at a pressure in the range of about 45 to about 250 bar, in other embodiments in the range of about 50 to about 250 bar, and in other embodiments in the range of about 70 to about 250 bar. In some embodiments, the flash-spinning is performed at a pressure in the range of about 45 to about 200 bar, in other embodiments in the range of about 50 to about 200 bar, and in other embodiments in the range of about 70 to about 200 bar. The region of lower pressure into which flash spinning occurs is usually at or around atmospheric pressure.

[0109] In some embodiments, the spin agent is present in the spin fluid in an amount of from about 72 to about 90 weight percent, based on the total amount of the spin fluid, and in other embodiments from about 76 to about 85 weight percent, based on the total amount of the spin fluid.

[0110] In some embodiments, the spin agent consists essentially of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1 H,2H- heptafluorocyclopentane, in other embodiments from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H,1H,2H-heptafluorocyclopentane, in other embodiments from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1H,1H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0111] In some embodiments, the spin agent consists essentially of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1H,1H,2H- heptafluorocyclopentane, in other embodiments from about 49 to about 82 weight percent 2- methylpentane and from about 51 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin agent consists essentially of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 65 to about 82 weight percent 2- methylpentane and from about 35 to about 18 weight percent 1H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1H,1H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0112] The spin fluid may include additives, such as antioxidants or acid scavengers in minor amounts, provided that their presence does not interfere with the azeotropic or azeotrope-like nature of the compositions of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane or 2- methylpentane and 1 H,1 H,2H-heptafluorocyclopentane described herein. In some embodiments, the spin fluid comprises additives in an amount of about 1.5 weight percent or less of the total amount of the spin agent, and in other embodiments in an amount of about 0.1 weight percent or less of the total amount of the spin agent.

[0113] In some embodiments, the spin agent consists of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1H,2H-heptafluorocyclopentane, in other embodiments from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H, 1 H,2H-heptafluorocyclopentane, in other embodiments from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1H,2H- heptafluorocyclopentane.

[0114] In some embodiments, the spin agent consists of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1H,2H- heptafluorocyclopentane, in other embodiments from about 49 to about 82 weight percent 2- methylpentane and from about 51 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. In some embodiments, the spin agent consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1H,1H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1H,1 H,2H-heptafluorocyclopentane. In other embodiments, the spin agent consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1H,1 H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H , 1 H ,2H-heptafluorocyclopentane.

[0115] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid, and the spin agent consists essentially of or consists of from about 57 to about 85 weight percent cyclopentane and from about 43 to about 15 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0116] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid, and the spin agent consists essentially of or consists of from about 54 to about 75 weight percent 2-methylpentane and from about 46 to about 25 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0117] The spin fluid can be used for a broad range of different polymers and blends / mixtures thereof. In some embodiments, the polymer is one or more polyolefins.

[0118] In some embodiments, polyolefins are polyethylene (PE), polypropylene (PP), polybutene- 1 , poly(4-methyl-1-pentene), and blends / mixtures thereof. Particularly preferred polyolefins are polyethylene (PE), in particular high-density polyethylene (HDPE), and blends / mixtures of high- density polyethylene (HDPE) and low-density polyethylene (LDPE), in particular linear low-density polyethylene (LLDPE). In some embodiments, the polyolefin is a high-density polyethylene (HDPE). In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1H,1 H,2H- heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H , 1 H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2- methylpentane and from about 42 to about 35 weight percent 1 H,1H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1H,1H,2H- heptafluorocyclopentane, or from about 70 to about 80 weight percent cyclopentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0119] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1 -pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1H,2H-heptafluorocyclopentane. In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1-pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H- heptafluorocyclopentane, or from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0120] In some embodiments, there is provided plexifilamentary fibrils of polymer obtainable by the process described herein.

[0121] The shape of the assembly of plexifilamentary fibrils of polymer discharged from each spin orifice may be modified by any methods known in the art. In some embodiments, the plexifilamentary fibrils of polymer discharged from each spin orifice may be modified by passing into a shroud such as described on US 3,387,326, in other embodiments by passing into a slotted outlet such as described in US 3,467,744 or US 5,788,993, and in other embodiments passing into a slot fan jet as described in US 8,114,325. In some embodiments, streams of fibrils from multiple orifices may exit via a common slot as described in US 3,564,088.

[0122] Preparation of Sheets of Nonwoven Flash-spun Plexifilamentary Fibrils by Collection, Consolidation, Bonding, Softening, and Articles Made from Sheets of Nonwoven Flash-spun Plexifilamentary Fibrils

[0123] Sheets comprising plexifilamentary fibrils of polymer can be formed by any method known in the art. In some embodiments, the stream of fibrils discharged from each spin orifice is directed towards a deflector device which alternately directs the stream of fibrils to the left and right onto a moving collecting device such that the fibrils accumulate in the form of a collected sheet of nonwoven flash-spun plexifilamentary fibrils, formed from fibrils oriented in an overlapping, multidirectional configuration. Deflection of the stream of fibrils may be achieved by any suitable means known in the art, including, but not limited to, those described in US 3,277,526 and US 3,387,326, US 3,169,899, US 3,497,918, US 3,456,156, US 3,593,074, US 3,851,023 and US 3,860,369, US 4,148,595, US 5,045,258, US 5,643,524, US 5,731,011 , US 5,750,152 and WO92 / 20511. The stream of fibrils may also be laid down to form a collected sheet of nonwoven flash-spun plexifilamentary fibrils without deflection as described in US 5,788,993 and US 8,114,325. The method of forming a collected sheet of nonwoven flash-spun plexifilamentary fibrils may further utilize structures in the spin cell such as those described in US 5,123,983, US 5,296,172, and WO92 / 20511.

[0124] In some embodiments, the streams of fibrils are discharged from spin orifices located on a rotating support, and the fibrils are collected on a collecting belt which surrounds the rotating arrangement circumferentially as described in US 7,118,698, US 7,621 ,731, US 7,786,034, and US 7,998,388.

[0125] In some embodiments, the collected sheet of nonwoven flash-spun plexifilamentary fibrils formed by flash-spinning as described herein may be consolidated by applying a small amount of pressure to the sheet to form a consolidated sheet of nonwoven flash-spun plexifilamentary fibrils. In some embodiments, the sheet may be passed under a roller which applies pressure to the sheet to form a consolidated sheet.

[0126] In some embodiments, a consolidated sheet as described herein is subjected to thermal or mechanical bonding as known in the art to form a thermally or mechanically bonded sheet. Bonding may also be achieved by impregnation of a consolidated sheet with a chemical bonding agent, either throughout the entire sheet, or at isolated points distributed over the sheet, or pattern-wise.

[0127] In some embodiments, the bonded sheet is subjected to a mechanical softening process to obtain a softened sheet of nonwoven flash-spun plexifilamentary fibrils.

[0128] In some embodiments, an antistatic treatment is applied to the bonded or softened sheet. In some embodiments, the antistatic treatment is applied by applying a coating composition comprising an antistatic compound.

[0129] Further embodiments relate to a multilayer structure comprising at least one sheet of nonwoven flash-spun plexifilamentary fibrils as described herein, and at least one further sheet or a film. In some embodiments, the sheet of nonwoven flash-spun plexifilamentary fibrils as described herein is a collected sheet, a consolidated sheet, a bonded sheet or a softened sheet.

[0130] The sheet of nonwoven flash-spun plexifilamentary fibrils as described herein has many uses and may be used in a variety of articles and applications, including, but not limited to, multilayer structures, garments (including, but not limited to, protective apparel), house wrap, roof lining, car covers, medical and non-medical packaging, filtration media, print media, tags and labels, and accessories.

[0131] EXAMPLES

[0132] A study has been performed for the phase behavior and flash spinning of polyethylene, polypropylene, and ethylene-hexene copolymer for azeotropic and azeotrope- 1 ike compositions. The experimental procedure and results are provided below. These examples are given to illustrate exemplary embodiments of the invention and should not be interpreted as limiting in any way.

[0133] Materials Used

[0134] 2-Methylpentane, CAS Number 107-83-5, has an atmospheric boiling point of 60 °C and a molecular weight of 84.9 g / mol. The 2-methylpentane used had a purity level above 99 %.

[0135] Cyclopentane, CAS Number 287-92-3, has an atmospheric boiling point of 45 °C and a molecular weight of 70.1 g / mol. The cyclopentane used had a purity level of above 97%.

[0136] 1 H,1 H,2H-heptafluorocyclopentane (HFCP, also known as 1 , 1 ,2, 2, 3,3,4- heptafluorocyclopentane), CAS Number 15290-77-4 has a melting point of 21 °C, an atmospheric boiling point of 82.5 °C and a molecular weight of 196.07 g / mol and. The 1 H,1H,2H- heptafluorocyclopentane used had a purity level of above 99 percent by weight.

[0137] Six different polyethylenes were used: Polyethylene A was a polyethylene having a density of 0.957 g / cm3(ISO 1183) and melt flow rates of 0.3 g / 10min (ISO 1133, 190 °C / 2.16 kg).

[0138] Polyethylene B was a polyethylene having a density of 0.950 g / cm3(ISO 1183), and melt flow rates of 0.08 g / 10min (ISO 1133, 190 °C / 2.16 kg) and 8.4 g / 10min (ISO 1133, 190 °C / 21.6 kg).

[0139] Polyethylene C was a polyethylene having a density of 0.963 g / cm3(ISO 1183) and a melt flow rate of 0.72 g / 10min (ISO 1133, 190 °C / 2.16 kg).

[0140] Polyethylene D was a polyethylene having a density of 0.950 g / cm3(ISO 1183) and a melt flow rate of 0.76 g / 10min (ASTM D1238, 190 °C / 2.16 kg).

[0141] Polyethylene E was a polyethylene having a density of 0.952 g / cm3(ISO 1183) and a melt flow rate 2.1 g / 10min (ISO 1133, 190 °C / 21.6 kg).

[0142] The ethylene-hexene copolymer used was an ethylene-hexene copolymer having a density of 0.927 g / cm3(ISO 1183) and a melt flow rate of 0.9 g / 10min (ISO 1133, 190 °C / 2.16 kg).

[0143] The polypropylene (PP) used was an isotactic polypropylene having a density of 0.905 g / cm3(ISO 1183), a melt flow rate of 4.5 g / 10 min (ISO 1133, 230 °C / 2.16 kg) and a melt peak temperature of 163 °C.

[0144] All polymers used were dried during a minimum of 8 hours in a vacuum oven at about 45- 50 °C before use.

[0145] Spinning Equipment

[0146] The apparatus used consisted of two high pressure cylindrical chambers, each equipped with a piston which was adapted to apply pressure to the contents of the vessel. The cylinders had an inside diameter of 1.0 inch (25.4 mm) and each had an internal capacity of 50 cubic centimeters. The cylinders were connected to each other at one end through a 3 / 32 inch (2.3 mm) diameter channel and a mixing chamber containing a series of fine mesh screens was used as a static mixer. In the channel, a Type J thermocouple was in contact with the spin fluid to record the temperature. Mixing was accomplished by forcing the contents of the vessel back and forth between the two cylinders through the static mixer. A spinneret assembly with a quick-acting means for opening the orifice was attached to the channel through a tee. The spinneret assembly consisted of a lead hole with a diameter of 0.25 inch (6.3 mm) and a length of about 2.0 inch (50.8 mm), and a spinneret orifice with a diameter of 0.020 inch (0.508 mm) and a length of 0.020 inch (0.508 mm). A pressure transmitter calibrated at the spin temperature was mounted in the lead hole to measure the pressure of the spin fluid. The pistons were driven by a high-pressure hydraulic system.

[0147] In operation, the apparatus was charged with polymer pellets and spin agent and a pressure of at least 50 bar was applied to the pistons to compress the charge and avoid the spin fluid from boiling during subsequent heating. The contents were then heated to mixing temperature and held at that temperature for about 30 to 45 minutes during which time a differential pressure was alternatively established between the two cylinders to repeatedly force the contents through the mixing channel from one cylinder to the other to provide mixing and effective formation of a spin fluid. The spin fluid temperature was then increased to the final spin temperature and held there for about 10 to 20 minutes to equilibrate. The pressure of the spin fluid was kept above the cloud point pressure during mixing and during the increase in temperature from the mixing temperature to the spin temperature. Mixing was continued throughout this period. At the end of the mixing cycle, the accumulator was set to the pressure desired for spinning. Next, the valve between the accumulator and the twin piston assembly was opened to reduce the pressure of the spin fluid to the desired spin pressure, and about two to five seconds later, the spinneret orifice was opened to release the spin fluid into conditions of atmospheric pressure. The delay of about two to five seconds corresponds to the residence time in the letdown chamber in a continuous spinning process. The resultant stream of flash-spun fibrils was collected in a stainless-steel open mesh screen basket. During spinning, the spin pressure was recorded just upstream of the spinneret.

[0148] For cloud point pressure determination, the spinneret assembly was replaced with a view cell assembly containing a 1 / 2 inch (12.3 mm) diameter high-pressure sight glass, through which the contents of the cell could be viewed as they flow through the channel. The window was lit by means of a fiber optic light guide, while the view through the sight glass was displayed using a digital camera. In the cell, a Type J thermocouple was located about 5 mm behind the high- pressure sight glass. The Type J thermocouple and a pressure measuring device located in close proximity to the window measured the pressure and temperature inside the view cell behind the sight glass and the pressure and temperature were continuously monitored by a computer. When, after a period of mixing, a clear, homogeneous spin fluid was established, the temperature was held constant and the differential pressure applied to the pistons was equalized so that the pistons stopped moving. Then, the pressure applied to the spin fluid in the view cell was gradually decreased until phase separation was observed through the sight glass, as the initially clear, homogeneous spin fluid became cloudy in appearance. The temperature and pressure were recorded when the thermocouple became no longer visible. This pressure was the phase 1 separation pressure or cloud point pressure for that spin fluid at that temperature. The pressure was then increased until the spin fluid returned to its transparent state, i.e., until the insoluble phase redissolved, and in this way, two or three repeat cloud point measurements could be made at an approximately constant temperature. Once this data was recorded, mixing was resumed while the spin fluid was heated to the next temperature at which the cloud point pressure was to be measured.

[0149] Results

[0150] Example 1 : Vapor liquid equilibrium for the composition of cyclopentane:

[0151] 1 H,1 H,2H-heptafluorocyclopentane

[0152] Figure 1 shows the calculated vapor liquid equilibrium for the composition of cyclopentane: 1 H,1 H,2H-heptafluorocyclopentane at 40 °C. The azeotropic composition of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane at 40 °C corresponds to about 60.4 wt% cyclopentane and about 39.6 wt% 1 H,1 H,2H-heptafluorocyclopentane. The bubble point pressure for the azeotropic composition is equal to about 82.5 kPa. The azeotrope- 1 ike composition of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane at a 5% deviation from the azeotrope point was found to be from about 57:43 wt% to 99:1 wt%.

[0153] Example 2: Cloud point study of polyethylene

[0154] Figure 2 shows the cloud point pressure curve of a spin fluid comprising 24 wt% polyethylene A and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight. This spin fluid comprising 24 wt% polyethylene shows a cloud point pressure curve suitable for flash spinning.

[0155] Example 3: Flash spinning performance of polyethylene

[0156] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 24 wt% polyethylene B and a spin agent of cyclopentane and 1H,1 H,2H- heptafluorocyclopentane in a 60:40 ratio by weight at a spin temperature of about 200 °C and a spin pressure of about 61 bar. Example 4: Cloud point study of polyethylene

[0157] Figure 3 shows the cloud point pressure curve of a spin fluid comprising 16 wt% polyethylene A and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 65:35 ratio by weight. This spin fluid comprising 16 wt% polyethylene shows a cloud point pressure curve suitable for flash spinning.

[0158] Example 5: Flash spinning performance of polyethylene

[0159] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 16 wt% polyethylene B and a spin agent of cyclopentane and 1H,1 H,2H- heptafluorocyclopentane in a 65:35 ratio by weight at a spin temperature of about 210 °C and a spin pressure of about 74 bar.

[0160] Example 6: Flash spinning performance of polyethylene

[0161] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 12 wt% polyethylene C and a spin agent of cyclopentane and 1 H,1 H,2H- heptafluorocyclopentane in a 65:35 ratio by weight at a spin temperature of about 195 °C and a spin pressure of about 46 bar.

[0162] Example 7: Cloud point study of ethylene-hexene copolymer

[0163] Figure 4 shows the cloud point pressure curve of a spin fluid comprising 22 wt% ethylenehexene copolymer and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight. This spin fluid comprising 22 wt% ethylene-hexene copolymer shows a cloud point pressure curve suitable for flash spinning.

[0164] Example 8: Flash spinning performance of ethylene-hexene copolymer

[0165] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 22 wt% ethylene-hexene copolymer and a spin agent of cyclopentane and 1H,1H,2H- heptafluorocyclopentane in a 60:40 ratio by weight at a spin temperature of about 210 °C and a spin pressure of about 79 bar. Example 9: Cloud point study of polypropylene

[0166] Figure 5 shows the cloud point pressure curve of a spin fluid comprising 17 wt% polypropylene and a spin agent of cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight. This spin fluid comprising 15 wt% polypropylene shows a cloud point pressure curve suitable for flash spinning.

[0167] Example 10: Flash spinning performance polypropylene

[0168] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 17 wt% polypropylene and a spin agent of cyclopentane and 1H,1 H,2H- heptafluorocyclopentane in a 60:40 ratio by weight at a spin temperature of about 220 °C and a spin pressure of about 56 bar.

[0169] Example 11 : Vapor liquid equilibrium for the mixture 2-methyl-pentane:1 H,1 H,2H- heptafluorocyclopentane

[0170] Figure 6 shows the calculated vapor liquid equilibrium for the composition of 2- methylpentane:1H,1H,2H-heptafluorocyclopentane at 40 °C. The azeotropic composition of 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane at 40 °C corresponds to about 54.9 wt% 2-methylpentane and about 45.1 wt% 1 H,1 H,2H-heptafluorocyclopentane. The bubble point pressure for the azeotropic composition is equal to about 59.6 kPa. The azeotrope-like composition of 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane at a 5% deviation from the azeotrope point was found to be from about 49:51 wt% to 73:27 wt%.

[0171] Example 12: Cloud point study of polyethylene

[0172] Figure 7 shows the cloud point pressure curve of a spin fluid comprising 20 wt% polyethylene A and a spin agent of 2-methylpentane: 1 H,1 H,2H-heptafluorocyclopentane in a 70:30 ratio by weight. This spin fluid comprising 20 wt% polyethylene shows a cloud point pressure curve suitable for flash spinning.

[0173] Example 13: Flash spinning performance of polyethylene

[0174] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 20 wt% polyethylene B and a spin agent of 2-methylpentaneand 1H,1H,2H- heptafluorocyclopentane in a 70:30 ratio by weight at a spin temperature of about 185 °C and a spin pressure of about 131 bar.

[0175] Example 14: Cloud point study of polyethylene

[0176] Figure 8 shows the cloud point pressure curve of a spin fluid comprising 18 wt% polyethylene E and a spin agent of 2-methylpentane and 1H,1 H,2H-heptafluorocyclopentane in a 70:30 ratio by weight. This spin fluid comprising 18 wt% polyethylene shows a cloud point pressure curve suitable for flash spinning.

[0177] Example 15: Flash spinning performance of polyethylene

[0178] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 18 wt% polyethylene E and a spin agent of 2-methylpentane and 1H,1 H,2H- heptafluorocyclopentane in a 70:30 ratio by weight at a spin temperature of about 195 °C and a spin pressure of about 145 bar.

[0179] Example 16: Cloud point study of polyethylene

[0180] Figure 9 shows the cloud point pressure curve of a spin fluid comprising 24 wt% polyethylene A and a spin agent of 2-methylpentane and 1H,1 H,2H-heptafluorocyclopentane in a 60:40 ratio by weight. This spin fluid comprising 24 wt% polyethylene shows a cloud point pressure curve suitable for flash spinning.

[0181] Example 17: Flash spinning performance of polyethylene

[0182] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 24 wt% polyethylene C and a spin agent of 2-methylpentane and 1H,1 H,2H- heptafluorocyclopentane in a 60:40 ratio by weight at a spin temperature of about 185 °C and a spin pressure of about 158 bar.

[0183] Example 18: Cloud point study of polypropylene

[0184] Figure 10 shows the cloud point pressure curve of a spin fluid comprising 15 wt% polypropylene and a spin agent of 2-methylpentane and 1H,1 H,2H-heptafluorocyclopentane in a 52:48 ratio by weight. This spin fluid comprising 15 wt% polypropylene shows a cloud point pressure curve suitable for flash spinning. Example 19: Flash spinning performance of polypropylene

[0185] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 15 wt% polypropylene and a spin agent of 2-methylpentane and 1H,1 H,2H- heptafluorocyclopentane in a 52:48 ratio by weight at a spin temperature of about 186 °C and a spin pressure of about 46 bar.

[0186] Table 1 : Summary of the flash spinning experiments of Examples 3, 5, 6, 8 and 10.

[0187] ‘assuming a GWP of essentially zero for the hydrocarbon cyclopentane and a GWP of 231 for the 1 H,1 H,2H-heptafluorocyclopentane (IPCC 2021 report)

[0188] Table 2: Summary of the flash spinning experiments of Examples 13, 15, 17 and 19.

[0189] ‘assuming a GWP of essentially zero for the hydrocarbon 2-methylpentane and a GWP of 231 for the 1 H,1 H,2H-heptafluorocyclopentane (IPCC 2021 report)

[0190] The above examples illustrate that the azeotropic or azeotrope-like compositions can be used as a spin agent for the flash spinning process of a range of polyolefins for different polymer concentrations, spin temperatures, and spin pressures. This allows an efficient preparation of plexifilamentary fibrils of polymer.

[0191] In addition, the azeotropic or azeotrope- 1 ike compositions exhibit a desirably low GWP value of below 200. This makes these compositions suitable as replacement for currently used spin agents.

[0192] Furthermore, the azeotropic or azeotrope- 1 ike compositions form a positive homogenous azeotrope with an advantageously low boiling temperature of about 45 °C. Such low boiling temperature correlates to a pressure at or around atmospheric pressure.

[0193] The azeotrope-like compositions which are centered around the azeotrope point exhibit only small differences between the bubble point pressure and the dew point pressure. This has the advantage that the azeotropic or azeotrope-like compositions do not change significantly during the different steps of the spin agent recovery process and thus allow the spin agent to be re-used / recycled in a commercial process. OTHER EMBODIMENTS

[0194] 1. In some embodiments, the present application provides an azeotropic or azeotrope- 1 ike composition comprising

[0195] (i) cyclopentane and 1 H,1H,2H-heptafluorocyclopentane; or

[0196] (ii) 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane.

[0197] 2. The azeotropic or azeotrope-like composition of embodiment 1 comprising from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H- heptafluorocyclopentane.

[0198] 3. The azeotropic or azeotrope- 1 ike composition of embodiment 2 consisting essentially or consisting of from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1H,2H-heptafluorocyclopentane.

[0199] 4. The azeotropic or azeotrope- 1 ike composition of embodiment 2 or 3 boiling at a temperature of about 20 °C to about 100 °C at a pressure of about 34 kPa to about 498 kPa.

[0200] 5. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 2 to 4 comprising from about 44 to about 80 weight percent cyclopentane and from about 56 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0201] 6. The azeotropic or azeotrope- 1 ike composition of embodiment 5 consisting essentially or consisting of from about 44 to about 80 weight percent cyclopentane and from about 56 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0202] 7. The azeotropic or azeotrope- 1 ike composition of embodiment 5 or 6 boiling at a temperature of about 20 °C to about 100 °C at a pressure of about 36.6 kPa to about 498 kPa.

[0203] 8. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 2 to 4 comprising from about 52 to about 99 weight percent cyclopentane and from about 48 to about 1 weight percent 1H,1H,2H-heptafluorocyclopentane. 9. The azeotropic or azeotrope- 1 ike composition of embodiment 8 consisting essentially or consisting of from about 52 to about 99 weight percent cyclopentane and from about 48 to about 1 weight percent 1 H,1H,2H-heptafluorocyclopentane.

[0204] 10. The azeotropic or azeotrope- 1 ike composition of embodiment 8 or 9 boiling at a temperature of about 20 °C to about 60 °C at a pressure of about 34 kPa to about 162 kPa.

[0205] 11. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 2 to 4 comprising from about 57 to about 99 weight percent cyclopentane and from about 43 to about 1 weight percent 1H,1H,2H-heptafluorocyclopentane.

[0206] 12. The azeotropic or azeotrope-like composition of embodiment 11 consisting essentially or consisting of from about 57 to about 99 weight percent cyclopentane and from about 43 to about 1 weight percent 1 H,1H,2H-heptafluorocyclopentane.

[0207] 13. The azeotropic or azeotrope-like composition of embodiment 11 or 12 boiling at a temperature of about 20 °C to about 40 °C at a pressure of about 34 kPa to about 83 kPa.

[0208] 14. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 2 to 4 comprising from about 45 to about 74 weight percent cyclopentane and from about 55 to about 26 weight percent 1 H , 1 H,2H-heptafluorocyclopentane.

[0209] 15. The azeotropic or azeotrope-like composition of embodiment 14 consisting essentially or consisting of from about 45 to about 74 weight percent cyclopentane and from about 55 to about 26 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0210] 16. The azeotropic or azeotrope-like composition of embodiment 14 or 15 boiling at a temperature of about 40 °C to about 100 °C at a pressure of about 79.9 kPa to about 498 kPa.

[0211] 17. The azeotropic composition of any one of the embodiments 2 to 16 consisting essentially of or consisting of from about 50 to about 65 weight percent cyclopentane and from about 50 to about 35 weight percent 1 H,1H,2H-heptafluorocyclopentane. 18. The azeotropic composition of embodiment 17 boiling at a temperature of about 20 °C to about 100 °C at pressure of about 38 kPa to about 498 kPa.

[0212] 19. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 65.3 weight percent cyclopentane and about 34.7 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0213] 20. The azeotropic composition of embodiment 19 boiling at temperature of about 20 °C at a pressure of about 38.0 kPa.

[0214] 21. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 60.4 weight percent cyclopentane and about 39.6 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0215] 22. The azeotropic composition of embodiment 21 boiling at temperature of about 40 °C at a pressure of about 82.5 kPa.

[0216] 23. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 57.4 weight percent cyclopentane and about 42.6 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0217] 24. The azeotropic composition of embodiment 23 boiling at temperature of about 60 °C at a pressure of about 161.7 kPa.

[0218] 25. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 50.1 weight percent cyclopentane and about 49.9 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0219] 26. The azeotropic composition of embodiment 25 boiling at temperature of about 100 °C at a pressure of about 497.7 kPa.

[0220] 27. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 60.0 weight percent cyclopentane and about 40.0 weight percent 1 H, 1 H,2H-heptafluorocyclopentane. 28. The azeotropic composition of embodiment 27 boiling at temperature of about 45.8 °C at a pressure of about 101.3 kPa.

[0221] 29. The azeotropic or azeotrope-like composition of embodiment 1 comprising from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0222] 30. The azeotropic or azeotrope- 1 ike composition of embodiment 29 consisting essentially of or consisting of from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0223] 31. The azeotropic or azeotrope-like composition of embodiment 29 or 30 boiling at a temperature of about -20 °C to about 100 °C at a pressure of about 3 kPa to about 385 kPa.

[0224] 32. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 29 to 31 comprising from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0225] 33. The azeotropic or azeotrope- 1 ike composition of embodiment 32 consisting essentially of or consisting of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0226] 34. The azeotropic or azeotrope-like composition of embodiment 32 or 33 boiling at a temperature of about -20 °C to about 60 °C at a pressure of about 3 kPa to about 121 kPa.

[0227] 35. The azeotropic or azeotrope- 1 ike composition of any one of embodiments 29 to 34 comprising from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0228] 36. The azeotropic or azeotrope- 1 ike composition of embodiment 35 consisting essentially of or consisting of from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane. 37. The azeotropic or azeotrope-like composition of embodiment 35 or 36 boiling at a temperature of about -20 °C to about 40 °C at a pressure of about 3 kPa to about 60 kPa.

[0229] 38. The azeotropic or azeotrope-like composition of any one of embodiments 29 to 37 comprising from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0230] 39. The azeotropic or azeotrope- 1 ike composition of embodiment 35 consisting essentially of or consisting of from about 54 to about 82 weight percent 2-methylpentane and from about 46 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0231] 40. The azeotropic or azeotrope-like composition of embodiment 38 or 39 boiling at a temperature of about -20 °C to about 20 °C at a pressure of about 3 kPa to about 27 kPa.

[0232] 41. The azeotropic or azeotrope-like composition of any one of embodiments 29 to 31 comprising from about 40 to about 65 weight percent 2-methylpentane and from about 60 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0233] 42. The azeotropic or azeotrope- 1 ike composition of embodiment 41 consisting essentially of or consisting of from about 40 to about 65 weight percent 2-methylpentane and from about 60 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0234] 43. The azeotropic or azeotrope-like composition of embodiment 41 or 42 boiling at a temperature of about 40 °C to about 100 °C at a pressure of about 57 kPa to about 385 kPa.

[0235] 44. The azeotropic composition of any one of the embodiments 29 to 43 consisting essentially of or consisting of from about 46 to about 66 weight percent 2-methylpentane and from about 54 to about 34 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0236] 45. The azeotropic composition of embodiment 44 boiling at a temperature of about -20 °C to about 100 °C at pressure of about 3 kPa to about 385 kPa. 46. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of from about 52 to about 66 weight percent 2-methylpentane and from about 48 to about 34 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0237] 47. The azeotropic composition of embodiment 46 boiling at a temperature of about -20 °C to about 60 °C at pressure of about 3 kPa to about 121 kPa.

[0238] 48. The azeotropic composition of any one of the embodiments 29 to 47 consisting essentially of or consisting of about 65.5 weight percent 2-methylpentane and about 34.5 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0239] 49. The azeotropic composition of embodiment 48 boiling at a temperature of about -20 °C at a pressure of about 3.4 kPa.

[0240] 50. The azeotropic composition of any one of the embodiments 29 to 47 consisting essentially of or consisting of about 58.2 weight percent 2-methylpentane and about 41.8 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0241] 51. The azeotropic composition of embodiment 50 boiling at a temperature of about 20 °C at a pressure of about 26.4 kPa.

[0242] 52. The azeotropic composition of any one of the embodiments 29 to 47 consisting essentially of or consisting of about 54.1 weight percent 2-methylpentane and about 45.9 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0243] 53. The azeotropic composition of embodiment 52 boiling at a temperature of about 40 °C at a pressure of about 59.6 kPa.

[0244] 54. The azeotropic composition of any one of the embodiments 29 to 47 consisting essentially of or consisting of about 51.8 weight percent 2-methylpentane and about 48.2 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0245] 55. The azeotropic composition of embodiment 54 boiling at a temperature of about 60 °C at a pressure of about 120.3 kPa. 56. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 46 weight percent 2-methylpentane and about 54 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0246] 57. The azeotropic composition of embodiment 56 boiling at a temperature of about 100 °C at a pressure of about 385 kPa.

[0247] 58. The azeotropic composition of any one of the embodiments 29 to 47 consisting essentially of or consisting of about 52.6 weight percent 2-methylpentane and about 47.4 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0248] 59. The azeotropic composition of embodiment 58 boiling at a temperature of about 54.8 °C at a pressure of about 101 .3 kPa.

[0249] 60. In some embodiments, the present application provides a spin fluid for flash spinning comprising

[0250] (a) from about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid and

[0251] (b) a spin agent, wherein the spin agent comprises an azeotropic or azeotrope- 1 ike composition comprising

[0252] (i) cyclopentane and 1 H,1H,2H-heptafluorocyclopentane; or

[0253] (ii) 2-methylpentane and 1H,1H,2H-heptafluorocyclopentane.

[0254] 61. The spin fluid of embodiment 60 comprising from about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid.

[0255] 62. The spin fluid of embodiment 60 or 61 comprising from about 72 to about 90 weight percent of a spin agent, based on the total amount of the spin fluid, and in other embodiments from about 76 to about 85 weight percent of a spin agent, based on the total amount of the spin fluid.

[0256] 63. The spin fluid of any one of embodiments 60 to 62, wherein the spin agent consists essentially of or consists of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1H,2H-heptafluorocyclopentane, or from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H,1H,2H- heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0257] 64. The spin fluid of any one of embodiments 60 to 62, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0258] 65. The spin fluid of any one of embodiments 60 to 62, the spin fluid comprises from about 15 to about 24 weight percent of a polymer based on the total amount of the spin fluid, and the spin agent consists essentially of or consists of from about 57 to about 85 weight percent cyclopentane and from about 43 to about 15 weight percent 1H,1H,2H-heptafluorocyclopentane

[0259] 66. The spin fluid of any one of embodiments 60 to 62, wherein the spin agent consists essentially of or consists of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, or from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 54 to about 82 weight percent 2- methylpentane and from about 46 to about 18 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0260] 67. The spin fluid of any one of embodiments 60 to 62, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H, 1 H,2H-heptafluorocyclopentane or from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1H,1H,2H- heptafluorocyclopentane, or from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0261] 68. The spin fluid of any one of embodiments 60 to 62, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0262] 69. The spin fluid of any one of embodiments 60 to 68, wherein the polymer is one or more polyolefins.

[0263] 70. The spin fluid of embodiment 69, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutene-1, poly(4-methyl-1-pentene), and blends / mixtures thereof.

[0264] 71. The spin fluid of embodiment 70, wherein the polyethylene is a high-density polyethylene (HDPE), a blend of a high-density polyethylene (HDPE) with a low-density polyethylene (LDPE), or a blend of a high-density polyethylene (HDPE) with a linear low-density polyethylene (LLDPE).

[0265] 72. The spin fluid of any one of embodiments 60 to 71 comprising about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1H,1H,2H-heptafluorocyclopentane.

[0266] 73. The spin fluid of any one of embodiments 60 to 71 comprising about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 65 to about 82 weight percent 2- methylpentane and from about 35 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, or from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0267] 74. The spin fluid of any one of embodiments 60 to 70 comprising about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1 -pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1H,1 H,2H- heptafluorocyclopentane.

[0268] 75. The spin fluid of any one of embodiments 60 to 70 comprising about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1 -pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H,1H,2H- heptafluorocyclopentane.

[0269] 76. The process of any one of embodiments 60 to 75, wherein the spin agent additionally comprises an additive, selected from antioxidants, acid scavengers, and blends thereof.

[0270] 77. In some embodiments, the present application provides a process for the preparation of plexifilamentary fibrils of polymer comprising the steps of:

[0271] (i) generating a spin fluid comprising

[0272] (a) about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid, and

[0273] (b) a spin agent, and

[0274] (ii) flash spinning the spin fluid at a pressure that is above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifilamentary fibrils of the polymer; wherein the spin agent comprises or consists essentially of

[0275] (1) an azeotropic or azeotrope-like composition comprising cyclopentane and 1H,1 H,2H-heptafluorocyclopentane, or

[0276] (2) an azeotropic or azeotrope-like composition comprising 2-methylpentane and 1 H , 1 H , 2 H - he ptaf I u orocycl o pe nta ne .

[0277] 78. The process of embodiment 77, wherein the spin fluid comprises from about 15 to about 24 weight percent of a polymer, based on the total amount of the spin fluid.

[0278] 79. The process of embodiment 77 or 78, wherein the spin fluid comprises from about 72 to about 90 weight percent of a spin agent, based on the total amount of the spin fluid, and in other embodiments from about 76 to about 85 weight percent of a spin agent, based on the total amount of the spin fluid.

[0279] 80. The process of any one of embodiments 77 to 79, wherein the spin agent consists essentially of or consists of from about 44 to about 85 weight percent cyclopentane and from about 56 to about 15 weight percent 1 H,1H,2H-heptafluorocyclopentane, or from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H,1H,2H- heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0280] 81. The process of any one of embodiments 77 to 79, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane and in other embodiments from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0281] 82. The process of any one of embodiments 77 to 79, the spin fluid comprises from about 15 to about 24 weight percent of a polymer based on the total amount of the spin fluid, and the spin agent consists essentially of or consists of from about 57 to about 85 weight percent cyclopentane and from about 43 to about 15 weight percent 1H,1H,2H-heptafluorocyclopentane

[0282] 83. The process of any one of embodiments 77 to 79, wherein the spin agent consists essentially of or consists of from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane, or from about 49 to about 82 weight percent 2-methylpentane and from about 51 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 54 to about 82 weight percent 2- methylpentane and from about 46 to about 18 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0283] 84. The process of any one of embodiments 77 to 79, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H, 1 H,2H-heptafluorocyclopentane or from about 65 to about 82 weight percent 2-methylpentane and from about 35 to about 18 weight percent 1 H,1 H,2H- heptafluorocyclopentane, or from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane. 85. The process of any one of embodiments 77 to 79, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1H,2H-heptafluorocyclopentane, and in other embodiments from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H, 1 H,2H-heptafluorocyclopentane.

[0284] 86. The process of any one of embodiments 77 to 85, wherein the polymer is one or more polyolefins.

[0285] 87. The process of embodiment 86, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutene-1, poly(4-methyl-1-pentene), and blends / mixtures thereof.

[0286] 88. The process of embodiment 87, wherein the polyethylene is a high-density polyethylene (HDPE), a blend of a high-density polyethylene (HDPE) with a low-density polyethylene (LDPE), or a blend of a high-density polyethylene (HDPE) with a linear low-density polyethylene (LLDPE).

[0287] 89. The process of any one of embodiments 77 to 88 comprising about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 50 to about 70 weight percent cyclopentane and from about 50 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 55 to about 70 weight percent cyclopentane and from about 45 to about 30 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

[0288] 90. The process of any one of embodiments 77 to 88 comprising about 15 to about 24 weight percent of a polyethylene, or a blend comprising polyethylene, based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 58 to about 65 weight percent 2-methylpentane and from about 42 to about 35 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 65 to about 82 weight percent 2- methylpentane and from about 35 to about 18 weight percent 1 H, 1 H,2H-heptafluorocyclopentane, or from about 70 to about 80 weight percent 2-methylpentane and from about 30 to about 20 weight percent 1 H,1 H,2H-heptafluorocyclopentane. 91. The process of any one of embodiments 77 to 87 comprising about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1 -pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 44 to about 60 weight percent cyclopentane and from about 56 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent cyclopentane and from about 55 to about 45 weight percent 1H,1 H,2H- heptafluorocyclopentane.

[0289] 92. The process of any one of embodiments 77 to 87 comprising about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poly(4-methyl-1-pentene), based on the total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 45 to about 60 weight percent 2-methylpentane and from about 55 to about 40 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or from about 45 to about 55 weight percent 2-methylpentane and from about 55 to about 44 weight percent 1 H,1H,2H- heptafluorocyclopentane.

[0290] 93. The process of any one of embodiments 77 to 92, wherein the spin agent additionally comprises an additive, selected from antioxidants, acid scavengers, and blends thereof.

[0291] 94. In some embodiments, the present application provides a use of the spin fluid of any of embodiments 60 to 76 for preparing of plexifilamentary fibrils of polymer by flash spinning.

[0292] 95. The plexifilamentary fibrils of polymer obtainable by the process of any one of embodiments 77 to 93.

[0293] 96. A sheet of nonwoven flash-spun plexifilamentary fibrils comprising plexifilamentary fibrils of polymer of embodiment 95.

[0294] 97. The sheet of embodiment 96, wherein the sheet is a collected sheet, a consolidated sheet, a bonded sheet, or a softened sheet.

[0295] 98. A bonded sheet obtainable by thermally or mechanically bonding the consolidated sheet of embodiment 97. 99. A softened sheet obtainable by softening the consolidated sheet of embodiment 97 or by softening the bonded sheet of embodiment 98.

[0296] 100. A multilayer sheet comprising two or more sheets wherein at least one sheet is a sheet according to any one of embodiments 96 to 99.

[0297] 101. An article comprising plexifilamentary fibrils of polymer of embodiment 95 and / or a sheet of any one of embodiments 96 to 99 and / or a multilayer sheet of embodiment 100.

[0298] 102. The article of embodiment 101 which is selected from garment, protective apparel, packaging material, house wrap, roof lining, car covers, medical and non-medical packaging, filtration media, print media, tags and labels, and accessories.

[0299] 103. The article of embodiment 102 wherein the garment is protective apparel.

[0300] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example, and not limitation. It will be apparent to persons skilled in the relevant art(s) that various changes in form and detail can be made therein without departing from the spirit and scope of the present invention. Thus, it should be appreciated that, while the invention has been described with reference to the above exemplary embodiments, other embodiments are within the scope of the claims. Moreover, it should be understood that the exemplary embodiments described herein may be combined to form other embodiments. After reading the above description, it will be apparent to one skilled in the relevant art(s) how to implement the invention in alternative embodiments. Thus, the present invention should not be limited by any of the above-described exemplary embodiments.

Claims

CLAIMS1. An azeotropic or azeotrope-like composition comprising(i) cyclopentane and 1 H,1H,2H-heptafluorocyclopentane; or(ii) 2-methylpentane and 1H,1H,2H-heptafluorocyclopentane.

2. The azeotropic or azeotrope-like composition of claim 1 comprising from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H- heptafluorocyclopentane.

3. The azeotropic composition of claims 1 or 2 consisting essentially of about 60.4 weight percent cyclopentane and about 39.6 weight percent 1 H,1H,2H-heptafluorocyclopentane.

4. The azeotropic composition of claim 3 boiling at a temperature of about 40 °C at a pressure of about 83 kPa.

5. The azeotropic or azeotrope-like composition of claim 1 comprising from about 38 to about 82 weight percent 2-methylpentane and from about 62 to about 18 weight percent 1H,1H,2H- heptafluorocyclopentane.

6. The azeotropic composition of any one of claims 1 or 5 consisting essentially of about 54.1 weight percent 2-methylpentane and about 45.9 weight percent 1 H,1H,2H- heptafluorocyclopentane.

7. The azeotropic composition of claim 6 boiling at a temperature of about 40 °C at a pressure of about 59.6 kPa.

8. A spin fluid for flash spinning comprising(a) from about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid and(b) a spin agent, wherein the spin agent comprises an azeotropic or azeotrope-like composition comprising(i) cyclopentane and 1 H,1H,2H-heptafluorocyclopentane; or(ii) 2-methylpentane and 1H,1H,2H-heptafluorocyclopentane.

9. The spin fluid of claim 8 comprising from about 72 to about 90 weight percent, or from about 76 to about 85 weight percent of the spin agent.

10. The spin fluid of claims 8 or 9, wherein the polymer is one or more polyolefins, or is selected from the group consisting of polyethylene, polypropylene, polybutene-1 , poly(4-methyl- 1 -pentene), and blends / mixtures thereof.

11. The spin fluid of any one of claims 8 to 10, wherein the spin agent comprises an azeotropic or azeotrope-like composition consisting essentially of(i) from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1H,1H,2H-heptafluorocyclopentane, or(ii) from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1H,2H-heptafluorocyclopentane.

12. A process for the preparation of plexifilamentary fibrils of polymer which comprises the steps of:(i) generating a spin fluid comprising(a) from about 10 to about 28 weight percent of a polymer, based on the total amount of the spin fluid, and(b) a spin agent, and(ii) flash-spinning the spin fluid at a pressure that is above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifilamentary fibrils of the polymer, wherein; the spin agent comprises an azeotropic or azeotrope-like composition comprising(1) cyclopentane and 1 H,1 H,2H-heptafluorocyclopentane; or(2) 2-methylpentane and 1 H,1 H,2H-heptafluorocyclopentane.

13. The process of claim 12, wherein the spin fluid comprises from about 72 to about 90 weight percent or from about 76 to about 85 weight percent of the spin agent.

14. The process of claim 12 or 13, wherein the polymer is one or more polyolefins, or is selected from the group consisting of polyethylene, polypropylene, polybutene-1 , poly(4-methyl- 1-pentene), and blends / mixtures thereof.

15. The process of any one of claims 12 to 14, wherein the spin agent comprises an azeotropic or azeotrope-like composition consisting essentially of(1) from about 44 to about 99 weight percent cyclopentane and from about 56 to about 1 weight percent 1 H,1 H,2H-heptafluorocyclopentane, or(2) from about 45 to about 82 weight percent 2-methylpentane and from about 55 to about 18 weight percent 1 H,1 H,2H-heptafluorocyclopentane.

16. Use of the spin fluid of any one of claims 8 to 11 for preparing of plexifilamentary fibrils of polymer by flash spinning.

17. Plexifilamentary fibrils of polymer obtainable by the process of any one of claims 12 to 15.

18. A sheet of nonwoven flash-spun plexifilamentary fibrils comprising plexifilamentary fibrils of polymer of claim 17.

19. The sheet of claim 18, wherein the sheet is a collected sheet, a consolidated sheet, a bonded sheet, or a softened sheet.

20. An article comprising the plexifilamentary fibrils of polymer of claim 17 and / or the sheet of claim 18 or claim 19.

21. The article of claim 20 which is selected from garment, protective apparel, packaging material, house wrap, roof lining, car covers, medical and non-medical packaging, filtration media, print media, tags and labels, and accessories.

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