Azeotropic and azeotrope-like compositions comprising 1,2-dichloroethylene and 1h,2h-octafluorocyclopentane and use of the compositions as flash spinning agents

Abstract

The present invention relates to (i) an azeotropic or azeotrope-like composition comprising (a) cis-1,2-dichloroethylene and cis-1H,2H-octafluorocyclopentane or comprising (b) trans-1,2-dichloroethylene and trans-1H,2H-octafluorocyclopentane, (ii) a spin fluid for flash spinning comprising these azeotropic or azeotrope-like compositions and a polyolefin, and (iii) a process for the preparation of plexifilamentary fibrils of polyolefin using the spin fluid.

Description

[0001] TITLE

[0002] AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS COMPRISING 1,2- DICHLOROETHYLENE AND 1H.2H-OCTAFLUOROCYCLOPENTANE 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 (a) cis-1,2-dichloroethyfene and ds-1H,2H-octafluorocydopentane or comprising (b) trans- 1,2-dichloroethylene and trans-1H,2H-octafluorocydopentane, (ii) a spin fluid for flash spinning comprising these azeotropic or azeotrope-like compositions and a polyolefin, and (Hi) a process for the preparation of ptexifilamentary fibrils of polyolefins 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 thepressure sufficiently below the spin fluid's cloud point pressure (i.e., the pressure at which the spin fluid transitions from a dear 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), (Hi) 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., ptexifilamentary 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, [hiring this step, ft 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.

[0008] One example of a solvent that can be used with polymers such as polyolefins is 1 ,2- dichloroefoylene (DCE). At practical op erating temperatures. DOE is too strong of a solvent and cannot be used as the only component in a spin agent composition for flash spinning because it dissolves polymers at relatively low pressures. In particular, because DCE dissolves polymers at relatively low pressures, foe doud point pressure of a spin fluid using a spin agent with only this chlorinated solvent is so dose to the bubble point pressure that use of such spin agent is not feasible. Weaker solvents such as hydrofluorocarbons can be mixed with DCE to reduce foe solvent strength of foe spin agent and increase foe spin fluid’s doud point pressure such that flash spinning can be readily accomplished. WO 2016 / 200873 A1 suggests spin agent compositions of 1,2-dichloroethylene with 1H,6H-perfluorohexane, 1H- perfluorohexane, or 1 H-perfluoroheptane. However, use at such linear hydrofluorocarbons in combination with DCE 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. Such spin agent composition should also form 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.

[0009] US 5,672,307 reports a flash spinning process using spin agent compositions of 1,2- dichloroethylene with fluorinated components, such as the cydic perfluorocarbons perfluoro- 1,2-dimethylcydobutane, and perfluoro-N-methylmorpholine. US 5,874,036, and US 5,977,237 report a flash spinning process using spin agent compositions of 1,2- dichloroefoylene with cydic partially fluorinated hydrocarbons, such as 1 ,1 ,2,2,3, 3- hexafluorocydopentane, and ds-1,1,2,2,3,3,4,5-octafluorocydopentane. However, the disclosed compositions complicate foe spin agent recovery process since (i) many of the disclosed fluorinated components are not miscible with chlorinated components such as DCE at ambient temperatures and pressures, which results In a heterogeneous liquid phase of the fluorinated component and the chlorinated component after condensation of the spin agent, i.e., to a liquid phase separation of the two components, and / or (ii) the disclosed compositions do not form an azeotropic or azeotrope-like composition at a ratio that is ideal for flash spinning. Where an azeotrope forms between a chlorinated solvent component and a non-chlorinated component, such as a fluorinated component, 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 ft. 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.

[0010] Accordingly, there is a need for, and the present inventors have discovered, low GWP azeotropic and azeotrope-like compositions of dichloroethylene and 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 (ii) provide suitable cloud point pressures for flash-spinning different polyolefins.

[0011] SUMMARY OF THE INVENTION in one embodiment the invention is directed to an azeotropic or azeotrope-like composition comprising

[0012] (a) ds-1,2-dichloroethylene and ds-1H^H-octefluorocydopentane, or

[0013] (b) trans-1,2-dichtoroethylene and trans-1H,2H-octafluoTOcydopentane.

[0014] In one embodiment the invention is directed to an azeotropic or azeotrope-like composition comprising ds-1,2-dichloroethylene and ds-1H,2H-octafluorocydopentane.

[0015] In a further embodiment the invention is directed to an azeotropic or azeotrope-like composition comprising trans- 1,2-dichloroethylene and trans-1H,2H-octafluorocydopentane.

[0016] In a further embodiment the invention is directed to a spin fluid for flash spinning comprising (a) from about 6 to about 24 weight percent of a polyolefin, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises (1) an azeotropic dr azeotrope-like composition comprising ds-1,2-d)chloroethylene and cis-1H,2H- octafluorocydopentane, or (2) an azeotropic or azeotrope-like composition comprising trans- 1 ,2-dichloroethylene and trans-1H,2H-octafluorocydopentane.

[0017] In a farther embodiment the present invention is directed to a process for the preparation of plexifilamentary fibrils of polyolefin. The process comprises the steps of.

[0018] (I) generating a spin fluid comprising

[0019] (a) from about 6 to about 24 weight percent of a polyolefin, 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 fibrils of the polyolefin, wherein the spin agent comprises

[0022] (1) an azeotropic or azeotrope-like composition comprising ds-1,2- dichloroethytene and cis-1H,2H-octafluorocydopentane, or

[0023] (2) ah azeotropic or azeotrope-iike composition comprising trans-1,2- dichloroethytene and trans-1H,2H-odafluorocydopentane.

[0024] BRIEF DESCRIPTION OF THE FIGURES

[0025] Fig. 1 shows the calculated vapor-liquid equilibrium (VLE) for the compositions of cis-1,2-dichloroethylene and ds-1H,2H-octafluorocydopentane at 40°C.

[0026] Fig. 2 shows the cloud point pressure curve of a spin fluid comprising 13 wt% polyethylene (PE) and a spin agent of ds-1,2-dichioroethylene and ds-1H,2H- octafluonocydopentane in a 72:28 ratio by weight.

[0027] Fig. 3 shows the cloud point pressure curve of a spin fluid comprising 13 wt% polyethylene (PE) and a spin agent of ds-1,2-dichioroethylehe and ds-lH,2H- octafluorocydopentane in a 68:32 ratio by weight.

[0028] Fig. 4 shows the doud point pressure curve of a spin fluid comprising 8 wt% polyethylene (PE) and a spin agent of ds-1,2-dichloroethylene and Cis-1H,2H- odafiuorocydopentane in a 66:34 ratio by weight.

[0029] Fig. 5 shows the doud point pressure curve of a spin fluid comprising 12 wt% polypropylene (PP) and a spin agent of ds-1,2-dichloroethylene and cis-1H,2H- octafluorocydppentane in a 60.40 ratio by weight.

[0030] Fig. 6 shows the calculated vapor-liquid equilibrium (VLE) for the compositions of trans-1,2-dichloroethylene and trans-1H,2H-octafluorocyclopentane at 40"C. DETAILED DESCRIPTION

[0031] Definitions and Clarification of Terms

[0032] 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.

[0033] Density is determined according to the method described in ISO 1183 (Plastics - Methods for determining the density of non-cellular plastics).

[0034] Matting 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.

[0035] 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 ttiermoplastics). The melt flow rate tor polyethylene is determined at a temperature of 190 °C and using a mass of 2160 grams, 5000 grams (5kg) or 21,800 gram (21 ,6kg), The melt flow rate for polypropylene is determined at a temperature of 230 °C and using a mass of 5000 grams. The melt flow rates of other polyolefins are performed aH different temperatures as specified in IS0 1133.

[0036] 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 Indude all possible geometrical configurations of the material. These configurations indude, but are not limited to, isotactic, syndiotactic, and random symmetries.

[0037] 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 we 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, and a melt flow rate (ISO 1133, 190 ”0 / 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 / IOmin.

[0038] 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, toe term “polypropylene* shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and random symmetries.

[0039] The term “polymer type* refers to toe chemical class into which toe polymer falls, for example, polyolefin, polyethylene, polypropylene, etc;

[0040] 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 toe 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.

[0041] The terms “spin agent” or “spin agent composition* refer 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.

[0042] 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.

[0043] The term “dew point pressure’ refers to toe pressure at which, at constant temperature, liquid starts condensing from a vapor, vapor mixture, or vapor-gas mixture.

[0044] The term "bubble point pressure* refers to the pressure at which, at constant temperature, a liquid, liquid mixture, or liquid-solution begins to boil.

[0045] 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. 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 thebubble 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-like composition boils without substantial change of the composition and behaves substantially as a single substance. The azeotropelike compositions described herein are determined in a temperature range of -20 °C to 100 °C and expressed in mass fractions.

[0046] The term “cloud point pressure” refers to the pressure at which, at constant temperature, a clear stogie phase spin fluid transitions from a dear solution to a cloudy, two- phase dispersion. At the cloud point pressure, a dear spin fluid becomes turbid.

[0047] Atmospheric pressure means 101.325 kPa. Essentially atmospheric pressure means 101.325 kPa 15 %.

[0048] As used herein, the singular forms "a," "an," and "the" indude the plural, and reference to a particular numerical value indudes at least that particular value, unless the context dearly dictates otherwise. When a range of values is expressed, another embodiment todUdes 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 indusive and combinable.

[0049] Azeotropic or Azeotrope-Ilka Compositions

[0050] Azeotropic or azeotrope-like compositions comprising cis-1 ,2-dlchloroethylene and cis-1 -octafluorocyclopentane

[0051] Provided herein are azeotropic or azeotrope-like compositions comprising cis-1 ,2- dichloroethylene and ds-1H,2H-octafluorocydopentane.

[0052] In some embodiments, the azeotropic or azeotrope-like compositions comprise from about 40 to about 99 weight percent ds-1,2-dichloroethylene and from about 60 to about 1 weight percent cis-1 H,2H-octafluorocyctopentane, or from about 45 to about 99 weight percent ds-1,2-dichloroethyiene and from about 55 to about 1 weight percent ds-1H,2H- octafluorocydopentane. 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 2 kPa to about 340 kPa. In other embodiments the azeotropic or azeotrope-like compositions comprise from about 50 to about 99 weight percent cis-1 ,2-dichloroethytene and from about 50 to about 1 weight percent ds-1H,2H-octafluorocydopentane, or from about 54 to about 99 weight percent cis-1 ,2- dichloroethylene and from about 46 to about 1 weight percent cis-1H,2H- octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 60eC and at a boiling pressure of about 2 kPa to about 105 kPa. In other embodiments the azeotropic or azeotrope-like compositions comprise from about 55 to about 99 weight percent ds-1,2-dichloroethylene and from about 45 to about 1 weight percent ds-1H,2H-octafluorocydopentane, or from about 58 to about 99 weight percent cis-1,2- dichloroethylene and from about 42 to about 1 weight percent ds-1H,2H- octafluorocydopentane. 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 2 kPa to about 52 kPa.

[0053] In some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about40 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 1 weight percent ds-1 H,2H-odafluorocydopentane, or from about 45 to about 99 weight percent cis-1,2-dichloroethylene and from about 55 to about 1 weight percent ds- 1H.2H-octafluorocydopentane. 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 2 kPa to about 340 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 50 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 50 to about 1 weight percent ds-1H,2H-octafluorocyc|opentane, or from about 54 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 46 to about 1 weight percent ds- 1H,2H-octafluorocydopentane. 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 2 kPa to about 105 kPa. In other embodiments, the azeotropic or seedrope-like compositions consist essentially of from about 55 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 45 to about 1 weight percent ds-1H,2H-octafluorocydopentane, or from about 58 to about 99 weight percent cis-1,2-dichloroethytene and from about 42 to about 1 weight percent ds- 1H,2H-octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20eC to about 40 °C and at a boiling pressure of about 2 kPa to about 52 kPa.

[0054] In some embodiments, the azeotropic or azeotrope-itke compositions consist of from about 40 to about 99 weight percent ds-1,2-dichloroethylene and from about 60 to about 1 weight percent ds-1H,2H-odafluorocydopentane, or from about 45 to about99 weight percent ds-1 ,2-dichloroethylene and from about 55 to about 1 weight percent ds-lH,2H- octafluorocydopentane. These azeotropic or azeotrope-like compositions boil ata temperature of about -20 °C to about 100 °C and at a boiling pressure of about 2 kPa to about 340 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist of from about 50 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 50 to about 1 weight percent cis-1H,2H-octafluorocyclopentane, or from about 54 to about 99 weight percent ds-1, 2- dichloroethylene and from about 46 to about 1 weight percent cis-1 H,2H- octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -206C to about 60 °C and at a boiling pressure of about 2 kPa to about 105 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist of from about 55 to about 99 weight percent ds-1 ,2-dichloroethylene and from about 45 to about 1 weight percent cfe-1H,2H-octafluorocyclopentane, or from about 58 to about 99 weight percent cis-1 ,2- dichloroethylene and from about 42 to about 1 weight percent ds-1H,2H- octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20 °C to about 40eC and at a boiling pressure of about 2 kPa to about 52 kPa.

[0055] In some embodiments, the composition comprising cis-1 ,2-dichloroethylene and ds- 1H,2H-octafluorocydopentane is azeotropic. In some embodiments, the azeotropic composition consists essentially Of from about 62 to about 79 weight percent cis-1 ,2- dichloroethylene and from about 38 to about 21 weight percent ds-1H,2H- octafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20eC to about 100 °C and at a boiling pressure of about 2 kPa to about 340 kPa. In some embodiments, the azeotropic composition consists of from about 62 to about 79 weight percent cis-1 ,2-dichloroethylene and from about 38 to about 21 weight percent ds-1H,2H- octaffuorocydopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 2 kPa to about 340 kPa. in some embodiments, the azeotropic composition consists essentially of about 78.9 weight percent ds-1,2-dichloroethylene and about 21.1 weight percent cis-1 H,2H- octafluorocydopentane at a pressure of about 2.84 kPa and at a boiling temperature of about -20’C. In some embodiments, the azeotropic composition consists of about 78.9 weight percent ds-1,2-dichloroethylene and about 21.1 weight percent Cis-1H,2H- octafluorocydopentane at a pressure of about 2.84 kPa and at a boiling temperature of about -20°C.

[0056] In some embodiments, the azeotropic composition consists essentially of about 73.9 weight percent cis-1 ,2-dichloroethylene and about 26.1 weight percent ds-lH,2H- octafluorocydopentane at a pressure of about 22.6 kPa and at a boiling temperature of about 20*C. In some embodiments, the azeotropic composition consists of about 73.9 weight percent cis- 1, 2-dichloroethylene and about 26.1 weight percent ds-1H,2H-odafluorocydopentane at a pressure of about 22.6 kPa and at a boiling temperature of about 20°C.

[0057] In some embodiments, the azeotropic composition consists essentially of about 71.0 weight percent ds-1, 2-dichloroethylene and about 29.0 weight percent cis-1H,2H- octafluorocydopentane at a pressure of about 51.4 kPa and at a boiling temperature of about 40*G. In some embodiments, the azeotropic composition consists of about 71.0 weight percent ds-1 ,2-dichloroethylene and about 29.0 weight percent ds-1H,2H-octafiuorocydopentane at a pressure of about 51.4 kPa and at a boiling temperature of about 40eC.

[0058] In some embodiments, the azeotropic composition consists essentially of about 68.1 weight percent cis- 1, 2-dichloroethylene and about 319 weight percent ds-1H,2H- octafluorocydopentane at a pressure of about 104.8 kPa and ata boiling temperature of about 60*C. In some embodiments, the azeotropic composition consists of about 68.1 weight percent ds-1 ,2-dichloroethylene and about 31.9 weight percent ds-1H,2H-octafluorocydopentane at a pressure of about 104.8 kPa and at a boiling temperature of about 60*0.

[0059] In some embodiments, the azeotropic composition consists essentially of about 62.0 weight percent ds-1, 2-dichloroethylene and about 38.0 weight percent ds-1H,2H- octafluorbcydopentane at a pressure of about 339.9 kPa and at a boiling temperature of about 100°C. In some embodiments, the azeotropic composition consists of about 62.0 weight percent ds-1 ,2-dichloroethylene and about 38.0 weight percent ds-1H,2H- octafluorocydopentane at a pressure of about 339.9 kPa and at a boiling temperature of about 100*0.

[0060] Azeotropic or azeotrope-like compositions comprising trane-1 ,2- dichloroethylene and trans-1H,2H-octafluorocyclopentane

[0061] Provided herein are azeotropic or azeotrope-like compositions comprising trans-1 ,2- dichloroethylene and trans-1H,2H-odafluorocyclopentane.

[0062] In some embodiments, the azeotropic or azeotrope-like compositions comprise from about 1 to about 55 weight percent trans-1, 2-dichloroethylene and from about 99 to about 45 weight percent trans- 1H,2H-octafluorocydoperitane, or from about 1 to about 52 weight percent trans- 1 ,2 -dichloroethylene and from about 99 to about 48 weight percent trans-1H,2H- octafluorocyclopentane. 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 6 kPa to about 589 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about 20 to about 55 weight percent trans-1, 2-dichloroethylene and from about 80 to about 45 weight percent trans-1H,2H-octafluorocydopentane, or from about 25 to about 52 weight percent trans-1,2-dicNoroethylene and from about 75 to about 48 weight percent trans-1H,2H- octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20eC to about 60 ”C and at a boiling pressure of about 6 kPa to about 200 kPa. In other embodiments, the azeotropic or azeotrope-like compositions comprise from about 25 to about 55 weight percent trans-1,2-dichloroethylene and from about 75 to about 45 weight percent trans-lH,2H-octafluorocydopentane, or from about 28 to about 52 weight percent trans-1,2-dichloroethylene and from about 72 to about 48 weight percent trans-lH,2H- octafluorocyclopentane. 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 6 kPa to about 104 kPa, in some embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 1 to about 55 weight percent trans-1,2-dichloroethylene and from about 99 to about 45 weight percent trans-1H,2H-octafluorocydopentane, or from about 1 to about 52 weight percent trans-1,2-dichloroethylene and from about 99 to about 48 weight percent trans-1H,2H-octafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20eC to about 100 °C and at a boiling pressure of about 6 kPa to about 589 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essential^ of from about 20 to about 55 weight percent frans-1,2- dichloroethylene and from about 80 to about 45 weight percent trans-1H,2H- octafluorocydopentahe, or from about 25 to about 52 weight percent trans-1,2- dichloroethylene and from about 75 to about 48 weight percent trans-lH,2H- octafluorocyclopentane. 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 6 kPa to about 200 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist essentially of from about 25 to about 55 weight percent trans- 1 ,2-dichloroethylene and from about 75 to about 45 weight percent trans-1H,2H-octefluorocydopentane, or from about 28 to about 52 weight percent trans- 1,2-dichloroethylene and from about 72 to about 48 weight percent trans- 1 H,2H- octafluorocydopentane. These azeotropic Or azeotrope-like compositions boil ata temperature of about -20 °C to about 40 °C and at a boiling pressure of about 6 kPa to about 104 kPa.

[0063] In some embodiments, the azeotropic or azeotrope-like compositions consist of from about 1 to about 55 weight percent trans-1,2-dichkxoethylene and from about 99 to about 45 weight percent trans-1H,2H-octafluorocydopentane. or from about 1 to about 52 weight percent trans- 1 ,2-dichloroethylene and from about 99 to about 48 weight percent trans-1 H,2H- odafluorocydopentane. These azeotropic or azeotrope-like compositions boil at a temperature of about -20eC to about 100 °C and at a boiling pressure of about 6 kPa to about 589 kPa. In other embodiments, the azeotropic or azeotrope-like compositions consist of from about 20 to about 55 weight percent trans-1,2-dichloroethytene and from about 80 to about 45 weight percent trans-1H,2H-octafiuorocyclopentane, or from about 25 to about 52 weight percent trans- 1,2-dichloroethy lane and from about 75 to about 48 weight percent trans-1H,2H- octafluorocydopentane. 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 6 kPa to about 200 kPa. In other embodiments, the azeotropic or azeotrope-lflce compositions consist of from about 25 to about 55 weight percent trans-1,2-dichloroethylene and from about 75 to about 45 weight percent trans-1H,2H-octafluorocyclopentane, or from about 28 to about 52 weight percent trans- 1,2-dichloroethy lane and from about 72 to about 48 weight percent trans-1H,2H- octafluorocyclopentane. 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 6 kPa to about 104 kPa.

[0064] In some embodiments, the composition comprising trans-1,2-dichloroethylene and trans-1H,2H-octafluorocyclopentane is azeotropic. In some embodiments, the azeotropic composition consists essentially of from about 32 to about 46 weight percent trans-1,2- dichloroethylene and from about 68 to about 54 weight percent trans-1H,2H- octafluorocyctopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 100 °C and at a boiling pressure of about 6 kPa to about 589 kPa. In some embodiments, the azeotropic composition consists of from about 32 to about 46 weight percent trans- 1,2-dichloroethylene and from about 68 to about 54 weight percent trans- 1H,2H- octafluorocyclopentane. These azeotropic compositions boil at a temperature of about -20 °C to about 100eC and ata tx>iiing pressure of about 6 kPa to about 589 kPa.

[0065] In some embodiments, the azeotropic composition consists essentially of about 45.6 weight percent trans-1,2-dichloroethylene and about 54.4 weight percent trans-1H,2H- octafluorocydopentane at a pressure of about 6.5 kPa and at a boiling temperature of about -20°C. In some embodiments, the azeotropic composition consists of about 45.6 weight percent trans-1,2-dichtoroethylene and about 54.4 weight percent trans-1H,2H- octafluorocydopentane at a pressure of about 6.5 kPa and at a boiling temperature of about-20eG.

[0066] In some embodiments, the azeotropic composition consists essentially of about 39.7 weight percent trans-1,2-dichloroethylene and about 60.3 weight percent trans-lH,2H- octafluorocydopentane at a pressure of about 48.1 kPa and at a boiling temperature of about 20°C. in some embodiments, the azeotropic composition consists of about 39.7 weight percent trans- 1 ,2-dichloroethylene and about 60.3 weight percent trans- 1 H^H-octafiuorocydopentane at a pressure of about 48.1 kPa and at a boiling temperature of about20°C.

[0067] In some embodiments, the azeotropic composition consists essentially of about 37.5 weight percent trans-1 ,2-dichloroethylene arid about 62.5 weight percent trans-1H,2H- octefluorocydopentane art a pressure of about 103.6 kPa and at a boiling temperature of about 40eC. In some embodiments, the azeotropic composition consists of about 37.5 weight percent trans-1 ,2-dichloroethylene and about 62.5 weight percent trans-1 H,2H-octafluorocyclopentane at a pressure of about 103.6 kPa and at a boiling temperature of about 40°C.

[0068] In some embcdiments, the azeotropic composition consists essentially of about 35.5 weight percent trans-1 ,2-dichloroethylene and about 64.5 weight percent trans-1 H,2H- octefluorocyclopentane at a pressure of about 200.1 kPa and at a boiling temperature of about 60’0. In some embodiments, the azeotropic composition consists of about 35.5 weight percent trans-1 ,2-dichloroethylene and about 64.5 weight percent trans-1 H,2H-octafluorocyctopentane at a pressure of about 200.1 kPa and at a boiling temperature of about 60eC.

[0069] In some embodiments, the azeotropic composition consists essentially of about 32.0 weight percent trans-1 ,2-dichloroethylene and about 68.0 weight percent trans-1 H,2H- octafluorocyclopentane at a pressure of about 589 kPa and at a boiling temperatire of about 100°C. In some embodiments, tire azeotropic composition consists of about 32.0 weight percent trans-1 ,2-dichloroethylene and about 68.0 weight percent trans-1H,2H- odafluorocydopentane at a pressure of about 589 kPa and at a boiling temperature of about 100°C.

[0070] Properties of the azeotropic or azeotrope-like compositions

[0071] The compound trans-1H,2H-octafluorocydopentane has a reported GWP-100 (global warming potential over a 100-year period) of 258 (IPCC 2021 report). While no specific date is available for cis-1H,2H-octefluorocydopentane this compound may also be assumed to have a GWP-100 of about 258. No calculated GWP value is available for either cis- or trans- 1,2- dichloroethylene. However, these compounds are expected to have short atmospheric lifetimes due to their relatively high reactivity, so a very low GWP-100 of essentially zero may be assumed. Accordingly, the azeotropic or azeotrope-like compositions combining the two compounds cis-1 ,2-dichloroethylene and ds-1H,2H-octafluorocydopentane or the two compounds trans-1,2-dichloroethylene and trans-1H,2H-octafluorocyclopentane have a low global warming potential (GWP). in some embodiments, the azeotropic or azeotrope-like compositions comprising ds-1 ,2-dichloroethylene and ds-1H,2H-octafluorocydopentane have a GWP-100 (global warming potential over a 100-year period) of less than about 160, in other embodiments of less than about 130, in other embodiments of less than about 120, and in other embodiments of less than about 105. In some embodiments the azeotropic or azeotropelike compositions comprising trans-1,2-didil6roethylene and trans-1H,2H- octafluorocyciopentane have a GWP-100 (global warming potential over a 100-year period) of less than about 256, in other embodiments of less than about 210, in other embodiments of less than about 195, and in other embodiments of less than about 165.

[0072] The azeotropic or azeotrope-like 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.

[0073] The azeotropic or azeotrope-like compositions are useful in a wide range of applications. In some embodiments, ths azeotropic or azeotrope-like compositions are used as spin agents for flash spinning, in other embodiments as cleaning agents, and in other embodiments as solvents.

[0074] Spin Agents and Spin Fluids for Flash Spinning in some embodiments, the azeotropic or azeotrope-like compositions are spin agents within spin fluids for flash spinning.

[0075] In some embodiments, the spin fluid comprises (a) from about 6 to about 24 weight percent of a polyolefin, 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 cis-1,2-dtchloroethyteneand cis-1H,2H-octafiuorocydopentane or the azeotropic or azeotrope-like composition comprising trans-1,2-dichtoroethylene and trans- 1H,2H-octafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 6 to about 20 weight percent of a polyolefin, based on the total amour# 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 ds-1,2-dichloroethytene and cts-1H,2H- octafluorocydopentane or the azeotropic dr azeotrope-like composition comprising trans-1 ,2- dichloroethylene and trans-1H,2H-octafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 20 weight percent of a polyolefin, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of toe azeotropic or azeotrope-like composition comprising cis-1 ,2-dichloroethylene and ds-1H,2H-octafluorocydopentane or the azeotropic or azeotrope-like composition comprising trans- 1 ,2-dichloroethylene and trans-1 H,2H-octefluorocyclppentane. In other embodiments, toe spin fluid canprises (a) from about 8 to about 18 weight percent of a polyolefin, based on toe 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 cis-1 ,2-dichloroethyiene and ds-1H,2H-octafluorocyclopentane or the azeotropic or azeotrope-like composition comprising trans-1 ,2-ctichloroethylene and trans-1 H,2H- octafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 14 weight percent of a polyolefin, 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 cis-1 ,2-dichloroethylene and cis-1 H,2H- octafluorocydopentane or the azeotropic or azeotrope-tike composition comprising trans-1, 2- dichloroethylene and trans-1 H,2H-octafluorocydopentane.

[0076] In some embodiments, the spin fluid comprises (a) from about 6 to about 24 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-metoyl-1- pentene), based on the total amount of the spin fluid, and (b) a spin agent, wherein toe spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising trans-1,2-dichloroethylene and trans-1 H,2H-octafluorocyclopentane. In other embodiments, toe spin fluid comprises (a) from about 6 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a' poly(4-methyi-1-pentene), based on toe total amount erf toe spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of the azeotropic or azeotrope-tike composition comprising trans- 1 ,2-dicMoroetoylene and transit H,2H-octafluorocyclopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1 , or a poly(4-methyH-pentene), based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of toe azeotropic or azeotrope-like composition comprising trans-1, 2- dichloroethylehe and trans-1H,2H-octafluorocyclopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 16 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyl-1-pentene), 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 trans- 1,2-dichloroethylene and trans-1H,2H-octafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 14 weight percent of a polydefin, selected from a polypropylene, a polybutene-1, or a pdy(4-methyl-1-pentene), 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 trans- 1,2-dichloroethylene and trans-lH,2H- odafluorocyclopentane.

[0077] In some embodiments, the spin fluid comprises from about 76 to about 94 weight percent of a spin agent, based on the total amount of the spin fluid. In some embodiments, the spin fluid comprises from about 80 to about 94 weight percent of a spin agent, based on the total amount of the spin fluid, in other embodiments from about 80 to about 92 weight percent, based on the total amount of the spin fluid, in other embodiments from about 84 to about 92 weight percent, based on the total amount of the spin fluid, and to other embodiments from about 86 to about 92 weight percent, based on the total amount of the spin fluid, to some embodiments, the spin fluid comprises from about 65 to about 80 weight percent of a spin agent, based on the total amount of the spin fluid. in some embodiments, the spin agent consists essentially of from about 40 to about 75 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 25 weight percent ds- 1H,2H-octafluorocyclopentane. In other embodiments, the spin agent consists essentially of from about 60 to about 75 weight percent ds-1 ,2-dichloroethylene and from about 40 to about 25 weight percent ds-1H,2H-octafluorocydopentane, or from about 65 to about 74 weight percent cis-1 ,2-dichloroethylene and from about 35 to about 26 weight percent ds-1H,2H- octafluorocydopentane. In some embodiments, the spin agent consists essentially of from about 40 to about 60 weight percent cis- 1,2-dichloroethylene and from about 60 to about 40 weight percent cis-1H,2H-octafluorocydopentane, to other embodiments from about 40 to about 50 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 50 weight percent ds-1 H,2H-octafluorocydopentane.

[0078] In someembodiments, the spin agent consists essentially of from about 30 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 70 to about 45 weight percent trans- 1H,2H-octafluorocydopentane. to some embodiments, the spin agent consists essentially tit from about 35 to about 55 weight percent trans-1, 2-dichloroethytene and from about 65 to about 45 weight percent trans-1 H,2H-octefluorocyclopentane, in other embodiments from about 35 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 48 weight percent trans-1H,2H-octafluorocydopentane, and in other embodiments from about 35 to about 45 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 55 weight percent trans-1 H,2H-octafluorocydopentane.

[0079] The spin fluid may indude 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 ds-1,2-dichloroethylene and ds-lH,2H-octafluorocydopentane or trans-1 ,2-dichloroethylene and trans-1 H,2H-odafluorocydopentane described herein, in some embodiments, the spin fluid comprises additives in an amount of about 1.5 weight percent or Jess 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

[0080] In some embodiments, the spin agent consists of from about 40 to about 75 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 25 weight percent ds-1H,2H- octafluorocyclopentane, in other embodiments from about 60 to about 75 weight percent cis- 1 ,2-dichloroethylene and from about 40 to about 25 weight percent ds-1H,2H- octafluorocydopentane, and in other embodiments from about 65 to about 74 weight percent ds-1 ,2-dichloroethylene and from about 35 to about 26 weight percent ds-1H,2H- octafluorocydopentane. In some embodiments, the spin agent consists of from about 40 to about 60 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 40 weight percent ds-1H,2H-odafluorocydopentane, in Other embodiments from about 40 to about 50 weight percent cis-1,2-dichloroethylene and from about 60 to about 50 weight percent ds-1 H,2H- octafluorocydopentane.

[0081] In some embodiments, the spin agent consists of from about 30 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 70 to about 45 weight percent trans-1 H,2H- odafluorocydopentane. In scene embodiments, the spin agent consists of from about 35 to about 55 weight percent trans- 1,2-dichloroethylene and from about 65 to about 45 weight percent trans-1 H,2H-octafluorocydopentane, in other embodiments from about 35 to about 52 weight percent trans-1 ,2-dichloroethyiene and from about 65 to about 48 weight percent trans- 1HJ2H-octafluorocydopentane, and in other embodiments from about 35 to about 45 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 55 weight percent trans-1H,2H- octafluorocydopentane.

[0082] The spin agent can be used for a broad range of different polyolefins and biends / mixtures thereof. In some embodiments, polyolefins are polyethylene (PE), polypropylene (PR), pofybutene-1, poty(4-methyl-1-pentene), and blends / mixtures thereof. Particularly preferred polyolefins are polyethylene (PE), in particular high-density polyethylene (HOPE), and blends / mixtures of high-density polyethylene (HOPE) and low-density polyethylene (LDPE), in particular linear tow-density polyethylene (LLDPE). In some embodiments, the polyolefin is a high-density polyethylene (HOPE). in some embodiments, the spin fluid the spin fluid comprises about 6 to about 24 weight percent, or about 6 to about 20 weight percent, or about 8 to about 20 weight percent, or about 8 to about 16 weight percent, or about 8 to about 14 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 60 to about 75 weight percent cis-1 ,2-dichloroethylene and from about 40 to about 25 weight percent ds-1H,2H- odafluorocydopentane, or from about 65 to about 74 weight percent cis-1 ,2-dichloroethylene and from about 35 to about 26 weight percent cis-1H,2H-octafluorocyclopentane. in some embodiments, the spin fluid Comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1 , or a poty(4-methyH-pentene), based on tile total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 40 to about 60 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 40 weight percent ds-1H,2H-octafiuorocydopentane, or from about 40 to about 50 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 50 weight percent ds-1H,2H- octafluorocyclopentane.

[0083] In some embodiments, the spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1, or a poly(4-methyM-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 30 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 70 to about 45 weight percent trans-1 H,2H-octafiuorocydopentane, or from about 35 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 45 weight percent trans- 1H,2H-octafluorocydopentane, or from about 35 to about 52 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 48 weight percent trans-lH,2H- octafluorocydopentane, or from about 35 to about 45 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 55 weight percent trans-1 H2H- octafluorocydopentane.

[0084] 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 SO 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-like 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 tire 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, arid 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.

[0085] When used as a spin agent, toe 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, toe azeotropic or azedtrope-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.

[0086] Preparation of Plexifllamentary Film-fibril Strands of Polyolefin

[0087] In some embodiments, there is provided a: process for the preparation of plexifllamentary fibrils of polyolefin. The process comprises the steps of:

[0088] (i) generating a spin fluid comprising

[0089] (a) about 6 to about 24 weight percent of a polyolefin, based on the total amount of the spin fluid, and

[0090] (b) a spin agent, and

[0091] (ii) flash spinning the spin fluid at a pressure above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifllamentary fibrils of the polyolefin; wherein the spin agent comprises or consists essentially of

[0092] (1) an azeotropic or azeotrope-like composition comprising ds-1,2- dichloroethylene and cis-1H,2H-octafluorocyclopentane, or (2) an azeotropic or azeotrope-like composition comprising trans-1 ,2- dichloroethylene and trans-1H,2H-octafluorocyclopentane.

[0093] 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 aboutOOO 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 to 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 aft a pressure in the range of about 45 to about 200 bar, to 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.

[0094] In some embodiments, the spin fluid comprises (a) from about 6 to about 20 weight percent of a polyolefin, based on the total amount of the spin fluid, and (b) a spin agent, whereto the spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising cis-1, 2-diChioroethylene and cis-1 H,2H-octafluorocydopentane or the azeotropic or azeotrope-like composition comprising trans-1 ,2-dichloroethylene and trans- 1H,2H-octafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 20 weight percent of a polyolefin, 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 cis-1 ,2-dichloroethylene arid ds-1H,2H- octafluorocyclopentane dr the azeotropic or azeotrope-like composition comprising trans-1, 2- dichloroethylene and trans-1 H,2H-octafluorocyclopentane. in other embodiments, the spin fluid comprises (a) from about 8 to about 16 weight percent of a polyolefin, based on the total amount of the spin fluid, and (b) a spin agent, wherein the spin agent comprises or consists essentially of ttie azeotropic or azeotrope-like composition comprising cis-1 ,2-dichloroethylene and cis-1 H,2H-octafluorocyctopentane or the azeotropic or azeotrope-like composition comprising trans- 1 ,2-dichloroethylene and trans-1 H,2H-octafluorocyclopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 14 weight percent of a polyolefin, based on the total amount of the spin fluid, and (b) a spin agent, wherein tihe spin agent comprises or consists essentially of the azeotropic or azeotrope-like composition comprising cis-1 ,2-dichloroethylene and cis-1 H,2H-octafluorocyclopentane or the azeotropic or azeotrope-like composition comprising trans- 1,2-dichloroethylene and trans-1H,2H- octafluorocyclopentane. In some embodiments, the spin fluid comprises (a) from about 6 to about 24 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyl-1- pentene), basal 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 trans-1,2-dicNoroethylene and trans-1H,2H-octafluorocyclopentane. In other embodiments, the spin fluid comprises (a) from about 6 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyl-1-pentene), 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 trans- 1,2-dichloroethylene and trans-1H,2H-octafluprocyclopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyH-pentene), 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 trans-1,2- dichloroethylene and trstiTS-1H,2H-octafluorocyclopentane. In other embodiments, toe spin fluid comprises (a) from about 8 to about 16 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyi-1-pentene), 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 trans- 1,2-dichloroethylene and trens-1H,2H-odafluorocydopentane. In other embodiments, the spin fluid comprises (a) from about 8 to about 14 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyl-1-pentene), 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 trans- 1,2-dichloroethylene and trans-1H,2H- octafluorocydopentane.

[0095] In some embodiments, the spin fluid comprises from about 76 to about 94 weight percent of a Spin agent, based on toe total amount of the spin fluid. In some embodiments, the spin fluid comprises from about 80 to about 94 weight percent of a spin agent, based on toe total amount of toe spin fluid, in other embodiments from about 80 to about 92 weight percent, based on toe total amount of the spin fluid, in other embodiments from about 84 to about 92 weight percent, based on the total amount of the spin fluid, and in other embodiments from about 86 to about 92 weight percent, based on the total amount of toe spin fluid. In some embodiments, the spin fluid comprises from about 65 to about 80 weight percent of a spin agent, based on the toted amount of toe spin fluid. In some embodiments, the spin agent consists essentially of from about 40 to about 75 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 25 weight percent ds- 1H2H-octafluorocydopentane, in other embodiments from about 60 to about 75 weight percent cis-1,2-dichloroethylene and from about 40 to about 25 weight percent cis-1 H,2H- octafluorocydopentane, and in other embodiments from about 65 to about 74 weight percent ds-1 ,2-dichloroethylene and from about 35 to about 26 weight percent ds-lH,2H- octafluorocydopentane. In some embodiments, the spin agent consists essentially of from about 40 to about 60 weight percent ds-l,2-dichloroethylene and from about 60 to about 40 weight percent cis-1 H,2H-octafluorocyclopentane, in other embodiments from about 40 to about 50 weight percent cis-1,2-dichloroethytene and from about 60 to about 50 weight percent ds-1 H,2H-octafluorocydopentane.

[0096] In some embodiments, the spin agent consists essentially of from about 30 to about 55 weight percent trans- 1 ,2-dichloroethylene and from about 70 to about 45 weight percent trans- 1H,2H-octafluorocydopentane. In some embodiments, the spin agent consists essentially of from about 35 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 45 weight percent trans-1 H,2H-octafluorocydopentane, in other embodiments from about 35 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 48 weight percent trans-1 H,2H-octafluorocydopentane, and in other embodiments from about 35 to about 45 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 55 weight percent trans-1 H,2H-octafluorocydopentane.

[0097] 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 cis-1 ,2-dichloroethylene and ds-IH^H-octafluorocydopentane or trans-1 ,2-dichloroethylene arid trans-1 H,2H-octafluarocydopentane 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 ah amount of about 0.1 weight percent or less of the total amount of the spin agent

[0098] In some embodiments, the spin agent consists of from about 40 to about 75 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 25 weight percent cis-1 H,2H- octafluorocydopentane, in other embodiments from about 60 to about 75 weight percent ds- 1 ,2-dichloroethylene and from about 40 to about 25 weight percent ds-1H,2H- octafluorocydopentane, and In other embodiments from about 65 to about 74 weight percent ds-1,2-dichloroethylene and from about 35 to about 26 weight percent cis-1 H,2H- octafluorocydopentane. In some embodiments, the spin agent consists of from about 40 to about 60 weight percent cis-1 ,2-dichkxoethytene and from about 60 to about 40 weight percent ds-1H,2H-octafluorocyctopentane, in other embodiments tram about 40 to about 50 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 50 weight percent ds-1H,2H- octafluorocyclopentane.

[0099] In some embodiments, the spin agent consists of from about 30 to about 55 weight percent trans-1 ,2-dichloroethyiene and from about 70 to about 45 weight percent trans- 1 H,2H- octafluorocydopentane. In some embodiments, the spin agent consists of from about 35 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 45 weight percent trans-1 H,2H-octafluorocyclopentane, in other embodiments from about 35 to about 52 weight percent trans- 1,2-dichloroethylene and from about 65 to about 48 weight percent trans- 1H,2H-octafluorocyclopentane, and in other embodiments from about 35 to about 45 weight percent trans-1 J2-dichloroettiylene and from about 65 to about 55 weight percent trans-1 H,2H- octafluorocydopentane.

[0100] The spin agent can be used for a broad range of different polyolefins and blends / mixtures thereof.

[0101] In some embodiments, polyolefins are polyethylene (PE), polypropylene (PR), pdybutene-1, poly(4-methyl-1-pentene), and blends / mixtures thereof. Particularly preferred polyolefins are polyethylene (PE), in particular high-density polyethylene (HOPE), and blends / mixtures of high-density polyethylene (HOPE) and low-density polyethylene (LDPE), in particular linear low-density polyethylene (LLDPE). In some embodiments, tile polyolefin is a high-density polyethylene (HOPE).

[0102] In some embodiments, the spin fluid the spin fluid comprises about 6 to about 24 weight percent, or about 6 to about 20 weight percent, or about 8 to about 20 weight percent, or about 8 to about 16 weight percent, or about 8 to about 14 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 60 to about 75 weight percent cis- 1,2-dichloroethylene and from about 40 to about 25 weight percent cis-1H,2H- octafluorocyclopentane, or from about 65 to about 74 weight percent cis-1 ,2-dichloroethylene and from about 35 to about 26 weight percent ds-1H^H-octafluorocyclopentane. 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 40 to about 60 weight percent ds-1 ,2-dichloroethylene and from about 60 to about 40 weight percent ds-1H,2H-octafluorocyclopentane, or from about 40 to about 50 weight percent ds-1,2-dichloroethylene and from about 60 to about 50 weight percent ds-1H,2H- octafluorocydopentane.

[0103] In some embodiments, toe spin fluid comprises about 15 to about 24 weight percent of a polypropylene, a polybutene-1, ora poly(4-methyl-1-pentene), based on toe total amount of the spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 30 to about 55 weight percent frans-1,2-dichloroethylene and from about 70 to about 45 weight percent trans-1 H,2H-octafluorocydopentane, or from about 35 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 65 to about 45 weight percent trans- 1H,2H-octafluorocydopentane, or from about 35 to about 52 weight percent trans-1 ,2- didiloroethylerie and from about 65 to about 48 weight percent trans-1H,2H- octafluorocyclopentane, or from about 35 to about 45 weight percent trans-1, 2- dlchloroethytene and from about 65 to about 55 weight percent trans-1 H.2H- octafluorocydopentane.

[0104] In some embodiments, there is provided plexifilamentary fibrils of polyolefin obtainable by the process described herein.

[0105] The shape off foe assembly of plexifilamentary fibrils (rf polyolefin discharged from each spin orifice may be modified by any methods known in the art In some embodiments, the plexifilamentary fibrils of polyolefin 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 fen 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.

[0106] Preparation of Sheets of Nonwoven Flash-epun Plexifilamentary Fibrite by Collection, Consolidation, Bonding, Softening, and Articles Made from Sheets of Nonwoven Flash-spun Plexifilamentary Fibrils

[0107] Sheets comprising plexifilamentary fibrils of polyolefin 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 toe fibrils accumulate in toe form of a collected sheet erf nonwoven flash-spun plexifilamentary fibrils, formed from fibrils oriented in an overlapping, multi-directional configuration. Defection 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 fibrite 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.

[0108] 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 descrfoed in US 7,118,698, US 7,621,731, US 7,786,034, and US 7,998,388. in some embodiments, the collected sheet of nonwoven flash-spun plexifilamentary fibrils formed by flashspinning 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 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.

[0109] In some embodiments, the bonded sheet is subjected to a mechanical softening process to obtain a softened sheet of nonwoven flash-spun plexifilamentary fibrils.

[0110] 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.

[0111] 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.

[0112] The sheet of nonwoven Hash-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, cargo covers, medical and non-medical packaging, filtration media, print media, tags and labels, and accessories.

[0113] EXAMPLES

[0114] A study has been performed for the phase behavior and flash spinning of polyethylene and polypropylene for azeotropic and azeotrope-like compositions. The experimental procedure and results are provided below. These examples are given to illustrate exemplary embodiments of the invention and should riot be interpreted as limiting in any way.

[0115] Materials Used

[0116] Cis-1 ,2-dichtoroethylene (ds-DCE), CAS Nr. 156-59-2 has an atmospheric boiling point of 54.4eC and a molecular weight of 96.9 g / mol. The ds-1 ,2-dichloroethylene used had a purity level above 97 percent by weight.

[0117] Trans-1,2-dichloroethylene (trans-DCE), CAS Nr. 156-60-5 has an atmospheric boiling point of 47.7 °C arid a molecular weight of 96.9 g / mol The trans-1,2-dichloroethylene used had a purity level above 98 percent by weight.

[0118] Cis-1 H,2H-octafluorocydopentane, CAS NT; 17481-95-7 has an atmospheric boiling point of 79 °C and a molecular weight of 214 g / mol. The trans- 1 H,2H-octafluorocyclopentane used had a purity level of above 98 percent by weight

[0119] Trans-1H,2H-octafluorocyclopentane, CAS Nr. 158389-18-5 has an atmospheric boiling point of 48.5 °C and a molecular weight of 214 g / mol. The trans-1H, 2H- octafluorocydopentane used had a purity level of above 98 percent by weight.

[0120] Two different polyethylenes were used:

[0121] Polyethylene A was a polyethylene having a density of 0.950 g / cm3(IS01183), and a melt flow rate of 0.76 g / 10min (ISO 1133 condition D, 190 °C / 2.16 kg).

[0122] Polyethylene B was a polyethylene having a density of 0.960 g / cm3(ISO 1183) arid a melt flow rate of 0.9 g / 10min (ISO 1133 condition D, 190*0 / 2.16 kg).

[0123] The ethylene-hexene copolymer used was an ethylene-hexene copolymer having a density of 0.934 g / cm3(IS01183) and a melt flow rate of 0.9 g / lOrnin (IS0 1133, 190 °C / 2.16 kfl).

[0124] The polypropylene (PP) used was an isotactic polypropylene with a melt peak temperature of 163 °C and a melt flow rate is 4.2 g / 10 min (IS0 1133, 2.16 kg-230 °C).

[0125] All polymere ware dried during a minimum of 8 hours in a vacuum oven at about 45- 50 °C before use. Spinning Equipment

[0126] 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 calbrated 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.

[0127] 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 whidi 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 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 opitrc light guide, while the view through foe sight glass was displayed using a digital camera, in foe cell, a Type J thermocouple was located about 5 mm behind foe high-pressure sight glass. The Type J thermocouple and a pressure measuring device located in dose proximity to the window measured the pressure and temperature inside the view cell behind foe sight glass and the pressure and temperature were continuously monitored by a computer. When, after a period of mixing, a dear, homogeneous spin fluid was established, the temperature was held constant and the differential pressure applied to foe pistons was equalized so that the pistons stopped moving. Then, the pressure applied to foe spin fluid in the view celt was gradually decreased until phase separation was observed through the sight glass, as the initially dear, homogeneous spin fluid became cloudy in appearance. The temperature and pressure were recorded when foe thermocouple became no longer visible. This pressure was the phase separation pressure or cloud point pressure for that spin fluid at that temperature. The pressure was then increased until foe spin fluid returned to its transparent state, i.e., until foe insoluble phase redissolved, and in this way, two or three repeat cloud point measurements could be made at an approximately constant temperatiro. Once this data was recorded, mixing was resumed while foe spin fluid was heated to the next temperature at which the cloud point pressure was to be measured.

[0128] Results

[0129] Example 1 : Vapor liquid equilibrium for the composition of cis-1 ,2-dichloro- ethylene and ds-1H,2H-octafluorocyclopentane

[0130] Figure 1 shows the calculated vapor liquid equilibrium for the composition of cis-1, 2- dkfoloroefoyiene and ds-1H,2H-octafluorocydopentane. The azeotropic composition of ds- 1 ,2-dichloroethylene and ds-1H ,2H-octafluorocyctopentane at 40”C corresponds to about 71.0 wt% ds-1,2-dichloroethytene and about 29.0 wt% cis-lH,2H-octaftoorocydopentane. The bubble point pressure for the azeotropic composition is equal to about 51.4 kPa. The azeotropic-like composition of ds-1 ,2-dichloroethylene and ds-1H,2H-odafluorbcydopentane at a 5% deviation from the azeotrope point was found to be from about 55:45 wt% to about 99:1 wt%.

[0131] Example 2: Cloud point study of polyethylene Figure 2 shows the doud point pressure curve of a spin fluid comprising 13 wt% polyethylene A and a spin agent of ds-1,2-dichloroethylene and ds-1H,2H- octafluorocydopentane in a 72:28 ratio by weight. This spin fluid comprising 13 wt% polyethylene was found to show a doud point pressure curve suitable for flash spinning.

[0132] Example 3: Cloud point study of polyethylene

[0133] Figure 3 shows the cloud point pressure curve a spin fluid comprising 13 wt% polyethylene A and a spin agent of cis-1,2-dichloroethylene and ds-1H,2H- odafluorocydopentane in a 68:32 ratio by weight. This spin fluid comprising 13 wt% polyethylene was found to show a doud point pressure curve suitable for flash spinning.

[0134] Example 4: Cloud point study of polyethylene

[0135] Figure 4 shows the doud point pressure curve of a spin fluid comprising 8 wt% polyethylene B and a spin agent of cte-1,2-dichloroethylene and ds-1H,2H- octafluorocydopentane in a 68:32 ratio by weight. This spin fluid comprising 8 wt% polyethylene was found to show a doud point pressure curve suitable for flash spinning.

[0136] Example 5: Cloud point study of polypropylene

[0137] Figure 5 shows the cloud point pressure curve of a spin fluid comprising 12 wt% polypropylene and a spin agent of ds-1,2-dichloroethylene and ds-1H,2H- octafluorocydopentane in a 60:40 ratio by weight. This spin fluid comprising 12 wt% polypropylene was found to show a doud point pressure curve suitable for flash spinning.

[0138] Example 6: Flash spinning performance of polyethylene

[0139] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 13 wt% polyethylene A and a spin agent of cis-1,2-dichloroethyiene and cis-1H,2H- octafluorocydopentane in a 68:32 ratio by weight at a spin temperature of about 195 °C and a spin pressure of about 59 bar. Example 7: Flash spinning performance of polyethylene

[0140] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 8 wt% polyethylene B and a spin agent of cis-1,2-dichloroethylene and cis-lH,2H- octafluonocydopentane in a 66:34 ratio by weight at a spin temperature of about 200 °C and a spin pressure of about 98 bar.

[0141] Examples: Flash spinning performance of polyethylene

[0142] Rash spinning was performed on the equipment described in the above for a spin fluid comprising 17 wt% polyethylene B and a spin agent of ds-l^-dichloroethylene and ds-1H,2H- odafluorocydopentane in a 68:32 ratio by weight at a spin temperature of about 205 °C and a spin pressure of about 59 bar.

[0143] Example s: Flash spinning performance of polyethylene

[0144] Flash spinning was perfamed on the equipment described in the above fa a spin fluid comprising 12 wt% polyethylene B and a spin agent of ds-1 ,2-dichloroethylene and ds-1H,2H- octafluorocydopentane in a 72:28 ratio by weight at a spin temperature of about 219 °C and a spin pressure of about 54 bar.

[0145] Example 10: Flash spinning performance polypropylene

[0146] Rash spinning was performed on the equipment described in the above for a spin fluid comprising 15 wt% of polypropylene arid a spinagent of ds-1,2-dichlao6thylene and ds- 1 H,2H-octafluorocyclopentane in a 45:55 ratio by weight at a spin temperature of about 220'C and a spin pressure of about 64 bar.

[0147] Example 11: Flash spinning performance ethylene-hexene copolymer - polypropylene

[0148] Flash spinning was performed on the equipment described in the above for a spin fluid comprising 15 wt% of a polymer blend of an ethylene-hexene copolymer and polypropylene in a 80:20 ratio by weight and a spinagent of cis-1,2-dlchloroethylene and ds- 1 H,2H-octafluorocydopentane in a 68:32 ratio by weight at a spin temperature of about 205°C and a spin pressure of about 70 bar. Example 12: Vapor liquid equilibrium for the mixture trans-1 ,2-dichloroethylene and trans-1 H,2H-octafluorocyclopentane

[0149] Figure 6 shows the calculated vapor liquid equilibrium for the composition of trans-1,2- dichloroethytene and trans-lH^H-octefluorocydopentane. The azeotropic composition of trans-1, 2-dichioroethylene and frans-1H,2H-octafluorocyclopentane at 40°C corresponds to about 37.5 wt% trans-1 ,2-dichloroethytene and about 62.5 wt% trans-1 H,2H- octafluorocyclopentane. The bubble point pressure for the azeotropic composition is equal to about 103.6 kPa. The azeotropic-like composition of trans-1, 2-dichkxoethylene and trans- 1H^H-octafluorocydopentane at a 5% deviation from the azeotrope point was found to be from about 25:75 wt% to about 52:48 wt%.

[0150] Table 1: Summary of the flash spinning experiments of Examples 6, 7, 8, 9, 10, and 11.

[0151] Example: 6 7 a 9 10 11

[0152] Spin agent component 1 (SA1) ds-DCE ds-DCE ds-DCE ds-DCE ds-DCE ds-DCE

[0153] Spin agent ds-OFCP ds-OFCP ds-OFCP ds-OFCP ds-OFCP dsOFCP

[0154] Ratio SA11 SA2 t%) 68 66:34 (W :32 68:32 7228 45:55 68:32

[0155] GWP* 83 88 83 72 142 83

[0156] Polymer PE A PE B PE B PEB PP Blend"

[0157] Polymer concentration (wt%) 13 8 17 12 15 15

[0158] Cloud point yes yes yes yes yes yes

[0159] Spin temperature

[0160] 195 200 205 219 220 205

[0161] CC)

[0162] Spin pressure

[0163] (bar) 59 98 59 54 64 70

[0164] * assuming a GWP of about 0 for the ds-1,2-dichloroethylene and a GWP of 258 for the cis-

[0165] 1 H,2H-octafluorocyclopentane

[0166] **. polymer blend of ethylene-hexene copolymer and polypropylene in a 60:20 ratio by weight

[0167] The above examples illustrate that the azeotropic or azeotrope-like compositions of ds- 1,2-dichloroethylene and ds-1H,2H-octafiuorocydopentane can be used as a spin agent for the flash spinning process of polyolefins for different polymer concentrations, spin temperatures, and spin pressures. This allows an efficient preparation of plexifilamentary fibrils of polyolefins.

[0168] In addition, the azeotropic or azeotrope-like compositions exhibit a desirably low GWP value of below 260. This makes these compositions suitable as replacement for currently used spin agents.

[0169] Furthermore, the azeotropic or azeotrope-like compositions form a positive homogenous azeotrope with an advantageously low boiling temperature of 60 °C. Such low boiling temperature correlates to a pressure around (or only slightly above) atmospheric pressure.

[0170] The azeotrope-like compositions which are centered around the azeotrope pant exhibit ally small differences between the bubble point pressure and the dew point pressure. This has the advantage that the azeotropic a 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 / recyded in a commercial process.

[0171] OTHER EMBODIMENTS

[0172] 1. In some embodiments, the present appfication provides an azeotropic or azectrope- like composition comprising

[0173] (a) ds-1 ,2-dichloroethylene and cis-1H^H-octafluorocyctopentane; or

[0174] (b) trans- 1 ,2-dichloroethylene end trans-1 H.2K-octafluorocydopentane.

[0175] 2. The azeotropic or azeotrope-like composition of embodiment 1 comprising from about

[0176] 40 to about 99 weight percent ds-1 ,2-dichloroethylene and from 60 to about 1 weight percent ds-1 H,2H-octafluorocydopehtane.

[0177] 3. The azeotropic or azeotrope-like composition of embodiment 2 consisting essentially of or consisting of from about 40 to about 99 weight percent ds-1 ,2-dichloroethylene and from 60 to about 1 weight percent ds-1H,2H-octafluorocydopentane.

[0178] 4. The azeotropic or azeotrope-like composition of any one of embodiments 2 to 3 comprising from about 45 to about 99 weight percent ds-1,2-dichtoroelhylene and from 55 to about 1 weight percent ds-1H,2H-octafluorocydopentane.

[0179] 5. The azeotropic or azeotrope-like composition of embodiment 4 consisting essentially of or consisting of from about 45 to about 99 weight percent ds-1 ,2-dichloroethylene and from 55 to about 1 weight percent ds-iH,2H-octafluorocydopentahe.

[0180] 6. The azeotropic or azeotrope-like composition of wry one of embodiments 2 to 5 boiling at a temperature of about -20 ’C to about 100 °C at a pressure of about 2 kPa to about 340 kPa.

[0181] 7. The azeotropic or azeotrope-like composition of any one of embodiments 2 to 6 comprising from about 50 to about 99 weight percent ds-1 ,2-dichloroethylene and from 50 to about 1 weight percent ds-1H,2H-octafluorocydopentane. 8. The azeotropic or azeotrope-like composition of embodiment 7 consisting essentially of or consisting of from about 50 to about 99 weight percent ds-1 ,2-dichloroethylene and from 50 to about 1 weight percent ds-1 H.2H-octafluorocydopentane.

[0182] 9. The azeotropic or azeotrope-like composition of any one of embodiments 7 to 8 comprising from about 54 to about 99 weight percent ds-1 ,2-dichloroethylene and from 46 to about 1 weight percent ds-1 H,2H-octafluorocydopentane.

[0183] 10. the azeotropic or azeotrope-like composition of embodiment 9 consisting essentially of or consisting of from about 54 to about 99 weight percent ds-1 ,2-dichloroethylene and from 46 to about 1 weight percent ds-1 H,2H-octafluorocydopentane.

[0184] 11. The azeotropic or azeotrope-like composition of any one of embodiments 7 to lOboiling at a temperature of about -20 °C to about 60 ’C at a pressure of about 2 kPa to about 105 kPa.

[0185] 12. The azeotropic or azeotrope-like composition of any One of embodiments 2 to 11 comprising from about 55 to about 99 weight percent ds-1,2-dichloroethylene and from 45 to about 1 weight percent ds-1H,2H-octafluorocydopentane.

[0186] 13. The azeotropic or azeotrope-like composition of embodiment 12 consisting essentially of or consisting of from about 55 to about 99 weight percent ds-1,2-dichloroethylene and from 45 to about 1 weight percent ds-1H,2H-octafluorocydopentane.

[0187] 14. The azeotropic or azeotrope-like composition of any one of embodiments 12 to 13 comprising from about 58 to about 99 weight percent cis-1,2-dichloroethylene and from 42 to about 1 weight percent ds-lH,2H-octafluorocydopentane.

[0188] 15, The azeotropic or azeotrope-like composition of embodiment 14 consisting essentially of dr consisting of from about 58 to about 99 weight percent ds-1 ,2-dichloroethylene and from 42 to about 1 weight percent ds-1H,2H-octafluorocydopentane.

[0189] 16. The azeotropic or azeotrope-like composition of any one of embodiments 12 to 15 boiling at a temperature of about -20eC to about 40 °C at a pressure of about 2 kPa to about 52 kPa. 17. The azeotropic composition of any one of the embodiments 2 to 16 consisting essentially of or consisting of from about 62 to about 79 weight percent cis-1 ,2-dichloroethytene and from about 38 to about 21 weight percent cis-1 H,2H-octafluorocyclopentane.

[0190] 18. The azeotropic composition of embodiment 17 boiling at a temperature of about -20 °C to about 100 °C at pressure of about 2 kPa to about 340 kPa.

[0191] 19. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 78.9 weight percent cis-1,2-dichloroethylene and about 21.1 weight percent cis-1 H,2H-octafluorocyclopentane.

[0192] 20. The azeotropic composition of embodiment 19 boiling at temperature of about -20eC at a pressure of about 2.84 kPa.

[0193] 21. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 73.9 weight percent cis-1,2-dichloroethylene and about 26.1 weight percent ds-1H,2H-octafluorocyclopentane.

[0194] 22. The azeotropic composition of embodiment 21 boiling at temperature of about 20°C at a pressure of about 22.6 kPa.

[0195] 23. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 71.0 weight percent ds-1,2-dichloroethylene and about 29.0 weight percent cis-1H,2H-octafluorocydopentane.

[0196] 24. The azeotropic composition of embodiment 23 boiling at temperature of about 40”C at a pressure of about 51 A kPa.

[0197] 25. The azeotropic composition of any one of the embodiments 2 to 18 consisting essentially of or consisting of about 68.1 weight percent cts-1,2-dichloroethyiene and about 31.9 weight percent cis-1H,2H-octafluorocyclopentane. 26. The azeotropic composition of embodiment 25 boiling at temperature of about 60°C at a pressure of about 104.8 kPa.

[0198] 27. The azeotropic composition of any on e of the embodiments 2 to 18 consisting essentially of or consisting of about 62.0 weight percent cis-1,2-dichloroethylene and about 38.0 weight percent ds-1H,2H-octafluorocydopentane.

[0199] 28. The azeotropic composition of embodiment 27 boiling at temperature of about 100°C at a pressure of about 339.9 kPa.

[0200] 29. The azeotropic or azeotrope-like composition of embodiment 1 comprising from about 1 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 99 to about 45 weight percent trans-1 H,2H-octafluorocydopentane.

[0201] 30. The azeotropic Or azeotrope-like composition of embodiment 29 consisting essentially of or Consisting of from about 1 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 99 to about 45 weight percent trans-1H,2H-octafluorocydopentane.

[0202] 31. The azeotropic or azeotrope-like composition of embodiment 29 or 30 comprising from about 1 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 99 to about 48 weight percent trans-1 H^H-octafluorocyclopentane.

[0203] 32. The azeotropic or azeotrope-like composition of embodiment 31 consisting essentially of or consisting of from about 1 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 99 to about 48 weight percent trans-1H,2H-octafluorocyclopentane.

[0204] 33. The azeotropic or azeotrope-like composition Of any one of embodiments 29 to 32 boiling at a temperature of about -20eC to about 100 °C at a pressure of about 6 kPa to about 589 kPa;

[0205] 34. The azeotropic or azeotrope-like composition of any one of embodiments 29 to 33 comprising from about 20 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 80 to about 45 weight percent trans-1H,2H-octafluorocyctopentane. 35. The azeotropic or azeotrope-like composition of embodiment 34 consisting essentially of or consisting of from about 20 to about 55 weight percent trans-1, 2-dichloroethylene and from about 80 to about 45 weight percent trans-1 H,2H-octafluorocydopentane.

[0206] 36. The azeotropic or azeotrope-like composition of embodiment 34 or 35 comprising from about 20 to about 52 weight percent trans-1 ,2-dichloroethylene and from aboutSO to about 48 weight percent trans-1 H^H-octafluorocydopentane.

[0207] 37. The azeotropic or azeotrope-like composition of embodiment 36 consisting essentially of or consisting of from about 20 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 80 to about 48 weight percent trans-1 H,2H-octafluorocydopentane.

[0208] 38. The azeotropic or azeotrope-like composition of any one of embodiments 34 to 37 boiling at a temperature of about -20eC to about 60 °C at a pressure of about 6 kPa to about 200 kPa.

[0209] 39. The azeotropic or azeotrope-like composition of any one of embodiments 29 to 38 comprising from about 25 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 75 to about 45 weight percent trans-1H,2H-octafluorocyclopentane.

[0210] 40. The azeotropic or azeotrope-like composition of embodiment 39 consisting essentially of or consisting of from about 25 to about 55 weight percent trans-1 ,2-dichloroethylene and from about 75 to about 45 weight percent trans-1 H,2H-octafluorocydopentane.

[0211] 41. The azeotropic or azeotrope-lfce composition of embodiment 39 or 40 comprising from about 25 to about 52 weight percent trahs-1 ,2-dichloroethylene and from about 75 to about 48 weight percent trans-1 H ,2H-octafluorocyclopentane.

[0212] 42. The azeotropic or azeotrope-like composition of embodiment 41 consisting essentially of or consisting of from about 25 to about 52 weight percent trans-1 ,2-dichloroethylene and from about 75 to about 48 weight percent trans-1 H,2H-octafluorocydopentane. 43. The azeotropic or azeotrope-like composition of any one of embodiments 39 to 42 boiling at a temperature of about -20eC to about 40 “C at a pressure of about 6 kPa to about 104 kPa.

[0213] 44. The azeotropic composition of any one of the embodiments 29 to 43 consisting essentially of or consisting of from about 32 to ebout 46 weight percent trans-1, 2- dichloroethylene and from about 68 to about 54 weight percent trans-1 H,2H- octafluorocydopentane.

[0214] 45. The azeotropic composition of embodiment 44 boiling at a temperature of about -20 °C to about 100 °C at pressure of about 6 kPa to about 589 kPa.

[0215] 46. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 45.6 weight percent trans-1 ,2-dichloroethylene and about 54.4 weight percent trare-1H,2H-octafluorocydopentane.

[0216] 47. The azeotropic composition of embodiment 46 boiling at temperature of about -20°C at ■a pressure of about 6.5 kPa.

[0217] 48. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 39.7 weight percent trans-1 ,2-dichloroethylene and about 60.3 weight percent trans-1 H,2H-octafluorocyclopentane.

[0218] 49. The azeotropic composition of embodiment 48 boiling at temperature of about 20°C at a pressure of about 48.1 kPa.

[0219] 50. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 37.5 weight percent trans-1 ,2-dichloroethylene and about 62.5 weight percent trans-1 H,2H-octafluorocydopentane.

[0220] 51. The azeotropic composition of embodiment 50 boiling at temperature of about 40eC at a pressure of about 103.6 kPa. 52. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 35.5 weight percent trans-1 ,2-dichloroethylene and about 64.5 weight percent trans-1H J2H-octafluorocydopentane.

[0221] 53. The azeotropic composition of embodiment 52 boiling at temperature of about 60°C at a pressure of about 200.1 kPa.

[0222] 54. The azeotropic composition of any one of the embodiments 29 to 45 consisting essentially of or consisting of about 32.0 weight percent trahs-1 ,2-dichloroethylene and about 68.0 weight percent trahs-1 H,2H-octafluorocyclopentane.

[0223] 55. The azeotropic composition of embodiment 54 boiling at temperature of about 100*0 at a pressure of about 589 kPa.

[0224] 56. In some embodiments, the present application provides a spin fluid for flash spinning comprising

[0225] (a) from about 6 to about 24 weight percent weight percent of a polyolefin, based on the total amount of the spin fluid, and

[0226] (b) -a spin agent, wherein the spin agent comprises or consists essentially of an azeotropic or azeotrope-like composition comprising

[0227] (i) cis-1,2-dichloroethylene and cis-1H,2H-octaf!uorocydopentane, or

[0228] (ii) trans- 1,2-dichloroethylene and trans-1H,2H-6ctafluorocyclopentane.

[0229] 57. The spin fluid of embodiment 56 comprising from about 6 to about 20 weight percent of a polyolefin, based on the total amount of the spin fluid, or from about 8 to about 20 weight percent of a polyolefin, based on the total amount of the spin fluid, or from about 8 to about 16 weight percent of a polyolefin, based on the total amount of the spin fluid, or from about 8 to about 14 weight percent of a polyolefin, based on the total amount of the spin fluid.

[0230] 58. The spin fluid of embodiment 56 or 57 comprising from about 6 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a pdy(4-methyl-1- pentene), based on the total amountof the spin fluid, or from about 8 to about 20 weight percent , of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyH-pentene), based on the total amount of the spin fluid, or from about 8 to about 16 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyi-1-pentene), based on the total amount of the spin fluid, or from about 8 to about 14 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a poly(4-methyl-1-pentene), based on the total amount of the spin fluid; the spin agent comprising or consisting essentially of an azeotropic or azeotrope-like composition comprising trans-1,2-dichloroethylene and trans-1H,2H-octafluorocydopentane.

[0231] 59. The spin fluid of any one of embodiments 56 to 58 comprising from about 76 to about 94 weight percent of the spin agent, based on the total amount of the spin fluid, or from about 80 to about 94 weight percent otthe spin agent, based on the total amount of the spin fluid, or from about 80 to about 92 weight percent of the spin agent, based on the total amount of the spin fluid, or from about 84 to about 92 weight percent of the spin agent, based on the total amount of the spin fluid, or from about 86 to about 92 weight percent of the spin agent, based on the total amount of the spin fluid.

[0232] 60. The spin fluid of any one of embodiments 56 to 59, wherein the spin agent consists essentially of or consists of from about 40 to about 75 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 25 weight percent ds-1H,2H-octafluorocyciopentane, or from about 60 to about 75 weight percent cis-1, 2-dichloroethylene and from about 40 to about 25 weight percent cis-1H,2H-octafluorocydopentane, or from about 65 to about 74 weight percent ds- 1, 2-dichloroethylene and from about 35 to about 26 weight percent ds-lH,2H- octafluorocydopentane.

[0233] 61. The spin fluid of any one of embodiments 56 to 59, wherein the spin agent consists essentially of or consists of from about 40 to about 60 weight percent cis-1 , 2-dichloroethylene and from about 60 to about 40 weight percent ds-1 H,2H-octafluorocydopentane, or from about 40 to about 50 weight percent ds-1,2-dichtoroethylene and from about 60 to about 40 weight percent cis-1 H,2H-octafluorocydopentane.

[0234] 62. The spin fluid of any one of embodiments 56 to 59, wherein the spin agent consists essentially of or consists of from about 30 to about 55 weight percent trans-1,2- dichloroethylene and from about 70 to about 45 weight percent trans-1H,2H- octafluorocyclopentane. 63. The spin fluid of any one of embodiments 56 to 59, wherein the spin agent consists essentially of or consists of from about 35 to about 55 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 45 weight percent trans-1H,2H- octafluorocyclbpentane, or from about 35 to about 52 weight percent trans-1 ,2- dichloroethytene and from about 65 to about 48 weight percent trans-1 H,2H- octafluorocyclopentane, or from about 35 to about 45 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 55 weight percent trans-1H,2H- octafluorocydopentane.

[0235] 64, The spin fluid of any one of embodiments 56 to 63, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutene-1, poly(4-methyl-1- pentene), and blends / mixtures thereof.

[0236] 65. The spin fluid of embodiment 64, wherein the polyethylene is a high-density polyethylene (HOPE), a blend of a high-density polyethylene (HOPE) with a low-density polyethylene (LOPE), or a blend of a high-density polyethylene (HOPE) with a linear low- density polyethylene (LLDPE).

[0237] 66. The spin fluid of any one of embodiments 56 to 65 comprising about 6 to about 24 weight percent, or about 6 to about 20 weight percent, or about 8 to about 20 weight percent, or about 8 to about 16 weight percent, or about 8 to about 14 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 60 to about 75 weight percent ds-l,2-dichloroethylen6 and from about 40 to about 25 weight percent cis- 1H,2H-octafluorocyctopentane, or from about 65 to about 74 weight percent cis-1,2- dichloroethylene and from about 35 to about 26 weight percent ds-1H,2H- octafluorocydopentane.

[0238] 67. The spin fluid of any one of embodiments 56 to 64 comprising about 15 to about 24 weight percent of a polypropylene, a polybutene-1, or a poly(4-methyH-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 40 to about 60 weight percent ds-1,2-dichloroethylene and from about 60 to about 40 weight percent ds-1H,2H-octefluorocydopentane, or from about 40 to about 50 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 50 weight percent ds-1H,2H-octafluorocydopentane.

[0239] 68. The spin fluid of any one of embodiments 56 to 64 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 30 to about 55 weight percent trans- 1 ,2-dichloroethylene and from about 70 to about 45 weight percent trans-1H,2H-octafluorocydopentane, or from about 35to about 55 weight percent trans- 1,2-dichloroethylene and from about 65 to about 45 weight percent trans-1 H,2H-octafluorocyclopentane, or from about 35 to about 52 weight percent trans- 1,2-dichloroethylene and from about 65 to about 48 weight percent trans-1 H,2H- octafluorocyclopentane, or from about 35 to about 45 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 55 weight percent trans-1 H,2H- octafluorocydopentane.

[0240] 69. The spin fluid of any one of embodiments 56 to 68, wherein the spin agent additionally comprises an additive, selected from antioxidants, acid scavengers, and blends thereof.

[0241] 70. In some embodiments, the present application provides a process for the preparation of plexifilamentary fibrils of polyolefin comprising the steps of:

[0242] (i) generating a spin fluid comprising

[0243] (a) about 6 to about 24 weight percent of a polyolefin, based on the total amount of the spin fluid, and

[0244] (b) a spin agent, and

[0245] (ii) flash spinning the spin fluid at a pressure above the vapor pressure of the spin fluid into a region of essentially atmospheric pressure to form plexifilamentary fibrils of the polyolefin; wherein the spin agent comprises or consists essentially of

[0246] (1) an azeotropic or azeotrope-like composition comprising ds-1 ,2- dichloroethylene and ds-1 H,2H-octafluorocydopentane. or

[0247] (2) an azeotropic or azeotrope-like composition comprising trans-1 ,2- dichloroethylene and trans-1 H,2H-octafluoro<^clopentane. 71. The process of embodiment 70, wherein the spin fluid comprises from about 6 to about 20 weight percent of a polyolefin, based on the total amount of the spin fluid, or from about 8 to about 20 weight percent of a polydefin, based on the total amount of the spin fluid, or from about 8 to about 16 weight percent of a polyolefin, based on toe total amount of the spin fluid, or from about 8 to about 14 weight percent of a polyolefin, based on the total amount of the spin fluid.

[0248] 72. The process of embodiment 70 or 71 , wherein the spin fluid comprises from about 6 to about 20 weight percent of a polyolefin, selected from a polypropylene, a pdybutene-1, or a poty(4-methyl-1 -pentene), based on toe total amount of the spin fluid, or from about 8 to about 20 weight percent of a polyolefin, selected from a polypropylene, a polybutene-1, or a pdy(4- methyl-1-pentene), based on the total amount of the spin fluid, or from about 8 to about 16 weight percent of a polyolefin, selected from a polypropylene, a pdybutene-1, or a poly(4- methyl-1-pentene), based on the total amount of the spin fluid, or from about 8 to about 14 weight percent of a polydefin, selected from a polypropylene, a polybutene-1, or a poly(4- methyl-1-pentene), based on the total amount of toe spin fluid; the spin agent Oomprising or consisting essentially of an azeotropic or azeotrope-like composition comprising trans-1,2- dichloroethylene and trans-1H,2H-odafluorocydopentane.

[0249] 73. The process of any one of embodiments 70 to 72, wherein the spin fluid comprises from about 76 to about 94 weight percent of the spin agent, based on the total amount of the spin fluid, or from about 80 to about 94 weight percent of the spin agent, based on toe total amount of the spin fluid, or from about 80 to about 92 weight percent of the spin agent, based on the total amount of the spin fluid, or from about 84 to about 92 weight percent of the spin agent, based on the total amount of toe spin fluid, or from about 86 to about 92 weight percent of the spin agent, based on toe total amount of toe spin fluid.

[0250] 74, The process of any one of embodiments 70 to 73, wherein the spin agent consists essentially of or consists of from about 40 to about 75 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 25 weight percent ds-1 H,2H-octafluorocydopentane, or from about 60 to about 75 weight percent ds-1,2-dichloroethylene and from about 40 to about 25 weight percent cis-1 H,2H-octafluorocydopentane, or from about 65 to about 74 weight percent cis- 1 ,2-dichloroethylene and from about 35 to about 26 weight percent cis-1 H,2H- octafluorocydopentane. 75. The process of any one of embodiments TO to 73, wherein the spin agent consists essentially of or consists of from about 40 to about 60 weight percent cis-1 ^idiloroethylene and from about 60 to about 40 weight percent cis-1 H,2H-octafluorocydopentane, or from about 40 to about 50 weight percent cis-1 ,2-dichtoroethylene and from about 60 to about 40 weight percent cis-1 H,2H-octafluorocydopentane.

[0251] 76. The process of any one of embodiments 70 to 73, wherein the spin agent consists essentially of or consists of from about 30 to about 55 weight percent trans-1,2- dichloroethylene and from about 70 to about 45 weight percent trans-1H,2H- octafluorocydopentane.

[0252] 77. The process of any one of embodiments TO to 73, wherein the spin agent consists essentially of or consists of from about 35 to about 55 weight percent frans-1,2- dichloroethylene and from about 65 to about 45 weight percent trans-1H,2H- octafluorocyclopentane, or from about 35 to about 52 weight percent trans-1,2- dichloroethylene and from about 65 to about 48 weight percent trans-1H,2H- octafluorocydopentane, or from about 35 to about 45 weight percent frans-1,2- dichloroethytene and from about 65 to about 55 weight percent trans-1H,2H- octafluorocydopentane.

[0253] 78. The process Of any one of embodiments 70 to 77, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, pdybutene-1, pdy(4-methyl-1- pentene), and blends / mixtures thereof .

[0254] 79. The process of embodiment 78, wherein the polyethylene is a high-density polyethylene (HOPE), a blend of a high-density polyethylene (HOPE) with a low-density polyethylene (LDPE), of a blend of a high-density polyethylene (HDPE) with a linear low- density polyethylene (LLDPE).

[0255] 80. The process of any one of embodiments 70 to 79, wherein the spin fluid comprises about 6 to about 24 weight percent, or about 6 to about 20 weight percent, or about 8 to about 20 weight percent, dr about 8 to about 16 weight percent, or about 8 to about 14 weight percent of a polyethylene, or a blend comprising polyethylene, based Oh the total amount of tie spin fluid, and a spin agent, wherein the spin agent consists essentially of or consists of from about 60 to about 75 weight percent ds-1,2-dichloroethylene and from about 40 to about 25 weight percent cis-1H,2H-octafluorocydopentane, or from about 65 to about 74 weight percent cis* 1 ,2-dichloroethylene and from about 35 to about 26 weight percent cis-1H,2H- octafluorbcydopentane.

[0256] 81. The process of any one of embodiments 70 to 78, wherein the spin fluid comprises about 15 to attout 24 weight percent of a polypropylene, a pdybutene-1, ora poly(4-methyl-l- pentene), based on the total amount of the spin fluid, and a spin agent, wherei n the spin agent consists essentially of or consists of from about 40 to about 60 weight percent ds-1,2- dichloroethylene and from about 60 to about 40 weight percent cis-1H,2H- octafluorocydopentane, or from about 40 to about 50 weight percent cis-1 ,2-dichloroethylene and from about 60 to about 50 weight percent ds-1H,2H-octafluonocyctopentane.

[0257] 82. The process of any one of embodiments 70 to 78, wherein 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 30 to about 55 weight percent trans-1 ,2- dichloroethylene and from about 70 to about 45 weight percent trans-1H,2H- octafluorocydopentarie, or from about 35 to about 55 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 45 weight percent trans-1 H,2H- octafluorocydopentane, or from about 35 to about 52 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 48 weight percent trans-1 H, 2 H- octafluorocydopentane, or from about 35 to about 45 weight percent trans-1 ,2- dichloroethylene and from about 65 to about 55 weight percent trans-1 H,2H- octafluorocydopentane.

[0258] 83. The process of any one of embodiments 70 to 82, wherein the spin agent additionally comprises an additive, selected from antioxidants, add scavengers, and blends thereof.

[0259] 84. In some embodiments, the present application provides a use of the spin fluid of any of embodiments 56 to 69 for preparing of plexifilamentary fibrils of polymer by flash spinning. 85. The plexifilamentary fibrils of polymer obtainable by the process of any one of embodiments 70 to 83.

[0260] 86. A sheet of nonwoven flash-spun plexifilamentary fibrils comprising plexifBamentary fibrils of polymer of embodiment 85,

[0261] 87. The sheet of embodiment 86, wherein the sheet is a collected sheet, a consolidated sheet, a bonded sheet, or a softened sheet.

[0262] 88. A bonded sheet obtainable by thermally or mechanically bonding the consolidated sheet of embodiment 87.

[0263] 89. A softened sheet obtainable by softening the consolidated sheet of embodiment 87 or by softening the bonded sheet of embodiment 88.

[0264] 90. A multilayer sheet comprising two or more sheets wherein at least one sheet is a sheet according to any one of embodiments 86 to 89.

[0265] 91. An article comprising plexifilamentary fibrils of polymer of embodiment 85 and / or a sheet of any one of embodiments 86 to 89 and / or a multilayer sheet of embodiment 90.

[0266] 92. The artide of embodiment 91 which is selected from garment, protective apparel, house wrap, roof lining, car covers, cargo covers, medical and non-medical packaging, filtration media, print media, tags and labels, and accessories.

[0267] 93. The article of embodiment 92 wherein the garment is protective apparel.

[0268] 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 daims. moreover, ft 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(a) ds-1,2-dichloroethylene and fe-1H»2H-octefluorocyctopentane, or(b) trans-1, 2-dichloroethylene and trans-1H,2H-octafluorocyclopentane.

2. The azeotropic or azeotrope-like composition of claim 1 comprising from about 40 to about 99 weight percent ds-1, 2-dichloroethylene and from 60 to about 1 weight percent ds- 1 H,2H-octafluorocyclopentane.

3. The azeotropic composition of any one of claims 1 or 2 consisting essentially of from about 62 to about 79 weight percent ds-1, 2-dichloroethylene and from about 38 to about 21 weight percent cis-1 H,2H-octafiuorocydopehtane.

4. The azeotropic composition of claim 3 boiling at a temperature of about -20 "C to about100 “C at a pressure of about 2 kPa to about 340 kPa.

5. The azeotropic or azeotrope-like composition of claim 1 comprising from about 1 to about 55 weight percent trans-1 ,2-<fichloroethyiene and from about 99 to about 45 weight percent trans-1 H,2H-octafluorocydopentane.

6. The azeotropic composition of any one of claims 1 or 5 consisting essentially of from about 32 to about 46 weight percent trans-1 , 2-dichloroethylene and from about 68 to about 54 weight percent trans-1 H^H-octafluorocydopentane.

7. The azeotropic composition of claim 6 boiling at a temperature of about -20 °C to about 100 “C at a pressure of about 6 kPa to about 589 kPa.

8. A spin fluid for flash spinning comprising(a) from about 6 to about 24 weight percent of a polyolefin, based on the total amount of the spin fluid, and(b) a spin agent, wherein the spin agent comprises an azeotropic or azeotropelike composition which(i) consists essentially of from about 40 to about 75 weight percent cis-1,2- dichloroethylene and from 60 to than about 25 weight percent ds-1H,2H- octafluorocyctopentane, or(ii) consists essentially of from about 25 to about 55 weight percent trans-1,2- dichlofoethylene and from about 75 to about 45 weight percent trans-1H,2H- octafluorocydopentane.

9. The spin fluid of claim 8 comprising from 76 to 94 weight percent of the spin agent, based on the total amount of the spin fluid, or from 80 to 94 weight percent of the spin agent, based on the total amount of the spin fluid.

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

11. A process for the preparation of plexifilamentary fibrils of polyolefin which comprises the stepsof;(t) generating a spin fluid comprising(a) from about 6 to about 24 weight percent of a polyolefin, 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 polyolefin; wherein the spin agent comprises an azeotropic or azeotrope-like composition which(i) consists essentially of from about 40 to about75 weight percent ds-1,2- dichloroethylene and from 60 to than about 25 weight percent ds-1 H,2H- octafluorocydopentane, of(ii) consists essentially of from about 25 to about 55 weight percent trans-1,2- dichloroethylene and from about 75 to about 45 weight percent trans- 1 H,2H- octafluorocydopentane.

12. The process of claim 11, wherein the spin fluid comprises from 76 to 94 weight percent of the spin agent, based on the total amount of the spin fluid, or from 80 to 94 weight percent of the spin agent, based on the total amount of the spin fluid.

13. The process of claim 11 or 12, wherein the polyolefin Is selected from the group consisting of polyethylene, polypropylene, polybutene- 1, poly(4-metoyl-1-pentene), and blends / mixtures thereof.

14. Use of the spin fluid of any one of claims 8 to 10 for preparing of plexifilamentary fibrils of pofyotefin by flash spinning.

15. Rexifilamentary fibrils of polyolefin obtainable by the process of any one of claims 11 to 13.

16. A sheet of nonwoven flash-spun ptexifilamentary fibrils comprising plexifilamentary fibrils of polyolefin of claim 15.

17. The sheet of claim 16, wherein the sheet is a collected sheet, -a consolidated sheet, a bonded sheet, or a softened sheet.

18. An article comprising the plexifilamentary fibrils of polyolefin of claim 15 and / or the sheet of claim 16 or claim 17.

19. The article of claim 18 which is selected from garment, protective apparel, house wrap, roof lining, car covers, cargo covers, medical and non-medtcal packaging, filtration media, print media, tags and labels, and accessories.

Images