SOLVENT STRIPPING PROCESS

A process for stripping solvent from solvent-laden fibers in a solution-spun fiber web is disclosed.

Background

The process of solution spinning involves dissolving a desired polymer into a suitable solvent, and spinning fibers from the polymer/solvent solution. Often, the solvent is an organic solvent which has undesirable properties in use of the so-formed fabric, such as adverse health effects, undesired odor and the like. It would be desirable to strip the unwanted solvent from the fibers or fabric during the production process, prior to shipping to the ultimate customer.

Solution spinning processes are frequently used to manufacture fibers and nonwoven fabrics, and in some cases have the advantage of high throughputs, such that the fibers or fabrics can be made in large, commercially viable quantities. Unfortunately, when solution spinning large quantities of fabric at high throughput through the spinning dies, significant quantities of residual solvent can be entrained in the collected fabrics or fibers. Ideally, the residual solvent would merely evaporate upon sitting, leaving the fabric solvent-free, but in many cases the ideal solvent used for the solution spinning process has a high chemical or physical affinity for the fiber polymer. In some cases, the fiber polymer is swollen by the solvent; i.e. the solvent is "dissolved" within the fiber polymer. In other cases the solvent chemically bonds to the fiber, such as by hydrogen bonding, Van der Waals forces, or even ionically via salt formation.

Further, in typical nonwoven fabric spinning processes, the fabric is spun and wound into a large roll in an essentially continuous operation, such that even if the solvent were amenable to evaporation upon sitting, only the solvent entrained in the fabric on the outside of the roll is effectively evaporated, since the underlying fabric within the roll is not exposed to the atmosphere. Detrimentally, even if the fabric were to be

provided sufficient time in the unrolled state to permit the spinning solvent to evaporate, an exceedingly long area would be necessary to provide room for the unrolled fabric, and recovery of the evaporated solvent would be difficult and expensive. In paper making processes, such as those disclosed in U.S. Patent

Nos. 3,503,134 and 6,986,830, dewatering of the wet laid cellulose fibers which form the paper is performed by passing the wet laid cellulose web over a vacuum-assisted porous drum, and the excess water from the forming process is drawn through and away from the paper web. U.S. Patent 3,503,134 discloses the use of hot air, superheated steam or a steam-air mix to enhance the drying effect of the vacuum assist. U.S. Patent No. 6,986,830 discloses positioning the wet laid paper web between two soft, porous cloth webs, wherein the porous cloths on either side of the paper web pull additional water from the paper by capillary action. However, in either case, while it is advantageous to remove as much water as possible from the wet laid paper web, residual water is non-toxic and would not cause adverse health effects if present in the finished product.

U.S. Published Patent Application No. 2002/0092423 discloses a solution spinning process for forming a nonwoven polymer web, in particular an electrospinning process, wherein polymeric microfibers or nanofibers are produced from a polymer solution exiting an electrically- charged rotating emitter and directed toward a grounded collector grid. However, according to the applicants thereof, the solvent is evaporated from the fibers "in flight" between the emitter and the collector grid. The throughput of the electrospinning process disclosed in U.S. Published Patent Application No. 2002/0092423 is relatively low at about 1.5 ml/min/emitter, and as such would form relatively light basis weight polymer webs.

SUMMARY OF THE INVENTION

In a first embodiment, the invention is a process for stripping chemically bonded spinning solvent from a solution-spun nonwoven web

comprising the steps of providing a nonwoven web comprising solvent- laden polymeric fibers having average fiber diameters of less than about 1 micrometer, and transporting the nonwoven web through a solvent stripping zone wherein a solvent stripping fluid heated to at least about 70°C impinges on the nonwoven web in order to reduce the solvent concentration of the fibers to less than about 10,000 ppmw.

In another embodiment, the invention is a solution-spun nonwoven web comprising polymeric fibers having average fiber diameters of less than about 1 micrometer and containing less than about 10,000 ppmw of spinning solvent which bonds with the fiber polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate the presently contemplated embodiments of the invention and, together with the description, serve to explain the principles of the invention.

Fig. 1 is a schematic of a prior art nanofiber web preparing apparatus for preparing a filtration medium according to the invention.

Fig. 2 is a schematic of a solvent stripping station according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to solvent-spun webs and fabrics for a variety of customer end-use applications, such as filtration media, protective apparel and the like, including at least one nanofiber layer, and a process for removing excess spinning solvent from the solution-spun nanofiber webs or fabrics.

There is a need for fibrous products made from a wide variety of polymers to suit various customer end-use needs. Many polymeric fibers and webs can be formed from melt spinning processes, such as spun bonding and melt blowing. However, the ability to use melt spinning is limited to spinning fibers from polymers which are melt processable, i.e. those which can be softened or melted and flow at elevated temperatures.

Still, in many end-uses, it is desirable to utilize polymers which are not melt processable, for example thermosetting polymers and the like, to form fibrous materials, fabrics and webs. In order to form these non-melt- processable polymers into fibrous materials, the technique of solution spinning is used.

As discussed above, solution spinning processes, such as wet spinning, dry spinning, flash spinning, electrospinning and electroblowing, involve dissolving a desired polymer into a suitable solvent, and spinning fibers from the polymer/solvent solution. Often, the solvent is an organic solvent which has undesirable properties in use of the so-formed fabric, such as adverse health effects, undesired odor and the like. It would be desirable to strip the unwanted solvent from the fibers or fabric during the production process, prior to shipping to the ultimate customer.

Unfortunately, when solution spinning large quantities of fabric at high throughput through the spinning dies, such as to form nonwoven webs having basis weights of greater than about 5 grams/square meter (gsm), significant quantities of residual solvent can be entrained in the collected fabrics or fibers, due to either or both of high physical or chemical affinities of the solvent for the polymer so spun, and the lack of sufficient time or space between fiber formation and fiber collection for complete evaporation of the spinning solvent. In many cases, the solvents used in the solution spinning processes demonstrate various levels of toxicity, or present negative environmental effects or cause adverse chemical reactions in particular end-uses. As such, it is preferred to remove as much residual solvent from the solution spun fibrous materials as possible.

Solvent removal is often complicated by the fact that any particular polymer/solvent spinning system is chosen based upon a strong affinity of the solvent for the polymer, in order to effect complete dissolution of the polymer in the solvent during the spinning operation. In some cases, the fiber polymer is swollen by the solvent; i.e. the solvent is "dissolved" within the fiber polymer. In other cases the solvent chemically bonds to the fiber,

such as by hydrogen bonding, Van der Waals forces, or even ionically via salt formation.

In some prior art solvent spinning processes, such as dry spinning, removal of high affinity solvents is accomplished by spinning the fibers into a hot gas "chimney" of as much as 30 feet in length, and passing high temperature gas (as high as 500 ⁰ C) through the chimney to drive off the unwanted solvent. As can be imagined, this process involves an expensive apparatus and is an energy-intensive process.

The present inventor has discovered that one manner of enhancing unwanted solvent removal from solution spun fibers is to reduce the diameter of the fibers themselves, since the diffusion de-volatilization mechanisms follow a 1 /diameter ² relationship. That is, entrained solvent will diffuse more readily out of fibers having smaller diameters than out of fibers having larger diameters. According to the present invention, it is preferred that solution spun fibers have diameters less than about 1 micrometer (nanofibers) to optimize the diffusion de-volatilization mechanism of solvent removal.

The term "nanofibers" refers to fibers having diameters varying from a few tens of nanometers up to several hundred nanometers, but generally less than about one micrometer, even less than about 0.8 micrometer, and even less than about 0.5 micrometer.

The solution spun fabrics and webs of the present invention include at least one layer of polymeric nanofibers. The nanofibers have average fiber diameters of less than about 1 μm, preferably between about 0.1 μm and about 1 μm, and high enough basis weights to satisfy a variety of commercial end-uses, such as for air/liquid filtration media, battery separator fabrics, protective apparel and the like.

The process for making commercial quantities and basis weights of nanofiber layer(s) is disclosed in International Publication Number WO2003/080905 (U.S. Serial No. 10/822,325), which is hereby incorporated by reference.- Figure 1 is a schematic diagram of an electroblowing apparatus useful for carrying out the process of the present invention using electroblowing (or "electro-blown spinning") as described

in International Publication Number WO2003/080905. This prior art electroblowing method comprises feeding a solution of a polymer in a solvent from mixing chamber 100, through a spinning beam 102, to a spinning nozzle 104 to which a high voltage is applied, while compressed gas is directed toward the polymer solution in a blowing gas stream 106 as it exits the nozzle to form nanofibers, and collecting the nanofibers into a web on a grounded collector 110 under vacuum created by vacuum chamber 114 and blower 112.

The moving collection apparatus is preferably a moving collection belt positioned within the electrostatic field between the spinning beam 102 and the collector 110. After being collected, the nanofiber layer is directed to and wound onto a wind-up roll on the downstream side of the spinning beam. Optionally, the nanofiber web can be deposited onto any of a variety of porous scrim materials arranged on the moving collection belt 110, such as spunbonded nonwovens, meltblown nonwovens, needle punched nonwovens, woven fabrics, knit fabrics, apertured films, paper and combinations thereof.

Due to the high throughput of the electroblowing apparatus, typically between about 0.1 to 5 mL/hole/min, and the large number of spinning nozzles (holes) 104 distributed across the spinning beam 102, a single nanofiber layer having a basis weight of between about 2 g/m ² and about 100 g/m ² , even between about 10 g/m ² and about 90 g/m ² , and even between about 20 g/m ² and about 70 g/m ² , as measured on a dry basis, i.e., after the residual solvent has evaporated or been removed, can be made by depositing nanofibers from a single spinning beam in a single pass of the moving collection apparatus. However, also due to the high throughput of the process and the speed at which the electroblown fibers are collected on the collection belt, significant quantities of residual spinning solvent, especially those solvents with strong affinities for the fiber polymers, can remain in the nanofiber webs so-formed.

It has been discovered that reducing fiber diameter, even to below 1 micrometer, or even to below about 0.8 micrometer, or even below about 0.5 micrometer, is alone insufficient to reduce or eliminate residual solvent

from the nanofiber web merely by vacuum-assisted collection.

Accordingly, the solvent stripping process and apparatus of the present invention, Fig. 2, which is disposed downstream of the collection belt 110 of the prior art apparatus (Fig. 1), acts to effect reduction or elimination of unwanted residual solvent from solution spinning processes in a continuous manner, prior to wind-up of the fabric or web.

The solvent stripping apparatus comprises a continuous moving belt 14 for supporting the solvent spun nanofiber web and its optional supporting scrim 10 and directing it through one or more solvent stripping stations 20, each of which comprise a fresh solvent stripping fluid heating apparatus 16, disposed on one side of the moving belt 14, and a vacuum apparatus 18, disposed on the opposite side of moving belt 14. The "fresh solvent stripping fluid" 17, typically air, is impinged upon the moving solution spun web, and the vacuum apparatus helps to draw the stripping fluid through the solution spun web to effect solvent stripping. Preferably, a spent solvent stripping fluid collector (not shown) is disposed downstream of the vacuum apparatus to scrub the excess spinning solvent from the spent stripping fluid for recycling or disposal.

The fresh solvent stripping fluid can be a gas selected from air, nitrogen, argon, helium, carbon dioxide, hydrocarbons, halocarbons, halohydrocarbons, and mixtures thereof, and is essentially free from vapors of the spinning solvent to be stripped, such that the partial pressure of the spinning solvent is much higher within the polymer fibers of the solution spun web than in the solvent stripping fluid, so as to drive diffusion of the residual stripping solvent from the solvent-laden polymer fibers into the solvent stripping fluid. However, even this differential in partial pressures is insufficient to extract a spinning solvent with high affinity for the fiber polymer down to concentration levels on or within the fibers which are suitable for many consumer uses. It has been discovered that in order to reduce the concentration level of solvents with strong affinities for the fiber polymer to less than 1 wt% (10,000 ppmw) in a continuous process, it is necessary to heat the fresh solvent stripping fluid to temperatures of at least about 70 ⁰ C, or at

least about 90 ⁰ C, or at least about 110 ⁰ C and even at least about 150 ⁰ C ₁ up to as high as the melting point of the polymer (in the case of a thermoplastic polymer) or just below the decomposition temperature of the polymer (in the case of a non-thermoplastic polymer) for short periods of time to avoid polymer melting or decomposition.

The present inventor deems the relatively high temperatures necessary to de-couple the spinning solvents from the polymers to be unexpected, as the skilled artisan would expect that the solvent would evaporate at room temperatures within the space between the spinning nozzles and the collector, as set forth in U.S. Published Patent Application No. 2002/0092423. Instead, it was found to be necessary to apply temperatures well-above the spinning solvent boiling point to reduce the spinning solvent levels to less than about 1000 ppmw in a continuous process and within a commercially viable time (see Examples, below). Utilizing the combination of "fresh" solvent stripping fluid (i.e. one having very low partial pressure of the spinning solvent) and increased temperature of the solvent stripping fluid, it is possible to reduce the solvent concentration on or in the fiber polymer to less than about 10,000 ppmw, even to less than 1000 ppmw, or even less than about 300 ppmw. Depending, of course, on the affinity of the particular spinning solvent for the fiber polymer, it may be advantageous to incorporate more than one solvent stripping station into the solvent stripping apparatus, so as to reduce the residual solvent concentration in multiple steps. The temperature, vacuum pressure and even the fresh solvent stripping fluid itself can be individually controlled within each solvent stripping station. Polymer/solvent combinations which can benefit from the present invention are those in which the polymer exhibits a strong affinity for the solvent, particularly those in which chemical bonding occurs between the polymer and the solvent, such as hydrogen bonding and the like. Some combinations of polymer/solvent which are difficult to separate are polyamide/formic acid and polyvinyl alcohol/water.

EXAMPLES

The examples below were prepared from a polymer solution having a concentration of 24 wt% of nylon 6,6 polymer, Zytel® FE3218 (available from E. I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in formic acid solvent at 99% purity (available from Kemira Oyj, Helsinki, Finland) that was electroblown to form a nonwoven web containing some residual solvent. The heavier basis weight examples were collected at lower collection belt speeds, and the solvent stripping parameters were varied as set forth in the Table. The residual formic acid content in the nonwoven sheets of nylon was determined using standard wet chemistry techniques and ion chromatography analysis. In a typical determination, a sample of known mass was placed in caustic solution. An aliquot of the resulting solution was analyzed by ion chromatography and the area under the peak corresponding to neutralized formic acid (formate anion) was proportional to the quantity of formic acid in the sample.

Comparative Example 1 (Control)

Example 1 was prepared as set forth above, but was not subjected to the solvent stripping process of the present invention. The initial level of solvent upon web laydown was 46.2 wt% of the nonwoven web.

Comparative Example 2

Comparative Example 2 was prepared in the manner of Comparative Example 1 , except rather than collecting and analyzing the nonwoven sheet directly after laydown, the nonwoven web was transported into a solvent stripping zone on a moving porous screen. A solvent stripping fluid of air at a temperature of 25 ⁰ C was impinged onto the nonwoven web from one side while a vacuum was applied to the other side of the nonwoven web. The vacuum was measured at 58 mm H ₂ O. The air pressure and the vacuum were coupled to yield a near constant atmospheric pressure in the solvent stripping zone. The nonwoven web remained in the solvent stripping zone for 9.5 seconds. The final basis

weight of the nonwoven web was 5.2 g/m ² . The final solvent level was 1.0 wt% of the nonwoven web.

Comparative Examples 3-4

Comparative Examples 3-4 were prepared in the same manner as Comparative Example 2, except a slower collection belt speed was employed, resulting in higher basis weights and longer residence times in the solvent stripping zone. At these higher basis weights it was necessary to employ higher vacuum levels to maintain solvent stripper fluid flow through the web. A consequence of the solvent stripping zone time increase was the removal of additional solvent (on a weight percentage basis) from the higher basis weight nonwoven webs. A cooling zone was not used. These data and the final solvent level are summarized in the Table.

Examples 1-4

Examples 1-4 were prepared in the same manner as Comparative Examples 2-4, except an elevated solvent stripping zone temperature was used. These data and the final solvent level are summarized in the Table.

TABLE

Solvent Stripping Efficiency

Temperature, Vacuum, Residence Measured Measured Example ⁰ C mm H ₂ O Time, sec Basis Weight, Solvent Cone,

(stripping zone) (stripping zone) (stripping zone) g/m ² wt% (ppm)

CE 1 NA , NA NA 5 46.2 (462,000)

CE 2 25 58 9.5 5.2 1.0 (10,000)

CE 3 25 96 38.1 19.9 2.5 (25,000)

CE 4 25 116 75.9 40.4 2.2 (22,000)

1 90 56 9.5 5.4 0.8 (8,000)

2 90 100 38.1 22.9 0.5 (5,000)

3 90 116 75.9 45.8 0.3 (3,000)

4 150 _* 38.3 30.0 0.03 (300)

"Vacuum Transducer not operational, but vacuum was applied. Air was forced through the sheet to maintain low formic acid partial pressure in vicinity of fibers.

Comparative Example 1 demonstrates the level of stripping solvent which is entrained in the nanofiber webs after the prior art electroblowing process.

Comparative Examples 2-4 show that residual formic acid levels are very high at low stripping temperatures. Even in these cases, the applied vacuum provided convective flow which maintained the low solvent activity levels in vicinity of the fibers, but not enough solvent was removed from the webs to satisfy most commercial applications. These examples also show the effect of residence time. Examples 1 -3 show the effect of elevated stripping temperatures, which removed more residual solvent to levels suitable for some commercial uses.

Example 4 shows that a stripping temperature well in excess of the boiling point of the solvent (101 ⁰ C for formic acid) results in extremely low residual solvent level in the electrospun web.

These examples demonstrate that the solvent stripping zone of the present invention can prepare a solution spun nonwoven web that is substantially free of spinning solvent. Review of the data from the Table show that increasing the solvent stripping zone temperature, vacuum and residence time, improves the efficiency of solvent removal from the nonwoven webs.