SORPTIVE ARTICLES

Abstract: A sorptive article is provided. The sorptive article includes a polyolefin, a wax which is miscible with the polyolefin at the melt temperature of the polyolefin but phase separates on cooling of the article, and sorptive particles distributed in the article. Also provided is a method for removing moisture or other vaporous or liquid material from air or an object in the environment utilizing a novel sorptive article of the invention.

Description: SORPTIVE ARTICLES Field ofthe Invention The present invention relates to polyolefin articles containing soφtive materials and methods of using such articles. Background ofthe Invention Soφtive materials such as desiccants can be supplied in a loose granular form but this can lead to contamination of product with which they come into contact. To overcome this problem, soφtive materials have been supplied as sachets with the particulate sorbent enclosed in a porous material. However, this can lead to clumping ofthe sorbent in one area ofthe sachet and consequent inefficient use ofthe sorbent. To overcome this problem, the soφtive material has been provided as a sachet having multiple discrete connected smaller areas. Soφtive materials have also been incoφorated into polyo ' lefin films, particularly where the soφtive material is used in a multilayer construction to protect a moisture-sensitive layer such as a film of an ethylene/vinyl alcohol copolymer. However, in such constructions the soφtive material absorbs water vapor at appreciable rates only when heated during a retort process. To overcome such problems, films have been developed wherein the films have a polymeric matrix with a system of interconnecting micropores and are loaded with particulate sorbent material which may be a desiccant material. Such films are produced by forming a melt blend ofthe sorbent particles, the polymer and a selected diluent, extruding the film and removing the diluent. The water to be sorbed, generally as water vapor, can then rapidly contact the particulate material through the pores ofthe polymeric matrix, and soφtion ofthe water by the particulate material can be achieved. However, when the sorbent particulate material is thus available for soφtion ofthe water, the film must be carefully stored prior to use to prevent premature soφtion of environmental water vapor and should be protected with a dry atmosphere during manufacturing and converting. In addition to desiccants for soφtion of water, there is also need to sorb other materials such as carbon dioxide and acidic gases and a wide variety of organic materials. Summary ofthe Invention The present invention relates to a soφtive article comprising a polyolefin, a wax which is miscible with the polyolefin at the melt temperature ofthe polyolefin but phase separates on cooling ofthe article, and particulate sorbents distributed in the article. Optionally, the articles ofthe invention may also contain a dispersant for the sorbent. The soφtive articles may be in the form of films, fibers, pellets, beads and other convenient shapes. The soφtive films ofthe invention can be used as formed or the films may be layered or laminated with other films and materials. The present invention further provides a method for removing moisture or other materials from air or an object in the environment comprising providing proximate to said air or object a soφtive article comprising a polyolefin, a wax compound which is miscible with the polyolefin at the melt temperature ofthe polyolefin but phase separates on cooling ofthe article, and soφtive particles distributed in the article. Detailed Description ofthe Invention Polyolefins useful in the present invention include polyethylenes such as high density polyethylene (HDPE), ultrahigh molecular weight polyethylene (UHMWPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE), polypropylene and blends thereof and copolymers of ethylene and propylene. Other useful polyolefins include polybutylene and ethylene vinyl acetate copolymer. Waxes useful in the present invention should be miscible with the polyolefin at the melt temperature ofthe polyolefin and include paraffin waxes, microcrystalline waxes, Fisher-Tropsch waxes, low molecular weight polyethylene waxes preferably having a number average molecular weight of less than about 10,000, more preferably less than about 5000, most preferably less than about 2500, and ethylene-propylene copolymers preferably having a number average molecular weight of less than about 10,000, more preferably less than about 5000, most preferably less than about 2500. Natural waxes such as beeswax, Carnauba wax or candelilla wax can be used, as can vegetable waxes such as obtained by hydrogenating vegetable oils. Molecular sieves are a particularly useful class of soφtive particles for providing desiccant properties to the articles ofthe invention and include synthetically produced crystalline metal alumino-silicates or naturally occurring sources containing crystalline metal alumino-silicates that have been activated for adsoφtion by removing their water of hydration. Because little or no change in structure occurs during this dehydration, unusually highly porous adsorbents are formed that have a strong affinity for water. The pores of any particular type of molecular sieve are uniform in size and of molecular dimensions. The molecular sieves are crystalline zeolites having a basic formula of M 2 /„OxAl 2 O 3 ySiO 2 zH 2 O where M is a cation of n valence. An example of a commercially available molecular sieve is Type 4 A which has the unit cell formula Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ]-27H 2 O. Other useful desiccants include silica gels, silica, clay, activated aluminum, calcium oxide (CaO), CaSO 4 , MgSO 4 and CoCl 2 . A strongly deliquescent desiccant such as CaCl 2 can result in excessive exudation of liquid to the surface ofthe film, which could limit its utility to certain applications. Another useful class of solid desiccants is organic polymers such as polyacrylic acid and salts thereof, polyacrylamides, sulfonated polymers, and cellulosics such as sodium carboxy methyl cellulose. Hydrophobic molecular sieves are also useful. Compared to the hydrophilic molecular sieves (such as Type 4A), these molecular sieves have greatly reduced or no aluminum. Abscents™ molecular sieves, sold by UOP, are an example of a hydrophobic molecular sieve. These are useful for adsoφtion of organic acids, ammonia, aldehydes, sulfur compounds, ketones, indoles, and amines. Hydrophilic molecular sieves are also capable of sorbing these types of organic materials but in the presence of water vapor, soφtion of water vapor tends to predominate. In addition to soφtion of water vapor, potassium carbonate and calcium oxide are useful for soφtion of acidic gases. Calcium hydroxide, formed from reaction of calcium oxide with water, is useful for soφtion of carbon dioxide. Molecular sieves are useful for soφtion of ethylene from wrapped vegetables, fruits, or cheese to extend storage life. Silica and various types of surface treated silicas are useful as adsorbents in a variety of chromatographic separations. For high density polyethylene and polypropylene which have a melt index of about 1 or less according to ASTM Test Method D1238 (190°C/5 kg for high density polyethylene and 230°C/2.16 kg for polypropylene), the soφtive article preferably comprises (1) about 20 to 80 parts by weight polyolefin, (2) about 80 to 20 parts by weight wax such that the sum ofthe parts by weight of polyolefin and wax is equal to 100 and (3) between about 110 volume percent soφtive particles based on the volume of wax and an amount to provide at least about 10 weight percent soφtive particles based on the weight of total film. (That is, there are about 110 volume parts or less soφtive particles measured in their dry state per 100 volume parts of wax; for molecular sieves, this is approximately equivalent to 140 weight parts per 100 weight parts of wax.) More preferably, polyolefin/wax proportions are (1) about 25 to 75 parts by weight polyolefin, and (2) about 75 to 25 parts by weight wax; and most preferably (1) about 30 to 45 parts by weight polyolefin, and (2) about 70 to 55 parts by weight wax.. For polyolefins which have higher melt indexes, e.g., above about 1, the soφtive article preferably comprises (1) about 50 to 80 parts by weight polyolefin, and (2) about 50 to 20 parts by weight wax; more preferably (1) about 55 to 75 parts by weight polyolefin, and (2) about 45 to 25 parts by weight wax; and most preferably (1) about 55 to 70 parts by weight polyolefin, and (2) about 45 to 30 parts by weight wax (the sum ofthe parts by weight of polyolefin and wax being equal to 100); and the soφtive particles comprise between about 110 volume percent soφtive particles based on the volume ofthe wax and an amount to provide at least about 10 weight percent soφtive particles based on the weight of total film. For ultrahigh molecular weight polyethylene (such as GUR 4132 made by Hoechst Celanese; UHMWPE generally has a molecular weight above about 2-6 million, and has a melt index of substantially zero), very high amounts of wax may be used. For example, a soφtive article comprising UHMWPE, generally comprises (1) about 2 to 50 parts by weight UHMWPE and (2) 98 to 50 parts by weight wax, and more preferably (1) about 4 to 20 parts by weight UHMWPE and (2) 96 to 80 parts by weight wax. Preferably, the soφtive particulate is provided as a fine powder and sufficiently dry such that it can be used without grinding or drying. If the soφtive particulate is not available in powdered form, beads or pellets can be readily ground and mechanically sieved to remove larger particles. Generally, the largest particles should be about ten times smaller than the smallest orifice that they must pass through during processing. A dispersant is optionally added to the mixture of wax and soφtive particulate to aid in wetting out and dispersing the soφtive particulate in the wax. The more thorough the dispersion of particles the better, though some sorbent particles have been found to be effective even when grouped or clumped together, i.e., agglomerated. On a macro scale, the distribution is generally rather uniform, e.g., adjacent cubic millimeters in the soφtive portions of articles ofthe invention preferably contain similar numbers of particles or agglomerates. The wax phase separates from the polyolefin in a distributed manner so that wax is distributed throughout the soφtive article. Preferably, the dispersant is a polymer which has a molecular weight below about 10,000 and which stabilizes the dispersion by steric interaction between the particles. Preferably, the dispersant is present in an amount of about 1 to 10 weight percent based on the weight ofthe soφtive particulate and is a solid at ambient temperatures to minimize exudation to the surface ofthe final shaped article. Useful dispersants include HYPERMER™ B246, HYPERMER™ LP1, and HYERMER™ LP4, available from ICI Specialty Chemicals Co. Nucleation ofthe polyolefin as the blend of polyolefin and wax cools and phase separation occurs may be enhanced (e.g., the rate of crystallization increased) in some articles ofthe invention by the effect of a nucleating agent. The particulate sorbent or crystallites ofthe wax in an article ofthe invention may act as a nucleating agent, such that a separate nucleating agent is not needed. Other useful nucleating agents have been taught in the prior art, especially when the polyolefin is polypropylene, to increase the rate of crystallization ofthe polymer, which tends to increase the strength ofthe article. Useful nucleating agents include aryl alkanoic acid compounds, benzoic acid compounds, and certain dicarboxylic acid compounds as disclosed in U.S. Pat. No. 4,726,989 (Mrozinski), which is incoφorated herein by reference. Polymeric pigments may also be used as nucleating agents as is known in the art. The nucleating agent preferably comprises about 0.1 to 5 parts by weight ofthe polyolefin weight. Soφtive articles ofthe invention that change color as vapor or other material is sorbed are advantageous to show that soφtion has occurred and to show the degree of soφtion that has occurred. Commercially available desiccants may have a color indicator incoφorated into the desiccant (color-indicating grades of molecular sieves, silica gel, and activated alumina from ADCOA and color indicating grade of Drierite (CaSO 4 ) from W. A. Hammond Drierite Co., for example). Products ofthe invention can be made color-indicating by incoφoration ofsuch color-indicating desiccants or other sorbent particulates. Other products ofthe invention are made color-indicating through incoφoration of other color-indicating agents such as finely powdered CoCl 2 . When mixed with a non-indicating soφtive particulate such as molecular sieves and silica gel, CoCl 2 achieves good correlation between color change and the percent of material sorbed. CoCl 2 itself is a desiccant having a fairly high adsoφtive capacity, picking up six waters of hydration, and may be used as a soφtive particle by itself. When CoCl 2 is used in an amount equal to about one percent of total film weight, it provides a color change that can be seen by eye for about 10 mil thick (250- micrometer-thick) films. The amount needed will depend upon film thickness and also on percent particulate in the film. In any case, this is something that can be determined easily through simple experimentation. CoCl 2 is deliquescent, but problems with exudation of liquid to the film surface can be avoided by grinding the CoCl 2 to a fine powder (< 50μ, more preferably <25, most preferably <10μ). Films made containing 5 wt. % of finely powdered CoCl 2 in combination with Type 4A molecular sieve or silica gel showed no liquid exudation when tested at 50% RH/20°C. The articles ofthe present invention can be prepared using either a batch or continuous method. In the batch process, the wax is melted, and the dispersant (if used) is added and mixed into the wax, whereupon the soφtive particulate is added while mixing continues. The polymer is added with continued mixing and heating until a homogeneous melt is formed. The melt can then be pressed between plates to form a film or molded into pellets, beads, or other desired forms. In the continuous process, the wax is heated to melt (e.g., by using a hot plate). Then, a dispersant (when used) is added, followed by addition ofthe soφtive particulate while mixing using a high shear mixer such as a dispersator. Mixing is continued until the soφtive particulate is well mixed in the wax. This wax particulate mixture is then heated at about 150 to 180°C for 15 to 45 minutes to degas it. The wax particulate mixture is fed to an extruder, preferably a twin screw extruder, concurrently with the polyolefin, where the wax particulate mixture and the polymer are thoroughly melt blended. The melt is extruded and quenched, for example by casting the extrudate as a film onto a temperature-controlled, smooth or patterned (e.g., as described in U.S. Pats. 5,120,594 and 5,238,623) casting wheel or by forming a blown film in air, to cause thermally induced phase separation. Alternatively, the melt may be extruded as pellets or fibers or ropes. At least for thicker material such as ropes or strands, the extrudate is generally quenched in a non-sorbent liquid such as a liquid fluorocarbon (e.g., 3M's Fluorinert FC 77) or in some cases in water followed by drying. The soφtive article can be used as formed or molded into other shapes as desired. With either the batch or continuous method, the article is completed without extracting the wax from the article. The presence ofthe wax moderates the adsoφtion rate ofthe soφtive particulate to provide rates which are much slower than for soφtive particulates (such as molecular sieves) in porous films and which are much faster than for soφtive particulates in polyolefin alone. Thus, the soφtive articles ofthe invention are storage stable, yet efficient. Another advantage arising from use ofthe wax is the ability to have higher loadings of soφtive particles than would otherwise be possible. The inclusion ofthe wax lowers the viscosity ofthe melt, which allows more particulate to be added. Also, the rate of soφtion can be affected through choice of wax and proportion of wax relative to polymer. Soφtive articles ofthe invention are soφtive whether or not they are porous. Apparently, vapor can pass through the polyolefin/wax mixture surrounding the soφtive particle. However, the wax generally retards soφtion (in comparison to an article in which there is a void in the article in the places otherwise occupied by the wax) and prevents premature soφtion. The rate of soφtion can be increased by making the soφtive article (generally a film, but also fibers, strands or ropes) porous by stretching. Soφtive articles of the invention can be sold as non-porous films and activated before use by stretching for rapid adsoφtion. Soφtive articles ofthe invention that become porous upon stretching generally include at least 15 or 20 volume percent soφtive particles. Best results so far have been achieved with molecular sieves. Articles ofthe invention, especially when in film form, may carry a film or sheet laminated to one or both sides, for example, to close or seal one side ofthe article and direct its soφtive activity to the other side. Also, removable films may be laminated to the article to protect the article from premature absoφtion. Good films for performing such a sealing or inhibiting function include film or sheets meeting United States Military Specification MLL-B-131H, Type 1, Class 1, such as Marvelseal 470 (from Ludlow Coφ., Laminating and Coating Division Exeter, NH) or FR 2175-B or Foil Pak 6 from Bell Fibre Products Coφ., Columbus, GA. Typically these sheets or films comprise a metal foil and often also include another layer such as a heat-sealable polymeric layer. In other embodiments, a film or other article ofthe invention is incoφorated into packaging such as envelopes, where the film or other article is protected from premature soφtion and is ready to act as a sorbent when contents needing protection are placed in the packaging. The following examples further illustrate this invention, but the particular materials and amounts thereof in these examples as well as other conditions and details, should not be construed to unduly limit this invention. In the examples, all parts and percentages are by weight unless otherwise specified. Soφtive Activity Test Films prepared were tested for water vapor soφtive activity according to the following method. A sample of film is weighed and exposed to 50% relative humidity at 20°C unless otherwise indicated. The sample is weighed periodically until no further increase in weight is observed. The time required for adsoφtion of 10%, 50% and 90% ofthe maximum quantity sorbed were determined by inteφolation ofthe data. For molecular sieves, the maximum weight increase was typically about 85 to 95% ofthe theoretical maximum which was calculated from the film weight, the percent molecular sieves in the film, and the soφtive activity of the molecular sieves. The soφtive activity of Type A molecular sieves was typically about 20-22% by weight as received and about 28% by weight for Type 13X. Mixing Method The examples teach films prepared by a continuous method using an extruder (described in Example 1, sometimes referred to as the Extruder Method) or a batch method (described in Examples 14-17, sometimes referred to as the Batch Method). Example 1 Wax, 55.2 weight percent of total film composition, X-2044, available from Petrolite Coφoration, and 1 weight percent HYPERMER™ B246 dispersant available from ICI Specialty Chemicals Co., were heated to about 100°C until melted. Desiccant, 11.4 weight percent of total film composition Type 4 A molecular sieve powder, obtained through Oxygen Service Co. (St. Paul, MN), was added to the wax mixture while mixing under high shear conditions using a dispersator, Model 89, available from Premier Mill Coφoration. After wetting out the desiccant in the molten mixture of wax and dispersant, the dispersator speed was increased to the maximum speed that did not cause discharge ofthe mixture from the mixing container, about 2000 φm, for 1 min. The dispersator speed was then lowered to a speed sufficient to continue the mixture stirring while maintaining the mixture at about 150°C for 30 min. The mixture was then pumped into a 25- mm-diameter-825- mm-long twin screw extruder using a gear pump. The gear pump was enclosed and the air around it heated. All lines were heated to a temperature at least as high as the melting point ofthe wax. The wax/desiccant mixture was pumped into an intermediate extruder zone. High density polyethylene, 32.8 weight percent GM 9255, available from Fina Oil and Chemical Co., was dropped into the feed throat using a gravimetric feeder. The extruder barrel temperature ranged from 270 to 170°C (520-340°F) down the length ofthe barrel with a screw speed of 120 φm. The mixture was extruded through a 20 cm wide die at about 245°C onto a smooth casting wheel maintained at about 71 °C. The thus-prepared film was wound on a plastic core, placed in a vapor tight container flushed with dry gas and sealed. The film was 0.25 mm thick and was tested for desiccant activity. The film adsorbed 10% the maximum quantity adsorbed in 0.8 hours, 50% in 22 hours and 90% in 63 hours. Examples 2-8 In Examples 2-8, films were prepared as in Example 1 except the extruder barrel temperature range was about 280 to 255°C, the die temperature was 255°C, the polyolefin was FINA™ 2804 high density polyethylene and the waxes used were AC 1702 low molecular weight polyethylene available from Allied- Signal Coφ. (Example 2), M-5150 microcrystalline wax available from Moore & Munger Marketing, Inc., (Example 3), X-2025 branched polyethylene/polypropylene copolymer wax available from Petrolite Coφ. (Example 4), PETROWAX™ 8618 microcrystalline wax available from Moore & Munger Marketing, Inc., (Example 5), X-2018 branched polyethylene/polypropylene copolymer wax available from Petrolite Cθφ..(Example 6), and PARAFLINT™ C80, a Fisher-Tropsch wax available from Moore & Munger Marketing, Inc. (Examples 7 and 8). Each film contained one weight percent dispersant and the amounts of wax and Type 4 A molecular sieves are set forth in Table 1. The films were tested for desiccant activity and the results are set forth in Table 2. Table 1 Table 2 Example Time Required to Reach Given No. Percent Adsoφtion in Hours at 50% RH/20°C 10% 50% 90% 2 2.0 23 90 3 1.8 45 129 4 2.6 39 115 5 4.5 87 276 6 2.9 47 157 7 6.8 79 264 8 8.2 73 232 Examples 9-13 In Examples 9-13, films were made as in Example 1 except the extruder barrel temperature range was about 250 to 190°C and the die temperature was about 190°C, the polyolefin was DS-5D45 polypropylene available from Shell Chemical Co., the wax was AC 1702 low molecular weight polyethylene available from Allied Signal Coφ., The desiccant type was as is indicated in Table 3, each being available from Oxygen Services Co., and the amounts of polypropylene, wax, dispersant and desiccant and the extruder conditions were as set forth in Table 3. MTLLAD™ 3905 from Milliken Chemical was added with the polypropylene at 0.3 wt. % relative to weight of polypropylene as nucleating agent. The films were 0.18 to 0.20 mm thick. The films were tested for desiccant activity and the results are also set forth in Table 4. Table 3 Table 4 Example Time to Reach Given % No. Adsoφtion (in hours) 10% 50% 90% 9 0.5 5.5 18.8 10 0.5 3.8 17.2 11 0.5 4.0 17.3 12 0.5 5.5 18.8 13 0.5 5.5 18.3 Examples 14-17 and Comparative Examples C1-C4 In Examples 14-17, films were made by the Batch Method containing 30 weight percent polyolefin, 54.2 weight percent AC 1702 wax, 15 weight percent Type 4A molecular sieves and 0.8 weight percent B246 dispersant. In Comparative Examples C1-C4, films were made containing 15 weight percent Type 4 A molecular sieves and 85 weight percent polyolefin. The polyolefins used were FINA™ 2804 high density polyethylene available from Fina Oil and Chemical Co. (Example 14 and Comparative Example Cl), ATTANE™ 4602 linear low density polyethylene available from Dow Chemical Co. (Example 15 and Comparative Example C2), HIMONT™ 6723 polypropylene available from Himont USA, Inc. (Example 16 and Comparative Example C3), and EXXON™ 3014 polypropylene available from Exxon Co. (Example 17 and Comparative Example C4). The polyolefin, wax and nucleating agent were mixed in a RHEOCORD SYSTEM 40™ available from Haake Buchler at 20 φm with heat until soft. The mixing speed was then increased to 100 φm and the dispersant and desiccant were added in small portions at two minute intervals. Mixing continued until the melt was homogeneous, 30 minutes at 270°C for Example 14 and Comparative Example Cl, 20 minutes at 230°C for Example 15 and Comparative Example C2, 20 minutes at 270°C for Example 16 and Comparative Example C3, and 20 minutes at 230°C for Example 17 and Comparative Example C4. A portion ofthe melt was withdrawn and pressed into a film between aluminum plates that were covered with 0.18- millimeter-thick polyester film using a hydraulic press heated to 180°C. The mixture was heated in the press for the indicated time and temperature with no force applied by the press during a 5 minute interval and then the press was closed fiilly for 15 seconds followed by opening ofthe press and removal ofthe resultant film. Shims were inserted to achieve film thickness of about 0.5 mm. Each film was tested for desiccant activity. The results are set forth in Table 5. Table 5 Example Time to Consume Given % of Theoretical No. Maximum Adsorbed (in hours) 10% 50% 90% 14 2.5 59 165 15 2.5 60 202 16 3 34 110 17 2 37 116 Cl 20 565 2100 C2 6 100 420 C3 11 210 740 C4 14 270 1100 Examples 18-26 In Examples 18-26, films were made by the Extrusion Method as in Example 1 except the films contained AC 1702 wax and the polyolefins used were GM 9255 high density polyethylene available from Fina Oil and Chemical Co. (Example 18), 2804 high density polyethylene available from Fina Oil and Chemical Co. (Example 19), 25355N high density polyethylene available from Dow Chemical Co. (Example 20), 65053 high density polyethylene available from Dow Chemical Co. (Example 21), 4005 low density polyethylene available from Dow Chemical Co. (Example 22), ATTANE™ 4602 linear low density polyethylene available from Dow Chemical Co. (Example 23), 6723 polypropylene available from Himont USA, Ltd. (Example 24), 7823 ethylene-propylene copolymer available from Himont USA, Ltd. (Example 25), and HTFAX RA061 ethylene-propylene copolymer available from Himont USA, Ltd. (Example 26). The amount of each component and the extruder conditions are set forth in Table 6. The desiccant was Type 4 A molecular sieve and the dispersant was Hypermer B246. The film of Example 24 also contained 0.1 wt. % Millad 3905 nucleating agent. Each film was tested for desiccant activity. The results are set forth in Table 7. Table 6 Table 7 Ex. No. Film % RH Time to Reach Given % Thickness 20°C Adsoφtion (in hours) (mm) 10% 50% 90% 18 0.24 50-60 0.4 9 28 19 0.23 50-60 0.6 13 42 20 0.28 50 1.5 18 .50 21 0.28 50 0.9 16 43 22 0.25 55-60 0.6 11 34 23 0.24 55-60 0.8 16 40 24 0.20 50-60 0.3 5 20 25 0.28 50 0.7 10 27 26 0.28 50 0.8 9 23 Example 27 A film was prepared by the Extrusion Method as in Example 1 except the film contained 63.2 parts by weight X-2044 ethylene-propylene copolymer wax available from Petrolite Coφ., 0.7 parts by weight HYPERMER™ B246 dispersant available from ICI Chemical Co., 15 parts by weight Type 4A desiccant, and 22 parts by weight DS-5D45 polypropylene available from Shell Chemical Co. The extruder barrel temperature was 270-193 °C (520-380°F), the die temperature was 193 °C (380°F), the screw speed was 120 φm. The film formed had a thickness of about 0.27 mm. The film was tested for desiccant activity. The film adsorbed 10% ofthe theoretical maximum in 1.9 hours, 50% adsoφtion in 31 hours and 90% adsoφtion in 111 hours. Examples 28 and 29 In Example 28, a film was prepared by the Extrusion Method as in Example 1 except the film contained 49.7 parts by weight AC 1702 wax available from Allied-Signal Coφ., no dispersant, 25.5 parts by weight Type 4A desiccant, and 24.8 parts by weight DS-5D45 polypropylene available from Shell Chemical Co. The extruder barrel temperature was 270-193°C (520-380°F), the die temperature was 193 °C (380°F), the screw speed was 150 φm. The film formed had a thickness of about 0.28 mm. The film was tested for desiccant activity. The film had 10% adsoφtion in 1 hour, 50% adsoφtion in 19.7 hours and 90% adsoφtion in 60 hours. In Example 29, a film was made as in Example 28 except 2.5 weight percent HYPERMER™ B246 disperant based on the weight ofthe desiccant was added. The film was tested for desiccant activity. The film had 10% adsoφtion in 1.0 hour, 50% adsoφtion in 21.3 hours and 90% adsoφtion in 65 hours. Example 30 A film was prepared using the Batch Method generally described in Examples 14-17 except the polyolefin was DS-5D45 polypropylene available from Shell Chemical Company. The wax was paraffin, Catalog No. 32720-4 from Aldrich Chemical Co., the desiccant was Type 4A molecular sieve and the dispersant was HYPERMER™ B246. The amounts of each component were: polypropylene - 30 parts by weight; wax - 54 parts by weight; desiccant - 15 parts by weight; dispersant - 0.8 parts by weight. The components were mixed in a batch mixer at 290°C for 20 min. and the resulting mixture was pressed at 135°C to achieve a film thickness of 0.22 mm. The film was tested for desiccant activity. The film had 10% adsoφtion in 0.7 hour, 50% adsoφtion in 22 hours and 90% adsoφtion in 89 hours. Examples 31-36 Soφtive films were prepared by the Batch Method using UHMWPE (ultrahigh molecular weight polyethylene; grade GUR 4132 from Hoechst-Celanese, specified by the manufacturer as having a molecular weight between 4 to 5 million); waxes (either AC 1702 from Allied Signal or M-5150 from Moore and Munger); and a molecular sieve (Type 4A, in powder form, from Oxygen Supply Services, St. Paul, MN). The batch mixing conditions were 150°C for 15 min. at 100 φm. The material was reheated in the press at 160°C for 3 minutes while gradually closing the press and then heated for 5 minutes with the press fully closed. Metal shims were used to limit press closure. Tables 8 and 9 provide compositions and water vapor adsoφtion results, respectively. Table 8 Example Wt. % Wax, Wt. % Desiccant, PE/Wax Thickness UHMWPE Wt. % Ratio mils (mm) 31 4.00 M-5150 4A MS, 7.7/92.3 10-11 48.00 48.00 (0.25-0.28) 32 0.84 AC 1702 4A MS, 2/98 9-10 41.42 57.74 (0.23-0.25) 33 4.00 AC 1702, 4A MS, 6/94 9-10 62.90 42.10 (0.23-0.25) 34 15.16 AC 1702, 4A MS, 30/70 10-12 35.37 49.47 (0.25-0.30) 35 29.45 AC 1702, 4A MS, 50/50 10-11 29.45 41.10 (0.25-0.28) 36 2.15 M-5150, Syloid AL-1 5/95 11-12 40.80 57.08 (0.28-0.30) Table 9 Example % of Theo. mg water/gram Time to Reach Given % of Actual Wt. Wt. Gain film Gain in Hours 10% 50% 90% 31 102 99 2.7 36.5 113.6 32 96 125 1.0 21 52 33 93 62 1.6 22.9 86.2 34 92 102 5.0 98 335 35 91 84 5.0 85 290 36 77 118 3.5 49 240 Examples 37 and 38 Soφtive films were prepared by the Batch Method using polybutylene (PB) (Example 37) and ethylene vinyl acetate (ENA) (Example 38) as polyolefins. The PB was grade DP 8010 (a co-polymer containing 6% ethylene), from Shell Chemical Co. The ENA was Elvax 265 (28% vinyl acetate), from the Du Pont Co. (Wilmington, DE). The wax was C 1702, from Allied Signal. In several examples, a small amount of Irganox 1010, an antioxidant from Ciba Geigy, was added to minimize degradation. Mixer conditions were 270°C for 30 min. at 100 φm for examples 37, 38 and comp. 5 and 150°C for 10 minutes at 100 φm for example Comp. 6.. Press conditions were 180°C for 5 min. for Examples 37, 38, and comp. 5 and 160°C for 5 min. for Comp. 6. Comparative examples (C5 and C6) were prepared without any wax. For Comparative Example 5, molecular sieves and PB without any wax, the rate of adsoφtion was slower than for Example 37, which contained wax. For Comparative Example 6, molecular sieves and ENA without any wax, the rate of adsoφtion was somewhat faster than for Example 38. In either case, addition of wax is useful for controlling the rate of adsoφtion through choice of type of wax and amount. Also, wax facilitates processing by, e.g., reducing the tendency of ENA to crosslink. Table 10 Table 11 Example % of Theo. mg water/gram Hours to Reach Given % of Actual Wt. Wt. Gain film Gain 10% 50% 90% 37 91.3 55.6 0.7 8.0 30.0 Comp. 5 86.7 50.1 1.1 18.0 65.0 38 74.7 39.2 0.4 2.7 16.0 Comp. 6 80.6 45.3 0.3 2.0 6.0 Examples 39 and 40 Soφtive films were prepared by the Batch Method from polypropylene, Type 4 A molecular sieve, and two different waxes: a higher molecular weight, highly branched wax (Epolene C-10; Eastman Chemical Co.; described by its manufacturer as a highly branched, medium molecular weight PE wax having an M w of 35,000 and M„ of 7,700 as determined by GPC) and beeswax (a bleached, white grade obtained from Aldrich; Cat. No. 24,322-1). Mixer conditions were 270°C for 30 min. at 100 φm. Press conditions were 180°C for 5 min. Table 12 Table 13 Example % of Theo. mg water/gram Hours to Reach Given % of Actual Wt. Wt. Gain film Gain 10% 50% 90% 39 91.9 53.1 1.5 26.0 83.0 40 104.6 60.4 1.5 21.0 66.0 Examples 41-46 Soφtive films were prepared by the Extrusion Method from polypropylene (PP) (Shell DS 5D451) (Examples 41-45) or high density polyethylene (Shell 1285) (HDPE) (Example 46) and AC 1702 a low-molecular- weight polyethylene wax from Allied Signal and dispersants and desiccants as listed in Table 16. Table 14 lists conditions under which the desiccants were dried before mixing into the wax, and also lists the weight gain of particles alone, before incoφoration into the soφtive film as determined at 50% RH 20°C. The calcium oxide used did not require drying. The other desiccants were dried at 250°C for 18 hours before using, except that potassium carbonate was dried at 150°C for 18 hours. The potassium carbonate was nominally -325 mesh powder but contained large agglomerates, so it was ground using an electric coffee grinder and passed through a 270 mesh wire sieve. Table 14 Desiccant Source/Cat. No. % Wt. Gain at Drying Conditions 50% RH/20°C Temp. (C) Hours Calcium Oxide Alfa/#10923 39.1 - - Potassium Carbonate Aldrich/34,782-5 107.6 150 18 Magnesium Sulfate Alfa/#33337 85.0 250 18 Syloid AL-1 Grace Davison 25.0 250 18 (silica gel) Hi-Sil SBG PPG Industries 7 250 18 (silica) Extrusion conditions are given in Table 15 and compositions in Table 16. The films were cast onto a pattemed casting wheel having a pattem of micro-sized pyramids on the surface with the wheel at a temperature of 120°F in Example 41 and at 150°F in the other examples. There were 100 pyramids per square inch (15.5 per square cm). The pyramids were 45°, four-sided, and were 5 mil (0.13 mm) high. Table 15 Example Extruder Barrel Temp. Screw RPM Die Temp. (°F Total lb./hr. Range (°F) (°C) (°C) (kg/hr) 41 520 to 350 (271-177) 120 350 (177) 8.25 (3.74) 42 520 to 360 (271-182) 120 360 (182) 7.88 (3.57) 43 520 to 350 (271-177) 120 350 (177) 8.10 (3.67) 44 520 to 350 (271-177) 150 350 (177) 8.62 (3.91) 45 520 to 360 (271-182) 120 360 (182) 7.86 (3.57) 46 520 to 460 (271-238) 120 460 (238) 7.85 (3.56) Table 16 Adsoφtion results for these films are given in Table 17. The results show that these desiccants in polyolefin/wax films adsorb a significant percent ofthe amount of water adsorbed by the same amount of virgin desiccant at 50% RH/20°C. In comparing rate results, it is helpful to also look at the total amount of water adsorbed by the film in terms of mg of water per gram of film. Thus, for Example 43, the time required to reach a given percent ofthe total amount adsorbed was long compared to the other examples but the amount of water adsorbed in the time required to reach 10% adsoφtion was large (10% of 242 mg water/g film=24 mg water). It is also useful to compare the initial rate of adsoφtion. Note in particular that there was a long induction period for calcium oxide during which little adsoφtion of water vapor took place. Two initial rates are given for calcium oxide: one for the very beginning ofthe adsoφtion curve (0.073 mg/g film-hr.) and for the following portion ofthe curve where the rate becomes much more rapid (0.75 mg/g film-hr.). This induction period is useful for providing an extended period of time during manufacturing and converting during which the film can be exposed to ambient conditions without significant loss of adsoφtive capacity. Table 17 Examples 47-50 Soφtive films were prepared by the Batch Method from compositions as described in Table 18. The desiccants were silica gel (grade Syloid AL-1 from Grace Davison; it was dried at 250°C for 18 hr. before mixing; the dried powder adsorbed 25.00 wt. % water at 50% RH/20°C); clay (obtained from sachets of Desiccite 25, obtained from Englehard Coφ. (Jackson, MS); the material from inside the sachet was ground using an electric coffee grinder and dried at 150°C for 24 hr.; the resultant powder adsorbed 20.1% by weight water at 50% RH/20°C); and cellulose gum (sodium carboxy methyl cellulose from Fisher Scientific Co. (Cat. No. S-170); it was dried at 70°C in a vacuum oven for 24 hr.; the dried powder adsorbed 23.1% by weight water when exposed at 50% RH/20°C). The polypropylene used was grade DS 5D45 from Shell. For Examples 47, 48, and 50, mixing conditions were 270°C for 30 min. at 100 φm, and then 230°C for 5 min. at 100 RPM. For Example 49, mixing conditions were 200°C for 30 min. at 100 RPM. Press conditions for these examples were 180°C for 5 min. A lower mixing temperature was used for Example 49 to avoid degradation ofthe cellulose gum. Results are given in Table 19. Table 18 Table 19 Example % of Theo. mg water/gram Initial Rate Time to Reach Given % Wt. Gain film mg water/ of Actual Wt. Gain in g film-hr. Hours 10% 50% 90% 47 60.2 29.6 1.34 2.0 23.0 87 48 79.8 40.1 0.69 6.0 68.0 273 49 86.9 51.0 2.84 1.1 28.0 124 50 78.0 68.2 3.65 1.2 24.0 96 For Examples 47 and 48, note that the film made using M-5150 wax had higher adsoφtivity than the analogous film made using AC 1702 wax. The same was true for Example 50 compared to Example 44. For porous desiccants such as clay, silica gel, and type 13X molecular sieves, lower adsoφtivity was observed typically for use of AC 1702 wax than for other waxes. This was not the case for type 3 A, 4A, and 5A molecular sieves. The reason for this is believed to be that low molecular weight components (oils) of AC 1702 wax penetrate the pores of desiccants having larger pores. Thus, for the noted types of porous desiccants, use of waxes having low oil content, higher MW waxes, and branched waxes will result in higher soφtivity after incoφoration into a polyolefin/wax film. Examples 51-64 The following examples illustrate preparation of soφtive films ofthe invention which change color upon adsoφtion of water. This was done in two ways: 1) by using a commercially available color-indicating desiccant which had the color-indicating substance integrated into the desiccant; or 2) by adding cobaltous chloride (CoCl 2 ) to the composition along with a desiccant. Compositions are given in Table 20 and results are reported in Tables 21 and 22. The PP used was grade DS 5D45 from Shell. The X-2044 wax used was a developmental grade from Petrolite Coφoration Polymers Division having an average molecular weight of 805 (by vapor phase osmometry). Cobaltous chloride hexahydrate from Mallinckrodt Chemical Works (St. Louis, MO) was dried at 150°C for 48 hr. For use in the Extrusion Method, the dried CoCl was ground in a ball mill (5 L jar, 1000 g of CoCl 2 , 2.5 L of balls ranging in size from 60 to 190 mm for 16 hr.). For use in the Batch Method, all desiccants were ground into a fine powder using an electric coffee grinder. Indicating Drierite (CaS0 4 plus CoCl 2 ), from W. A. Hammond Drierite Co. (Xenia, OH), was ground into a fine powder using an electric coffee grinder for 2 min. and dried at 180°C. for 24 hr. Indicating grades of molecular sieve, silica gel (grade GR 42), and activated alumina (grade F- 200) from Adsorbents and Desiccants Coφ. of America (Gardena, CA) were ground into a fine powder using an electric coffee grinder for 2 min. but used without additional drying. Syloid AL-1 silica gel in fine powder form from Grace Davison was dried at 250°C for 24 hr. For the Extrusion Method, extrusion conditions were: barrel temperature, 271-182°F; screw φm, 120; die temperature, 182°F; micropyramid-surfaced casting wheel (described in Ex. 41-46) at 66°C; and 5.58 kg/hr. total throughput rate for Example 55 and 4.63 kg/hr. for Example 61. Compositions made by the Extrusion Method also contained 1.3 wt. % Hypermer B246 dispersant. For the Batch Method, mixing conditions were 270°C for 30 min. at 100 φm and pressing conditions were 2 min. at 180°C for Examples 53, 57, and 60 and 5 min. at 180°C for the others. Water vapor adsoφtion experiments were done at 50% RH/20°C using an environmental chamber from Thermotron, except for Examples 57 and 60, which were evaluated under ambient conditions (66 to 73% RH 21 to 23°C). Useful color changes were observed in most cases. The final color change corresponded typically to about 80% or higher ofthe observed maximum weight gain, except for Examples 57 and 59. It is desirable for the indicator to display the final color change after a high percent ofthe desiccant has been used up. For films containing added CoCl 2 , the theoretical weight gain was calculated using the weight of desiccant in the film times its activity plus the weight of CoCl 2 in the film times its activity. Example 51 illustrates use of just CoCl 2 by itself as both desiccant and color change agent. Examples 52-55 illustrate the use of Type 4 A molecular sieve (MS) as the desiccant in combination with added CoCl 2 . The lower than usual % wt. gain for Example 53 was due to longer than usual exposure ofthe molecular sieves during film preparation. Note that a blue to pink color change was observed for Examples 52 and 53, whereas the color change for Example 54 was blue to gray. This was due to use of CoCl 2 at a significantly lower % of total film weight than for Examples 53 and 54, 1 wt. % vs. about 5 wt. %. Note that the color change is affected by the color ofthe polymer and the wax and by color, usually tan, that develops due to degradation during processing in the batch mixer. At lower loadings of CoCl 2 , these other sources of color will affect the overall color to a greater extent. Example 55 is similar to Example 53 except that the former was prepared using the extruder, whereas the latter was prepared using the batch mixer. The difference in color change between Examples 53 and 55 was due to the use of a dispersant in Example 55 (1.3 wt. % Hypermer B246) whereas no dispersant was used in Example 53. The color change for Example 55 was from blue to lighter blue, whereas the color change for Example 53 was the more typical blue to pink change. Example 56 illustrates the use of a color-indicating grade of molecular sieve which resulted in a change in color from turquoise to tan. Examples 57-61 illustrate the use of silica gel (Syloid Al-1) in combination with added CoCl 2 at various loadings using two different waxes, AC 1702 and X2044, respectively. Examples 57-60 and 62 were made using the batch mixer and Example 61 (which also included 1.3 wt. % Hypermer LPl) using the extruder. Note the higher % of theoretical weight gain for the examples using X-2044 wax, Example 57 compared to AC 1702 wax, Example 61. The lack of color change for Example 60 as compared to Examples 56-59 and 61 showed that about >0.8 wt. % CoCl 2 as a percent of total film weight is needed in this composition to obtain a perceptible color change. The indicating grade of silica gel, GR 42, was used for Example 62, for which no perceptible color change from the initial gray occurred. This material as purchased consisted of very large, pale blue crystals, so it wasn't suφrising that the amount of color indicator present wasn't sufficient to show a color change after grinding into fine particulate. Table 20 Example PP Wax, Wt. Desiccant, Wt. % Added CoCl 2 , Irganox Method Wt. % % Wt. % 1010, Wt. % 51 24.7 AC 1702 - 25.0 None Batch 50.00 % 52 24.7 X-2044 4A MS 4.9 % None Batch 45.6 % 24.7 % 53 24.7 AC 1702 4A MS 4.9 % None Batch 45.6 % 24.7 % 54 24.7 AC 1702 4A MS 1.0 % Yes Batch 49.5 % 24.7 % 55 22.8 AC 1702 4A MS 5.5 % None Extrusion 49.5 % 20.9 % 56 26.0 X-2044 Indicating MS None None Batch 48.0 % 26.0 % 57 24.7 X-2044 Syloid AL-1 4.9 % None Batch 48.0 % 24.7 % 58 24.75 X-2044 Syloid AL-1 0.99 % None Batch 49.51 24.75 59 19.84 X-2044 Syloid AL-1 0.79 None Batch 39.68 39.68 60 24.88 X-2044 Syloid AL-1 0.50 None Batch 49.75 24.88 Example PP Wax, Wt. Desiccant, Wt. % Added CoCl 2 , Irganox Method Wt. % % Wt. % 1010, Wt. % 61 20.7 AC 1702 Syloid AL-1 5.4 % None Extrusion 50.8 % 21.8 % 62 26.0 X-2044 GR 42 Silica Gel None None Batch 48.0 % 26.0 % 63 25.0 AC 1702 F-200 Activated None None Batch 50.0 % Alumina 25.0 % 64 25.0 AC 1702 Indicating Drierite None Yes Batch 50.0 % 25.0 % Table 21 Table 22 Example Hours to Reach Given % of Color Change % of Max. Wt. Maximum Wt. Gain Gain at Final Color Change 10% 50% 90% 51 4.3 80 285 blue-pink 87.5 52 3.2 44 166 blue-pink 93.0 53 2.1 15 58 blue-pink 84.3 54 1.5 26 81 blue-gray 96.1 55 2.1 28 87 blue-light blue 93.0 56 1.2 19 64 turquoise-tan 96.8 57 5 42 145 blue-pink 50.7 58 1.7 26 117 gray - tan 87.7 59 0.3 4.5 44 turquoise - peach 54.6 60 1.2 24 96 None (gray-gray) NA 61 1.7 26 117 blue - pink 76.8 62 0.7 6.5 48 gray-gray NA 63 1.1 18 70 blue-pink 82.8 64 1.4 14 37 blue-colorless 73.7 Examples 65-67 Examples 65-67 illustrate the formation of porous films by stretching polyolefin/wax films that contain hydrophilic molecular sieves. The rate of water vapor adsoφtion is shown to be much faster after stretching than before. Compositions are given in Table 23, processing conditions (the Extrusion Method with a smooth casting wheel) in Table 24, and results in Tables 25 and 26. Table 23 Example Polyolefin Wax 4A MS Hypermer B246 Wt. % Wt. % Wt. % Wt. % 65 PP AC 1702 35.0 % 1.8 % 16.2 % 47.0 % 66 PP AC 1702 45.3 % 2.3 % 13.1 % 39.3 % 67 PP AC 1702 15.8 % 0.8 % 61.9 % 21.5 % The PP used was grade DS 5D45 from Shell and the HDPE was grade 2804 from Fina. CP-11 wax, a copolymer having a MW of 1100 by vapor phase osmometry, was obtained from Petrolite Polymers Division. Table 24 The films were stretched using a film stretcher from the T. M. Long Co. (Somerville, NJ) using a stretch ratio of 2 x 2, and a set point of 110°C. The films were heated for 30 sec. before stretching and for 2 min. after stretching to heat set the films. Development of porosity was shown by the fact that the films became white, and development of through porosity was shown by the bubble point and Gurley results given below. The bubble point is a measure ofthe largest pore size in the film (ASTM F-316) and the Gurley is a measure of resistance to air flow. This value is a measurement of time in seconds to pass 50 cc of air through a film according to ASTM D-726 Method A. Bubble points were determined using Fluoroinert FC-43 (bubble point = 6.64/breakthrough pressure in psi or bubble point = 4.58 x 10 4 /pressure in pascals) available from 3M. Table 25 Example Bubble Point Gurley microns sec/50 cc 65 0.60 91.5 66 6.6 11.3 67 0.09 2840 Results given in the table below for the rate of water vapor adsoφtion show that the rate of adsoφtion is much greater after stretching. Note that for films having the same composition, a thinner film will use up a given percent of its adsoφtive capacity in a shorter time than a thicker film, but the effect of development of porosity in a film on the rate of adsoφtion is much greater than a change in film thickness. In general, higher percentages of sorbent particulate and higher percentages of wax result in larger bubble points, lower Gurleys, and faster rates of adsoφtion. Table 26 Examples 68 - 70 The following examples illustrate soφtion of water vapor by films that did not become through-porous when stretched, though they did become micro-voided since they were whiter than the unstretched film. Though not through-porous, the rate of adsoφtion was much higher for stretched films. Some of this increase in rate was due merely to the decrease in film thickness due to stretching, but the magnitude ofthe increase was much larger than what would be expected due to the decrease in film thickness. Example 68 A film having the following composition was prepared using the Extrusion Method with a smooth casting wheel: 25.0 wt. % HDPE (grade 2804 from Fina), 56.0 % CP 11 wax (a copolymer from Petrolite Polymers having a MW of 1100 by vapor phase osmometry), 18.1 wt. % Type 4 A molecular sieve (obtained from Oxygen Services Company, St. Paul), and 0.9 wt. % Hypermer B246 dispersant (from ICI Americas). The film thickness was about 10.5 mil (0.27 mm). Extrusion conditions were: barrel temperature range, 282-266°C; die, 254°C, screw φm, 135, and casting wheel temperature set point, 88°C. Pieces of this film were stretched by 1.75 x 1, Example 69, and 2 x 2, Example 70, using a film stretcher from the T. M. Long Company at a set point of 110°C (30 sec. pre-heat, 2 min. heat set). The stretched films were non-through- porous as indicated by lack of a measurable Gurley or bubble point. Soφtion of water vapor was determined at 50 % RH/20°C. The molecular sieves used for these films had an adsoφtivity of 22.3 % by weight. Example Stretch Thicknes % of mg Initial Rate Hours to Reach Given Ratio s mils Theo. water/ mg/g film - % Adsoφtion (mm) Wt. gram hr. Gain film 10% 50% 90% 68 0 5 - 7 84.7 34.2 1.6 5.5 208 756 0.13- 0.18 69 1.75 x 7 - 9 82.5 33.3 10.9 0.3 36.9 143 1 0.18- 0.23 70 2 x 2 10.5 93.1 37.6 40.0 0.1 8.9 100 0.27 Examples 71 - 72 These examples demonstrate soφtion of ammonia vapors by films containing a hydrophobic type of molecular sieve, Abscents 3000™, sold by UOP (Molecular Sieve Department, Mt. Laurel, New Jersey). This molecular sieve wasn't completely hydrophobic, as indicated by the soφtion of about 2.4 % water vapor by weight, as determined at 50 % RH/20°C. For hydrophilic molecular sieves, such as Type 4A, up to 28 % by weight water can be sorbed, though soφtion by commercially available material is typically about 20 to 24 % by weight. Example 71 A film was prepared which contained 34.6 wt. % Abscents 3000™, 17.1 wt. % polypropylene (grade DS 5D45, from Shell), 46.6 wt. % AC 1702 wax (from Allied Signal), and 1.7 wt. % Hypermer B246 dispersant (from ICI Americas). This film was prepared using the Extrusion Method and the same micropyramid- surfaced casting wheel used in Examples 41-46 at a set point temperature of 32°C. Extruder temperature ranges were: barrel, 271-171°C; die, 171 °C, screw φm, 120; and total throughput rate of 8.2 lb./hr. (3.72 kg/hr). Film thickness was about 11.0 mil (0.28mm). -33- SUBSTmJTE SHEET (RULE 26) Example 72 A piece of film from Example 71 was stretched 2.5 x 2.5 using a film stretcher from the T. M. Long Company and using a set point of 49°C (30 sec. pre¬ heat and 2 min. heat set). The stretched film was white, about 5.0 mil (0.13 mm) thick, and had a bubble point of 1.1 microns (as determined using FC-43) and a Gurley of 620 sec/50 cc. Stretched and unstretched films were evaluated for soφtion of ammonia by placing them in a covered desiccator containing a pool of concentrated ammonium hydroxide in the bottom and determining the weight ofthe film as a function of time. A shallow layer of virgin Abscents 3000™ powder was exposed similarly. Results for the films are given in the table below. The virgin powder sorbed 17.% % by weight and times required to sorb 10%, 50 % and 90 % of this weight gain were 0.2, 3.5, and 70 hr. Example Stretch mg Initial Rate % of Theo. Time to Reach Given Ratio sorbed/ mg/g film - Wt. Gain % of Maximum Wt. g film hr. Gain 10% 50% 90% 71 None 47.7 11.5 27.8 0.4 5.4 58 72 2.5 x 52.2 23.6 30.9 0.2 3.0 74 2.5 The results showed that either porous or non-porous films of this invention containing Abscents 3000™ were useful for sorbing ammonia vapors. Examples 73 - 74 The following examples illustrate soφtion by calcium oxide in an unstretched film and in a film ofthe same composition that became porous upon stretching. Example 73 The film composition was: 20.0 wt. % polypropylene (grade DS 5D45 from Shell), 38.1 wt. % AC 1702 wax (from Allied Signal), 39.4 wt. % (15.0 vol. %) calcium oxide (catalog number 33299, from Alfa), and 2.5 wt. % Hypermer LPl dispersant (from ICI Americas). It was prepared by the Extrusion Method using a smooth casting wheel at a set point of 77°C. Extrusion temperature ranges were: barrel, 271-171°C; screw φm, 120; die, 171°C, and total throughput of 4.63 kg/hr. Film thickness ranged from about 11 - 12 mils (0.28-0.30 mm). Example 74 A piece ofthe film from Example 73 was stretched 2 x 2 using a film stretcher from the T. M. Long Company at a set point temperature of 71 °C (30 sec. pre-heat, 2 min. heat set). The resultant film was off-white in color, had a bubble point of 0.05 microns (as determined using FC-43), and a Gurley of about 8000 sec/50 cc. Examples 73 and 74 were evaluated at 50 % RH/20°C. The calcium oxide used showed an increase of 39 wt. % under these same conditions. As for Example 41, there was very little soφtion during the first 8 hr. of exposure, followed by a period of more rapid adsoφtion. The results showed that the rate of adsoφtion was faster for the film that had been stretched. Example Stretch Thickness % of Theo. mg water/ Hours to Reach Given % Adsoφtion Ratio mils Wt. Gain gram film (mm) 10% 50% 90% 73 0 11-12 86.1 132.0 30 87 161 0.28-0.30 74 2 x 2 5.5-6.5 87.9 135 13.8 40 90 0.14-0.17 Example 75 This example demonstrates the preparation of a film containing calcium oxide at about the same volume % of particulate to wax as for Example 33, which contained about 112 vol. % Type 4 A molecular sieve relative to the volume of wax used. The densities used for these calculations were 1.1 g/cc for type 4A molecular sieve (dry), 3.3 g/cc for CaO (dry), and 0.88 g/cc for AC 1702 wax. The following composition was prepared using the Batch Method: 4.60 wt. % HDPE (grade 2804 from Fina), 18.30 wt. % AC 1702 wax (from Allied Signal), and 77.10 wt. % CaO (from Alfa, cat. no. 10923). Mixer conditions were 100 φ at 270°C for 15 min. Press conditions were 180°C for 5 min. The film was quenched by immersion in room temperature water after removing from the press and wiped quickly to remove water from it. The resultant film thickness ranged from about 10 to 12 mils. A piece of this film was evaluated at 50 % RH/20°C. It was found to sorb 291 mg/g of film. The times in hours to reach 10 %, 50 %, and 90 % ofthe maximum amount sorbed were 77, 142, and 631, respectively. The rate of soφtion was very slow during the first 50 hr., which was followed by a period of more rapid adsoφtion. Examples 76 - 77 These examples demonstrate preparation and evaluation of films, unstretched and stretched, containing activated carbon as the sorbent. The activated carbon was a coconut based-carbon from Calgon, grade PCB-GHP, a developmental grade that was pulverized to provide a particle size distribution for which 90 % by volume ofthe particles were less than about 11 microns. Example 76 The following composition was prepared using the Batch Method: 18.4 wt. % polypropylene (grade DS 5D45 from Shell), 34.1 wt. % M-5150 wax (from Moore and Munger), and 47.5 wt. % activated carbon. Mixer conditions were 100 φm at 270°C for 30 min. Press conditions were 200°C for 7 min. The film was quenched in room temperature water. The resultant film was about 12 mil (0.30 mm) thick. Example 77 A piece of film from Example 76 was stretched 1.25 x 1 at a set point of 132°C (30 sec. pre-heat, no heat set) using a film stretched from T. M. Long. This film was found to have a bubble point of about 0.1 micron (using FC-43) and a very large Gurley (in excess of about 65,000 sec/50 cc). Examination by scanning electron microscopy showed that the bulk ofthe film was porous but that there was a skin on both surfaces. This skin was evidently thin enough to be ruptured in the bubble point experiment. Pieces of unstretched and stretched films were exposed to TCE (trichloroethylene) vapors by placing inside a desiccator containing a pool of TCE in the bottom at room temperature. A sample ofthe virgin carbon was exposed similarly. The sample weight was followed as a function of time until the maximum amount of TCE had been sorbed: for unstretched film (Example 76), 227 mg/g of film (108 mg/g of carbon in film) was sorbed after 20 hr.; for stretched film (Example 77), 325 mg/g of film (154 mg/ g of carbon in film) was sorbed after 23.5 hr., and for virgin activated carbon, 600 mg TCE was sorbed per gram of carbon after 48 hr. Thus, while the carbon in the films had lower soφtivity than the virgin carbon, these results demonstrated that carbon in a non-porous film as well as in a porous film having surface skins (not through-porous) still displayed soφtive activity.

Claims: What is claimed is: 1. A soφtive article comprising a polyolefin, a wax which is miscible with the polyolefin at the melt temperature ofthe polyolefin but phase-separates from the polyolefin upon cooling ofthe article, and soφtive particles distributed in the article. 2. The soφtive article of claim 1 wherein said polyolefins are selected from polyethylenes, polypropylene, copolymers of ethylene and propylene, polybutylene, ethylene vinyl acetate, and blends thereof 3. The soφtive article of claim 2 wherein said polyethylenes are selected from high-density polyethylene, low-density polyethylene, linear low- density polyethylene, and ultrahigh molecular weight polyethylene. 4. The soφtive article of claim 1 wherein said waxes are selected from paraffin waxes, microcrystalline waxes, Fisher-Tropsch waxes, low molecular weight polyethylene waxes and low molecular weight ethylene-propylene copolymers, and waxes found in nature. 5. The soφtive article of claim 4 wherein the low molecular weight polyethylene waxes and the low molecular weight ethylene-propylene copolymers have a number average molecular weight of less than about 10,000. 6. The soφtive article of claim 1 in which the soφtive particles comprise water sorbent molecular sieves. 7. The soφtive article of claim 6 wherein the molecular sieves are synthetically produced crystalline metal alumino-silicates or naturally occurring sources containing crystalline metal alumino-silicates that have been activated for adsoφtion by removing their water of hydration. 8. The soφtive article of claim 1 in which the soφtive particles comprise hydrophobic molecular sieves. 9. The soφtive article of claim 1 in which the soφtive particles sorb vapors other than water vapor. 10. The soφtive article of claim 1 further comprising a dispersant for the soφtive particles. 11. The soφtive article of claim 1 wherein when the polyolefin is a polyethylene or polypropylene which has a melt index of about 1 or less, the soφtive article comprises 20 to 80 parts by weight polyolefin, 80 to 20 parts by weight wax such that the sum ofthe parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on the volume ofthe wax and an amount to provide at least 10 weight percent soφtive particulate based on the weight ofthe total film. 12. The soφtive article of claim 1 wherein when said polyolefin has a melt index above about 1, the soφtive article comprises about 50 to 80 parts by weight polyolefin, about 50 to 20 parts by weight wax such that the sum ofthe parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on the volume of wax and an amount to provide at least 10 weight percent soφtive particulate based on the weight ofthe total film. 13. The soφtive article of claim 1 wherein when the polyolefin is ultra high molecular weight polyethylene (UHMWPE), with a melt index of substantially zero, the soφtive article comprises about 2 to 50 parts by weight UHMWPE, and 98 to 50 parts by weight wax, such that the sum ofthe parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on the volume of wax and an amount to provide at least 10 weight percent soφtive particles based on the weight ofthe total film. 14. The soφtive article of claim 1 which has been stretched to make the article porous. 15. The soφtive article of claim 1 which includes an indicator that changes the color ofthe article upon soφtion of material into the article. 16. The soφtive article of claim 1 which includes a film on at least one side that limits transmission of vapor into the article. 17. A method for removing material from the air or an object in the environment comprising providing proximate to said air or object a soφtive article comprising a polyolefin, a wax compound which is miscible with the polyolefin at the melt temperature ofthe polyolefin but phase-separates from the polyolefin upon cooling ofthe article, and soφtive particles dispersed in the article. 18. The method of claim 17 wherein the polyolefins ofthe soφtive article are selected from polyethylene, polypropylene, or copolymers of ethylene and propylene, polybutylene, ethylene vinyl acetate, and blends thereof. 19. The method of claim 17 wherein the waxes ofthe soφtive article are paraffin waxes, microcrystalline waxes, Fisher-Tropsch waxes, low molecular weight polyethylene waxes and low molecular weight ethylene-propylene copolymers, and waxes found in nature. 20. The method of claim 17 in which the soφtive particles comprise water sorbent molecular sieves. 21. The method of claim 17 wherein said molecular sieves of said desiccant article are synthetically produced crystalline metal alumino-silicates or naturally occurring sources containing crystalline metal alumino-silicates that have been activated for adsoφtion by removing their water of hydration. 22. The method of claim 17 in which the soφtive particles comprise hydrophobic molecular sieves. 23. The method of claim 17 in which the soφtive particles sorb vapors other than water vapor. 24. The method of claim 17 further comprising a dispersant to aid dispersion ofthe soφtive particles in the soφtive article. 25. The method of claim 17 further comprising a nucleating agent in the soφtive article promoting nucleation ofthe polyolefin. 26. The method of claim 17 wherein, when the polyolefin ofthe soφtive article has a melt index of about 1 or less, the soφtive article comprises 20 to 80 parts by weight polyolefin, 80 to 20 parts by weight wax such that the sum ofthe parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on the weight ofthe wax and an amount to provide at least 10 weight percent soφtive particulate based on the weight of total film. 27. The method of claim 17 wherein, when the polyolefin ofthe soφtive article has a melt index of above about 1, the soφtive article comprises about 50 to 80 parts by weight polyolefin, 50 to 20 parts by weight wax such that the sum of the parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on weight of wax and an amount to provide at least 10 weight percent of soφtive particulate based on weight of total film. 28. The method of claim 17 wherein, when the polyolefin ofthe soφtive article has a melt index of substantially zero the soφtive article comprises about 2 to 50 parts by weight ofthe polyolefin, and 98 to 50 pats by weight wax, such that the sum ofthe parts by weight of polyolefin and wax is equal to 100, and between about 110 volume percent soφtive particulate based on the volume ofthe wax and an amount to provide at least 10 weight percent soφtive particles based on the weight ofthe total film. 29. The method of claim 17 wherein the soφtive article has been stretched to make the article porous. 30. The method of claim 17 wherein the soφtive article includes an indicator that changes the color ofthe article upon soφtion of material into the article. 31. The method of claim 17 wherein the soφtive article includes a film laminated to at least one side ofthe article which limits transmission of vapor into the article.

Inventors: LARSON JAMES M, LARSON, JAMES, M.
Applicants: LARSON JAMES M, MINNESOTA MINING & MFG, LARSON, JAMES, M., MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1996
Main classification: B01J20
IPC codes: B01D53, B01J20