MXPA01012354A

MXPA01012354A - Inverse phase blends of poly(ethylene oxide) and polyolefin and reactive extrusion method of making inverse phase blends.

Info

Publication number: MXPA01012354A
Application number: MXPA01012354A
Authority: MX
Inventors: David M Schertz
Original assignee: Kimberly Clark Co
Priority date: 1999-06-07
Filing date: 1999-06-15
Publication date: 2002-07-30
Also published as: AU4681899A; WO2000075228A1

Abstract

Inverse phase compositions comprising a polyolefin, such as polyethylene, and poly(ethylene oxide) and methods of making inverse phase compositions are described. The inverse phase compositions exhibit an inverse phase in which the volume minority constituent, the poly(ethylene oxide), forms a continuous phase and volume majority constituent, the polyolefin, forms a dispersed or discontinuous phase in the continuous poly(ethylene oxide) phase. The inverse phase compositions have beneficial water degradable properties and can be used in the manufacture of disposable personal hygiene articles. In at least one desirable embodiment, the polyolefin and the poly(ethylene oxide) are grafted with a polar, vinyl monomer in a reactive extrusion process.

Description

REVERSE PHASE MIXES OF POLY (ETHYLENE OXIDE) AND POLYOLEFIN AND REACTIVE EXTRUSION METHOD TO MAKE REVERSE PHASE MIXTURES FIELD OF THE INVENTION The present invention relates to reverse phase blends of polyolefin and poly (ethylene oxide) and methods for making reverse phase blends.

BACKGROUND OF THE INVENTION There is a wide variety of disposable plastic items manufactured in use today. Due to their low cost and convenience, these are very popular and have a high demand by the consumer. However, many of these items are not degradable or easily disposable. As a result, these have caused and continue to cause a waste disposal problem.

Personal care products, such as diapers, sanitary napkins, adult incontinence garments, and the like are generally constructed of a number of materials and different components. Such items typically have some part, usually a bottom layer, a liner, or a separator that is _ ^ ^ ^ - ^ ^ ^ ^ ^ ^ ^ ^ * 3 * ij ** gjfj ^ ^ composed of a film constructed of a liquid-repellent material. This repellent material is suitably constructed to minimize or prevent the exudate of the liquid absorbed from the article and to obtain a greater utilization of the absorbent capacity of the product. The liquid repellent film commonly used includes plastic materials such as polyethylene films and the like.

Although such products are relatively inexpensive, sanitary and easy to use, the disposal of a product once soiled is not without problems. An ideal disposal method for such products may be the use of municipal sewer treatment and residential private septic systems. The appropriate products for disposal in sewer systems can be discarded with water jets in a convenient toilet and are called "Disposable with jets of water". While discarding such articles with water jets may be convenient, the liquid repellent material which normally does not disintegrate in water tends to clog the toilets and sewer pipes. Therefore, it becomes necessary, although not convenient, to separate the barrier film material from the absorbent article before it is discarded with water jets.

In an attempt to overcome the problem of discharging water jets from a waterproof film of the prior art, it has modified the polymer resistant to ? áJ k A ^ l ^ ¿^ i ^ water. One of the most useful ways to modify the. Polymers involve mixing them with other polymers of different structures and properties. In a few cases, the polymer blend combinations are thermodynamically miscible and exhibit mechanical compatibility. However, by far a greater number of mixtures are separate phases and generally exhibit poor mechanical compatibility. The separated phase mixtures may in some cases exhibit mechanical compatibility where the polymer compositions are similar, for example, mixed with polyolefin with other similar polyolefins, or where the interfacial agents are aggregated to improve the compatibility at the interface between the constituents of the polymer mixture.

The polymer blends of polyolefins and poly (ethylene oxide) are processed melts but exhibit very little mechanical compatibility. This poor mechanical compatibility is particularly manifested in mixtures having greater than 50% by weight of polyolefin. Generally the film is not affected by water because typically the majority phase, for example polyolefin, will be able to surround and encapsulate the minor phase, for example poly (ethylene oxide). The encapsulation of the poly (ethylene oxide) effectively avoids any waste advantage with water jets and / or degradation that can be acquired by the use of poly (ethylene oxide).

In view of the problems of the prior art, it remains highly desirable to provide water degradable compositions comprising poly (ethylene oxide) that incorporates higher amounts of low cost polyolefin (s) while maintaining or at least significantly not decreasing the response to the water of the composition. Advantageously, such compositions can be used to make disposable films with jets of water and disposable fibers with inexpensive water jets. These films 10 and the fibers can be used as components in personal care products that are designed to be discarded with water jets in conventional toilets. Additionally, the unique water-related properties of the compositions described herein make the compositions 15 disposable compositions for the manufacture of filter membranes.

SYNTHESIS OF THE INVENTION Briefly, the present invention provides for compositions comprising a volume of poly (ethylene oxide) and a larger volume of polyolefin relative to the volume of poly (ethylene oxide) wherein the compositions exhibit a reverse phase morphology. As used here the 25"reverse phase morphology" means that the bulk constituent, which can normally be expected to form the continuous phase in the composition, is the phase --__ »? - TÍ-l_ -feL¿aate. dispersed and the volumetric minority constituent forms the continuous phase in which the volumetric majority constituent is dispersed. Poly (ethylene oxide) and reverse phase polyolefin compositions are desirable because they have an improved water response and water dispersibility compared to compositions comprising the same relative amounts of the aforementioned polymers that do not have the morphology of reverse phase described above.

The compositions of the present invention lose a substantial amount of mass when exposed to water. Consequently, the films, fibers and articles made with the compositions of the present invention exhibit a significant decrease in their mechanical properties when exposed to water compared to dry mechanical properties prior to exposure to water. The compositions of the present invention are substantially water degradable and can be used to produce disposable articles, fibers and films with water jets. Significantly, films, fibers and articles can be produced which incorporate greater amounts of essentially water-insoluble polyolefins relative to the amount of water-soluble poly (ethylene oxide) while remaining disposable with water jets and degradable with the water. Water. Therefore, disposable articles with water jets such as diapers and Pads for women can be manufactured with small amounts of resins with water and soluble with water, at low cost.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross-sectional view of a 4 mil (0.004 inch) film of the composition of Comparative Example A, a 60% blend of LDPE linear density polyethylene weight and 40% by weight of poly (ethylene oxide) PEO having no reverse phase morphology.

Figure 2 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross sectional view of a 4 mil film. of the composition of Example 1, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% weight of poly (ethylene oxide) PEO which are grafted with about 3% by weight of ether methacrylate ethyl poly (ethylene glycol) PEGMA.

Figure 3 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross sectional view of a 4 mil composition. From Example 2, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO grafted to about 5.5% by weight of ethyl ether methacrylate monomer of poly (ethylene glycol) PEGMA.

Figure 4 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross sectional view of a 4 mil film. of the composition of Example 3, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO which are grafted with about 9% by weight of meta-plate monomer of ethyl ether of poly (ethylene glycol) PEGMA.

Figure 5 is an electron scanning electron microscope photomicrograph of a secondary electron image of a topological view of a 4 mil film. of the composition of example 11, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO which are grafted with about 5% by weight of methacrylate monomer of 2-hydroxyethyl HEMA.

Figure 6 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross sectional view of a 4 thousand movie. of the composition of example 11, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO which are grafted with about 5% by weight of methacrylate monomer of 2-hydroxyethyl HEMA.

Figure 7 is a photomicrograph of electron scanning microscope, a secondary electron image of a topological view of a 4 mil film. of the composition of example 13, a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO which are grafted with about 15% by weight of methacrylate monomer of 2-hydroxyethyl HEMA.

Figure 8 is an electron scanning electron microscope photomicrograph of a backscatter electron image of a cross sectional view of a 4 mil film. of the composition of example 13, or a reverse phase mixture of 60% by weight of LDPE linear density polyethylene and 40% by weight of poly (ethylene oxide) PEO which are grafted with about 15% by weight of monomer of 2-hydroxyethyl methacrylate HEMA.

Figure 9 is a graph illustrating the dry and wet stress curves of a film of the non-reversed phase composition of Comparative Example A.

Figure 10 is a graph illustrating the dry and wet stress curves of a film of the reverse phase composition of Example 10.

Figure 11 is a graph illustrating the dry and wet stress curves of a film of the reverse phase composition of example 11.

Figure 12 is a graph illustrating the dry and wet stress curves of a film of the reverse phase composition of Example 12.

Figure 13 is a graph illustrating the dry and wet stress curves of a film of the reverse phase composition of example 13.

Figure 14 is a bar graph comparing the dry and wet mechanical properties of a film of the reverse phase composition of Example 10 against the dry and wet mechanical properties of a film of the non-reversed phase composition of Comparative Example A.

Figure 15 is a bar graph comparing the dry and wet mechanical properties of a film of the reverse phase composition of Example 10 against the dry and wet mechanical properties of a film of the non-reversed phase composition of Comparative Example A.

Fig. 16 is a bar graph comparing the dry and wet mechanical properties of a film of the reverse phase composition of Example 12 against the mechanical properties dry and wet film of the non-reverse phase composition of Comparative Example A.

Figure 17 is a bar graph comparing the dry and wet mechanical properties of a film of the reverse phase composition of Example 13 against the dry and wet mechanical properties of a film of the non-reversed phase composition of Comparative Example A.

DETAILED DESCRIPTION OF THE INVENTION Although the present invention is described with reference to a film, one of skill in the art will be able to understand the utility of the invention towards polymer compositions and articles that can be manufactured using polymer compositions. The compositions of the present invention comprise a larger volume of a polyolefin and a smaller volume of a poly (ethylene oxide) where the poly (ethylene oxide) comprises the continuous phase and the polyolefin comprises the discontinuous phase. In one embodiment, the reverse phase compositions of the present invention comprise a majority of the volume of a polyolefin. As used here, "bulk" means a greater amount by volume. The compositions of the examples are described by reference to the percentages by weight of the polyolefin component, the low density polyethylene, and the poly (ethylene oxide) component. Due to the higher density of poly (ethylene oxide), about 1.2 grams per cubic centimeter, relative to the low density of polyethylene, about 0.9 to 0.94 grams per cubic centimeter, the volume percentage of polyolefin incorporated into the compositions of the examples is greater than the weight percentage, for example 55% by weight of low density polyethylene is equal to about 60% volume of low density polyethylene.

The compositions of the present invention may comprise as little as 51% by volume and as much as 99% by volume of a polyolefin in any amount of poly (ethylene oxide) as long as there is a sufficient amount of poly (ethylene oxide) to form a continuous phase around the polyolefin. In one embodiment, in the compositions of the present invention it comprises from about 51% by volume to about 95% by weight of a polyolefin and from about 49% by volume to about 5% by volume of a poly (ethylene oxide). ethylene) which can be grafted with a vinyl monomer. In another desirable embodiment, the compositions of the present invention comprise from about 60% by volume to about 85% by volume of a polyolefin and from about 40% by volume to about 15% by volume of a polyolefin. ethylene) neither .- . A .db ** ----.--. -Aat ». - »? .a ^^. > 5¿¡ ^^ k¿ grafted with a polar vinyl monomer. Desirably, the polyolefin and the poly (ethylene oxide) are grafted with at least one polar vinyl monomer. Unexpectedly it has been discovered that a reverse phase morphology, where the hydrophobic half constitutes the continuous phase, can be achieved by a minor component in the film to largely expand the sensitivity and degradability to water of a film. Desirably, the composition of the present invention comprises a blend of from about 60% by volume to about 85% by volume of a polyolefin, such as polyethylene, and from about 40% by volume to about 15% by volume of a poly (ethylene oxide) with an effective amount of grafted monomer in the polyolefin and in the poly (ethylene oxide) to return the inversion phase.

Suggested polyolefins useful for the practice of the invention include, but are not limited to, various thermoplastic polyethylenes, polypropylenes, polypropylenes and saturated ethylene polymers. The suggested saturated ethylene polymers useful in the practice of this invention are ethylene homopolymers or copolymers and are essentially linear in structure. As used herein, the term "saturated" refers to polymers that are completely saturated, but also includes polymers containing up to about 5% without saturation. Ethylene homopolymers include, but are not limited to, those prepared under either low pressure, for example, high density polyethylene or linear low density, or high pressure polyethylene, for example, low density or branched polyethylene. High density polyethylenes are generally characterized by a density that is more or less equal to or greater than 0.94 grams per cubic centimeter (g / cc). Generally, the high density polyethylenes useful as the base resin in the present invention have a density in the range of about 0.94 grams per cubic centimeter to about 0.97 grams per cubic centimeter. The polyolefin can have a melt index, as measured at 2.16 kilograms and 190 ° C, in the range of about 0.005 decigrams per minute (dg / min) to 100 decigrams per minute. Desirably, the polyolefin has a melt index of 0.01 decigrams per minute at about 50 decigrams per minute and more desirably at 0.05 decigrams per minute about 25 decigrams per minute. Alternatively, in the polyolefin blends, particularly in the polyethylenes can be used as the polyolefin base resin in producing the graft copolymer compositions of the present invention, and such blends should have a melt index greater than 0.005 decigrams per minute at less than about 100 decigrams per minute.

The low density polyethylene used as the polyolefin component in the following examples has a density of less than 0.94 grams per cubic centimeter and is usually in the range of 0.91 grams per cubic centimeter to around 0.93 grams per cubic centimeter. Low density polyethylene has a melt index in the range from about 0.05 decigrams per minute to about 100 decigrams per minute and desirably from 0.05 decigrams per minute to about 20 decigrams per minute. The ultra low density polyethylene can be used in accordance with the present invention. Generally, ultra-low density polyethylene has a density of less than 0.90 grams per minute.

The above polyolefins can also be manufactured by the well-known use of Ziegler-Natta multi-site catalysts or the more recent single-site metallocene catalysts. Metallocene catalyzed polyolefins have better controlled polymer microstructures than polyolefins manufactured using Ziegler-Natta catalysts, which include a narrower molecular weight distribution, better controlled chemical composition distribution, a comonomer sequence length distribution, and stereoregularity . Metallocene catalysts are known to polymerize propylene in atactic, isotactic, syndiotactic, isotactic-atactic stereoblock copolymer. Desirably, the polyolefin component of the compositions of the present invention is thermoplastic in order to facilitate the production of the compositions of the invention and to facilitate the processing of compositions into articles, particularly films.

The ethylene copolymers which may be useful in the present invention may include, but are not limited to, copolymers of ethylene with one or more additional unsaturated, polymerizable monomers. Examples of such copolymers include, but are not limited to, copolymers of ethylene and alpha olefins such as propylene, butene, hexene or octene) including linear low density polyethylene, ethylene copolymers and esters of vinyl of branched or linear carboxylic acids having from 1 to 24 carbon atoms such as ethylene vinyl acetate copolymers, and ethylene copolymers and methacrylic or acrylic esters of cyclic alkanols by branched, linear having 1 to 24 carbon atoms. to 28 carbon atoms. Examples of these latter copolymers include the ethylene alkyl (meth) glass copolymers, such as the ethylene methyl acrylate copolymers.

The poly (ethylene oxide) polymers suitable for the present invention include homopolymers and ethylene oxide copolymers which are water soluble. The poly (ethylene oxide) component of the present invention may have molecular weights in the range of about 50,000 to about 8,000,000 grams per mole and, desirably, may be in the range from about e 100,000 to about 8,000,000 grams per mole. More desirably, the average molecular weight of the poly (ethylene oxide) component of the present invention is in the range of from about 200,000 to about 6,000,000 grams per mole. When the poly (ethylene oxide) component of the compositions of the present invention has an average molecular weight of less than 200,000 grams per mole, in addition to the monomer and the subsequent grafting of the monomer is not necessary to obtain the desired investment phase . In example four below, the reverse phase composition of poly (ethylene oxide) and polyolefin was achieved by mixing by casting 60% by weight of a low density polyethylene and a poly (ethylene oxide) of 100,000 grams per mole Commercially suggested examples for water-soluble poly (ethylene oxide) are available from Union Carbide Corporation under the brand name POLYOX®. Typically, poly (ethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65 ° C, above which the poly (ethylene oxide) resin becomes thermoplastic and can be formed by melting, extrusion and other methods known in the art.

The poly (ethylene oxide) and polyolefin components of the compositions of the present invention isá-i.) -. ?, 4¡¿ * A * Í. -, .- * - «-» > -., Ai.,. " An effective amount of polar vinyl monomer is grafted onto them. The grafted unexpectedly produces compositions and films having a reverse phase morphology. A variety of polar vinyl monomers may be useful in the practice of this invention. The term "monomer (s)" as used herein includes the traditional definition of a monomer as well as macromonomers which are oligomers and polymers capable of polymerization. As used herein the monomers also include mixtures of monomers, oligomers and / or polymers as described above and any other reactive chemical species, which is capable of covalently binding to the parent polymer (s). Ethylenically unsaturated monomers containing a polar functional group, such as hydroxyl, carboxyl, amine, carbonyl, halo, glycidyl, cyano, thiol, sulphonic, sulfonate, etc. they are appropriate for this invention and are suggested. Ethylenically unsaturated monomers include acrylates and methacrylates. The suggested polar vinyl monomers include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, poly (ethylene glycol) acrylates, poly (ethylene glycol) acrylates, diacrylates of poly (ethylene glycol), acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, acrylamide, glycidyl methacrylate, 2-bromoethyl methacrylate, carboxyethyl acrylate, sodium acrylate, methacrylate 3 -hydroxypropyl, 3-hydroxypropyl acrylate, 2-chloroacrylonitrile, 4-chlorophenyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, 4-nitrophenyl acrylate, pentabromophenyl acrylate, poly (propylene glycol) acrylates, poly (propylene glycol) methacrylates , 2-proprene-l-sulfonic acid and its sodium salt, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and their derivatives and analogs thereof. Suggested derivatives include, but are not limited to, poly (ethylene glycol) ethyl ether acrylates, poly (ethylene glycol) alkyl ether acrylates, alkyl ether methacrylates of poly (ethylene glycol), and ethylene ether methacrylates of poly (ethylene glycol) of various molecular weights.

Any polar vinyl monomer or a mixture of monomers including a polar vinyl monomer or monomers can be added to reactivate the mixture of the component polymers with or separated from the polymers during the mixing process. The addition of a polar vinyl monomer initiator of the process is desirable when a poly (ethylene oxide) of molecular weight greater than about 100,000 grams per mole is used as the minor volume component of the reverse phase mixture. The polymers and the monomer (s) can be added simultaneously. For example, the polymer, the initiator and the monomer (s) can be added together in the barrel hopper # 1 of the extruder. It is more desirable to add the polymers first to the reactive vessel and melt the polymers before adding either the initiator or the monomer. Examples of such methods include melting the polymers and then injecting a solution comprising the initiator and the monomer into the melted polymers; and add the initiator and then add the monomer or monomer mixture to the molten polymers. It is even more desirable to add and disperse the monomer (s) in the molten polymers before adding the initiator. Therefore, it is desirable to add the polymers first to the extruder and then inject and disperse the monomer (s) in the polymers before adding the initiator.

The compositions of the present invention may be by any of several methods. For example, the components, the polyolefin, the poly (ethylene oxide), the monomer and the initiator can be mixed before heat joining to produce a reverse phase composition. Alternatively, the components can be added simultaneously or separately to a reaction vessel for melting and bonding. Desirably, the polyolefin and the poly (ethylene oxide) should be fused together before adding the monomer or initiator. The monomer and the initiator can be added to the melted polymers separately or combined in a solution comprising the monomer and the initiator. In a reactive extrusion process, it is desirable to feed the polyolefin and the poly (ethylene oxide) into an extruder before adding the monomer further in lil - l.j-A -.-- i :. - "•" ^ ir- -i & ^^^? Ji? &A? ÁÁ .. in the extruder and add the initiator further inside the extruder. This sequence facilitates the mixing of the monomer or the mixture of the monomers in the polymers before the initiator is added and the radicals are created.

One of skill in the art may expect compositions comprising two or more different polymers such as a polyolefin and a water soluble polymer such as a poly (ethylene oxide) to form heterogeneous mixtures of the different polymers where in the polymer component which comprises the majority of the volume of the mixture, greater than 50% by volume, forms a continuous phase and the polymer component comprising the minority of the mixture, less than 50% by volume, forms the dispersed or discontinuous phase of the mixture . The discontinuous phase is also referred to as the dispersed phase because it is dispersed in the continuous phase formed by the majority component. This is illustrated in Figure 1. Figure 1 is an electron scanning electron microscope (SEM) photomicrograph of a backscatter electron image of a cross sectional view of a 4 mil film. (0.004 inches) of comparative example A, a mixture of 60% by weight of an ungrafted polyethylene, a darker phase shown in the photomicrograph, and 40% by weight of a poly (ethylene oxide) without grafting, the most clear shown in the photomicrographs. Due to the density difference between polyethylene and poly (ethylene oxide), the volume percentage of polyethylene in the mixture of the comparative example 1 is about 67% and the percentage volume of poly (ethylene oxide) is only about 33%. In figure 1, it is observed that the bulk component of the mixture, the darker polyethylene, forms the continuous phase and the minor volume component of the mixture, the lighter poly (ethylene oxide), forms the dispersed phase / discontinuous.

In contrast, the minor volume component of the compositions of the present invention forms a continuous phase and the majority volume component forms in a discontinuous phase. This is illustrated in Figures 2 to 8. Figures 2 to 8 include photo electron microscopy of electron scanning of the backscatter electron images of the topographic and cross section views by secondary electron images of the 4 mil films. of examples 1, 2, 3, 11 and 13. As can be seen from the photomicrographs, the compositions of the present invention comprise a majority volume of a polyolefin and a minor volume of poly (ethylene oxide) yet exhibit phase morphology reverse. Specifically, the poly (ethylene oxide) which is the minor component of the compositions of the examples appears as the clear phase in photomicrographs is the continuous phase although the poly (ethylene oxide) is the minor volume of the composition component and comprises less than half the volume of the compositions herein ^^^ ¡^^^^^ ^ ^ ^^^^^^^ I ^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^ invention. The major component, the darker polyolefin phase, is discontinuous and forms the dispersed phase in the compositions of the present invention. Therefore, the compositions and films of the present invention have a poly (ethylene oxide) as the continuous phase and a polyolefin as the discontinuous phase although there is a significantly higher amount of polyolefin. For example, many of the reverse phase compositions shown herein have a volume ratio of polyolefin to poly (ethylene oxide) of about 2 to 1.

The amount of polar vinyl monomer grafted to the polyolefin and to the poly (ethylene oxide) can vary and can range from a total of about 0.1% by weight to about 30% by weight, based on the sum of the weight of polyolefin and poly (ethylene oxide). Desirably, the polyolefin and the poly (ethylene oxide) have a total of about 1% by weight to about 20% by weight of monomer grafted therein. More desirably, the polyolefin and the poly (ethylene oxide) have a total of from about 1% by weight to about 10% by weight of monomer grafted therein. It is believed that the polar groups of the polar grafted vinyl monomer reduce the interfacial tension between the poly (ethylene oxide) phase and the polyolefin phase. The reduction in interfacial tension is believed to stabilize the polyolefin phase and allows the & _! -... & -. . ,. polyolefin to exist as the dispersed phase in the mixture with poly (ethylene oxide).

To prepare the compositions of the present invention, a polyolefin and a poly (ethylene oxide) are reactivated with a monomer and the presence of a free radical initiator. The initiator serves to initiate the free radical grafting of the monomer into the polyolefin and the poly (ethylene oxide). A method for grafting the polymer blends includes melt-bonding the desired volume or weight ratio of a mixture of the polyolefin and a poly (ethylene oxide) and adding a monomer and a free radical initiator in an extruder and a reaction temperature where the polyolefin and the poly (ethylene oxide) are converted to a molten state. Therefore, a preferred method includes adding the polyolefin, the poly (ethylene oxide), the monomer and the free radical initiator simultaneously to the extruder before the polymer constituents, for example, the polyolefin and the poly (melt) have been melted. ethylene oxide) . Desirably, the casting extruder used to join by casting can introduce various constituents into the mixture at different locations along the length of the screw. For example, a polar vinyl monomer and the initiator can be grafted into the mixture before or after one or more of the polymer constituents are melted or completely mixed. More preferably, a polyolefin and a poly (ethylene oxide) are added at the beginning of the ------ -: - »- --- ^ A ----- > Extruder and the polar vinyl monomer is added to the molten polymers further inside the barrel of the extruder, a free radical initiator is also fed to the molten mixture. The methods for making the blends are described in the patent application of the United States of America Serial No. 08 / 777,226 registered on December 31, 1996 and entitled "Polyolefin and Poly (Ethylene Oxide) Mixtures and Processes for Making Mixtures "now U.S. Patent No. 5,700,872, the full description of which is incorporated herein by reference.

In an embodiment of the invention, the method for making the compositions is achieved by reactive mixing, desirably by a reactive extrusion process. The compositions of the present invention can be made by a bulk mixing process or a continuous process. For example, the desired amounts of polyolefin, poly (ethylene oxide), monomer and initiator can be combined in a vessel and heated and mixed to graft the monomer into the polyolefin and into the poly (ethylene oxide) and form of a reverse phase composition. Another method for making the compositions of the present invention includes the melt bonding of desired amounts of polyolefin and poly (ethylene oxide) in an extruder. In an extruder, the monomer and the initiator can be added to the polyolefin and the poly (ethylene oxide) contemporaneously with the polymers while they are fed into the extruder, .t --- m -? ..... M. -ta- a-- -. fa. After the polymers are fed into the extruder and even between the separate feed of the polymers in the extruder, the polymer is fed to the extruder. Desirably, in the reverse phase compositions are granulates. The extruded granules have the desired reverse phase morphology and can be processed into various articles, including but not limited to films having reverse phase morphology.

The excluded compositions can be used to make various articles including granules for further use and further processing. Desirably, the compositions of the present invention and can be used to make films and other articles that can be discharged with water jets, water sensitive, water responsive, water dispersible or water soluble, depending on the needs of the manufacturer . Generally, waste with water jets, water sensitivity, water response, water dispersibility and water solubility of compositions, films and articles can be increased by increasing the proportion of the water component. poly (ethylene oxide), soluble in water. The compositions of the present invention are receptive to the melting process and to conventional thermoplastic processing techniques. The films can be made from compositions using compression, blow molding and casting processes.

The processes used to make non-woven fabrics of films excluded from the compositions of the present invention are described in greater detail in U.S. Patent Application Serial Nos. 09 / 001,781 and 09 / 001,791, the full descriptions of the which are incorporated herein by reference. In an embodiment of the process for making non-woven fabrics, a film of a reverse phase mixture is extruded and exposed to water. The water washes and removes most of the water-soluble poly (ethylene oxide) from the polyolefin non-woven fabric. The polyolefin non-woven fabric may be a grafted polyolefin of 2-hydroxyethyl methacrylate or polyolefin fabric grafted to ethyl ether methacrylate of poly (ethylene glycol). The non-woven fabric has been observed to be soft, very covering and similar to the "silk" in texture. The non-woven fabric is also wettable and has runoff and water spreading properties that are desirable for many personal care applications. For example, the non-woven fabric can be used as a lining material in diapers, in pads for women and in pant lining.

A variety of containers can be used in the practice of this invention. The reverse phase modification of the polymers can be carried out in any vessel always when the necessary mixing of the polymers, the monomer and the initiator is achieved insufficient thermal energy ia¡] iá? ksM H > t «?" ±.? d * ,. ,. - > _. ,,. "., ^ -c». ... is provided to carry out the grafting. Desirably, such containers and include any suitable mixing devices, such as Bradender Plasticorders, Haake extruders, and multiple or 5 simple screw extruders, or any other mechanical mixing devices which can be used to mix, combine, process or make polymers. In a desired embodiment, the reaction device is a twin screw extruder that rotates from right to left, such as a Haake extruder. 10 available from Haake, 53 West Century Road, Paramus, NJ 07652 or a co-rotating twin screw extruder, such as a twin-screw composite extruder ZSK-30 manufactured by Werner & Pfleiderer Corporation of Ramsey, New Jersey. It should be noted that a variety of extruders can be used 15 to combine the polymers of the component according to the invention whenever mixing and heating occur.

Free radical initiators which can be used to graft the monomer into the polyolefin include, but are not limited to, acyl peroxides such as benzoyl peroxide; the dialkyl; or the aralkyl peroxides such as di-t-butyl peroxide, • dicumyl peroxide; cumyl butyl peroxide; 1,1- 25 di-t-butyl peroxy-3,5,5,5-trimethylcyclohaxane; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexino-3 and bis (a-t-butyl peroxyisopropylbenzene); peroxyesters such as t-butyl peroxypivalate; the t-butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2,5-di (perbenzoate); t-butyl di (perftalate); the dialkyl peroxymonocarbonates and the peroxydicarbonates; hydroperoxides such as t-butyl hydroperoxide; p-methane hydroperoxide, pineane hydroperoxide and eumeno hydroperoxide and acetone peroxides such as cyclohexanone peroxide and methyl ethyl acetone peroxide. Azo compounds such as azobisisobutyronitrile can also be used as an initiator for grafting in the present invention.

The amount of free radical initiator added to the polyolefin and poly (ethylene oxide) should be in an amount sufficient to graft about 1% to 100% of the polar vinyl monomer in the polyolefin and in the poly (oxide). ethylene). The amount of initiator may vary and should be in the range of about 0.05% by weight about 1% by weight, desirably, from about 0.1% by weight to about 0.75% by weight and, more desirably, around of 0.1% by weight of about 0.5% by weight. The above weight ranges are based on the weight of the initiator added to the combined total weight of the polyolefin and the poly (ethylene oxide) used to produce the composition.

Characteristic of the invention, a film when observed using an electron scanning microscope and using backscatter electron detector images shows that the poly (ethylene oxide) forms the continuous phase wherein the polyolefin is in a discontinuous phase, that is, dispersed through the poly (ethylene oxide) phase. The image tracing backscatter electron detector produces an image where the constituent of the upper average atomic number produces a higher intensity of backscattering electrons that appear brighter in the photographic image. A constituent that has a lower atomic number produces a lower intensity of backscattering electrons that appear as darker images in the photograph. The electron scanning microscope is described in more detail in Polymer Microscopy, by Linda C. Sawyer and David T., Chapman &; Hall, London, 1987, p.25. Desirably, the polyolefin portions of the thermoplastic film have a cross-sectional diameter per average in the range of about 0.1 microns to about 50 microns, preferably from about 0.5 microns to about 30 microns and more preferably around 0.5 microns. microns to around 25 microns. Such "polyolefin parts" can be solidified polyolefin bags, fibers or combinations thereof.

The present invention is illustrated in more detail by the specific examples presented below. Is -_-_ to..-. It should be understood that these examples are illustrative embodiments and are not intended to be limiting of the invention, but rather should be broadly construed within the scope and content of the appended claims.

COMPARATIVE EXAMPLE A A 60/40% by weight blend of low density polyethylene resin and poly (ethylene oxide) (hereinafter abbreviated as PEO) was melt bonded using an extruder. The low density polyethylene has a melt index of 1.9 decigrams per minute (dg / min) and a density of 0.917 grams per cubic centimeter (g / cc) (Dow 5031, available from Dow Chemical Company, Midland, MI). The poly (ethylene oxide) PEO has a molecular weight of 200,000 grams per mole (POLYOX® WSRN-80, available from Union Carbide Corp.). The extruder used to make the mixture was a Werner & Pfeiderer ZSK-30 (available from Werner &Pfleiderer Corporation, Ramsey, New Jersey). The resin mixture was fed to the extruder at a rate of 34 pounds per hour. The extruder had a pair of co-rotating screws arranged in parallel. The central distance between the two axes was 26.2 millimeters. The nominal screw diameter was 30 millimeters. The diameter of the real external screw was 30 millimeters. The inner screw diameter was 21.3 millimeters. The thread depth was 4.7 millimeters. He ~. & *. í. * Extruder had 14 barrels of processing, with 13 heated barrels divided into 7 heated ones. The total processing length was 1340 millimeters. The seven heating zones were all set at 180 degrees Celsius (° C). The screw speed was set at 300 revolutions per minute.

All films were bonded by casting in this comparative example and examples 1 through 9 were made using a twin screw extruder rotating from right to left Haake (available from Haake, 53 West Century Road, Paramus, NJ, 07652) equipped with a four inch slit die. The extruder had a length of 300 millimeters. The tapered screws had a diameter of 30 millimeters in the feed port and a diameter of 20 millimeters in the die. The extruder had four heating zones placed at 170, 180, 180 and 190 ° C. The screw speed was 30 revolutions per minute. The cooling roller was operated at a sufficient speed to form a film having a thickness of about 4 mils. (about 0.004 of 1 inch) and was maintained at a temperature of 15 to 20 ° C.

Referring to Figure 1, the polyethylene formed the continuous phase and the poly (ethylene oxide) formed the discontinuous phase.

EXAMPLES 1 to 3 According to the invention, 60/40% by weight of the mixture of low density polyethylene (LDPE) resin and poly (ethylene oxide), as described above in the comparative example, was fed into the ZSK- extruder. 30 at a rate of 34 pounds per hour. Seven heating zones were all placed at 180 ° C. The screw speed was 300 revolutions per minute. In barrel 4 of the extruder, a monomer, an ethyl ether methacrylate of poly (ethylene glycol) (PEG-MA, available from Aldrich Chemical Company, Milwaukee, Wl), was added in a specific ratio. In barrel 5 of the extruder, a free radical initiator (2,5-dimethyl-2,5-di (t-butylperoxy) hexane, supplied by Atochem, 2000 Market St., Philadelphia, PA under the brand name Lupersol 101) was added in a specific proportion.

For example 1, the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 1.0 pounds per hour and the proportion of the initiator was 0.068 pounds per hour.

For example 2, the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 1.9 pounds per hour and the proportion of the initiator was 0.068 pounds per hour. l < aUk-fc »_c - _.- lj, nA_-A., For example 3, the feed ratio of the ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 3.1 pounds per hour and the Initiator ratio was 0.17 pounds per hour.

Referring to Figures 2 to 4, the thermoplastic film of the invention exhibited reverse phase morphology. The reverse phase compositions and the films of Examples 1 to 3 comprise a smaller volume / amount of poly (ethylene oxide) as the continuous phase and a volume / greater amount of polyolefin as the dispersed phase. Particularly, Examples 1 to 3 are believed to comprise a continuous phase of ethyl ether methacrylate of poly (ethylene glycol) -gives-poly (ethylene oxide) PEGMA-g-PEO and a discontinuous phase of ethyl ether methacrylate of poly (ethylene glycol) -glasses-linear density polyethylene PEGME-g-LDPE.

EXAMPLE 4 A 60/40% by weight mixture of low density polyethylene resin (Dow 5031) and poly (ethylene oxide) having a molecular weight of 100,000 grams per mole (POLYOX® WSRN-10) was fed to the ZSK extruder -30 at a rate of 35 pounds per hour. The seven heating zones were all placed at 180 ° C. At screw speed it was 300 revolutions per minute. A resin film bonded with cast iron exhibited a phase morphology Inverse is the poly (ethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.

EXAMPLE 5 to 9 A resin blend having a 60/40 weight ratio of low density polyethylene (Dow 5031) and poly (ethylene oxide) (POLYOX® WSRN-80) was fed to a Haake extruder at 5.0 pounds per hour. The Haake extruder was similar to that described above in the comparative example except that the extruder included a cord punch from the holes instead of the four inch slit punch. Simultaneously with the polymer fed to the extruder, specific amounts of the monomer, of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA, and the free radical initiator (Lupersol 101) were added to the feeder throat. The extruder had four heating zones placed at 170, 180, 180 and 190 ° C. The screw speed of the extruder was 150 revolutions per minute. The cords were cooled in air and granulated.

For example 5 the mixture was 60/40 polyethylene / poly (ethylene oxide) PE / PEO, and the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 0.50 pounds per hour and the proportion of the initiator was 0.025 pounds per hour.

For example 6 the mixture was 65/35 polyethylene / poly (ethylene oxide) PE / PEO, and the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 0.50 pounds per hour and the proportion of the initiator was 0.025 pounds per hour.

For example 7 the mixture was 70/30 polyethylene / poly (ethylene oxide) PE / PEO, in the feed proportion of the ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 0.50 pounds per hour and the proportion of the initiator was 0.025 pounds per hour.

For Example 8 the mixture was 75/25 polyethylene / poly (ethylene oxide) PE / PEO, the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 0.50 pounds per hour and the proportion of the initiator was 0.025 pounds per hour.

For example 8 the mixture was 80/20 polyethylene / poly (ethylene oxide) PE / PEO, the feed ratio of ethyl ether methacrylate of poly (ethylene glycol) PEG-MA was 0.50 pounds per hour and the proportion of the initiator was 0.025 pounds per hour.

The films and the compositions of the examples 5 to 9 exhibit reverse phase morphology having a poly (ethylene oxide) grafted from polar vinyl monomer as the continuous phase and a polyolefin grafted from polar vinyl monomer as the discontinuous phase. For example 5, the amount of monomer grafted to the poly (ethylene oxide) was determined, by the proton NMR spectroscope in deuterated water, to be 9.52% by weight based on the amount of poly (ethylene oxide) in the mixture. The amount of unreacted monomer was determined, by the proton nuclear magnetic resonance (NMR) spectroscope in deuterated water, to be 2.02% by weight based on the amount of polyethylene and poly (ethylene oxide) in the mixture. The amount of monomer grafted in the polyethylene was determined to be 0.51% by weight by Fourier-Transform Infrared (FT-IR) and oxygen content analysis as described in the copending United States of America patent application No. 08 / 733,410 registered October 18, 1996 the full contents of which is incorporated herein by reference.

EXAMPLES 10 to 13 According to the invention, a 60/40% by weight mixture of low density polyethylene resin and poly (ethylene oxide), as described above in comparative example A, was fed to the extruder ZSK-30 in a proportion of 34 pounds per hour. The seven heating zones were all placed at 180 ° C. The screw speed was 300 revolutions per minute. In barrel 4 of the extruder, a monomer, a 2-hydroxyethyl methacrylate (abbreviated as H MA; commercially available from Aldrich Chemical Company of Milwaukee, Wl) was added to the specific ratio. In barrel 5 of the extruder, a free radical initiator was added in the specific ratio. The free radical initiator used in the following examples was 2, 5-dimethyl-2,5-di (t-butylperoxy) hexane and is commercially available from Atochem of Philadelphia, PA under the brand name Lupersol 101.

For example 10, the feeding ratio of the 2-hydroxyethyl methacrylate HEMA was 0.75 pounds per hour and the proportion of the initiator was 0.068 pounds per hour.

For example 11, the feeding ratio of the 2-hydroxyethyl methacrylate HEMA was 1.5 pounds per hour and the proportion of the initiator was 0.068 pounds per hour.

For example 12, the feeding ratio of the 2-hydroxyethyl methacrylate HEMA was 3 pounds per hour and the proportion of the initiator was 0.068 pounds per hour.

For example 13, the feeding ratio of the 2-hydroxyethyl methacrylate HEMA was 4.5 pounds per hour and the proportion of the initiator was 0.17 pounds per hour.

-JM-at--, Referring to Figures 5 to 8, 60/40 films of 2-hydroxyethyl methacrylate HEMA grafted linear density polyethylene by poly (ethylene oxide) LDPE / PEO exhibited reverse phase morphology that they have 2-hydroxyethyl-g-poly (ethylene oxide) HEMA-g-PEO methacrylate as the continuous phase and linear density 2-hydroxyethyl-g-polyethylene methacrylate HEMA-g-LDPE as the discontinuous phase.

The wet and dry mechanical properties of the four 60/40 polyethylene films by poly (ethylene oxide) PE / PEO of Examples 10 to 13 and Comparative Example A were determined and are presented in Table 1 below. The thickness of the films tested was measured and reported in thousands of an inch. The elongation to the break or tightness to the break of the tested films was measured and are reported as a percentage. The peak voltage or tensile strength of the films tested was measured and reported in units of MPa. The energy to the break or the resistance of the films tested was measured and reported in units of MJ / m3. And, the modulus or rigidity of the films tested was measured and is reported in units of MPa.

Table 1 Properties of Wet and Dry Stress Example No. A 10 11 12 13 Test Condition S H S H S H S H S H Thickness Film 4.5 4.4 4.5 4.6 4.2 4.7 4.5 4.5 5.0 4.6 Elongation at Break 650 650 580 80 650 70 700 70 580 50 Peak Voltage 15.3 12.8 13.3 3.3 9.0 1.5 10.3: 2.4 8.7 1.9 Energy at Breakthrough 70.3 69.3 55.5 1.5 44.5 0.6 54.5 0 .9 39.2 0.6 Module 109 58 64 23 76 11 60 17 65 14 Percentage of Loss on Woven Dry Property to Elongated Wet Breaking 0% 86% 90% 90% 91% Peak voltage 16% 75% 83% 77% 78% Energy at break 2% 97% 99% 98% 98% Module 47% 64% 85% 71% 79% The films comprising the compositions of the present invention are wettable and lose a significant part of their water soluble component, poly (ethylene oxide), upon exposure to water or aqueous solutions. Consequently, such films lose most of their mechanical properties when exposed to water and possess only a small fraction of their dry mechanical properties. The decrease in the mechanical properties of the wet films of the present invention, examples 10 to 13, against the dried films is illustrated in table 1 above. The films of the present invention have comparable dry properties with non-phase films .-C - .. J ..

Inverse of the same content of polyolefin and poly (ethylene oxide) but have significantly lower wet properties than films of non-reverse phase morphology.

The wet and dry tension curves for the non-reverse phase mixture of Comparative Example A are shown in Figure 9. As can be seen in Figure 9, a non-reverse phase mixing film does not lose an appreciable amount of its mechanical properties. when it is exposed to water. Specifically, the non-reverse phase film of Comparative Example A shown here does not lose, 0%, the elongation at break, and 16%, 2% and 47% lose at peak voltage, break energy and modulus, respectively. The non-reversed phase film of Comparative Example A was observed to be non-wettable. In contrast, the compositions and films of the present invention are wettable and lose a significant amount of their mechanical properties, including resistance to stress, when exposed to water. A significant decrease in tensile strength is illustrated in Figure 10. Figure 10 shows the dry and wet stress curves of a film of Example 10. It was determined that the film lost most of its tensile strength after 30 seconds of exposure to water.

Other mechanical properties of the films were measured before exposure to water (dry) and after -feá- --fcjjl-ist ^. -fa --- to exposure to water (wet). From dry to wet, the percentages in loss of mechanical properties for the film of Example 10 in tension (elongate to break), strength (peak tension), hardness (energy at break), and stiffness (modulus) are 86%, 75 %, 97% and 64% respectively. The bar graph of Figure 14 gives an illustration of a comparison of the mechanical properties of the wet and dry films of Example 10 against Comparative Example A. Such decreases in mechanical properties after exposure to water are desirable in many applications. Disposable with jets of water. Additionally, the film of example 10 was observed to be wettable by water and the surface of the film becomes sticky when immersed in water.

The wet and dry voltage curves for the reverse phase mixtures of Examples 11, 12 and 13 are shown in Figures 11, 12 and 13, respectively. Similarly, comparison bar graphs comparing the mechanical properties of the dry and wet films of examples 15, 16 and 17 against comparative example A are illustrated in figures 15, 16 and 17.

While the invention has been described with reference to a preferred embodiment, those skilled in the art will appreciate that various substitutions, omissions, changes and modifications can be made without depart from the spirit of it. Therefore, it is the intention that the above examples be considered merely exemplary of the present invention and not be considered a limitation thereof.

Claims

R E I V I N D I C A C I O N S

A reverse phase composition comprising: a) a polyolefin as a main constituent; Y b) a poly (ethylene oxide) as a minor constituent, whereby said reverse phase composition exhibits a reverse phase morphology so that the minor constituent forms a continuous phase in said composition and said main constituent forms a phase dispersed in said composition.
2. The reverse phase composition as claimed in Clause 1 further characterized in that it comprises an amount of polar vinyl monomer grafted to said polyolefin and said poly (ethylene oxide).
3. The reverse phase composition as claimed in Clause 1 characterized in that said polyolefin comprises more than 50 percent by volume of said reverse phase composition and said poly (ethylene oxide) it comprises at least one percent volume of said reverse phase composition.
4. The reverse phase composition as claimed in Clause 1 characterized in that said polyolefin comprises from 51 percent by volume to 99 percent by volume of said polyolefin or a combination of polyolefins including said polyolefin and a sufficient amount of said poly (ethylene oxide) or a combination of water-soluble polymers including said poly (ethylene oxide) to form a continuous phase around the dispersed polyolefin phase.
5. The reverse phase composition as claimed in Clause 1 characterized in that said composition comprises from about 55 volume percent to about 95 volume percent of said polyolefin or a combination of polyolefins including said polyolefin and from about 45 percent by volume to about 5 percent by volume of said poly (ethylene oxide or a combination of water-soluble polymers including said poly (ethylene oxide).
6. The reverse phase composition as claimed in Clause 1 characterized in that said composition comprises from about 60 percent by volume to about 85 percent by volume of said íí? L & tÁii A +? polyolefin or a combination of polyolefins including said polyolefin and from about 40 volume percent to about 15 volume percent of said poly (ethylene oxide) or a combination of water soluble polymers including said poly (ethylene oxide) ).
7. The reverse phase composition as claimed in Clause 2 characterized in that said polar vinyl monomer is selected from the group consisting of acrylates, methacrylates, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, poly (ethylene glycol) acrylates, poly (ethylene glycol) methacrylates, poly (ethylene glycol) diacrylates, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, acrylamide, glycidyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl metacrate, carboxymethyl acrylate, sodium acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-chloroacrylonitrile, 4-chlorophenyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, 4-nitrophenyl acrylate, pentabromophenyl acrylate, poly (propylene glycol) acrylates, poly (propylene glycol) methacrylates, 2-propene- l- sulfonic acid and its sodium salt, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfapropyl acrylate, 3-sulfopropyl methacrylate, poly (ethylene glycol) alkyl ether acrylates , poly (ethylene glycol) alkyl ether methacrylates, poly (ethylene glycol) ethyl ether acrylates, poly (ethylene glycol) ethyl ether methacrylates and derivatives and analogues thereof.
8. The reverse phase composition as claimed in Clause 2 characterized in that said polar vinyl monomer is selected from the group consisting of acrylates, methacrylates, 2-hydroxytyl acrylate, 2-hydroxyethyl methacrylate, poly (ethylene glycol) acrylates, poly (ethylene glycol) methacrylates, poly (ethylene glycol) alkyl ether acrylates, poly (ethylene glycol) alkyl ether methacrylates, poly (ethylene glycol) ethyl ether acrylates, poly (ethylene glycol) ethyl ether methacrylates and derivatives and analogs thereof.
9. The reverse phase composition as claimed in Clause 2 characterized in that said polar vinyl monomer comprises 2-hydroxyethyl methacrylate.
10. The reverse phase composition as claimed in Clause 1 characterized in that a total of about 0.1 percent by weight to about 30 percent by weight, based on the total amount of polyolefin and poly (ethylene oxide) , of the polar vinyl monomer is grafted onto said polyolefin and said poly (ethylene oxide).
11. The reverse phase composition as claimed in Clause 1 characterized in that a total of about 1 weight percent to about 20 weight percent, based on the total amount of polyolefin and poly (ethylene oxide) of a polar vinyl monomer is grafted onto said polyolefin and said poly (ethylene oxide).
12. The reverse phase composition as claimed in Clause 1 characterized in that a total of about 1 weight percent to about 10 weight percent, based on the total amount of polyolefin and poly (ethylene oxide) of the Polar vinyl monomer is grafted onto said polyolefin and said poly (ethylene oxide).
13. A film comprising a reverse phase composition as claimed in Clause 1.
14. The movie as claimed in the Clause 13 characterized in that the polyolefin in the dispersed phase has an average cross-sectional diameter of from about 0.1 microns to about 50 microns.
15. The movie as claimed in the Clause 13 characterized in that the polyolefin in the dispersed phase has an average cross-sectional diameter of from about 0.5 microns to about 30 microns.
16. The movie as claimed in the Clause 13 characterized because the polyolefin in the phase . «-.-- i -----. -ri-t.- "- • * ******." * _- "- dispersed has an average cross-sectional diameter of from about 0.5 microns to about 25 microns.
17. A film comprising at least one layer, wherein said at least one layer comprises: a) a volume of poly (ethylene oxide); Y b) a polyolefin volume greater than said volume of poly (ethylene oxide) and said at least one layer exhibits a reverse phase morphology so that said poly (ethylene oxide) forms a continuous phase in said at least one polyolefin layer and said form a phase dispersed in said at least one layer.
18. The film as claimed in Clause 17 characterized in that the ratio of the volume of polyolefin to the volume of poly (ethylene oxide) in at least one layer is greater than 1.1.
19. The film as claimed in Clause 17 characterized in that the volume ratio of the polyolefin to the volume of the poly (ethylene oxide) in said at least one layer is greater than 1.2.
20. The film as claimed in Clause 17 characterized in that the volume of the __ & ---, -...-.-.- * .- ,. -_5. --- -_. - ^^ - ^ e -. ^^ - l ----- a-. ethylene) comprises a grafted poly (ethylene oxide) and the polyolefin volume comprises a grafted polyolefin.
21. The film as claimed in Clause 17 characterized in that the volume of the poly (ethylene oxide) comprises a 2-hydroxyethyl methacrylate grafted to the poly (ethylene oxide) and the volume of polyolefin comprises a grafted polyolefin of 2-hydroxyethyl methacrylate .
22. A thermoplastic film comprising: a) from about 55 percent by volume to about 85 percent by volume of polyethylene; b) from about 45 volume percent to about 15 volume percent poly (ethylene oxide) and c) from about 0.1 weight percent to about 30 weight percent, based on the total amount of polyolefin and poly (ethylene oxide), of the polar vinyl monomer grafted to said polyethylene and said poly (oxide) of ethylene) so that said film exhibits a reverse phase morphology so that said poly (ethylene oxide) forms a continuous phase and said polyethylene forms k * xt «t * i! * ...__. au ..... a discontinuous dispersed phase in said thermoplastic film.
23. The thermoplastic film as claimed in Clause 22 characterized in that the polar vinyl monomer is poly (ethylene glycol) methacrylate or 2-hydroxyethyl methacrylate.
24. A reverse phase composition comprising: a) a polyolefin as a constituent of volumetric majority; Y b) poly (ethylene oxide) as a constituent of volumetric minority, said poly (ethylene oxide) has an average molecular weight of less than 200,000 grams per mole, wherein said reverse phase composition exhibits a reverse phase morphology so that the volumetric minority constituent forms a continuous phase in said composition and said bulk constituent forms a phase dispersed in said composition.
25. The reverse phase composition as claimed in Clause 24 characterized in that said - "" - • * - «- a-a-M aah» ».. A --.- j-i» J: .. »-. > .- _. The polymer (ethylene oxide) has an average molecular weight of less than about 150,000 grams per mole.
26. The composition reverse phase as claimed in clause 24 wherein said poly (ethylene oxide) consists essentially of a poly (ethylene oxide) having an average molecular weight of no more than about 100,000 grams per mole .
27. A reverse phase composition comprising: a) a polyolefin as the main volume component; Y b) a poly (ethylene oxide) as a minor volume component, wherein said lower volume component of poly (ethylene oxide) consists essentially of a poly (ethylene oxide) having an average molecular weight of not more than about 150,000 grams per mole or a poly (ethylene oxide) grafted with a polar vinyl monomer, whereby said reverse phase composition exhibits a reverse phase morphology so that said poly (ethylene oxide) forms a continuous phase in said composition and said polyolefin forms a phase dispersed in said continuous phase.
28. A method for making a reverse phase composition comprising combining: a) a volume of poly (ethylene oxide); b) a polyolefin volume, wherein said polyolefin volume is greater than said volume of the poly (ethylene oxide); c) a polar vinyl monomer; Y d) an initiator in a reaction vessel; and mixing the poly (ethylene oxide), polyolefin, initiator and monomer level polar vinyl under cutting conditions and temperatures sufficient to graft the polar vinyl monomer in the poly (ethylene oxide) or polyolefin and produce a Inverse phase composition, said reverse phase composition is characterized by a continuous phase of poly (ethylene oxide) and a dispersed polyolefin phase. -.-..- Ma ----- ~ - < - ~ - .. < - OR. rf-J-a., --l- -AjUiáH
29. The method as claimed in Clause 28 characterized in that the initiator is a caliber radical initiator.
30. The method as claimed in Clause 28 wherein the polar vinyl monomer is selected from the group consisting of acrylates, methacrylates, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, poly (ethylene glycol) acrylates, poly (ethylene glycol) methacrylates, poly (ethylene glycol) diacrylates , acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, acrylamide, glycidyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl methacrylate, carboxyetil acrylate, sodium acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-cloroacrinolitrilo, 4 -chlorophenyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, 4-nitrophenyl acrylate, pentabromophenyl acrylate, poly (propylene glycol) acrylates, poly (propylene glycol) methacrylates, 2-propene-l-sulphonic acid and its sodium salt, 2-sulfoethyl acrylate, sulfoethyl methacrylate 2-3-sulfapropil acrylate, sulfopropyl methacrylate 3-poly (ethylene glycol) ether alkyl acrylates, poly (ethylene glycol) ether alkyl methacrylates, poly (ethylene glyco l) ethyl ether acrylates, poly (ethylene glycol) ethyl ether methacrylates and derivatives and analogs thereof.
31. The method as claimed in Clause 28 characterized in that the polar vinyl monomer is a poly (ethylene glycol) methacrylate or 2-hydroxyethyl methacrylate.
32. The method as claimed in Clause 28 wherein the poly (ethylene glycol) methacrylate is poly (ethylene glycol) ethyl ether methacrylate and has an average molecular weight of not more than number of about 5,000 grams per mole.
33. The method as claimed in Clause 28 characterized in that the polar vinyl monomer is 2-hydroxyethyl methacrylate.
34. The method as claimed in Clause 28 characterized in that the reaction vessel is an extruder.
35. The method as claimed in Clause 7 characterized in that the extruder is a twin screw extruder.
36. The method as claimed in Clause 1 wherein sufficient to graft the polar vinyl monomer and comprise heating and mixing melt the poly (ethylene oxide), polyolefin, polar vinyl monomer and conditions the initiator.
37. The method as claimed in clause 34, wherein the conditions sufficient to graft the polar vinyl monomer in the poly (ethylene oxide) or polyolefin comprising heating the poly (ethylene oxide), polyolefin, the polar vinyl monomer and the free radical initiator at a temperature within the range of the melting point of the polyolefin at the decomposition temperature of the poly (ethylene oxide).
38. The method as claimed in Clause 28 wherein the conditions sufficient to graft the polar vinyl monomer in the poly (alkylene oxide dß ethylene) or polyolefin comprising heating the poly (ethylene oxide), the vinyl monomer polar and the free radical initiator at a temperature in the range of about 120 ° C to about 220 ° C.
39. The method as claimed in Clause 28 characterized in that the poly (ethylene oxide) has an initial approximate molecular weight ranging from about 50,000 grams per mole to about 8,000,000 grams per mole.
40. The method as claimed in Clause 39 characterized in that the poly (ethylene oxide) has an initial approximate molecular weight ranging from about 100,000 grams per mole to about 8,000,000 grams per mole.
41. The method as claimed in Clause 40 characterized in that the poly (ethylene oxide) has an initial approximate molecular weight ranging from about 200,000 grams per mole to about 6,000,000 grams per mole.
42. The method as claimed in Clause 28 characterized in that the polar vinyl monomer is added within the range of from about 0.1 to about 20 weight percent relative to the weight of the poly (ethylene oxide and polyolefin).
43. The method as claimed in Clause 42 wherein the polar vinyl monomer is added within the range of about 0.5 to about 10 percent by weight relative to the weight of poly (ethylene oxide) and the polyolefin.
44. The method as claimed in Clause 28 characterized in that the initiator is added within the range of about 0.05 to about 1 weight percent relative to the weight of the poly (ethylene oxide) and the polyolefin. . _ &- - -Mt "- * .- -«. _t_- ..? k mA »M-, fflrifru ^ ---- - * -
45. The method as claimed in Clause 44 characterized in that the initiator is added within the range of about 0.1 to about 0.75 percent by weight in relation to the weight of poly (ethylene oxide) and polyolefin.
46. The method as claimed in Clause 45 characterized in that the initiator is added within the range of about 0.1 to about 0.5 percent by weight relative to the weight of the poly (ethylene oxide) and the polyolefin.
47. The method as claimed in Clause 34 characterized in that said polyolefin and said poly (ethylene oxide) are supplied to the extruder before any of the initiator or monomer is supplied to the extruder.
48. The method as claimed in Clause 47 characterized in that the monomer and the initiator are added and supplied to the extruder by injection of a solution comprising the initiator and the monomer and the polyolefin and the poly (ethylene oxide) after that the polyolefin and the poly (ethylene oxide) have been melted and mixed.
49. The method as claimed in Clause 47 characterized in that the monomer is fed into the extruder and is dispersed in the polyolefin and in the poly (ethylene oxide) before the initiator has been added.
50. A reverse phase composition produced by the method as claimed in Clause 28.
51. A method for making a reverse phase composition comprising: add to a reaction vessel a volume of poly (ethylene oxide), a volume of polyolefin greater than the volume of poly (ethylene oxide), of from about 0.1 to about 20 weight percent relative to the weight of the poly (ethylene oxide) and polyolefin of a polar vinyl monomer and from about the range of about 0.05 to about 0.1 weight percent relative to the weight of poly (ethylene oxide) and of the polyolefin of an initiator of free radical. mix the poly (ethylene oxide), the polyolefin, the polar vinyl monomer and the free radical initiator; Y heating the mixture to above the melting point of the poly (ethylene oxide) to form a reverse phase composition characterized by a continuous phase, of poly (ethylene oxide) and a dispersed phase of polyolefin.
52. A method for making a reverse phase composition comprising: adding a volume of poly (ethylene oxide), a volume of polyolefin greater than the volume of poly (ethylene oxide), of from about 0.1 to about 20 weight percent of a polar vinyl monomer in relation to weight of the poly (ethylene oxide), and a free radical initiator inside of an extruder; Y mixing and heating the poly (ethylene oxide), the polyolefin, the polar vinyl monomer and the free radical initiator while they are extruded so as to form a reverse phase composition characterized by a continuous phase of poly (ethylene oxide) and a dispersed phase of polyolefin.
53. A method for making a reverse phase composition comprising: combining a volumetric majority of polyolefin and a volumetric minority of poly (ethylene oxide) said poly (ethylene oxide) has an average molecular weight of íffHí "'^» &gil; --il & ---. t ... ^ A-¿??, ----. less than 200,000 grams per mole, wherein said reverse phase composition exhibits a reverse phase morphology such that said volumetric minority of the poly (ethylene oxide) forms a continuous phase in said composition and said volumetric majority of said polyolefin constituent forms a phase dispersed in said composition.
54. The method for making a reverse phase composition as claimed in Clause 53 characterized in that said poly (ethylene oxide) has an average molecular weight of less than about 150,000 grams per mole.
55. The method for making a reverse phase composition as claimed in Clause 53 characterized in that said poly (ethylene oxide) consists essentially of a poly (ethylene oxide) having an average molecular weight of not more than about 100,000 grams per mole
56. A method for making a reverse phase composition comprising: melt mixing a volume of polyolefin and a volume of poly (ethylene oxide) said volume of polyolefin is greater than said volume of poly (ethylene oxide) and said poly (ethylene oxide) consists essentially of a poly (oxide) of ethylene) having an average molecular weight of no more than about 150,000 grams per mole or a poly (ethylene oxide) grafted with a polar vinyl monomer, whereby said reverse phase composition exhibits a reverse phase morphology of said poly (ethylene oxide) forms a continuous phase in said composition and said polyolefin forms a phase dispersed in said continuous phase. U M E N Reverse phase compositions comprising a polyolefin, such as polyethylene, and poly (ethylene oxide) and methods for making the reverse phase compositions are described. The reverse phase compositions exhibit in a reverse phase in which the minor constituent of volume, the poly (ethylene oxide), forms a continuous phase and the bulk constituent, the polyolefin, forms a discontinuous or dispersed phase in the continuous poly (ethylene oxide) phase. The reverse phase compositions have beneficial water degradable properties and can be used in the manufacture of disposable personal hygiene articles. In at least one desirable embodiment, the polyolefin and the poly (ethylene oxide) are grafted with a polar vinyl monomer in reactive extrusion processes. Lt-JM-I ^ ...