CA2275669A1 - Water-modifiable flushable polyolefin-containing film - Google Patents
Water-modifiable flushable polyolefin-containing film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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Abstract
A water-modifiable polyolefin-containing film having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of poly(ethylene oxide). Desirably, the polyolefin can be modified by grafting onto the polyolefin from about 0.1 weight percent to about 30 weight percent of a monomer selected from 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate. More desirably, the polyolefin and poly(ethylene oxide) have grafted thereto a total of from about 0.1 weight percent to about 30 weight percent of the monomer. The polyolefin-containing film, when immersed in water for about 30 seconds, will have a loss of a least 10 % in two or more of the tensile properties: percent strain-to-break, peak stress, energy-to-break and modulus when compared to the dry or pre-immersion values.
Description
WATER-MODIFIABLE FLUSHABLE POLYOLEFIN-CONTAINING FILM
The application claims priority from the U.S. Provisional Application 60/034,616 filed December 31,1996, the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to a flushable polyolefin-containing film. More particularly, the present invention relates to a flushable polyolefin-containing film having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide).
BACKGROUND OF THE INVENTION
Personal care products, such as diapers, sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components and materials. Such articles typically have some portion, usually the backing layer) liner, or baffle constructed of a liquid repellent film material. This repellent material is appropriately constructed to minimize or prevent the exudation of the absorbed liquid from the article and to obtain greater utilization of the absorbent capacity of the product.
The liquid repellent ~Im commonly used includes plastic materials such as polyethylene films and the like.
Although such products are relatively inexpensive) sanitary and easy to use, disposal of a soiled product is not without its problems. With greater interest being placed in protecting the environment today, there is a need to develop materials that are more compatible with the existing and developing waste disposal technologies while still delivering performance consumers have come to expect. An ideal disposal alternative would be to use municipal sewage treatment and private residential septic systems.
Products suited for disposal in sewage systems can be flushed down a convenient toilet and are termed "fiushable." While flushing such articles would be convenient, the liquid repellent material which normally does not disintegrate in water tends to plug toilets and sewer pipes. It therefore becomes necessary, although undesirable, to separate the barrier film material from the absorbent article prior to flushing.
In addition to the article itself, typically the packaging in which the disposable article is distributed is also made from a water resistant material. Water resistivity is necessary to prevent the degradation of the packaging from environmental conditions and to protect the disposable articles therein. Although this packaging may be safely stored with other refuse for commercial disposal, and especially in the case of individual w packaging of the products, it is often more convenient to dispose of the packaging in the toilet with the discarded disposable article. However) in the cases where such packaging is composed of a water resistant material, plugging of the drains to the toilet typically results.
Desirably, a commercial, flushable product should be relatively responsive to water and be transportable in a sewer system. Commercially available water soluble polymers, such as polyethylene oxide (PEO), polyvinyl alcohol (PVOH), acrylamide polymers, acrylic acid-based polymers, and cellulose derivatives, possess the desired characteristics for flushability, such as water solubility andlor water dispersibility.
However, due to their in-use degradability and storage degradation, these materials function poorly as components in personal care products. Other disadvantages are that these polymers are difficult to process and are substantially more expensive than polyolefins.
The requirements for a functional and flushable product provide a substantial challenge in finding suitable materials with the desired properties. In an attempt to overcome the flushability problem of a water resistant film the prior art has modified the water resistant polymer. One of the more useful ways of modifying polymers involves blending them with other polymers of different structures and properties.
Polymer blends of polyolefins and pofy(ethylene oxide) have been shown to be water modifiable at expectedly low weight % polyolefin levels. Such blends would be anticipated to be flushable when exposed to water in a toilet but do not possess the dry mechanical properties required for functionality in use. Moreover, the high content of poiy(ethylene oxide) makes such materials prohibitively expensive for use in a disposable personal hygiene article such as a sanitary napkin, diaper and the like.
Polymer blends of polyolefins and polyethylene oxide) containing greater than about 45 weight percent of polyolefin are generally water resistant and are not water modifiable.
in view of the problems of the prior art, it remains highly desirable to provide a water modifiable film having a substantial portion of thereof composed of a polyolefin.
More desirably, the water modifiable film should have greater than about 55 weight percent of a polyolefin. When dry, the film should have the mechanical properties necessary for functionality. When wet, the films should lose at least a portion of its mechanical properties which would render the film flushable and transportable in a sewer system. Such films could be used for making flushable barrier films for personal care products.
SUMMARY OF THE INVENTION
Briefly) the present invention provides for a water-modifiable film or other thermoplastic article having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide). As used herein "water modifiable"
means that a four mil (one mil equals 0.001 of an inch) thick film, when immersed in water for 30 seconds, will have modified by greater than 10~o two or more of the following tensile properties: percent strain-to-break, peak stress, energy-to-break and modulus.
To determine the degree of modification, the 'Snret" values are compared to the pre-immersed or "dry" film values.
Another embodiment of the invention is a water-mod~able film having greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of poly{ethylene oxide). The polyolefin is modified by having from about 1 weight percent to about 30 weight percent, based on the total weight of the polyolefin and polyethylene oxide), of a monomer grafted onto the polyoiefin backbone.
Preferably the monomer is 2-hydroxyethyi methacrylate or polyethylene glycol ethyl ether methacrylate.
Another embodiment of the invention is a water modifiable film having greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of a modified poly(ethyiene oxide). The polyolefin and polyethylene oxide) are modified by having a total of from about 1 weight percent to about 30 weight percent, based on the weight of the combined pofyolefin and poiy(ethyfene oxide), of a monomer grafted thereto. Preferably the monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate.
It is an object of the invention to provide a polyolefin-containing film that is water modifiable. More specifically, it is an object of the invention to provide a polyolefin-containing film having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide) that is water modifiable.
It is another object of the invention to provide a water modifiable, polyolefin-containing film that when immersed in water for about 30 seconds at least two of the following tensile properties: percent strain-to-break, peak stress, energy-to-break and modutus lose at least 10% of its value relative to the dry film value.
The application claims priority from the U.S. Provisional Application 60/034,616 filed December 31,1996, the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to a flushable polyolefin-containing film. More particularly, the present invention relates to a flushable polyolefin-containing film having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide).
BACKGROUND OF THE INVENTION
Personal care products, such as diapers, sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components and materials. Such articles typically have some portion, usually the backing layer) liner, or baffle constructed of a liquid repellent film material. This repellent material is appropriately constructed to minimize or prevent the exudation of the absorbed liquid from the article and to obtain greater utilization of the absorbent capacity of the product.
The liquid repellent ~Im commonly used includes plastic materials such as polyethylene films and the like.
Although such products are relatively inexpensive) sanitary and easy to use, disposal of a soiled product is not without its problems. With greater interest being placed in protecting the environment today, there is a need to develop materials that are more compatible with the existing and developing waste disposal technologies while still delivering performance consumers have come to expect. An ideal disposal alternative would be to use municipal sewage treatment and private residential septic systems.
Products suited for disposal in sewage systems can be flushed down a convenient toilet and are termed "fiushable." While flushing such articles would be convenient, the liquid repellent material which normally does not disintegrate in water tends to plug toilets and sewer pipes. It therefore becomes necessary, although undesirable, to separate the barrier film material from the absorbent article prior to flushing.
In addition to the article itself, typically the packaging in which the disposable article is distributed is also made from a water resistant material. Water resistivity is necessary to prevent the degradation of the packaging from environmental conditions and to protect the disposable articles therein. Although this packaging may be safely stored with other refuse for commercial disposal, and especially in the case of individual w packaging of the products, it is often more convenient to dispose of the packaging in the toilet with the discarded disposable article. However) in the cases where such packaging is composed of a water resistant material, plugging of the drains to the toilet typically results.
Desirably, a commercial, flushable product should be relatively responsive to water and be transportable in a sewer system. Commercially available water soluble polymers, such as polyethylene oxide (PEO), polyvinyl alcohol (PVOH), acrylamide polymers, acrylic acid-based polymers, and cellulose derivatives, possess the desired characteristics for flushability, such as water solubility andlor water dispersibility.
However, due to their in-use degradability and storage degradation, these materials function poorly as components in personal care products. Other disadvantages are that these polymers are difficult to process and are substantially more expensive than polyolefins.
The requirements for a functional and flushable product provide a substantial challenge in finding suitable materials with the desired properties. In an attempt to overcome the flushability problem of a water resistant film the prior art has modified the water resistant polymer. One of the more useful ways of modifying polymers involves blending them with other polymers of different structures and properties.
Polymer blends of polyolefins and pofy(ethylene oxide) have been shown to be water modifiable at expectedly low weight % polyolefin levels. Such blends would be anticipated to be flushable when exposed to water in a toilet but do not possess the dry mechanical properties required for functionality in use. Moreover, the high content of poiy(ethylene oxide) makes such materials prohibitively expensive for use in a disposable personal hygiene article such as a sanitary napkin, diaper and the like.
Polymer blends of polyolefins and polyethylene oxide) containing greater than about 45 weight percent of polyolefin are generally water resistant and are not water modifiable.
in view of the problems of the prior art, it remains highly desirable to provide a water modifiable film having a substantial portion of thereof composed of a polyolefin.
More desirably, the water modifiable film should have greater than about 55 weight percent of a polyolefin. When dry, the film should have the mechanical properties necessary for functionality. When wet, the films should lose at least a portion of its mechanical properties which would render the film flushable and transportable in a sewer system. Such films could be used for making flushable barrier films for personal care products.
SUMMARY OF THE INVENTION
Briefly) the present invention provides for a water-modifiable film or other thermoplastic article having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide). As used herein "water modifiable"
means that a four mil (one mil equals 0.001 of an inch) thick film, when immersed in water for 30 seconds, will have modified by greater than 10~o two or more of the following tensile properties: percent strain-to-break, peak stress, energy-to-break and modulus.
To determine the degree of modification, the 'Snret" values are compared to the pre-immersed or "dry" film values.
Another embodiment of the invention is a water-mod~able film having greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of poly{ethylene oxide). The polyolefin is modified by having from about 1 weight percent to about 30 weight percent, based on the total weight of the polyolefin and polyethylene oxide), of a monomer grafted onto the polyoiefin backbone.
Preferably the monomer is 2-hydroxyethyi methacrylate or polyethylene glycol ethyl ether methacrylate.
Another embodiment of the invention is a water modifiable film having greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of a modified poly(ethyiene oxide). The polyolefin and polyethylene oxide) are modified by having a total of from about 1 weight percent to about 30 weight percent, based on the weight of the combined pofyolefin and poiy(ethyfene oxide), of a monomer grafted thereto. Preferably the monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate.
It is an object of the invention to provide a polyolefin-containing film that is water modifiable. More specifically, it is an object of the invention to provide a polyolefin-containing film having greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide) that is water modifiable.
It is another object of the invention to provide a water modifiable, polyolefin-containing film that when immersed in water for about 30 seconds at least two of the following tensile properties: percent strain-to-break, peak stress, energy-to-break and modutus lose at least 10% of its value relative to the dry film value.
WO 98l29S02 PCTILTS97123810 DETAILED DESCRIPTION OF THE INVENTION
Although the present invention is described with reference to a water modifiable film, one skilled in the art would understand the utility of the invention toward other thermoplastic articles that can be extruded or injection molded. In one embodiment of the invention) the water modifiable film comprises greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide).
Desirably, the water-modifiable film comprises from about 55 weight percent to about 85 weight percent of a polyolefin and from about 45 weight percent to about 15 weight percent of polyethylene oxide). More desirably, the water-modifiable film comprises from about 65 weight percent to about 85 weight percent of a polyolefin and from about 35 weight percent to about 15 weight percent of polyethylene oxide). The polyethylene oxide) useful in making the film should have a molecular weight of less than about 200,000 and more preferably about 700,000.
The saturated ethylene polymers useful in the practice of this invention are homopolymers or copolymers of ethylene and polypropylene and are essentially linear in structure. As used herein, the term "saturated" refers to polymers which are fully saturated, but also includes polymers containing up to about 5% unsaturation.
The homopolymers of ethylene include those prepared under either low pressure, i.e., linear low density or high density polyethylene, or high pressure) i.e., branched or low density polyethylene. The high density polyethylenes are generally characterized by a density that is about equal to or greater than 0.94 grams per cubic centimeter (glcc).
Generally, the high density potyethylenes useful as the base resin in the present invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc. The polyethylenes can have a melt index, as measured at 2.16 kg and 190°C, ranging from about 0.005 decigrams per minute (dg/min) to 100 dg/min. Desirably, the polyethylene has a melt index of 0.01 dglmin to about 50 dglmin and more desirably of 0.05 dg/min to about 25 dg/min.
Alternatively) mixtures of polyethylene can be used as the base resin in producing the graft copolymer compositions, and such mixtures can have a melt index greater than 0.005 dg/min to less than about 100 dglmin.
The low density polyethylene has a density of less than 0.94 glcc and are usually in the range of 0.91 g/cc to about 0.93 g/cc. The low density polyethylene has a melt index ranging from about 0.05 dg/min to about 100 dg/min and desirably from 0.05 dglmin to about 20 dglmin. 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.s0gicc.
Generally, polypropylene has a semi-crystalline structure having a molecular weight of about 40,000 or more, a density of about 0.90 g/cc) a melting point of 168 to 171 °C for isotactic polypropylene and a tensile strength of 5000 psi.
Polypropylene can also have other tacticities including syndiotactic and atactic.
The above polyolefins can also be manufactured by using the well known multiple-site Ziegler-Natta catalysts or the more recent single-site metallocene catalysts.
The metallocene catalyzed polyolefins have better controlled polymer microstructures than palyolefins manufactured using Ziegler Natta catalysts) including narrower molecular weight distribution, well controlled chemical composition distribution, co-monomer sequence length distribution, and stereoregularity. Metallocene catalysts are known to polymerize propylene into atactic, isotactic, syndiotactic, isotactio-atactic stereoblock copolymer.
Copolymers of ethylene which can be useful in the present invention may include copolymers of ethylene with one or more additional polymerizable, unsaturated monomers. Examples of such copolymers include) but are not limited to, copolymers of ethylene and alpha olefins (such as propylene, butane, hexane or octane) including linear low density polyethylene, copolymers of ethylene and vinyl esters of linear or branched carboxylic acids having 1-24 carbon atoms such as ethylene-vinyl acetate copolymers, and copolymers of ethylene and acrylic or methacrylic esters of linear) branched or cyclic alkanols having 1-28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acrylate copolymers) such as ethylene-methyl acrylate copolymers.
Polyethylene oxide) is available from Union Carbide Corporation under the trade name of POLYOX~. Typically, polyethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65°C, above which polyethylene oxide) resin becomes thermoplastic and can be formed by molding, extrusion and other methods known in the art.
In another embodiment of the invention, the water modifiable film comprises greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of poly(ethyiene oxide). Desirably, the water modifiable film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of polyethylene oxide). More desirably, the water modifiable ~Im comprises from about 65 weight percent to about 85 weight percent of a modified polyofe~n and from about 35 weight percent to about 15 weight percent of polyethylene oxide). The polyolefin is modified by having grafted thereto from about 0.1 weight percent to about 30 weight percent, based on the weight of the polyolefin and poly(ethyiene oxide), of a monomer. Desirably, the polyolefin is modified by having grafted thereto from about 1 weight percent to about 20 weight percent, and more desirably, from about 1 weight percent to about 10 weight percent, based on the weight of the polyolefin and polyethylene oxide)) of a monomer.
Generally, the modified polyolefin is made by feeding to an extruder an amount of polyolefin, monomer and a free radical initiator. Preferably the monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate. The modified polyolefin and polyethylene oxide) is then melt blended in an extruder to form the water modifiable film. The method of making the modified polyolefin is described in greater detail in copending U.S. patent application 081733,410 filed October 18,1996 entitled "METHOD
HYDROXYETHYL METHACRYLATE GRAFTED THERETO", the entire disclosure of which is incorporated herein by reference. In accordance with this embodiment of the invention) suitable polyethylene oxide) polymers can have an average molecular weight ranging from 100,000 to about 8,000,000.
The free radical initiators which can be used to graft the monomer onto the pofyolefin include acyl peroxides such as benzoyl peroxide; dialkyl; diaryl;
or aralkyl peroxides such as di-t-butyl peroxide; dicumyl peroxide; cumyl butyl peroxide;
1,1-di-t-butyl peroxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis {t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene);
peroxyesters such as t-butyl peroxypivalate; t butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2,5-di(perbenzoate); t-butyl di(perphthalate); dialkyl peroxymonocarbonates and peroxydicarbonates; hydroperoxides such as t-butyl hydroperoxide, p-methane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. Azo compounds such as azobisisobutyronitrile may also be used.
In yet another embodiment of the invention a water modifiable film comprises greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of modified poly{ethylene oxide). Preferably the water modifiable film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of modified polyethylene oxide). More desirably) the water modifiable film comprises from about 65 weight percent to about 85 weight percent of a modified polyolefin and from about 35 weight percent to about 15 weight percent of modified polyethylene oxide).
Polyethylene oxide) polymers suitable for this embodiment of the present invention can have a molecular weight ranging from 100,000 to 8,000,000. The polyolefin and polyethylene oxide) are modified by grafting thereto a total of from about 0.1 weight percent to about 30 weight percent, based on the weight of the polyolefin and polyethylene oxide), of the monomer. Desirably, the polyolefin and poly(ethyiene oxide) have a total of from about 1 weight percent to about 20 weight percent of the monomer grafted thereto. More desirably) the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 10 weight percent of the monomer grafted thereto.
The water modifiable film of the present invention can be made as described in copending U.S. patent application having U.S. serial no. 081777,226 filed on December 31) 1996 and entitled "BLENDS OF POLYOLEFIN AND POLYETHYLENE OXIDE) AND
PROCESS FOR MAKING THE BLENDS", the entire disclosure of which is incorporated herein by reference. Generally, the film is made by melt blending the desired weight ratios of a mixture of the polyolefin, polyethylene oxide), the monomer and the free radical initiator in an extruder and at a reaction temperature where the polyolefin and polyethylene oxide) are converted to a molten state. Preferably) the polyolefin and polyethylene oxide) are added at the beginning of the extruder. After melting, the monomer is added to the melt blend. Further down the extruder barrel, the free radical initiator is fed to the melt blend.
When modifying the polyolefin alone or together with the polyethylene oxide), the amount of free radical initiator added to the extruder should be an amount sufficient to graft from about 1 percent to 100 percent of the monomer onto the polymer) i.e., the polyolefin or polyolefin and polyethylene oxide). This can range from about 0.1 weight percent to about 2 weight percent of initiator. Preferably, the amount of initiator added to the extruder ranges from about 0.1 weight percent to about 1 weight percent wherein all such ranges are based on the amount of monomer added to the melt blend.
The water-modifiable polyolefin films of the present invention will, when immersed in water for about 30 seconds, have modified at least two of the tensile properties:
percent stain-to-break, peak stress, energy-to break and modulus by greater than 10%.
Desirably, at least two of the tensile properties will be reduced greater than about 25%.
More desirably, at least two of the tensile properties will be reduced from about 25% to about 98%, and even more desirably at least two of the tensile properties:
percent stain-to-break, peak stress, energy-to break and modulus will be reduced from about 30% to about 80%. The values in determining the extent of the tensile property or properties modification are relative to the dry condition, i.e. pre-immersion value for that measured property.
The present invention is illustrated in greater detail by the specific examples presented below. It is to be understood that these examples are illustrative embodiments and are not intended to be limiting of the invention, but rather are to be construed broadly within the scope and content of the appended claims.
COMPARATIVE EXAMPLE A
A 60140 weight percent blend of low density polyethylene {PE) having 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) and polyethylene oxide) (PEO) having a molecular weight of 200,000 g/mol (POLYOX~
WSRN-80 available from Union Carbide Corp.) was fed to a Haake counter rotating twin screw extruder at a rate of 5 pounds per hour (Iblhr). The extruder had a length of 300 millimeters. Each conical screw had 30 millimeters diameter at the feed port and a diameter of 20 millimeters at the die. The extruder had four heating zones set at 170, 180, 180 and 190°C. The screw speed of the extruder was 150 rpm.
Film processing of all the blends was performed using a Haake extruder counter-rotating twin screw extruder as described above with the following modifications. The extruder included a 4 inch slit die at a temperature of 195 °C. The screw speed was at 30 rpm. A chilled wind-up roll was used to collect the film. The chilled roll was operated at a speed sufficient to form a film having a thickness of about 4 mils (about 0.004 of an inch) and was maintained at a temperature of 15-20°C.
Dry tensile tests were performed on a Sintech 1lD tensile tester available from MTS Systems Corp., Machesny Park, IL. The film was cut into a type V dogbone shape in accordance with ASTM D638. The test was pertormed with a grip separa#ion of millimeters and a crosshead speed of 4 millimeterslsecond.
Wet tensile tests were pertormed on a Vitrodyne V1000 mini-tensile tester available from Chatillon, Greensboro, NC. The film samples were placed in the grips and the testing apparatus was submerged in ambient temperature, non-stirred water for 30 seconds. The test was then run under the same conditions as the dry tensile test. Peak stress, percent strain-to-break, energy-to-break (as area under stress versus strain curve) and modulus were calculated using the actual stress versus strain values recorded from the tensile tester for each dry or wet tensile test. The peak stress was recorded as the greatest stress value. The percent stain-to-break was recorded as the percent strain value at break. The energy-to-break (area under stress versus stain curve) was calculated by the summation of rectangular slices" under the curve determined for each strain value recorded from the tensile test, using the following formula:
((Strain valuex - Strain valuex.,) x (Stress valueX + Stress valuex_~)) / 2 where "x" is the sequential number of the slice. The modulus was calculated by linear regression of the initial region of the stress versus strain curve.
The dry and wet properties of the ~Im produced from the blend in Comparative Example A are indicated in Table 1 below.
Example #- ~ #A
dry wet Thickness (mil) 4.1 4.2 Strain-to-Break 330 300 Peak Stress - (MPa)16.6 16.2 Energy-break (x10 39.4 38.4 Jlm') Modulus (MPa) 128.4 103.8 Loss from Dry to ~ #A
Wet Strain-to-Break 9%
Peak Stress 2~
Energy-to-Break 3%
Modulus 20%
This example shows typical polymer blends in which the volumetric majority of the blend is water resistant. The polymer blend was not water modifiable after 30 seconds of submersion in water.
For Examples 1-3) the low density polyethylene (Dow 5031) was modified by grafting thereto polyethylene glycol methacrylate (PEG-MA; available from Aldrich Chemical Company, Milwaukee, WI). A Haake extruder as described in Comparative Example A above was used. The extruder had four heating zones set at 770, 780, and 190°C. The screw speed of the extruder was 150 rpm. The feed to the extruder comprised contemporaneously adding, at the extruder feed throat, 5 Iblhr of polyethylene and the specified amounts of PEG-MA and free radical initiator ((2,5-dimethyl-2,5-di(t-butylperoxy) hexane, supplied by Atochem) 2000 Market St.) Philadelphia, PA
under the tradename Lupersol 101).
For Example 1 the PEG-MA feed rate was 0.125 Iblhr and the initiator rate was 0.0125 Ib/hr.
For Example 2 the PEG-MA feed rate was 0.25 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 3 the PEG-MA feed rate was 0.5 Ib/hr and the initiator rate was 0.025 Ib/hr.
A 60/40 weight percent blend. of polyethylene and polyethylene oxide) was prepared following the procedure of Comparative Example A, except the modified polyethylene of each example was substituted for the unmodified polyethylene of Comparative Example A.
The dry and wet properties of the film produced from the blends in Examples 1-are indicated in Table 2 below.
Example #- #1 #2 #3 dry wet dry wet dry wet Thickness (mil) 4.5 4.5 4.0 4.0 5.0 5.0 Strain-to-Break 330 110 320 70 170 30 Peak Stress - (MPa)13.8 7.0 11.4 4.9 12.2 3.1 Energy-break (x10 32.7 6.7 27.6 2.4 16.5 0.5 J/m ) Modutus (MPa) 117.874.4103.7 56.3119.4 39.4 Loss from Dry to #1 #2 #3 Wet Strain-to-Break 65% 79% 82%
Peak Stress 49% 57% 75%
Energy-to-Break 80% 91 % 97%
Modulus 37% 46% 33%
In accordance with the invention, Examples 1-3 illustrate a water modifiable film having a modified polyethylene where the polyethylene has PEG-MA grafted thereto and unmodified polyethylene oxide). The films were water modifiable after 30 seconds of submersion in water.
Examples 4-7 A 60/40 weight percent resin blend of tow density polyethylene, Dow 5031, and polyethylene oxide) having a molecular weight of 200,000 g/mol (POLYOX~ WSRN-80) was fed to a Haake extruder as described in Comparative Example A at a rate of pounds per hour (Iblhr). Contemporaneously with the polymer feed to the extruder, specified amounts of the monomer, PEG-MA) and free radical initiator (Lupersol 101 }
were added at the feed throat. The extruder had four heating zones set at 170, 180, 180 and 190°C. The screw speed of the extruder was 150 rpm.
For Example 4 the PEG-MA feed rate was 0.125 tb/hr and the initiator rate was 0.0125 Iblhr.
For Example 5 the PEG-MA feed rate was 0.25 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 6 PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
For Example 7 the PEG-MA feed rate was 0.75 Ib/hr and the initiator rate was 0.0375 Ib/hr.
The dry and wet properties of the film produced from the blends in Examples 4-are indicated in Table 3 below.
Example #- #4 ~ #6 #7 #5 ~
dry wet dry wet dry wet dry wet Thickness (mil) 4.4 4.4 5.6 5.5 4.2 4.2 4.9 4.6 %Strain 400 70 280 50 590 90 250 50 Peak Stress - (MPa)9.3 3.7 8.3 3.1 9.2 3.5 5.2 1.3 Energy-break (x10 30.61.7 18.1 0.9 46.8 2.0 9.8 0.3 J/m ) Modulus (MPa) 90.141.991.2 32.786.2 38.064.414.5 Loss from Dry to #4 #5 ~ #6 #7 Wet Strain 83% 83% 85% 81 Peak Stress 60% 63% 62% 75%
Energy-to-Break 94% 95% 96% 97%
Modulus 53% 64% 56% 77%
For Examples 4-7 the amount of monomer grafted to polyethylene was 0.65 weight percent) 1.03 weight percent, 0.51 weight percent and 1.13 weight percent) respectively. The weight percent of monomer grafted to the polyethylene was determined by FT-IR and elemental oxygen content analysis as described in copending U.S. patent application 081733,410 filed October 18, 1996. For Example 6 the amount of monomer grafted to the polyethylene oxide) was determined to be 9.66 weight percent by proton NMR spectroscopy.
In accordance with the invention, Examples 4-7 the water modifiable films were polymer blends of 60 weight percent of a modified polyethylene and 40 weight percent a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have PEG-MA grafted thereto. The films of these polymer blends were water-modifiable after 30 seconds of submersion in water. A dramatic loss in tensile properties was observed for the films from dry to wet.
Examples 8-11 For Examples 8-11, a low density polyethylene) Dow 5031, and polyethylene oxide) (V1ISRN-80) blend was prepared following the procedure of Example 4 having the respective resin weight ratios, PEG-MA feed rates and initiator rates indicated.
For Example 8 the blend was 65/35 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 9 the blend was 70/30 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
For Example 10 the blend was 75125 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 lb/hr.
For Example 11 the blend was 80/20 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
The dry and wet properties of the film produced from the btends in 8-11 are indicated in Table 4 below.
Exampte #- #8 #9 #10 #11 ~~
dry wet dry wet dry wet dry wet Thickness (mil) 5.0 4.8 5.0 5.1 4.6 4.4 4.4 5.2 %Strain 340 80 300 130 260 220 180 150 Peak Stress - (MPa)7.5 3.6 10.35.8 11.3 10.5 11.4 11.4 Energy-break (x10 21.1 1.6 23.46.2 22.8 16.2 16.8 14.7 J/m) Modulus {MPa) 91.1 41.090.955.6 119.972.5 138.480.6 Loss from Dry to #8 #9 #10 #11 Wet Strain 76% 57% 15% 17%
Peak Stress 52% 44% 7% 0%
Energy-to-Break 92% 74% 29% 13%
Modulus 55% 39% 40% 42%
In accordance with the invention, Examples 8-11 were films from polymer blends having greater than about 60 weight percent of a modified polyethylene and less than about 40 weight percent of a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have PEG-MA grafted thereto. The films of these polymer blends was water modifiable after 30 seconds of submersion in water. A loss in tensile properties was observed for the films from dry to wet.
Examples 12-15 For Examples 12-15) a 60/40 weight percent resin blend of low density polyethylene (Dow 5031} and polyethylene oxide) (V1lSRN-80} was prepared following the procedure of Example 4) except the monomer used was 2-hydroxyethyl methacrylate.
The respective monomer feed rates and initiator rates are indicated.
For Example 12 the 2-hydroxyethyl methacrylate feed rate was 0.125 Iblhr and the initiator rate was 0.0125 Ib/hr.
For Example 13 the 2-hydroxyethyl methacrytate feed rate was 0.25 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 14 the 2-hydroxyethyl methacrylate feed rate was 0.5 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 15 the 2-hydroxyethy! methacrylate feed rate was 0.75 lblhr and the initiator rate was 0.0375 Ib/hr.
The dry and wet properties of the film produced from the blends in 12-15 are indicated in Table 5 below.
Example #- #12 #13 #14 #15 dry wet dry wet dry wet dry wet Thickness (mil) 4.5 4.6 4.2 4.7 4.5 4.5 5.0 4.6 %Strain 350 50 390 40 420 40 350 30 Peak Stress - (MPa)13.33.3 9.0 1.5 10.32.4 8.7 1.9 Energy-break (x10' 33.30.8726.7 0.3632.70.51 23.60.37 J/m) Modulus (MPa) 107 38.8126 18.499.628.7 109 23.2 Loss from Dry to #12 #13 #14 #15 Wet Strain 86% 90% 90% 91 Peak Stress 75% 83% 77% 78%
Energy-to-Break 97% 99% 98% 98%
Modulus 64% 85% 71 % 79%
In accordance with this invention) Examples 12-15 were films of polymer blends having 60 weight percent of a modified polyethylene and 40 weight percent of a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have 2-hydroxyethyl methacrylate grafted thereto. The dims of these polymer blends was water-modifiabte after 30 seconds of submersion in water.
Example 16 a For Examples 16, a Wemer & Pfleiderer ZSK-30 extruder (available from Wemer & Pfleiderer, Ramsey, New Jersey) was used. The extruder had a pair of co-rotating screws arranged in parallel. The center distance between the two shafts was 26.2 mm.
The nominal screw diameter was 30 mm. The actual outer screw diameter was 30 mm.
The inner screw diameter was 21.3 mm. The thread depth was 4.7 mm. The extruder had 14 processing barrels, with 13 heated ban-els divided into 7 heating zones. The overall processing length was 1340 mm.
A 60140 weight percent resin. blend of low density polyethylene (Dow 5031) and poly(ethytene oxide) having a molecular weight of 100,000 g/mol (POLYOX~ WSRN-10) was fed to the ZSK-30 extruder at a rate of 35 Iblhr. The seven heating zones were all set at 180 degrees C. The screw speed was 300 rpm.
The dry and wet properties of the film produced from the blend in Example 16 are indicated in Table 6 below.
Example #- #16 dry wet Thickness (mil) 3.2 3.2 ~Strain 430 60 Peak Stress - (MPa)11.3 3.6 Energy-break (x10 39.5 1.6 Jlm') Modulus (MPa) 160 45.3 Loss from Dry to #16 Wet Strain 86%
' Peak Stress 680 Energy-to-Break 96%
Modulus 72%
In accordance with the invention, Example 16 was a film of a polymer blend of weight percent of an unmodified polyethylene and 40 weight percent an unmodified polyethylene oxide). The film of this polymer blend was water modifiable after seconds of submersion in water.
Examples 17-18 For Examples 17-18, a 60140 weight percent resin blend of low density polyethylene (Dow 5031) and polyethylene oxide) having a molecular weight of 200,000 glmol (POLYOX~ WSRN-80) was fed to a ZSK-30 extruder as described in Examples at a rate of 34 Ib/hr. The seven heating zones were all set at 180 degrees C.
The screw speed was 300 rpm. At barrel 4, the monomer (PEG-MA) was added at the specified rate. At barrel 5, the free radical initiator (Lupersol 101 ) was added at the specified rate.
For Example 17, the PEG-MA feed rate was 1.02 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 18, the PEG-MA feed rate was 3.06 Ib/hr and the initiator rate was 0.17 Ib/hr.
The dry and wet properties of the film produced from the blends in Examples 17-18 are indicated in Table 7 below.
Example #- #17 #18 dry wet dry wet Thickness (mil) 3.0 4.1 4.2 4.8 %Strain 420 60 310 60 Peak Stress - (MPa)9.4 1.0 9.1 1.0 Energy-break (x10 33.9 0.44 24.5 0.37 JIm3) Modulus (MPa) 85.1 18.6 86.5 25.8 Loss from Dry to #17 #,18 Wet Strain 86% 81 Peak Stress 89% 89%
Energy-to-Break 990 98%
Modulus 78% 70%
16 .
In accordance with the invention, Examples 17-18 were films of polymer blends with 60 weight percent of a modified polyethylene and 40 weight percent of a modified polyethylene oxide) where both polyethylene and polyethylene oxide) have PEG-MA
grafted thereto. The films of these polymer blends was water modifiable after seconds of submersion in water.
While the invention has been described with reference to the preferred embodiments and illustrated with regard to a range of optional features, those skilled in the art will appreciate that various substitutions, omissions, changes and modifications may be made without departing from the spirit of the invention. Accordingly, it is intended that the foregoing description be deemed merely exemplary of the preferred scope of the present invention and not be deemed a limitation thereof.
Although the present invention is described with reference to a water modifiable film, one skilled in the art would understand the utility of the invention toward other thermoplastic articles that can be extruded or injection molded. In one embodiment of the invention) the water modifiable film comprises greater than about 55 weight percent of a polyolefin and less than about 45 weight percent of polyethylene oxide).
Desirably, the water-modifiable film comprises from about 55 weight percent to about 85 weight percent of a polyolefin and from about 45 weight percent to about 15 weight percent of polyethylene oxide). More desirably, the water-modifiable film comprises from about 65 weight percent to about 85 weight percent of a polyolefin and from about 35 weight percent to about 15 weight percent of polyethylene oxide). The polyethylene oxide) useful in making the film should have a molecular weight of less than about 200,000 and more preferably about 700,000.
The saturated ethylene polymers useful in the practice of this invention are homopolymers or copolymers of ethylene and polypropylene and are essentially linear in structure. As used herein, the term "saturated" refers to polymers which are fully saturated, but also includes polymers containing up to about 5% unsaturation.
The homopolymers of ethylene include those prepared under either low pressure, i.e., linear low density or high density polyethylene, or high pressure) i.e., branched or low density polyethylene. The high density polyethylenes are generally characterized by a density that is about equal to or greater than 0.94 grams per cubic centimeter (glcc).
Generally, the high density potyethylenes useful as the base resin in the present invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc. The polyethylenes can have a melt index, as measured at 2.16 kg and 190°C, ranging from about 0.005 decigrams per minute (dg/min) to 100 dg/min. Desirably, the polyethylene has a melt index of 0.01 dglmin to about 50 dglmin and more desirably of 0.05 dg/min to about 25 dg/min.
Alternatively) mixtures of polyethylene can be used as the base resin in producing the graft copolymer compositions, and such mixtures can have a melt index greater than 0.005 dg/min to less than about 100 dglmin.
The low density polyethylene has a density of less than 0.94 glcc and are usually in the range of 0.91 g/cc to about 0.93 g/cc. The low density polyethylene has a melt index ranging from about 0.05 dg/min to about 100 dg/min and desirably from 0.05 dglmin to about 20 dglmin. 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.s0gicc.
Generally, polypropylene has a semi-crystalline structure having a molecular weight of about 40,000 or more, a density of about 0.90 g/cc) a melting point of 168 to 171 °C for isotactic polypropylene and a tensile strength of 5000 psi.
Polypropylene can also have other tacticities including syndiotactic and atactic.
The above polyolefins can also be manufactured by using the well known multiple-site Ziegler-Natta catalysts or the more recent single-site metallocene catalysts.
The metallocene catalyzed polyolefins have better controlled polymer microstructures than palyolefins manufactured using Ziegler Natta catalysts) including narrower molecular weight distribution, well controlled chemical composition distribution, co-monomer sequence length distribution, and stereoregularity. Metallocene catalysts are known to polymerize propylene into atactic, isotactic, syndiotactic, isotactio-atactic stereoblock copolymer.
Copolymers of ethylene which can be useful in the present invention may include copolymers of ethylene with one or more additional polymerizable, unsaturated monomers. Examples of such copolymers include) but are not limited to, copolymers of ethylene and alpha olefins (such as propylene, butane, hexane or octane) including linear low density polyethylene, copolymers of ethylene and vinyl esters of linear or branched carboxylic acids having 1-24 carbon atoms such as ethylene-vinyl acetate copolymers, and copolymers of ethylene and acrylic or methacrylic esters of linear) branched or cyclic alkanols having 1-28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acrylate copolymers) such as ethylene-methyl acrylate copolymers.
Polyethylene oxide) is available from Union Carbide Corporation under the trade name of POLYOX~. Typically, polyethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65°C, above which polyethylene oxide) resin becomes thermoplastic and can be formed by molding, extrusion and other methods known in the art.
In another embodiment of the invention, the water modifiable film comprises greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of poly(ethyiene oxide). Desirably, the water modifiable film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of polyethylene oxide). More desirably, the water modifiable ~Im comprises from about 65 weight percent to about 85 weight percent of a modified polyofe~n and from about 35 weight percent to about 15 weight percent of polyethylene oxide). The polyolefin is modified by having grafted thereto from about 0.1 weight percent to about 30 weight percent, based on the weight of the polyolefin and poly(ethyiene oxide), of a monomer. Desirably, the polyolefin is modified by having grafted thereto from about 1 weight percent to about 20 weight percent, and more desirably, from about 1 weight percent to about 10 weight percent, based on the weight of the polyolefin and polyethylene oxide)) of a monomer.
Generally, the modified polyolefin is made by feeding to an extruder an amount of polyolefin, monomer and a free radical initiator. Preferably the monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate. The modified polyolefin and polyethylene oxide) is then melt blended in an extruder to form the water modifiable film. The method of making the modified polyolefin is described in greater detail in copending U.S. patent application 081733,410 filed October 18,1996 entitled "METHOD
HYDROXYETHYL METHACRYLATE GRAFTED THERETO", the entire disclosure of which is incorporated herein by reference. In accordance with this embodiment of the invention) suitable polyethylene oxide) polymers can have an average molecular weight ranging from 100,000 to about 8,000,000.
The free radical initiators which can be used to graft the monomer onto the pofyolefin include acyl peroxides such as benzoyl peroxide; dialkyl; diaryl;
or aralkyl peroxides such as di-t-butyl peroxide; dicumyl peroxide; cumyl butyl peroxide;
1,1-di-t-butyl peroxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis {t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene);
peroxyesters such as t-butyl peroxypivalate; t butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2,5-di(perbenzoate); t-butyl di(perphthalate); dialkyl peroxymonocarbonates and peroxydicarbonates; hydroperoxides such as t-butyl hydroperoxide, p-methane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. Azo compounds such as azobisisobutyronitrile may also be used.
In yet another embodiment of the invention a water modifiable film comprises greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of modified poly{ethylene oxide). Preferably the water modifiable film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of modified polyethylene oxide). More desirably) the water modifiable film comprises from about 65 weight percent to about 85 weight percent of a modified polyolefin and from about 35 weight percent to about 15 weight percent of modified polyethylene oxide).
Polyethylene oxide) polymers suitable for this embodiment of the present invention can have a molecular weight ranging from 100,000 to 8,000,000. The polyolefin and polyethylene oxide) are modified by grafting thereto a total of from about 0.1 weight percent to about 30 weight percent, based on the weight of the polyolefin and polyethylene oxide), of the monomer. Desirably, the polyolefin and poly(ethyiene oxide) have a total of from about 1 weight percent to about 20 weight percent of the monomer grafted thereto. More desirably) the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 10 weight percent of the monomer grafted thereto.
The water modifiable film of the present invention can be made as described in copending U.S. patent application having U.S. serial no. 081777,226 filed on December 31) 1996 and entitled "BLENDS OF POLYOLEFIN AND POLYETHYLENE OXIDE) AND
PROCESS FOR MAKING THE BLENDS", the entire disclosure of which is incorporated herein by reference. Generally, the film is made by melt blending the desired weight ratios of a mixture of the polyolefin, polyethylene oxide), the monomer and the free radical initiator in an extruder and at a reaction temperature where the polyolefin and polyethylene oxide) are converted to a molten state. Preferably) the polyolefin and polyethylene oxide) are added at the beginning of the extruder. After melting, the monomer is added to the melt blend. Further down the extruder barrel, the free radical initiator is fed to the melt blend.
When modifying the polyolefin alone or together with the polyethylene oxide), the amount of free radical initiator added to the extruder should be an amount sufficient to graft from about 1 percent to 100 percent of the monomer onto the polymer) i.e., the polyolefin or polyolefin and polyethylene oxide). This can range from about 0.1 weight percent to about 2 weight percent of initiator. Preferably, the amount of initiator added to the extruder ranges from about 0.1 weight percent to about 1 weight percent wherein all such ranges are based on the amount of monomer added to the melt blend.
The water-modifiable polyolefin films of the present invention will, when immersed in water for about 30 seconds, have modified at least two of the tensile properties:
percent stain-to-break, peak stress, energy-to break and modulus by greater than 10%.
Desirably, at least two of the tensile properties will be reduced greater than about 25%.
More desirably, at least two of the tensile properties will be reduced from about 25% to about 98%, and even more desirably at least two of the tensile properties:
percent stain-to-break, peak stress, energy-to break and modulus will be reduced from about 30% to about 80%. The values in determining the extent of the tensile property or properties modification are relative to the dry condition, i.e. pre-immersion value for that measured property.
The present invention is illustrated in greater detail by the specific examples presented below. It is to be understood that these examples are illustrative embodiments and are not intended to be limiting of the invention, but rather are to be construed broadly within the scope and content of the appended claims.
COMPARATIVE EXAMPLE A
A 60140 weight percent blend of low density polyethylene {PE) having 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) and polyethylene oxide) (PEO) having a molecular weight of 200,000 g/mol (POLYOX~
WSRN-80 available from Union Carbide Corp.) was fed to a Haake counter rotating twin screw extruder at a rate of 5 pounds per hour (Iblhr). The extruder had a length of 300 millimeters. Each conical screw had 30 millimeters diameter at the feed port and a diameter of 20 millimeters at the die. The extruder had four heating zones set at 170, 180, 180 and 190°C. The screw speed of the extruder was 150 rpm.
Film processing of all the blends was performed using a Haake extruder counter-rotating twin screw extruder as described above with the following modifications. The extruder included a 4 inch slit die at a temperature of 195 °C. The screw speed was at 30 rpm. A chilled wind-up roll was used to collect the film. The chilled roll was operated at a speed sufficient to form a film having a thickness of about 4 mils (about 0.004 of an inch) and was maintained at a temperature of 15-20°C.
Dry tensile tests were performed on a Sintech 1lD tensile tester available from MTS Systems Corp., Machesny Park, IL. The film was cut into a type V dogbone shape in accordance with ASTM D638. The test was pertormed with a grip separa#ion of millimeters and a crosshead speed of 4 millimeterslsecond.
Wet tensile tests were pertormed on a Vitrodyne V1000 mini-tensile tester available from Chatillon, Greensboro, NC. The film samples were placed in the grips and the testing apparatus was submerged in ambient temperature, non-stirred water for 30 seconds. The test was then run under the same conditions as the dry tensile test. Peak stress, percent strain-to-break, energy-to-break (as area under stress versus strain curve) and modulus were calculated using the actual stress versus strain values recorded from the tensile tester for each dry or wet tensile test. The peak stress was recorded as the greatest stress value. The percent stain-to-break was recorded as the percent strain value at break. The energy-to-break (area under stress versus stain curve) was calculated by the summation of rectangular slices" under the curve determined for each strain value recorded from the tensile test, using the following formula:
((Strain valuex - Strain valuex.,) x (Stress valueX + Stress valuex_~)) / 2 where "x" is the sequential number of the slice. The modulus was calculated by linear regression of the initial region of the stress versus strain curve.
The dry and wet properties of the ~Im produced from the blend in Comparative Example A are indicated in Table 1 below.
Example #- ~ #A
dry wet Thickness (mil) 4.1 4.2 Strain-to-Break 330 300 Peak Stress - (MPa)16.6 16.2 Energy-break (x10 39.4 38.4 Jlm') Modulus (MPa) 128.4 103.8 Loss from Dry to ~ #A
Wet Strain-to-Break 9%
Peak Stress 2~
Energy-to-Break 3%
Modulus 20%
This example shows typical polymer blends in which the volumetric majority of the blend is water resistant. The polymer blend was not water modifiable after 30 seconds of submersion in water.
For Examples 1-3) the low density polyethylene (Dow 5031) was modified by grafting thereto polyethylene glycol methacrylate (PEG-MA; available from Aldrich Chemical Company, Milwaukee, WI). A Haake extruder as described in Comparative Example A above was used. The extruder had four heating zones set at 770, 780, and 190°C. The screw speed of the extruder was 150 rpm. The feed to the extruder comprised contemporaneously adding, at the extruder feed throat, 5 Iblhr of polyethylene and the specified amounts of PEG-MA and free radical initiator ((2,5-dimethyl-2,5-di(t-butylperoxy) hexane, supplied by Atochem) 2000 Market St.) Philadelphia, PA
under the tradename Lupersol 101).
For Example 1 the PEG-MA feed rate was 0.125 Iblhr and the initiator rate was 0.0125 Ib/hr.
For Example 2 the PEG-MA feed rate was 0.25 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 3 the PEG-MA feed rate was 0.5 Ib/hr and the initiator rate was 0.025 Ib/hr.
A 60/40 weight percent blend. of polyethylene and polyethylene oxide) was prepared following the procedure of Comparative Example A, except the modified polyethylene of each example was substituted for the unmodified polyethylene of Comparative Example A.
The dry and wet properties of the film produced from the blends in Examples 1-are indicated in Table 2 below.
Example #- #1 #2 #3 dry wet dry wet dry wet Thickness (mil) 4.5 4.5 4.0 4.0 5.0 5.0 Strain-to-Break 330 110 320 70 170 30 Peak Stress - (MPa)13.8 7.0 11.4 4.9 12.2 3.1 Energy-break (x10 32.7 6.7 27.6 2.4 16.5 0.5 J/m ) Modutus (MPa) 117.874.4103.7 56.3119.4 39.4 Loss from Dry to #1 #2 #3 Wet Strain-to-Break 65% 79% 82%
Peak Stress 49% 57% 75%
Energy-to-Break 80% 91 % 97%
Modulus 37% 46% 33%
In accordance with the invention, Examples 1-3 illustrate a water modifiable film having a modified polyethylene where the polyethylene has PEG-MA grafted thereto and unmodified polyethylene oxide). The films were water modifiable after 30 seconds of submersion in water.
Examples 4-7 A 60/40 weight percent resin blend of tow density polyethylene, Dow 5031, and polyethylene oxide) having a molecular weight of 200,000 g/mol (POLYOX~ WSRN-80) was fed to a Haake extruder as described in Comparative Example A at a rate of pounds per hour (Iblhr). Contemporaneously with the polymer feed to the extruder, specified amounts of the monomer, PEG-MA) and free radical initiator (Lupersol 101 }
were added at the feed throat. The extruder had four heating zones set at 170, 180, 180 and 190°C. The screw speed of the extruder was 150 rpm.
For Example 4 the PEG-MA feed rate was 0.125 tb/hr and the initiator rate was 0.0125 Iblhr.
For Example 5 the PEG-MA feed rate was 0.25 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 6 PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
For Example 7 the PEG-MA feed rate was 0.75 Ib/hr and the initiator rate was 0.0375 Ib/hr.
The dry and wet properties of the film produced from the blends in Examples 4-are indicated in Table 3 below.
Example #- #4 ~ #6 #7 #5 ~
dry wet dry wet dry wet dry wet Thickness (mil) 4.4 4.4 5.6 5.5 4.2 4.2 4.9 4.6 %Strain 400 70 280 50 590 90 250 50 Peak Stress - (MPa)9.3 3.7 8.3 3.1 9.2 3.5 5.2 1.3 Energy-break (x10 30.61.7 18.1 0.9 46.8 2.0 9.8 0.3 J/m ) Modulus (MPa) 90.141.991.2 32.786.2 38.064.414.5 Loss from Dry to #4 #5 ~ #6 #7 Wet Strain 83% 83% 85% 81 Peak Stress 60% 63% 62% 75%
Energy-to-Break 94% 95% 96% 97%
Modulus 53% 64% 56% 77%
For Examples 4-7 the amount of monomer grafted to polyethylene was 0.65 weight percent) 1.03 weight percent, 0.51 weight percent and 1.13 weight percent) respectively. The weight percent of monomer grafted to the polyethylene was determined by FT-IR and elemental oxygen content analysis as described in copending U.S. patent application 081733,410 filed October 18, 1996. For Example 6 the amount of monomer grafted to the polyethylene oxide) was determined to be 9.66 weight percent by proton NMR spectroscopy.
In accordance with the invention, Examples 4-7 the water modifiable films were polymer blends of 60 weight percent of a modified polyethylene and 40 weight percent a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have PEG-MA grafted thereto. The films of these polymer blends were water-modifiable after 30 seconds of submersion in water. A dramatic loss in tensile properties was observed for the films from dry to wet.
Examples 8-11 For Examples 8-11, a low density polyethylene) Dow 5031, and polyethylene oxide) (V1ISRN-80) blend was prepared following the procedure of Example 4 having the respective resin weight ratios, PEG-MA feed rates and initiator rates indicated.
For Example 8 the blend was 65/35 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 9 the blend was 70/30 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
For Example 10 the blend was 75125 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 lb/hr.
For Example 11 the blend was 80/20 PEIPEO, the PEG-MA feed rate was 0.5 Iblhr and the initiator rate was 0.025 Iblhr.
The dry and wet properties of the film produced from the btends in 8-11 are indicated in Table 4 below.
Exampte #- #8 #9 #10 #11 ~~
dry wet dry wet dry wet dry wet Thickness (mil) 5.0 4.8 5.0 5.1 4.6 4.4 4.4 5.2 %Strain 340 80 300 130 260 220 180 150 Peak Stress - (MPa)7.5 3.6 10.35.8 11.3 10.5 11.4 11.4 Energy-break (x10 21.1 1.6 23.46.2 22.8 16.2 16.8 14.7 J/m) Modulus {MPa) 91.1 41.090.955.6 119.972.5 138.480.6 Loss from Dry to #8 #9 #10 #11 Wet Strain 76% 57% 15% 17%
Peak Stress 52% 44% 7% 0%
Energy-to-Break 92% 74% 29% 13%
Modulus 55% 39% 40% 42%
In accordance with the invention, Examples 8-11 were films from polymer blends having greater than about 60 weight percent of a modified polyethylene and less than about 40 weight percent of a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have PEG-MA grafted thereto. The films of these polymer blends was water modifiable after 30 seconds of submersion in water. A loss in tensile properties was observed for the films from dry to wet.
Examples 12-15 For Examples 12-15) a 60/40 weight percent resin blend of low density polyethylene (Dow 5031} and polyethylene oxide) (V1lSRN-80} was prepared following the procedure of Example 4) except the monomer used was 2-hydroxyethyl methacrylate.
The respective monomer feed rates and initiator rates are indicated.
For Example 12 the 2-hydroxyethyl methacrylate feed rate was 0.125 Iblhr and the initiator rate was 0.0125 Ib/hr.
For Example 13 the 2-hydroxyethyl methacrytate feed rate was 0.25 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 14 the 2-hydroxyethyl methacrylate feed rate was 0.5 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 15 the 2-hydroxyethy! methacrylate feed rate was 0.75 lblhr and the initiator rate was 0.0375 Ib/hr.
The dry and wet properties of the film produced from the blends in 12-15 are indicated in Table 5 below.
Example #- #12 #13 #14 #15 dry wet dry wet dry wet dry wet Thickness (mil) 4.5 4.6 4.2 4.7 4.5 4.5 5.0 4.6 %Strain 350 50 390 40 420 40 350 30 Peak Stress - (MPa)13.33.3 9.0 1.5 10.32.4 8.7 1.9 Energy-break (x10' 33.30.8726.7 0.3632.70.51 23.60.37 J/m) Modulus (MPa) 107 38.8126 18.499.628.7 109 23.2 Loss from Dry to #12 #13 #14 #15 Wet Strain 86% 90% 90% 91 Peak Stress 75% 83% 77% 78%
Energy-to-Break 97% 99% 98% 98%
Modulus 64% 85% 71 % 79%
In accordance with this invention) Examples 12-15 were films of polymer blends having 60 weight percent of a modified polyethylene and 40 weight percent of a modified polyethylene oxide) where both the polyethylene and polyethylene oxide) have 2-hydroxyethyl methacrylate grafted thereto. The dims of these polymer blends was water-modifiabte after 30 seconds of submersion in water.
Example 16 a For Examples 16, a Wemer & Pfleiderer ZSK-30 extruder (available from Wemer & Pfleiderer, Ramsey, New Jersey) was used. The extruder had a pair of co-rotating screws arranged in parallel. The center distance between the two shafts was 26.2 mm.
The nominal screw diameter was 30 mm. The actual outer screw diameter was 30 mm.
The inner screw diameter was 21.3 mm. The thread depth was 4.7 mm. The extruder had 14 processing barrels, with 13 heated ban-els divided into 7 heating zones. The overall processing length was 1340 mm.
A 60140 weight percent resin. blend of low density polyethylene (Dow 5031) and poly(ethytene oxide) having a molecular weight of 100,000 g/mol (POLYOX~ WSRN-10) was fed to the ZSK-30 extruder at a rate of 35 Iblhr. The seven heating zones were all set at 180 degrees C. The screw speed was 300 rpm.
The dry and wet properties of the film produced from the blend in Example 16 are indicated in Table 6 below.
Example #- #16 dry wet Thickness (mil) 3.2 3.2 ~Strain 430 60 Peak Stress - (MPa)11.3 3.6 Energy-break (x10 39.5 1.6 Jlm') Modulus (MPa) 160 45.3 Loss from Dry to #16 Wet Strain 86%
' Peak Stress 680 Energy-to-Break 96%
Modulus 72%
In accordance with the invention, Example 16 was a film of a polymer blend of weight percent of an unmodified polyethylene and 40 weight percent an unmodified polyethylene oxide). The film of this polymer blend was water modifiable after seconds of submersion in water.
Examples 17-18 For Examples 17-18, a 60140 weight percent resin blend of low density polyethylene (Dow 5031) and polyethylene oxide) having a molecular weight of 200,000 glmol (POLYOX~ WSRN-80) was fed to a ZSK-30 extruder as described in Examples at a rate of 34 Ib/hr. The seven heating zones were all set at 180 degrees C.
The screw speed was 300 rpm. At barrel 4, the monomer (PEG-MA) was added at the specified rate. At barrel 5, the free radical initiator (Lupersol 101 ) was added at the specified rate.
For Example 17, the PEG-MA feed rate was 1.02 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 18, the PEG-MA feed rate was 3.06 Ib/hr and the initiator rate was 0.17 Ib/hr.
The dry and wet properties of the film produced from the blends in Examples 17-18 are indicated in Table 7 below.
Example #- #17 #18 dry wet dry wet Thickness (mil) 3.0 4.1 4.2 4.8 %Strain 420 60 310 60 Peak Stress - (MPa)9.4 1.0 9.1 1.0 Energy-break (x10 33.9 0.44 24.5 0.37 JIm3) Modulus (MPa) 85.1 18.6 86.5 25.8 Loss from Dry to #17 #,18 Wet Strain 86% 81 Peak Stress 89% 89%
Energy-to-Break 990 98%
Modulus 78% 70%
16 .
In accordance with the invention, Examples 17-18 were films of polymer blends with 60 weight percent of a modified polyethylene and 40 weight percent of a modified polyethylene oxide) where both polyethylene and polyethylene oxide) have PEG-MA
grafted thereto. The films of these polymer blends was water modifiable after seconds of submersion in water.
While the invention has been described with reference to the preferred embodiments and illustrated with regard to a range of optional features, those skilled in the art will appreciate that various substitutions, omissions, changes and modifications may be made without departing from the spirit of the invention. Accordingly, it is intended that the foregoing description be deemed merely exemplary of the preferred scope of the present invention and not be deemed a limitation thereof.
Claims (29)
1. A water modifiable polyolefin-containing film comprising greater than about weight percent of a polyolefin and less than about 45 weight percent of poly(ethylene oxide) wherein said poly(ethylene oxide) has a molecular weight of less than about 100,000, said film having a loss of at least 10% in two or more tensile properties selected from percent strain-to-break, peak stress, energy-to-break and modulus after being immersed in water for 30 seconds.
2. The film of claim 1 wherein said film comprises from about 55 weight percent to about 85 weight percent of a polyolefin and from about 45 weight percent to about 15 weight percent of poly(ethylene oxide).
3. The film of claim 1 wherein said film comprises from about 65 weight percent to about 85 weight percent of a polyolefin and from about 35 weight percent to about 15 weight percent of poly(ethylene oxide).
4. The film of claim 1, 2 or 3 wherein said polyolefin is polyethylene or polypropylene.
5. The film of claim 1, 2 or 3 wherein said loss in two or more of the tensile properties is greater than 25% after being immersed in water for 30 seconds.
6. The film of claim 1, 2 or 3 wherein said loss in two or more of the tensile properties is from about 25% to about 98% after being immersed in water for 30 seconds.
7. The film of claim 1, 2 or 3 wherein said loss in two or more of the tensile properties is from about 30% to about 80% after being immersed in water for 30 seconds.
8. A polyolefin-containing film comprising greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of poly(ethylene oxide) wherein said film has a loss of at least 10% in two or more tensile properties selected from percent strain-to-break, peak stress, energy-to-break and modules after being immersed in water for 30 seconds.
9. The film of claim 8 wherein said film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of poly(ethylene oxide).
10. The film of claim 8 wherein said film comprises from about 65 weight percent to about 85 weight percent of a modified polyolefin and from about 35 weight percent to about 15 weight percent of poly(ethylene oxide).
11. The film of claim 8, 9, or 10 wherein said polyolefin is polyethylene or propylene.
12. The film of claim 11 wherein said modified polyolefin has from about 0.1 weight percent to about 30 weight percent of a monomer grafted onto said polyolefin.
13. The film of claim 11 wherein said modified polyolefin has from about 1 weight percent to about 20 weight percent of a monomer grafted onto said polyolefin.
14. The film of claim 11 wherein said modified polyolefin has from about 1 weight percent to about 10 weight percent of a monomer grafted thereto.
15. The film of claim 11 wherein said loss in two or more of the tensile properties is greater than 25% after being immersed in water for 30 seconds.
16. The film of claim 11 wherein said loss in two or more of the tensile properties is from about 25% to about 98% after being immersed in water for 30 seconds
17. The film of claim 11 wherein said loss in two or more of the tensile properties is from about 30% to about 80% after being immersed in water for 30 seconds.
18. The water modifiable polyolefin-containing film of claim 12 wherein said monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate.
19. A polyolefin-containing film comprising greater than about 55 weight percent of a modified polyolefin and less than about 45 weight percent of a modified poly(ethylene oxide) wherein said film has a loss of at least 10% in two or more tensile properties selected from percent strain-to-break, peak stress, energy-to-break and modulus after being immersed in water for 30 seconds.
20. The film of claim 19 wherein said film comprises from about 55 weight percent to about 85 weight percent of a modified polyolefin and from about 45 weight percent to about 15 weight percent of a modified poly(ethylene oxide).
21. The film of claim 19 wherein said film comprises from about 65 weight percent to about 85 weight percent of a modified polyolefin and from about 35 weight percent to about 15 weight percent of a modified poly(ethylene oxide).
22. The film of claim 19, 20 or 21 wherein said polyolefin is polyethylene or propylene.
23. The film of claim 22 wherein said modified polyolefin and said modified poly(ethylene oxide) have a total of from about 0.1 weight percent to about 30 weight percent of a monomer grafted onto said polyolefin and said poly(ethylene oxide).
24. The film of claim 22 wherein said modified polyolefin and said modified poly(ethylene oxide) have a total of from about 1 weight percent to about 20 weight percent of a monomer grafted onto said polyolefin and said poly(ethylene oxide).
25. The film of claim 22 wherein said modified polyolefin and said modified poly(ethylene oxide) have a total of from about 1 weight percent to about 10 weight percent of a monomer grafted onto said polyolefin and said poly(ethylene oxide).
26. The film of claim 22 wherein said loss in two or more of the tensile properties is greater than 25% after being immersed in water for 30 seconds.
27. The film of claim 22 wherein said loss in two or more of the tensile properties is from about 25% to about 98% after being immersed in water for 30 seconds
28. The film of claim 22 wherein said loss in two or more of the tensile properties is from about 30% to about 80% after being immersed in water for 30 seconds.
29. The water modifiable polyolefin-containing film of claim 23 wherein said monomer is 2-hydroxyethyl methacrylate or polyethylene glycol ethyl ether methacrylate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3461696P | 1996-12-31 | 1996-12-31 | |
| US60/034,616 | 1996-12-31 | ||
| US81357197A | 1997-03-06 | 1997-03-06 | |
| US08/813,571 | 1997-03-06 | ||
| PCT/US1997/023810 WO1998029502A1 (en) | 1996-12-31 | 1997-12-19 | Water-modifiable flushable polyolefin-containing film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2275669A1 true CA2275669A1 (en) | 1998-07-09 |
Family
ID=26711181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002275669A Abandoned CA2275669A1 (en) | 1996-12-31 | 1997-12-19 | Water-modifiable flushable polyolefin-containing film |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU5618698A (en) |
| CA (1) | CA2275669A1 (en) |
| WO (1) | WO1998029502A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6111014A (en) * | 1996-12-31 | 2000-08-29 | Kimberly-Clark Worldwide, Inc. | Film of monomer-grafted polyolefin and poly(ethylene oxide) |
| US6153700A (en) * | 1996-12-31 | 2000-11-28 | Kimberly-Clark Worldwide, Inc. | Water-degradable flushable film of polyolefin and poly(ethylene oxide) and personal care article therewith |
| US6100330A (en) * | 1996-12-31 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Water-degradable film of monomer grafted to polyolefin and poly(ethylene oxide) |
| AU2016899A (en) * | 1997-12-31 | 1999-07-19 | Kimberley-Clark Worldwide, Inc. | Flushable fiber compositions comprising modified polypropylene and modified poly(ethylene oxide) and process for making the same |
| US6160200A (en) * | 1998-06-29 | 2000-12-12 | The Procter & Gamble Company | Directionally preferential waste passage member for use with disposable absorbent article |
| MXPA01012354A (en) * | 1999-06-07 | 2002-07-30 | Kimberly Clark Co | Inverse phase blends of poly(ethylene oxide) and polyolefin and reactive extrusion method of making inverse phase blends. |
| AU5897000A (en) * | 1999-06-29 | 2001-01-31 | Kimberly-Clark Worldwide, Inc. | Compositions comprising a blend of poly(ethylene oxide) and grafted polyolefin and method of making the same |
| US6515075B1 (en) * | 2001-07-12 | 2003-02-04 | Kimberly-Clark Worldwide, Inc. | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
| US6509419B1 (en) * | 2001-07-12 | 2003-01-21 | Kimberly-Clark Worldwide, Inc. | Chemically modified polyethylene oxide compositions with improved environmental stability |
| US6783826B2 (en) | 2001-12-21 | 2004-08-31 | Kimberly-Clark Worldwide, Inc. | Flushable commode liner |
| JP2008090133A (en) | 2006-10-04 | 2008-04-17 | Konica Minolta Medical & Graphic Inc | Copolymer and heat developable photosensitive material containing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415691A (en) * | 1980-09-29 | 1983-11-15 | The Dow Chemical Company | Anti-block additives for olefin polymers |
| US4812505A (en) * | 1987-05-18 | 1989-03-14 | Union Carbide Corporation | Tree resistant compositions |
| US5464687A (en) * | 1992-12-07 | 1995-11-07 | Lyondell Petrochemical Company | Wettable polyolefin fiber compositions and method |
-
1997
- 1997-12-19 CA CA002275669A patent/CA2275669A1/en not_active Abandoned
- 1997-12-19 WO PCT/US1997/023810 patent/WO1998029502A1/en active Application Filing
- 1997-12-19 AU AU56186/98A patent/AU5618698A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998029502A1 (en) | 1998-07-09 |
| AU5618698A (en) | 1998-07-31 |
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