MX2014009100A - Substituted cellulose acetates and uses thereof. - Google Patents

Substituted cellulose acetates and uses thereof.

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Publication number
MX2014009100A
MX2014009100A MX2014009100A MX2014009100A MX2014009100A MX 2014009100 A MX2014009100 A MX 2014009100A MX 2014009100 A MX2014009100 A MX 2014009100A MX 2014009100 A MX2014009100 A MX 2014009100A MX 2014009100 A MX2014009100 A MX 2014009100A
Authority
MX
Mexico
Prior art keywords
cellulose acetate
substituted cellulose
present
further characterized
substituted
Prior art date
Application number
MX2014009100A
Other languages
Spanish (es)
Inventor
Michael T Combs
Thomas S Garrett
Original Assignee
Celanese Acetate Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Celanese Acetate Llc filed Critical Celanese Acetate Llc
Publication of MX2014009100A publication Critical patent/MX2014009100A/en

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Classifications

    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/08Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/067Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068Biodegradable or disintegrable
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • D04H1/4258Regenerated cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/013Regenerated cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/07Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments otherwise than in a plane, e.g. in a tubular way
    • D04H3/077Stick, rod or solid cylinder shaped

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The present invention relates to substituted cellulose acetates and methods of use thereof. One embodiment of the present invention provides a cigarette filter material having a filter having a substituted cellulose acetate having a polar substituent that has an oxygen atom covalently bonded to a nonmetal selected from the group of sulfur, phosphorus, boron, and chlorine; wherein the nonmetal is present in at least 0.01% by weight of the substituted cellulose acetate.

Description

SUBSTITUTE CELLULOSE ACETATS AND USES OF THEMSELVES BACKGROUND OF THE INVENTION The present invention relates to synthetic polymers and, in particular, to substituted cellulose acetates, and methods of using them.
Cellulose acetate is an acetate ester derived from cellulose, a naturally occurring biopolymer comprising units of ß-D-glucose monomer, and is widely used to make a variety of consumer products. The cellulose that occurs naturally is insoluble in water and most of the organic solvents. However, the three free hydroxyl groups of each cellulose glucose monomer unit can be derivatives to modify certain properties, for example, solubility in certain solvents. It is thought that cellulose acetate is among the most commercially useful cellulose derivatives, and its specific chemical and physical properties generally depend greatly on the degree of acetate substitution in the three free hydroxyl groups of a glucose monomer unit.
Since its first synthesis, cellulose acetate has been used, among other things, as a film base in photography, a component in adhesives, and raw material used in the manufacture of cigar filters. One of the key attributes of cellulose acetate is that it can be processed in many different ways and forms, including, films, fibers, flakes, filaments, and solids, depending on the desirability of the application. For example, cellulose acetate fiber is used mainly in the manufacture of cigar filters.
More generally, cellulose derivatization is performed using acid catalysts at elevated reaction temperatures. The synthesis of cellulose acetate involves acetylation of cellulose, which is commonly obtained from wood pulp, in the presence of acids and acetic anhydride. Acetic acid and sulfuric acid are two acids usually present during the acetylation reaction. In this reaction, acetic anhydride serves as the main acetylating agent; acetic acid is used mainly as a diluent; and a small amount of sulfuric acid is used as the catalyst. In general, cellulose monomer units have three hydroxyl groups that are readily available by substitution, for example, via acetylation. The monomeric units at both ends also have an additional hydroxyl group that is typically involved with inter-sugar bonds.
The product of the acetylation reaction is a primary cellulose acetate that usually contains high concentration levels of acetate or, in other words, has a high degree of substitution (DS) of acetate. As used herein, "degree of acetate substitution" generally refers to the average number of acetates per glucose monomer unit. The structure of cellulose acetate can be generally characterized by specifying the degree of substitution of the acetate. Exhaustively acetylated cellulose is commonly referred to as cellulose triacetate, where, in accordance with the guidelines of the Federal Trade Commission, at least 92% of the hydroxyl groups are substituted with acetyl groups. For example, when there are at least about two acetyl groups per cellulose monomer unit (that is, a DS of about 2), acetyl cellulose can become significantly less biodegradable until at least some of the acetyl groups are removed via hydrolysis enzymatic or chemical Acetylated cellulose having reduced DS of acetate can be prepared by controlled hydrolysis of cellulose triacetate.
Next, the primary cellulose acetate is hydrolyzed in the presence of acetic acid and sulfuric acid to reduce the DS of primary cellulose acetate acetate. The resulting hydrolysis product is usually a cellulose acetate flake having a DS of the order of about 2.4 to about 2.6.
Once the cellulose acetate flake is obtained, it can be further processed to process the cellulose acetate to its desired shape. For example, cellulose acetate fiber can be formed by dissolving the cellulose acetate flakes in acetone, placing the cellulose acetate solution through a series of filtration processes, and dry spinning the acetone additive through holes. microscopic in a spinning nozzle. When the acetate Cellulose moves through this extrusion process, cellulose acetate filaments are collected. These filaments are generally integrated and then compressed to ensure cohesion of the fiber band as well as the desired volume. The end result is a cellulose acetate fiber, which is essentially a continuous band composed of several thousand filaments that are held together loosely by compression. The cellulose acetate fiber filaments are usually very thin and can be packed tightly together to create a filter. As used herein, "cellulose acetate fiber" generally refers to sets of post-synthesis processed cellulose acetate filaments.
Cellulose acetate is also ecological because it is an easily degradable material made mainly from a renewable source, wood pulp. Although cellulose acetates that vary in their acetate DS are structurally similar, this variation may have some effect on the biodegradability of cellulose acetate. In higher degrees of acetyl substitution, the rate of biodegradation can be significantly reduced in relation to naturally occurring cellulose or cellulose that has lower acetyl substitution. Cellulose acetates that have a lower DS of acetate biodegrade more easily than cellulose acetates that have a higher DS of acetate. It is believed that this trend decreases in lower SD than acetate values because the material becomes insoluble in water. In an example, the speeds of Biodegradation of cellulose acetate having DS values of 1.85, 2.07 and 2.57 was tested for its biodegradability (Figure 1). Cellulose acetate with a DS of 1.85 showed the highest biodegradation rate while cellulose acetate with an acetyl value of 2.57 showed the slowest biodegradation rate.
Although cellulose acetate is a versatile composition with many commercial uses, the properties of certain cellulose acetate derivatives have not been studied exhaustively. For example, in a typical synthesis, residual sulfate groups are typically removed to improve thermal stability. As a result, the cellulose acetates synthesized by typical means will have approximately 0.005% or less of sulfur atoms by weight. As such, there are potential cellulose acetate derivatives that can provide improved properties for many of the cellulose acetate consumer applications.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to synthetic polymers and, in particular, to substituted cellulose acetates, and methods of using them In some embodiments, the present invention provides diapers comprising: an inner layer comprising an absorbent core comprising a substituted cellulose acetate comprising a substituent polar comprising an oxygen atom covalently bound to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate; and an outer layer.
In other embodiments, the present invention provides bandages comprising: an absorbent layer comprising a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently attached to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of substituted cellulose acetate; and a band is designed to place the absorbent layer in contact with a wound.
In still other embodiments, the present invention provides compost land compositions comprising: an organic compost; and an absorbent composition comprising a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bound to a non-metal selected from the group consisting of: sulfur, phosphorus, boron and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate.
In still other embodiments, the present invention provides modified earth compositions comprising: a ground composition; and a water retention additive comprising a substituted cellulose acetate comprising a polar substituent comprising a oxygen atom covalently bonded to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate.
In still other embodiments, the present invention provides articles comprising: a nonwoven layer comprising fibers of a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently attached to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate.
In still other embodiments, the present invention provides methods comprising: providing a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bound to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of substituted cellulose acetate; and placing the substituted cellulose acetate in an absorbent article.
In still other embodiments, the present invention provides methods comprising: providing an absorbent material comprising a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bound to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; in wherein the non-metal is present in at least about 0.01% by weight of substituted cellulose acetate; and place the absorbent material in a diaper.
The features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of the preferred embodiments below.
BRIEF DESCRIPTION OF THE DRAWINGS The following figures are included to illustrate certain aspects of the present invention, and should not be considered exclusive modalities. The subject matter described is subject to considerable modification, alteration, and equivalents in form and function, as will occur for those skilled in the art and having the advantage of this disclosure.
Figure 1 shows a biodegradability graph of cellulose acetate with varying degrees of substitution.
Figure 2 shows water absorbency data as described in Example 3.
Figure 3 shows water absorbency data as described in Example 3.
Figure 4 shows water absorbency data as described in Example 3.
Figure 5 shows water absorbency data as described in Example 3.
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to synthetic polymers and, in particular, to substituted cellulose acetates, and methods of using them.
The present invention provides compounds, methods, and processes related to substituted cellulose acetates that have several desirable advantages and / or properties. The substituted cellulose acetates of the present invention can be used in a variety of applications including various consumer products, especially where absorbency, tackiness and / or degradability can be useful.
As used herein, the term "substituted cellulose acetate" generally refers to a cellulose acetate having at least one polar substituent substituted on the hydroxyl group of a cellulose polymer. As used herein, a "polar substituent" is a non-acetyl chemical moiety that comprises an electronegative atom (e.g., oxygen) attached to a non-metal atom (e.g., sulfur, phosphorus, boron, and chlorine).
It has surprisingly been discovered in accordance with the present invention that the substituted cellulose acetate composition that has relatively high weight percent of at least one non-metal atom corresponding to a polar substituent having a relatively high degree of substitution can be provided. Furthermore, it has also been surprisingly discovered that the weight percentage of non-metal atoms can be adjusted and / or modified to produce or improve various properties of substituted cellulose acetate as described herein.
The substituted cellulose acetates of the present invention are, in some embodiments, versatile materials (i.e., possess many different desirable chemical and physical properties) and ecological materials (ie, made from appropriate renewable, degradable, biodegradable, etc. sources). for use in various consumer products.
As used herein, "degradable" refers to the ability of a material to decompose and / or break into simpler parts. As used herein, "biodegradable" refers to the ability of a material to degrade by the action of living things. Depending on the application, the definition of "biodegradable" may be subject to the results of standard tests, for example, the test protocols of the Organization for Economic Co-operation and Development (OECD).
Without being limited by theory, it is believed that by adjusting the weight percent of the non-metal atom of a polar substituent, a substituted cellulose acetate of the present invention can provide new or improved physical and / or chemical properties. For example, it is believed that certain polar substituents (eg, sulfate) can increase the hydrophilicity of the substituted cellulose acetate as well as increase the potential for electrostatic interaction.
The substituted cellulose acetate compositions, which are described in more detail hereinafter, have certain advantageous properties and commercial roles (eg, as an adhesive, chemical stabilizer, absorbent) that can be imparted or improved based on the percentage by weight of the non-metal atom present. In some embodiments, readjusting the weight percent of the non-metal atom can remove or reduce an undesirable quality or property in the substituted cellulose acetate.
A substituted cellulose acetate can be described by the concentration of its polar substituents which, in turn, can be specified in terms of the degree of substitution of the polar substituent (i.e., average number of the substituent per glucose monomer unit) or as a percentage by weight of the non-metal atom (eg, sulfur, phosphorus, boron and chlorine) present relative to the total weight of the substituted cellulose acetate. In practical terms, modifying the degree of substitution of a polar substituent will also modify the weight percent of the non-metal atom or a substituted cellulose acetate by a predictable amount and vice versa. Correspondingly, it can be assumed that increasing the degree of substitution of a polar substituent will generally increase the weight percent of the non-metal atom present in a substituted cellulose acetate. In In practical terms, decreasing the degree of substitution of a polar substituent will generally lower the weight percent of the non-metal atom present in a cellulose acetate substituted by a predictable amount.
In theory, the weight percent of the non-metal atom in a substituted cellulose acetate can vary from about 0.01% to about 25%, which corresponds to a cellulose acetate having few polar substituents (in some cases, significantly and surprisingly more than the cellulose acetate typically prepared) and a cellulose acetate which has been extensively replaced. Although the present invention is preferably practiced by specifying the weight percent of the non-metal of the polar substituent, the present invention can be practiced equivalently by specifying the degree of substitution of the polar substituent or other similar concentration measurements. The degree of substitution of a polar substituent may vary from about 0.005 to about 3.
Various embodiments described herein utilize substituted cellulose acetate having a polar substituent over a wide range of consumer products. By adjusting the weight percent of the non-metal atom of the polar substituent, it is believed that the substituted cellulose acetate compositions of the present invention can be used, among many things, as an effective absorbent, an adhesive, a chemical stabilizer, and an agent for Stabilization film formation. For example, adjusting the weight percentage of a sulfur atom (for example, a substituent of sulfate), the substituted cellulose acetate of the present invention can range from a water-soluble material to a water-swellable material. In some embodiments, the water swellable substituted cellulose acetate composition can be used as a degradable coating to encapsulate, for example, a pharmaceutical composition such that the release of the pharmaceutical composition is retarded in the body. Other properties that can be adjusted include, but are not limited to, solubility in certain solvents, ability to stabilize emulsions, adhesiveness to various surfaces, and biodegradability. These properties can be further adjusted by modifying the weight percent of the non-metal atom of the polar substituent present in the substituted cellulose acetate as needed. One skilled in the art should be able to modify the weight percent of non-metal as necessary to practice the many embodiments of the present invention.
In some embodiments, modifying the degree of substitution of the acetate can also produce or improve certain properties of the substituted cellulose acetate. In some embodiments, the water-soluble substituted cellulose acetate has a degree of acetate substitution between about 0.4 to about 1. In some embodiments, the water-swellable substituted cellulose acetate has a degree of acetate substitution between about 1 to about 2. When the degree of substitution of acetate varies between 0.05 to 3, the appropriate solvent system may change. In some modalities, in the degree of Relatively lower acetate substitution, water is an appropriate solvent. In some embodiments, in the relatively higher degree of acetate substitution, an organic solvent is required. The degree of substitution can be varied such that a solvent system that is appropriate for the intended end use can be selected.
In some embodiments, the degree of substitution of a polar substituent may be kept relatively fixed while the degree of substitution of the acetate is adjusted. In some embodiments, the combination of adjusting the degree of substitution of the polar substituent and the degree of substitution of acetate provides the cellulose acetate with the desired properties. In some embodiments, the range of the degree of substitution of the polar substituent may affect the range of the degree of substitution of the acetate that is needed to provide the substituted cellulose acetate with the desired properties. In some embodiments, the range of the degree of substitution of the acetate may affect the range of the degree of substitution of the polar substituent that is needed to provide the substituted cellulose acetate with the desired properties.
Potential commercial uses of the substituted cellulose acetate of the present invention vary widely and include, but are not limited to, household articles such as buttons, cups, coatings, blouses, dresses, party and wedding attire, home furnishings, curtains , upholstery, covers, and the like. Other commercial uses include filters that include cigars, ink tanks, playing cards, and the like, and products with high absorbency such as diapers and surgical products.
In some embodiments, as an absorbent, the substituted cellulose acetates of the present invention have a water absorption capacity of several times (eg, from about 8 times to about 24 times) their weight in a water-base fluid ( for example, water, saline, etc.) depending on the percentage by weight of the non-metal atom present in the substituted cellulose acetate.
In some embodiments, the substituted cellulose acetates of the present invention may be effective as an adhesive, capable of bonding a variety of substrates including, but not limited to, cardboard, plastic, paper, glass, wood, hemp, sawdust, composites ( for example, reinforced fiber composites, wood residues and the like It is believed that the substituted cellulose acetates of the present invention can be an effective chemical / colloidal stabilizer capable of stabilizing various emulsion mixtures.
In some embodiments, the substituted cellulose acetates of the present invention can be used as a stabilizing film forming agent to promote film formation of a given mixture. In some modalities, the formed film can be clear.
Substituted cellulose acetate can exist in many different forms and be used in many different ways. In some embodiments, the substituted cellulose acetate may be filaments, woven fabrics, non-woven fabrics, fibers or fiber bands (open or non-open), flakes, foams, emulsions, films, gels, dispersions, solutions, pastes, suspensions, and combinations thereof. In some embodiments, the substituted cellulose acetate can be used as coatings, additives, films, layers, cores and the like.
In some embodiments, the present invention also provides processes for forming substituted cellulose acetate in various forms of substituted cellulose acetate (e.g., substituted cellulose acetate fiber). These processes typically place the substituted cellulose acetate in a better form to be used in certain applications. For example, substituted cellulose acetate fibers may have the desirable properties particularly of being capable of selectively absorbing and removing levels of certain organic chemicals; be soluble in water or swellable in water; have a high surface area; and be compatible with dyes. It is also believed that the substituted cellulose acetate fibers can have fungal and mold resistance. A substituted cellulose acetate may be desirable particularly in textile applications.
Although at least some embodiments relate to cellulose acetates having at least one polar substituent, derivatives of cellulose acetates having at least one polar substituent may also be used in accordance with any of the compatible embodiments of the present invention. The cellulose acetate derivatives may include, but are not limited to, cellulose acetate esters, mixed esters of cellulose acetate, and the like. Appropriate examples of cellulose acetate esters include, but are not limited to, cellulose acetate propionates, cellulose acetate butyrates, and the like. The degree of esterification of cellulose acetate esters will depend, at least in part, on the particular application and will be apparent to those skilled in the art.
The substituted cellulose acetate of the present invention can be characterized as having a polar substituent comprising an oxygen atom covalently linked to a non-metal selected from the group consisting of: sulfur, phosphorus, and boron; wherein the non-metal is present in at least 0.01% by weight of the substituted cellulose acetate. In some embodiments, the non-metal may be present in no more than about 25% by weight of the substituted cellulose acetate. Without being limited by theory, it is believed that the upper limit of 25% by weight corresponds to a completely substituted cellulose derivative (eg, sulfate). The exact range of the percentage by weight of the non-metal will depend on, among other things, the chemical processing of the polar substituent.
Generally, at least a portion of the hydroxyl groups in a substituted cellulose acetate will be replaced by acetate. In some embodiments, the degree of acetate substitution will be from about 0.05 to about 3, preferably from about 0.4 to about 2. In some embodiments, the ratio of the degree of substitution of acetate to the degree of substitution of the polar substituent may adjust to produce or improve the desired property of a substituted cellulose acetate of the present invention. In some embodiments, the acetate DS is greater than the DS of the polar substituent.
Optionally, the substituted cellulose acetate can further comprise or be mixed with a plasticizer. Suitable examples of plasticizers include, but are not limited to, glycerin, glycerin esters (including mono, di or triacetyl glycerin and glycerin esters), polyethylene glycol, diethylene glycol, propylene glycol, dimethyl sulfoxide, glycerol triacetate, triethylene glycol diacetate, derivatives thereof, combinations thereof, and mixtures thereof. In some embodiments, the plasticizer comprises a plasticizer selected from the group consisting of esters of saturated dibasic acids, esters of saturated polyhydric alcohols, fatty acid esters, sulfonamide resins, derivatives thereof, and combinations thereof. Plasticizers can be incorporated into the substituted cellulose acetate to lower the vitreous transition temperature (Tg) and the melting point of the composition. Plasticizers generally work to facilitate processing and increase the flexibility and hardness of the final product. It is believed that certain plasticizers (e.g., ether ester, simple ester type, etc.) can increase the capacity of the substituted cellulose acetate filters for phenol removal which is a useful property in cigar filters.
In some embodiments, the polar substituent may be selected from the group consisting of sulfates, phosphates, borates, carbonates, and combinations thereof. In some embodiments, the polar substituent is present in at least about 0.03% by weight of the substituted cellulose acetate. In some embodiments, the non-metal of the polar substituent is present in no more than about 75% by weight of the substituted cellulose acetate. The exact range of the weight percentage of the polar substituent will depend on, among other things, the chemical processing of the polar substituent.
In one or more embodiments, the substituted cellulose acetate can have properties that can be imparted or enhanced by increasing or decreasing the concentration of the polar substituents or non-metal atoms. In some embodiments, the substituted cellulose acetate may be soluble in water. In some embodiments, the substituted cellulose acetate can be swellable in water. In some embodiments, the substituted cellulose acetate may be water resistant. In some embodiments, it may be desirable for the substituted cellulose acetate to have a relatively high percentage of sulfur and a relatively high degree of substitution for acetate. In particular, water-swellable materials are often marked by their ability to absorb water and are used as a material for water, water-retaining material, material supplies and the like. In some embodiments, the substituted cellulose acetate may be degradable. In some embodiments, the substituted cellulose acetate may be biodegradable.
The substituted cellulose acetate of the present invention can Used as an absorbent material for various consumer applications. The present invention provides, in some embodiments, diapers comprising an absorbent core comprising the substituted cellulose acetate of the present invention and an outer layer. Optionally, the diaper may further comprise a layer distribution designed to transfer moisture to the absorbent core and / or an outer shell that covers at least a portion of the absorbent core.
In some embodiments, the distribution layer is interposed between the absorbent core and the outer layer. In some embodiments, the distribution layer may be waterproof.
In some embodiments, the outer layer surrounds the absorbent core. In some modalities, the outer layer is waterproof. In some embodiments, the outer layer is configured to receive an insertion of the absorbent core. The outer layer can also be with color or with designs of ornamental feature that increases the visual appeal of the diaper. In some embodiments, the outer layer is configured with an opening to receive an insertion of an absorbent core. In some embodiments, the outer layer may be reusable.
In some embodiments, the outer layer is made of a material comprising a material selected from the group consisting of polyethylene, non-woven film, composite film, fabric, and combinations thereof.
In some embodiments, the diaper may be disposable. In In some embodiments, at least a portion of the diaper can be reusable.
The present invention provides, in some embodiments, bandages comprising an absorbent layer comprising a substituted cellulose acetate of the present invention and a band designed to hold the absorbent layer in contact with a wound. Optionally, the absorbent layer further comprises an active ingredient selected from the group consisting of antibiotics, analgesics, antipyretics, antimicrobials, antiseptics, anti-allergens, anti-acne, anesthetics, anti-inflammatories, hemostats, cosmetics, vitamins, vasodilators, emollients, regulators, pH, antipruritic, contrairritantes, antihistamines, steroids and combinations thereof.
In some embodiments, the antiseptic may comprise at least one transition metal. Suitable examples of a transition metal include, but are not limited to, aluminum, nickel, copper, zinc, titanium, iron, and silver.
In some embodiments, the wound is an incision, a laceration, an abrasion, a puncture wound, a penetration wound, or any combination thereof.
In some modalities, the band can be elastic. In some embodiments, the band may be adhesive. In some embodiments, the web comprises a material selected from the group consisting of: woven fabric, non-woven fabric, plastic, latex, and combinations thereof.
In some embodiments, the cigarette filter materials of the present invention comprise a segmented filter or a section of a filter comprising a substituted cellulose acetate of the present invention. In some embodiments, the cigarette filter materials of the present invention further comprise a conventional secondary cellulose diacetate. Optionally, the cigar filter materials further comprise a plasticizer. Without being limited by theory, it is believed that the substituted cellulose acetate should increase the degradability of the cigar filter material.
Suitable examples of plasticizers for use with the cigarette filter material related to embodiments include phthalate, triethyl acetyl citrate, triethyl citrate, acetyl tributyl citrate, dibutyl sebacate, triacetin, glycerin triacetate, polyethylene glycol, propylene glycol, and glycerin.
In some embodiments, the substituted cellulose acetate may be a fiber. In some embodiments, the substituted cellulose acetate is molded into a rod form.
In some embodiments, the smoking devices of the present invention comprise a smokable substance and a cigarette filter comprising a substituted cellulose acetate filament of the present invention. As used herein, a "smokable substance" includes any (for example, tobacco) that can be burned and its smoke can be tasted or inhaled. A variety of different forms may be used including, but not limited to, dry, fermented, cured, cut, and Similar.
In some embodiments, a smoking device may comprise a cigar, a pipe, a cigar, a vaporizer, and the like.
In some embodiments, the coated seeds of the present invention comprise a seed that is coated with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coated seeds further comprise a coating of secondary growth enhancement. Suitable examples of secondary growth augmentation coating may be selected from the group consisting of primary nutrients, secondary nutrients, hormones, insecticides, pesticides, herbicides, fungicides, bactericides, pigments, binders, surfactants, glidants, and combinations thereof.
Suitable examples of primary nutrients for use in combination with some embodiments of the present invention may include, but are not limited to, ammonium, nitrate, urea, ammonium phosphate, ammonium sulfate, urea phosphate, ammonium molybdate, potassium nitrate. , potassium phosphate, potassium hydroxide, potassium sulfate, and potassium chloride.
Suitable examples of secondary nutrients are selected from the group consisting of magnesium sulfate, calcium nitrate, sodium borate, magnesium nitrate, chelated complex of copper, calcium, iron, zinc, magnesium, manganese, ammonium molybdate, sodium molybdate , acid benzoic, and salicylic acid.
Suitable examples of binders for use in combination with some embodiments of the present invention may include, but are not limited to, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvidone, copolyvidone, derivatives thereof, and combinations thereof. the same.
Suitable examples of surfactants for use in combination with some embodiments of the present invention may include, but are not limited to, lecithin, sodium lauryl sulfate, polysorbate 60, polysorbate 80, polyoxyethylene, polyoxypropylene polyoxypropylene block copolymer, derivatives thereof , and combinations thereof.
Appropriate examples of pigments for use in combination with some embodiments of the present invention may include, but are not limited to, titanium dioxide, iron oxide, natural pigments, natural dyes, FD &C dyes, D &C lacquers, derivatives of the same, and combinations thereof.
Suitable examples of glidants for use in combination with some embodiments of the present invention may include, but are not limited to, talcum, colloidal silicon dioxide, stearic acid, derivatives thereof, and combinations thereof.
Suitable examples of herbicides for use in combination with some embodiments of the present invention may include, but are not limited to, glyphosate, dicamba, alanchlor, melachlor, oxabetrinyl, thiocarbamate, 5-ethyl-N, N-dipropyl thiocarbamate, acetochlor, derivatives thereof, and combinations thereof.
Suitable examples of antidotal compounds for use in combination with some embodiments of the present invention may include, but are not limited to, fluorazol, cymindinyl, N, N-diallyl dichloroacetamide, derivatives thereof, and combinations thereof.
Suitable examples of fungicides, bactericides, insecticides, and pesticides for use in combination with some embodiments of the present invention may include, but are not limited to, inorganic coppers, heavy metal compounds, propenoic acids, oximine ethers, substituted oximine ethers , derivatives thereof, and combinations thereof.
Suitable examples of hormones for plant for use in combination with some embodiments of the present invention may include, but are not limited to, auxins, gibberellic acids, cytokines, derivatives thereof, and combinations thereof.
In some embodiments, the coated pharmaceutical compositions of the present invention comprise a pharmaceutical composition that is coated with a coating comprising a substituted cellulose acetate of the present invention.
In some embodiments, the pharmaceutical composition for use in combination with some embodiments of the present invention may include, but is not limited to, analgesics, anti-inflammatory agents, anti-arrhythmic agents, anti-asthma agents, antibacterial agents, antiviral agents, anticoagulants, anti-dementia agents, antidepressants, antidiabetics, anti-hypertensive agents, anti-malarials, antimigraine agents, anti-muscarinic agents, anti-neoplastic agents, immunosuppressants , anti-protozoal agents, anti-thyroid agents, antitussive, anxiolytics, sedatives, hypnotics, neuroleptics, neuroprotective agents, beta-blockers, cardiac inotropic agents, cell adhesion inhibitors, corticosteroids, modulators of cytokine receptor activity, diuretics, antiparkinson agents, gastrointestinal agents, H-receptor antagonists of histamine, keratolytics, lipid regulating agents, muscle relaxants, nitrates, antifungal agents, anti-anginal agents, non-steroidal anti-asthmatic agents, nutritional agents, sex hormones, stimulants, anti-erectile dysfunction agents, anesthetics, antihistamines, decongestants, suppressants of coughs, demulcents, specifiers, derivatives thereof, combinations thereof, and mixtures thereof.
In some embodiments, the pharmaceutical composition for use in combination with some embodiments of the present invention may include, but is not limited to, pseudoephedrine, phenylpropanolamine, phenylephrine, ephedrine, dextromethorphan, chlorphedianol, carbetapentane, caramiphen, noscapine, diphenhydramine, codeine, menthol. , hydrocodone, hydromorphone, fominoben, glyceryl guaiacolate, terpine hydrate, ammonium chloride, N-acetylcysteine, bromhexine, ambroxol, chlorpheniramine, brompheniramine, dexchlorpheniramine, dexbrompheniramine, tripolidine, azatadine, doxylamine, tripelenamine, ciproheptadine, hydroxyzine, elemastine, carbinoxamine, fenindamine, bromodifenidramine, pumlamine, acrivastine, AHR-11325, astemizole, azelastine, cetirizine ebastine, cetotifen, lodoxamide, loratidine, levocabastine, mequitazine, oxatomide , setastine, taziphiline, temelastine, terfenadine, terbutaline, atropine, aminophylline, epinephrine, isoprenaline, metaproterenol, bitoterol, theophylline, albuterol, aspirin, acetaminophen, ibuprofen, naproxen, phenol benzocaine, hexyl resorcinol, dyclonine, derivatives thereof, combinations of the same, the pharmaceutically acceptable salts thereof, and mixtures thereof.
The present invention provides kits for detection of an analyte comprising a reporter molecule that is coated with a coating comprising a substituted cellulose acetate of the present invention.
The reporter molecule for use in combination with some embodiments of the present invention may include, but is not limited to, an antibody, a protein, an enzyme, a peptide, a nucleic acid, a small molecule, a fluorophore, derivatives thereof , and combinations thereof.
In some embodiments, the coating is water soluble or water swellable. In general, the coating provides a protective layer that can retard or prevent the degradation (eg, denaturation, separation) of the reporter molecule during storage.
In some embodiments, the coated stents of the present invention comprise a stent having an outer coating layer comprising a substituted cellulose acetate of the present invention and an inner coating layer comprising a pharmaceutical composition.
In some embodiments, the stent comprises a shape memory material. Suitable examples of shape memory material for use in combination with some embodiments of the present invention may include, but are not limited to, zinc alloys, copper alloys, gold alloys, iron alloys, copper-zinc alloys- aluminum-nickel, copper-aluminum-nickel alloys, and nickel-titanium alloys.
In some embodiments, the stent comprises a polymer. Suitable examples of polymer for use in combination with some embodiments of the present invention may include, but are not limited to, fibrin, polylactic acid, silicones, polyurethanes, polyesters, vinyl homopolymers, vinyl copolymers, acrylate homopolymers, acrylic copolymers , polyethers, cellulosics, derivatives thereof, and combinations thereof.
In some embodiments, the pharmaceutical composition is selected from the group consisting of: glucocorticoids, heparin, hirudin, tocopherol, angiopetin, aspirin, growth factors, oligonucleotides, anti-platelet agents, anti-coagulant agents, antimitotic agents, anti- oxidants, anti-metabolite agents, anti-inflammatory agents, and combinations thereof.
In some embodiments, the compost soil compositions of the present invention comprise an organic compost and an absorbent composition comprising a substituted cellulose acetate of the present invention. Optionally, the compost soil composition may further comprise at least one component selected from the group consisting of marl, diatomaceous earth component, Perlite component, and combinations thereof.
In some embodiments, marl includes components selected from the group consisting of sand, silt, mud, and combinations thereof.
In some embodiments, the diatomaceous earth component comprises at least one component selected from the group consisting of diatomaceous earth, phosphate, magnesium, potassium, nitrogen, and combinations thereof.
In some embodiments, the modified soil compositions of the present invention comprise a soil composition and a water retention additive comprising a substituted cellulose acetate of the present invention. Optionally, the modified soil composition may further comprise an additive selected from the group consisting of sand, silt, mud, calcined mud, iron oxide, dry resin, and combinations thereof.
Suitable examples of dry resins for use in combination with some embodiments of the present invention may include, but are not limited to, acrylic polymer, polyvinyl acetate polymer, vinyl acetate copolymer, derivatives thereof, and combinations thereof .
In some embodiments, the drilling fluids of the present invention comprise a base fluid and a viscosifier comprising a substituted cellulose acetate of the present invention. Optionally, the drilling fluid may further comprise an additive selected from the group consisting of fluid loss control agents, mud inhibitors, lubricants, weighting agents, viscosifiers, and any combinations thereof.
In some embodiments, the base fluid may be an aqueous fluid, an oil-based fluid, a synthetic fluid, or an emulsion.
In some embodiments, the present invention provides articles comprising a non-woven layer comprising fibers of a substituted cellulose acetate of the present invention.
In some embodiments, the non-woven layer may include, but is not limited to, diapers, feminine hygiene products, wet tissues, bandages, disposable towels, disposable slippers, surgical gowns, drapery and surgical covers, surgical scrub suit, caps, filters (eg, HEPA filters, water, coffee, tea bags, liquid cartridges, vacuum bags, geotextiles (eg, geomembranes), carpet reinforcers; wrappers.
In some embodiments, the present invention provides a process for making a substituted cellulose acetate fiber comprising spinning an additive comprising a solution of cellulose diacetate and substituted cellulose acetate of the present invention; and solvent; winding the filaments of substituted cellulose acetate as spinning; forming a fiber of the substituted cellulose acetate filaments; compress the fiber; condition the compressed fiber; and pack the dry compressed fiber. Optionally, the process may further comprise the step of lubricating the filaments of substituted cellulose acetate.
In some embodiments, the solvent is water, acetone, methyl ethyl ketone, methylene chloride, dioxane, dimethylformamide, methanol, ethanol, glacial acetic acid, supercritical C02, any suitable solvent capable of dissolving the aforementioned polymers, or any combination thereof. By way of non-limiting example, a solvent for cellulose acetate can be an acetone / methanol mixture.
In some embodiments, the substituted cellulose acetate is spun into a spinneret. In some embodiments, the nozzle for spinning comprises holes. The holes may be of any form that is compatible with one or more embodiments of the present invention. The design of the spinneret and / or spinning parameters can affect the rate at which the solvent evaporates from the filament, which can affect the size, cross-sectional shape, strength, and capacity of the filament. filament processing. In some modalities, a nozzle for spinning can comprise a plurality of holes separated by at least 0.177 centimeters (0.070 inches). In some embodiments, the spinning nozzles for use in conjunction with the present invention may comprise a plurality of extrusion holes in a donut configuration. As used herein, "donut configuration" refers to any shape (circular, ovular, polygonal, and the like) having a gap in the middle, wherein the gap has no holes for extrusion. As used herein, the terms "holes" and "extrusion holes", when used in conjunction with a nozzle design for spinning, can be used interchangeably generally referring to openings through which the additive is Extruded In some embodiments, the extrusion holes may be conical, for example, countersinks, with capillary outlets. The conicity may be at a constant angle or at more than one angle. In some embodiments, the extrusion holes within a single nozzle for spinning may have different taper angles. In some embodiments, the extrusion holes and / or capillary outlets may have a cross-sectional shape that produces a cross-sectional shape of the desired filament. Examples of cross-sectional shapes of extrusion hole and / or capillary outlet may include, but are not limited to, circular, substantially circular, ovulate, substantially ovulate, crescent, multiple lobes, polygonal (e.g., as tripods, tetrapods , stars, triangles, squares, trapezoids, pentagons, hexagons, etc. with sides of uniform lengths or variable lengths), polygonal with rounded corners, and any hybrid thereof. In some embodiments, a spinner may comprise at least two extrusion holes and / or capillary outlets in different cross-sectional shapes. In some embodiments, a nozzle for spinning can comprise at least two extrusion holes and / or capillary outlets of different sizes. In some embodiments, the size and / or cross-sectional shape of an extrusion hole may vary from those of the corresponding capillary outlet.
In some embodiments, the spin parameters may include extruding filaments at a level descending ratio (fiber exit velocity to winding speed) ranging from about 0.7 to about 1.6.
It should be understood by one skilled in the art that extrusion does not involve a single method or action for the production of the filaments and could be interchanged with, at least, spinning, ejecting, and the like.
In some embodiments, the methods of the present invention comprise providing substituted cellulose acetate of the present invention and placing the substituted cellulose acetate in an absorbent article. In some embodiments, the absorbent article can be any article (e.g., a garment, a gel, a piece of furniture, etc.) that can use an absorbent material. Appropriate examples of absorbent articles they may include, but are not limited to, diapers, incontinence garments, bandages, surgical pads, heat and cold therapy packages, water beds, artificial snow, and combinations thereof. In some embodiments, the absorbent article is disposable and / or degradable.
In some embodiments, the substituted cellulose acetate can be placed in the inner portion of an absorbent article. In some embodiments, the substituted cellulose acetate can be placed in the outer portion of an absorbent article. In some embodiments, the substituted cellulose acetate may be part of the outer portion of an absorbent article. The term "place" is not intended to limit the present invention to any specific mode of action.
In some embodiments, the methods of the present invention comprise coating a seed with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coating may further comprise at least one ingredient selected from the group consisting of a plasticizer, a binder, a wax, a stabilizer, and a colorant.
In some embodiments, the methods of the present invention comprise coating a pharmaceutical composition with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coating further comprises an additive selected from the group consisting of a plasticizer, a tempering agent, an emulsifying agent, an emulsion stabilizer, and combinations thereof.
In some embodiments, the tempering agent comprises a water soluble polymer selected from the group consisting of hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, methyl ethyl cellulose, polyvinyl pyrrolidone, sodium carboxymethyl cellulose, derivatives thereof, and combinations thereof.
In some embodiments, the methods of the present invention comprise providing an adhesive comprising a substituted cellulose acetate of the present invention and applying the adhesive on a surface. In some embodiments, the surface may be selected from the group consisting of wood, plastic, paper, glass, cardboard and combinations thereof. In some embodiments, the adhesive is a dispersion. Optionally, the adhesive may further comprise a solvent and / or an additive.
In some embodiments, the solvent may be aqueous. In some embodiments, the solvent may be a mixture such as an organic solvent / water. In some embodiments, the solvent may be present in about 40% by weight to about 99% by weight of the adhesive.
In some embodiments, the additive comprises an additive selected from the group consisting of multi-valent salts (e.g., zirconium salts such as zirconium carbonate), epichlorohydrin polyamide resins, aldheidos (e.g., glyoxal, gluteraldehyde, hydroxyadipaldehyde), formaldehyde crosslinkers (eg, zero-formaldehyde, low-formaldehyde crosslinkers), polyvinyl acetates, polyvinyl alcohols, polystyrenes, polylactic acids, derivatives thereof, and combinations thereof.
In some embodiments, the present invention provides a paint composition comprising a pigment and a stabilizing film forming agent comprising a substituted cellulose acetate of the present invention and coating a surface with the paint. Optionally, the paint may further comprise at least one element selected from the group consisting of: a solvent, a filler, an antifreeze additive, a catalyst, a thickener, an adhesion promoter, a UV stabilizer, a de-brightened agent, a biocide, and combinations thereof.
Suitable examples of solvents include, but are not limited to, an aliphatic solvent, an aromatic solvent, an alcohol, a ketone, a hydrocarbon, an ester, a petroleum distillate, water, derivatives thereof, and combinations thereof.
Suitable examples of pigments include pigments selected from the group consisting of clay, calcium carbonate, mica, silica, talc, titanium dioxide, derivatives thereof, and combinations thereof.
Suitable examples of filters include fillers selected from the group consisting of: diatomaceous earth, talc, lime, barite, clay, derivatives thereof, and combinations thereof.
In still other embodiments, the present invention provides a method for providing a paint comprising a pigment; and a stabilization film forming agent comprising a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently attached to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate; and cover a surface with the paint.
The methods of the present invention comprise providing a stabilizing film forming agent comprising a substituted cellulose acetate of the present invention and incorporating the stabilizing film forming agent into an emulsion. Suitable examples of the emulsion include, but are not limited to, cosmetic products, hair styling products, photographic film, clipping fluid, skin cream, paste, balm, oil, wax, detergent, beverage and combinations thereof.
The methods of the present invention comprise providing a thickening agent comprising a substituted cellulose acetate of the present invention and incorporating the thickening agent into a food composition. Compositions for appropriate foods may include, but are not limited to, soups, sauces, desserts, jellies, sweets and the like.
To facilitate a better understanding of the present invention, the following examples of the preferred embodiments are given. In no way should the following examples be read as limiting or to define the scope of the invention.
EXAMPLE 1 Some adhesive compositions comprising the substituted cellulose acetate of the present invention were tested for their adhesive properties on various substrates including wood and cardboard using an overlap shear test. The results were compared with commercially available adhesive (for example, ELMER'S GLUE ALL®). A summary of the results is shown below in Tables 1A and 1B.
TABLE 1A Overlap shear test results TABLE 1 B Results of the Lapping Shearing Test Substituted cellulose acetates with high sulfur content in accordance with one or more embodiments of the present invention (lots of Cellulose Acetate Adhesive 1-5) were prepared and tested as a wood adhesive using INSTRON® (Model 3366) the Lapping Shear test. The results, including the amount of sulfur in the solution (mg of sulfur per kg of sulfur), are summarized in Tables 1A and 1B above. Two small wooden blocks were glued together using a 10% aqueous solution of the adhesives and allowed to dry. The resulting blocks were difficult to separate (ie, none of the blocks were broken in tension test configuration used). When enough force was applied to separate the blocks, the wood fibers broke, suggesting that the substituted cellulose acetate adhesive is as strong as the wood fibers. The substituted cellulose acetate adhesives were also used to glue cardboard. The cardboard was also difficult to separate. The substituted cellulose acetate adhesives were optically clear and have a high gloss which may be desirable in commercial applications. The substituted cellulose acetate adhesives were dried in less than 30 minutes at ambient conditions.
This example shows, among many things, that the high sulfur content substituted cellulose aceto is effective as an adhesive on a variety of substrates.
EXAMPLE 2 This example describes the synthesis of a sulfate substituted cellulose acetate of the present invention. In the first step, cellulose it was acetylated in the presence of acetic anhydride and sulfuric acid. The preparation of cellulose, acetic acid, acetic anhydride and sulfuric acid is similar to the preparation involved in a production of standard secondary cellulose acetate diacetate. Then, the reagents were combined to initiate the acetylation reaction. This reaction was allowed to reach its term and then reacted with any excess of anhydride by the incorporation of water. The reaction rate and temperature can be monitored closely and varied to control certain polymer properties.
Next, the acetylated cellulose (i.e., cellulose acetate) was hydrolyzed in the presence of acetic acid without precipitation and subsequent redissolution steps. This reduced the cellulose acetate to the DS levels of target acetate by carefully controlling the time and the reaction temperature. Water was incorporated as necessary to maintain the solubility of the polymer. This produced a sulfate-substituted cellulose acetate product having surprisingly high and unexpected sulfur content.
Finally, the solid was precipitated from the solvent system using the appropriate diluent. The product was washed as necessary to remove the excess solvent and dried to the desired solids level.
EXAMPLE 3 In this Example, water-swellable cellulose acetate (low sulfur content) and substituted cellulose acetate (high sulfur content) were tested for their ability to absorb water using a thermogravimetric analysis (TGA). Each sample was placed in a TGA system and subjected to the following temperatures. The samples were increased to 1 10 ° C at 20 ° C / min. The temperature was maintained at 110 ° C for 30 minutes. Then the temperature was increased to 650 ° C at 20 ° C / min. The gas sample was then changed to air and the temperature was maintained at 650 ° C for 30 minutes. In each test run, cellulose acetate samples were limited to less than 00 mg.
Figures 2-5 show the various runs of the TGA analysis measuring the water absorbency of high sulphate substituted cellulose acetate and low sulphate substituted cellulose acetate.
Figure 2 shows a TGA analysis of dry sample of water-swellable cellulose acetate, saturated with water (WSCA) 1036 RT-16. WSCA 1036 RT-16 is a sample of high sulfate substituted cellulose acetate particles containing approximately 0.5% sulfur by weight of cellulose acetate. When the temperature is increased and maintained at 110X, the total weight of the sample saturated with water decreases when the water dries. The temperature of the TGA system was then increased and maintained at 650 ° C, allowing the decomposition of the high sulphate substituted cellulose acetate. WSCA 1036 RT-16 was able to absorb approximately 1440% water by weight as the dry sample or over 14 times its weight in water.
Figure 3 shows duplicate runs of TGA for two dry samples WSCA 1037 RT-16. Compared to the WSCA 1036 RT-16, the WSCA 1037 RT-16 is a cellulose acetate substituted with low sulfur (DS of acetates are similar). The water absorption detected for the two samples were 76.91% and 81.31%, which correspond to water ratios to dry WSCA of 3.35 and 4.37 respectively.
Figure 4 shows duplicate runs of TGA for two samples RT-16 WSCA 1036 (high sulfate) saturated (-0.9%) of saline water. The two samples contained 87.05% and 92.14% saline water which corresponds to water to dry WSCA ratios of 7.48 and 13.6 respectively.
Figure 5 shows runs in duplicate of TGA for sample RT-16 WSCA 1037 saturated (-0.9%) of saline water. The two samples contained 78.31% and 83.91% of saline water, which corresponded to dry WSCA ratios of 3.72 and 5.46 respectively.
This Example shows, among other things, that the substituted cellulose acetate having a high sulfur content is capable of absorbing water (both deionized and saline) several times its weight. When compared with substituted cellulose acetate with low sulfur content, the high sulfur substituted cellulose acetate displayed superior water absorption (both DI and salina).
EXAMPLE 4 Several alternatives were incorporated into some adhesive compositions comprising substituted cellulose acetate of the present invention. The resulting compositions were tested for their adhesive properties on wood substrates (0.635 cm (1/4") 3.81 (1 .5") wide pine strips) using the INSTRON® Lapping Shear Test (Model 3366). Summaries of the results are shown below in Tables 2 and 3 below.
TABLE 2 Adhesive of cellulose acetate 6 (620 mg / kq sulfur) * average of 6 replicas ** area overlap shear 3.81 x 2.54 cm (1.5"x 1") TABLE 3 Cellulose acetate adhesive 7-8 As shown in Table 2, the incorporation of zirconium can increase the force required to break the bond formed by the cellulose acetate adhesive compositions (high sulfur content substituted cellulose acetate). Table 3 shows the results of the overlap shear test of cellulose acetate adhesives 7 and 8 with zirconium ammonium carbonate (0.08% Zr), MW 140,000 polyvinyl acetate (14% solid) and MW 150,000 polyvinyl alcohol (14% solid). The sulfur content of cellulose acetate adhesives 6, 7, and 8 are 620 mg / kg, 520 mg / kg, and 557 mg / kg respectively.
Therefore, the present invention is well adapted to achieve the ends and advantages mentioned, as well as those that are inherent to it. The particular embodiments disclosed above are only illustrative, since the present invention can be modified and practiced in different but equivalent ways apparent to those skilled in the art having the benefit of teachings in the present. In addition, no limitations are intended to the details of construction or design shown herein, other than those described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above can be altered, combined or modified and all of these variations are considered within the scope and spirit of the present invention. The invention described illustratively herein can be carried out suitably in the absence of any element that is not specifically described herein and / or any optional element described herein. Although the compositions and methods are described in terms of "comprising", "containing", or "including" various components or steps, compositions and methods may also "essentially consist of" or "consist of" the various components and steps. All numbers and ranges disclosed above may vary by a certain amount. When a numerical range with a lower limit and upper limit is disclosed, any number and any included ranges that fall within the range are specifically disclosed. In particular, each range of values (of the form, "from about a to about b," or, equivalently, "from about aab," or, equivalently, "from about ab") disclosed herein has It is understood that it exposes each number and range covered within the widest range of values. Also, the terms in the claims have their plain and ordinary meaning, unless the patent holder defines it explicitly and clearly in another way. In addition, the indefinite articles "a" or "an", as used in the claims, are defined herein as meaning one or more of the element they introduce. If there is any conflict in the uses of a word or term in this specification and one or more patents or other documents that may be incorporated herein as a reference, definitions that are consistent with this specification shall be adopted.

Claims (1)

  1. NOVELTY OF THE INVENTION CLAIMS 1 .- A filter material for cigar comrpende: a filter comprising a cellulose diacetate and a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bound to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least 0.01% by weight of the substituted cellulose acetate. 2. - The cigarette filter material according to claim 1, further characterized in that the non-metal is present in not more than about 25% by weight of the substituted cellulose acetate. 3 - . 3 - The cigarette filter material according to claim 1, further characterized in that it additionally comprises a plasticizer. 4. - The cigarette filter material according to claim 3, further characterized in that the plasticizer comprises a plasticizer selected from the group consisting of: esters of saturated dibasic acids, esters of saturated polyhydric alcohols, fatty acid esters and sulfonamide resins. 5. - The cigarette filter material according to claim 1, further characterized by the cellulose acetate replaced is a fiber. 6. - A smoking device comprising: a smokable substance; and a cigarette filter comprising a cellulose diacetate and a substituted cellulose acetate filament comprising a polar substituent comprising an oxygen atom covalently linked to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate. 7. - The smoking device according to claim 6, further characterized in that the non-metal is present in no more than about 25% by weight of the substituted cellulose acetate. 8. - The smoking device according to claim 6, further characterized in that the smokable substance is tobacco. 9. - The smoking device according to claim 8, further characterized in that the tobacco has undergone a treatment comprising a treatment selected from the group consisting of: drying, fermenting, curing, cutting and any combination thereof. 10. - The smoking device according to claim 6, further characterized in that the device for smoking is a cigar, a pipe, a cigar, or a vaporizer. 1 - A process for making a substituted cellulose acetate fiber comprising: spinning an additive comprising a solution of cellulose diacetate; substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently attached to a non-metal selected from the group consisting of: sulfur, phosphorus, boron, and chlorine; wherein the non-metal is present in at least about 0.01% by weight of the substituted cellulose acetate; and solvent; collecting the filaments of substituted cellulose acetate as spinning; forming a fiber of the substituted cellulose acetate filaments; compress the fiber; condition the compressed fiber; and pack the dry compressed fiber. 12. - The process according to claim 1, further characterized in that the non-metal is present in not more than about 25% by weight of the substituted cellulose acetate. 13. - The process according to claim 1, further characterized in that the solvent is selected from the group consisting of: water, acetone, methyl ethyl ketone, methylene chloride, dioxane, dimethylformamide, methanol, ethanol, glacial acetic acid, supercritical C02, and any combination of them. 14. - The process according to claim 1, further characterized in that the substituted cellulose acetate is spun into a spinneret. 15. - The process according to claim 14, further characterized in that the spinning nozzle comprises holes. 16. - The process according to claim 1, further characterized in that it further comprises the step of lubricating the filaments of substituted cellulose acetate.
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CA2861037A1 (en) 2013-08-01
EP2811852A4 (en) 2015-12-23
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KR20140116537A (en) 2014-10-02
US20130192613A1 (en) 2013-08-01
BR112014018021A8 (en) 2017-07-11
WO2013112502A1 (en) 2013-08-01

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