KR20140116537A - Substituted cellulose acetates and uses thereof - Google Patents

Abstract

The present invention relates to substituted cellulose acetates and methods for their use. One embodiment of the invention has a substituted cellulose acetate having a polar substituent having an oxygen atom covalently bonded to a nonmetal selected from the group of sulfur, phosphorus, boron, and chlorine, wherein the base metal is selected from the group consisting of substituted cellulose acetate Tobacco filter material having a filter present at least 0.01% by weight.

Description

[0001] SUBSTITUTED CELLULOSE ACETATES AND USES THEREOF [0002]

The present invention relates to synthetic polymers, particularly substituted cellulose acetate, and methods of use thereof.

Cellulose acetate is a naturally occurring biopolymer containing acetate ester derivatives of cellulose, i.e., beta -D-glucose monomer units, and is widely used in the manufacture of a variety of consumer goods. Naturally occurring cellulose is insoluble in water and most organic solvents. However, three free hydroxyl groups of each glucose monomer in the cellulose can be derivatized to modify specific properties, for example solubility in a particular solvent. Cellulose acetate is considered to be one of the most useful derivatives of commercially available cellulose and its specific physical and chemical properties are mainly dependent on the degree of substitution of the acetate on the three free hydroxyl groups of the glucose monomer unit.

Since its initial synthesis, cellulose acetate has been used in particular as a raw material for use in the production of film bases in photographic, components in adhesives, and tobacco filters. One of the important attributes of cellulose acetate is that it can be processed into a number of different shapes and forms, including films, tows, flakes, fibers and solids, depending on the application's desirability. For example, cellulose acetate tow is mainly used in the manufacture of cigarette filters.

Most typically, the derivatization of cellulose is carried out using an acidic catalyst at a high reaction temperature. The synthesis of cellulose acetate generally involves acetylating the cellulose obtained in wood pulp in the presence of acetic anhydride and an acid. Acetic acid and sulfuric acid are the two acids normally present during the acetylation reaction. In this reaction, acetic anhydride functions as a main acetylating agent, acetic acid is mainly used as a diluent, and a small amount of sulfuric acid is used as a catalyst. In general, the monomer units of cellulose have three hydroxyl groups which can be readily used for substitution, for example, through acetylation. The monomer units at both ends typically have additional hydroxyl groups included in the inter-sugar linkage.

The product of the acetylation reaction is primary cellulose acetate, which typically contains a high concentration of acetate, i. E., A high degree of substitution (DS) of acetate. As used herein, "degree of substitution of acetate" generally refers to the average number of acetates per glucose monomer unit. The structure of cellulose acetate is generally specified by defining the degree of substitution of the acetate. Fully acetylated cellulose is commonly referred to as cellulose triacetate, where according to the Federal Trade Commission guidelines, at least 92% of the hydroxyl groups are replaced by acetyl groups. For example, if there are at least about 2 acetyl groups per unit of cellulose monomer (i.e., DS is about 2), the acetylcellulose is removed until at least a portion of the acetyl group is removed through chemical hydrolysis or enzymatic hydrolysis Can be significantly less biodegradable. Acetylated cellulose with 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 decrease the DS of the acetate of the primary cellulose acetate. The resulting hydrolysis product is typically a cellulose acetate flake having a DS of about 2.4 to about 2.6.

Once a cellulose acetate flake is obtained, it can be applied to further processing to process the cellulose acetate into its preferred form. For example, a cellulose acetate tow can be formed by dissolving a cellulose acetate flake in acetone, passing the cellulose acetate solution through a series of filtration processes, and dry-spinning an acetone dope through fine holes in the spinnerette. The cellulose acetate is passed through this extrusion process and the filaments of the cellulose acetate are collected. These filaments are typically bundled and then crimped to ensure desirable bulk as well as tobacco cohesion. The end result is a cellulose acetate tow, which is essentially a continuous band consisting of thousands of filaments loosely held together by a crimp. Cellulose acetate tow filaments are typically very thin and tightly packed together to produce a filter. As used herein, "cellulose acetate tow" refers generally to the post-synthesis processing bundle of filaments of cellulose acetate

Cellulose acetate is also environmentally friendly in that it is an easily degradable material made predominantly from wood pulp, which is a renewable source. While the DS of the acetate is structurally similar to the other cellulose acetate, this difference may have some effect on the biodegradability of the cellulose acetate. In higher acetyl substitution degrees, the rate of biodegradation can be significantly reduced as compared to naturally occurring cellulose or cellulose having a low acetylation degree of substitution. Cellulose acetate with DS of lower acetate is more readily biodegradable than cellulose acetate with DS of higher acetate. This tendency is believed to diminish at lower DS values of acetate, because the material becomes insoluble in water. In one embodiment, for their biodegradability, the biodegradation rate of cellulose acetate with DS values of 1.85, 2.07, and 2.57 was tested (Figure 1). Cellulose acetate having a DS of 1.85 showed the highest rate of biodegradation, while cellulose acetate having an acetyl value of 2.57 showed the lowest rate of biodegradation.

Cellulose acetate is a multipurpose composition with many commercial uses, but the properties of certain cellulose acetate derivatives are not fully explored. For example, in a typical synthesis, the remaining sulfate groups are typically removed to improve thermal stability. As a result, the cellulose acetate synthesized by typical methods will have less than about 0.005 weight percent sulfur atoms. Thus, there are potential derivatives of cellulose acetate that can provide improved properties for many consumer applications of cellulose acetate.

Summary of the Invention

The present invention relates to synthetic polymers, particularly substituted cellulose acetate, and methods of use thereof.

In some embodiments, the present invention includes a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a nonmetal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the non- An inner layer comprising an absorbent core present in at least about 0.01 weight percent of the substituted cellulose acetate, and an outer layer.

In another embodiment, the invention comprises a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a base metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the base metal is a substituted cellulose An absorbent layer present at least about 0.01 weight percent of the acetate, and a strip designed to rest upon the absorbent layer in contact with the wound.

In another embodiment, the present invention provides a process for preparing substituted cellulose acetates comprising an organic com- post and a polar substituent comprising an oxygen atom covalently bonded to a nonmetal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, Wherein the nonmetal is present in an amount of at least about 0.01% by weight of the substituted cellulose acetate.

In another embodiment, the invention comprises a soil composition and a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a base metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein The nonmetal provides an amended soil composition comprising a water retention additive present in at least about 0.01% by weight of the substituted cellulose acetate.

In another embodiment, the present invention provides a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a base metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the base metal is selected from the group consisting of substituted cellulose acetate At least about 0.01% by weight, based on the total weight of the nonwoven layer).

In another embodiment, the present invention provides a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a non-metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the non- At least about 0.01% by weight of the cellulose acetate being present, and introducing the substituted cellulose acetate into the absorbent article.

In another embodiment, the invention comprises a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a non-metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the non- Providing an absorbent material present in at least about 0.01 weight percent of the cellulose acetate, and introducing the absorbent material to the diaper.

The features and advantages of the present invention will be readily apparent to those skilled in the art from a reading of the following description of the preferred embodiments.

The following drawings are included to illustrate certain aspects of the present invention and should not be considered as exclusive embodiments. The disclosed subject matter can be significantly modified, modified, and equivalents in form and function as will be apparent to those skilled in the art and as persons skilled in the art having the benefit of this disclosure will appreciate.
Figure 1 shows a biodegradable plot of cellulose acetate with varying degrees of substitution.
Fig. 2 shows water absorbency data as described in Example 3. Fig.
Figure 3 shows water absorbency data as described in Example 3;
Fig. 4 shows water absorbency data as described in Example 3. Fig.
Figure 5 shows water absorbency data as described in Example 3;

The present invention relates to synthetic polymers, particularly substituted cellulose acetate, and methods of use thereof.

The present invention provides compositions, methods and processes related to substituted cellulose acetates having a number of advantages and / or desirable properties. The substituted cellulose acetate of the present invention may be used in a variety of applications, including consumer goods, particularly consumer goods where absorbent, adhesive and / or degradable properties may be useful.

As used herein, the term "substituted cellulose acetate" refers generally to cellulose acetate having at least one polar substituent substituted on the hydroxyl group of the cellulosic polymer. As used herein, a "polar substituent" refers to a non-ionic group that includes an electronegative atom (e.g., oxygen) bonded to a nonmetal (e.g., sulfur, phosphorus, boron, and chlorine) non-acetyl chemical moiety.

Surprisingly, it has been found in accordance with the present invention that it is possible to provide a substituted cellulose acetate composition having relatively high weight percentages of at least one nonmetallic atom corresponding to a polar substituent having a relatively high degree of substitution. Moreover, it has further been surprisingly found that adjusting and / or altering the weight percent of non-metallic atoms can exhibit or enhance various properties of the substituted cellulose acetate as described in the present invention.

In some embodiments, the substituted cellulose acetate of the present invention is versatile (i.e., possesses a number of distinct and desirable chemical properties and properties) suitable for use in a number of consumer products and is environmentally friendly (i.e., Degradable, biodegradable, etc.).

As used herein, "degradable" refers to the ability of a material to be broken down and / or truncated into simpler parts. As used herein, "biodegradable" refers to the ability of a substance to degrade by the action of an organism. Depending on the application, the definition of "biodegradability" may be applied to the results of standard tests, for example the OECD test protocol.

Without wishing to be bound by theory, it is believed that by adjusting the weight percent of nonmetal atoms of the polar substituent, the substituted cellulose acetate of the present invention can provide new and improved chemical properties and / or properties. For example, it is believed that certain polar substituents (e. G., Sulfates) can increase the hydrophilicity of the substituted cellulose acetate and increase the potential for electrostatic interactions.

The substituted cellulose acetate compositions described in more detail below have particular beneficial properties and commercial roles (e.g., as adhesives, chemical stabilizers, absorbents) that can be imparted or enhanced based on the weight percentages of non-metallic atoms present . In some embodiments, the weight percent of non-metallic atoms can be tuned to eliminate or reduce undesirable quality or characteristics of the substituted cellulose acetate.

The substituted cellulose acetate is advantageously used in view of the degree of substitution of the polar substituents (i. E., The average number of substituents per glucose monomer unit), or the amount of the base metal (e. G., Sulfur, phosphorus, Boron, and chlorine) atoms, as the weight percent of atoms. In practical terms, modifying the degree of substitution of polar substituents is also to modify the weight percent of non-metallic atoms on the substituted cellulose acetate to a predictable amount, and vice versa. Thus, it is predicted that increasing the degree of substitution of polar substituents will generally increase the weight percent of non-metallic atoms present on the substituted cellulose acetate. Conversely, reducing the degree of substitution of polar substituents will generally reduce the weight percent of non-metallic atoms present in the substituted cellulose acetate to a predictable amount.

Theoretically, the weight percent of non-metallic atoms in the substituted cellulose acetate can range from about 0.01% to about 25%, which is substantially free of polar substituents (in some cases considerably and surprisingly, more than the typically prepared cellulose acetate ) ≪ / RTI > cellulose acetate and fully substituted cellulose acetate. Although the present invention is preferably carried out by specifying the weight percent of the base metal of the polar substituent, the present invention can be equally practiced by specifying a measure of the degree of substitution of the polar substituent or other similar concentration. The degree of substitution of polar substituents may range from about 0.005 to about 3.

Various embodiments described herein utilize substituted cellulose acetate with polar substituents in a wide variety of consumer products. By adjusting the weight percent of the nonmetal atoms of the polar substituent, the substituted cellulose acetate compositions of the present invention can be used as particularly effective absorbents, adhesives, chemical stabilizers and stabilizing film forming agents. For example, by adjusting the weight percent of a sulfur atom (e.g., a sulfate substituent), the substituted cellulose acetate of the present invention can be converted 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, for example, to encapsulate a pharmaceutical composition so that release of the pharmaceutical composition is delayed in the body. Other properties that may be adjusted include, but are not limited to, solubility in a particular solvent, ability to stabilize the emulsion, adhesion to various surfaces and biodegradability. This property can also be further adjusted by changing the weight percent of the non-metal atoms of the polar substituents present in the substituted cellulose acetate as needed. One skilled in the art will be able to change the weight percent of base metal as necessary to practice many embodiments of the present invention.

In some embodiments, altering the degree of substitution of the acetate can also yield or enhance the specific properties of the substituted cellulose acetate. In some embodiments, the water-soluble substituted cellulose acetate has a degree of substitution of about 0.4 to about 1 acetate. In some embodiments, the water swellable substituted cellulose acetate has a degree of substitution of about 1 to about 2 of acetate. Since the substitution degree of acetate varies from 0.05 to 3, an appropriate solvent system can be changed. In some embodiments, in the degree of substitution of the relatively low acetate, water is a suitable solvent. In some embodiments, in the degree of substitution of the relatively high acetate, an organic solvent is required. The degree of substitution can be varied to select a solvent system suitable for the desired end use.

In some embodiments, the degree of substitution of the polar substituents can be kept relatively constant while adjusting the degree of substitution of the acetates. In some embodiments, the degree of substitution of polar substituents and the degree of substitution of acetates are combined to provide substituted cellulose acetates having desirable properties. In some embodiments, the degree of substitution of the polar substituent may affect the degree of substitution of the acetate required to provide the substituted cellulose acetate with the desired properties. In some embodiments, the degree of substitution of the acetate can affect the degree of substitution of the polar substituents required to provide the substituted cellulose acetate with the desired properties.

Potential commercial uses of the substituted cellulose acetate of the present invention are varied and include household articles such as buttons, glass, lining, blouses, dresses, wedding and party costumes, home furnishing, Drapes, covers, slip covers, and the like, but are not limited thereto. Other commercial uses include filters included in cigarettes, ink reservoirs, playing cards, and the like, and highly absorbent products such as diapers and surgical products.

In some embodiments, as an absorbent, the substituted cellulose acetate of the present invention may be prepared by reacting a substituted cellulose acetate of the formula (I) in a water-based fluid (e.g., water, saline solution, etc.) (E.g., about 8 times to about 24 times) the water absorption capacity.

In some embodiments, the substituted cellulose acetate of the present invention includes, but is not limited to, cardboard, plastic, paper, glass, wood, hemp, sawdust, composites (e.g., fiber reinforced composites, In addition, the substituted cellulose acetate of the present invention may be an effective chemical / colloidal stabilizer capable of stabilizing various emulsion mixtures.

In some embodiments, the substituted cellulose acetate of the present invention can be used as a stabilizing film-forming agent to promote film formation of a given mixture. In some embodiments, the formed film may be transparent.

The substituted cellulose acetate can be present in a number of different forms and can be used in a number of different ways. In some embodiments, the substituted cellulose acetate is selected from the group consisting of fibers, wovens, nonwovens, tows or tow bands (open or non-open), flakes, foams, emulsions, films, , 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 a method of forming a substituted cellulose acetate in a variety of configurations of substituted cellulose acetate (e.g., a substituted cellulose acetate tow). This method typically makes the substituted cellulose acetate a better form for use in certain applications. For example, the fibers of the substituted cellulose acetate can selectively absorb and remove the level of certain organic chemicals, have a water-soluble or water-swellable, high surface area, and have particularly desirable properties compatible with the dye. It is also believed that the fibers of the substituted cellulose acetate may have resistance to mold and mildew. Substituted cellulose acetate may be particularly preferred in textile applications.

Although at least some embodiments relate to cellulose acetate having at least one polar substituent, derivatives of cellulose acetate having at least one polar substituent may also be used in accordance with any of the compatible embodiments of the present invention. Derivatives of cellulose acetate include, but are not limited to, cellulose acetate esters, cellulose acetate mixed esters, and the like. Suitable examples of cellulose acetate esters include, but are not limited to, cellulose acetate propionate, cellulose acetate butyrate, and the like. The degree of esterification of the cellulose acetate ester 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 has a polar substituent comprising an oxygen atom covalently bonded to a base metal selected from the group consisting of sulfur, phosphorus, and boron, wherein the base metal is present in at least 0.01 weight percent of the substituted cellulose acetate . In some embodiments, the base metal may be present at up to about 25 weight percent of the substituted cellulose acetate. While not wishing to be bound by theory, it is believed that an upper limit of 25 wt% corresponds to a fully substituted substituted cellulose derivative (e.g., sulfate). The actual range of weight percentages of the base metal will depend in particular on the chemical makeup of the polar substituents.

Generally, at least a portion of the hydroxyl groups on the substituted cellulose acetate will be replaced by acetate. In some embodiments, the degree of substitution of the acetate will be from about 0.05 to about 3, preferably from about 0.4 to about 2. In some embodiments, the degree of substitution of acetate and the degree of substitution of the polar substituent may be adjusted to produce or enhance the desired properties of the substituted cellulose acetate of the present invention. In some embodiments, the DS of the acetate is higher than the DS of the polar substituent.

Optionally, the substituted cellulose acetate may further comprise a plasticizer or be mixed with a plasticizer. Suitable examples of plasticizers include 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, 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. The plasticizer may be added to the cellulose acetate substitutions in order to lower the composition's glass transition temperature (T _g) and melting point. Plasticizers typically serve to facilitate processing and to increase the flexibility and toughness of the final product. In addition, certain plasticizers (e. G., Ether esters, simple ester types, etc.) can increase the ability of substituted cellulose acetate for phenol removal, a useful property in tobacco filters.

In some embodiments, polar substituents may be selected from the group consisting of sulfate, phosphate, borate, carbonate, 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 nonmetal of the polar substituent is present at less than about 75 weight percent of the substituted cellulose acetate. The actual range of weight% of polar substituents will depend in particular on the chemical composition of the polar substituents.

In one or more embodiments, the substituted cellulose acetate may have properties that can be imparted or enhanced by increasing or decreasing the concentration of a polar substituent or nonmetal atom. In some embodiments, the substituted cellulose acetate may be water-soluble. In some embodiments, the substituted cellulose acetate may be water swellable. 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 degree of substitution for relatively high acetate. In particular, water-swellable materials are often represented by their ability to absorb water and are used as water-stopping materials, water-retaining materials, 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 be used as an absorbent material for many consumer applications. In some embodiments, the present invention provides an absorbent core comprising a substituted cellulose acetate of the present invention and a diaper comprising an outer layer. Optionally, the diaper may further comprise a distribution layer designed to deliver moisture to the outer shell covering at least a portion of the absorbent core and / or 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 embodiments, the outer layer is waterproof. In some embodiments, the outer layer is configured to accept insertion of the absorbent core. The outer layer may also be colored or may feature an ornamental design that increases the visual appeal of the diaper. In some embodiments, the outer layer comprises an opening for receiving the insertion of the absorbent core. In some embodiments, the outer layer can be reused.

In some embodiments, the outer layer is made from a material comprising a material selected from the group consisting of polyethylene, nonwoven films, composite films, cloth, and combinations thereof.

In some embodiments, the diaper may be disposable. In some embodiments, at least a portion of the diaper can be reused.

In some embodiments, the present invention provides a bandage comprising an absorbent layer comprising a substituted cellulose acetate of the present invention and a strip designed to contact the absorbent layer with a wound. Optionally, the water absorbent layer may be selected from the group consisting of antibiotics, analgesics, antipyretics, antimicrobials, disinfectants, antiallergy, anti-acne, anesthetics, anti-inflammatories, hemostats, cosmetics, vitamins, emollients, An antipruritic agent, a counterirritant agent, an antihistamine agent, a steroid, and a combination thereof.

In some embodiments, the disinfectant may comprise at least one transition metal. Examples of suitable transition metals include, but are not limited to, aluminum, nickel, copper, zinc, titanium iron and silver.

In some embodiments, the wound is incision, laceration, abrasion, puncture wound, penetration wound, or any combination thereof.

In some embodiments, the strip may be elastic. In some embodiments, the strip may be an adhesive. In some embodiments, the strip comprises a material selected from the group consisting of wovens, nonwovens, plastics, latexes, and combinations thereof.

In some embodiments, the tobacco filter material of the present invention comprises a portion of a segmentation filter or filter comprising a substituted cellulose acetate of the present invention. In some embodiments, the tobacco filter material of the present invention further comprises conventional secondary cellulosic diacetate. Optionally, the tobacco filter material further comprises a plasticizer. While not wishing to be bound by theory, it is believed that substituted cellulose acetate can increase the degradability of the tobacco filter material.

Examples of plasticizers suitable for use with embodiments involving tobacco filter materials include but are not limited to phthalates, acetyl triethyl citrate, triethyl citrate, acetyl tributyl citrate, dibutyl sebacate, triacetin, glyceryl triacetate, polyethylene Glycols, propylene glycol, and glycerin.

In some embodiments, the substituted cellulose acetate may be a tow. In some embodiments, the substituted cellulose acetate is formed into a rod shape.

In some embodiments, the smoking device of the present invention comprises a smoking material, and a cigarette filter comprising a substituted cellulose acetate filament of the present invention. As used herein, "smokable material" includes any thing that can be burned and its smoke is inspired and inhaled (e.g., tobacco). The tobacco leaf may be used in any number of different forms including, but not limited to, drying, fermenting, curing, cutting, and the like.

In some embodiments, the smoking device may include a cigar, a pipe, a cigarette, a vaporizer, and the like.

In some embodiments, the coated seed of the present invention comprises a seed coated with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coated seed further comprises a secondary growth augmentation coating. Suitable examples of secondary growth-enhancing coatings include those comprising primary nutrients, secondary nutrients, hormones, insecticides, pesticides, herbicides, fungicides, bactericides, pigments, binders, surfactants, glidants, Lt; / RTI >

Examples of primary nutrients suitable for use with some embodiments of the present invention include ammonium nitrate, urea, ammonium phosphate, ammonium sulfate, urea phosphate, ammonium molybdate, potassium nitrate, potassium phosphate, potassium hydroxide, potassium sulfate, But is not limited thereto.

Suitable examples of secondary nutrients are selected from the group consisting of magnesium sulfate, calcium nitrate, sodium borate, magnesium nitrate, chelate complexes of copper, calcium, iron, zinc, magnesium, manganese, ammonium molybdate, sodium molybdate, benzoic acid and salicylic acid do.

Examples of suitable binders for use with some embodiments of the present invention include, but are not limited to, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, polyvinylalcohol, polyvinylacetate, povidone, copolyvidone, Combinations thereof, but are not limited thereto.

Examples of surfactants suitable for use with some embodiments of the present invention include lecithin, sodium lauryl sulfate, polysorbate 60, polysorbate 80, polyoxyethylene polyoxypropylene block copolymers, derivatives thereof And combinations thereof, but are not limited thereto.

Examples of pigments suitable for use with some embodiments of the present invention include, but are not limited to, titanium dioxide, iron oxides, natural pigments, natural dyes, FD & C colorants, D & C rake, their derivatives and combinations thereof.

Examples of suitable excipients for use with some embodiments of the present invention include, but are not limited to, talc, colloidal silicon dioxide, stearic acid, derivatives thereof, and combinations thereof.

Examples of herbicides suitable for use with some embodiments of the present invention include glyphosate, dicamba, alanochlor, mechlorochlor, oxabetrynyl, thiocarbamate, 5-ethyl-N, Thiocarbamates, acetochlorides, derivatives thereof, and combinations thereof, but are not limited thereto.

Examples of detoxifying compounds suitable for use with some embodiments of the present invention include, but are not limited to, fluorazoles, siomethrionyl, N, N-diallyldichloroacetamide, derivatives thereof, and combinations thereof .

Examples of fungicides, fungicides, insecticides and pesticides suitable for use with some embodiments of the present invention include inorganic copper, organic copper, heavy metal compounds, propenoic acid, oxime ethers, substituted oxime ethers, Combinations thereof, but are not limited thereto.

Examples of plant hormones suitable for use with some embodiments of the present invention include, but are not limited to, auxin, gibberellic acid, cytokines, derivatives thereof, and combinations thereof.

In some embodiments, the coated pharmaceutical composition of the present invention comprises a pharmaceutical composition coated with a coating comprising a substituted cellulose acetate of the present invention.

In some embodiments, pharmaceutical compositions for use with some embodiments of the invention include, but are not limited to, analgesics, anti-inflammatory agents, antiarrhythmic agents, anti-asthmatics, anti-bacterial agents, antiviral agents, anticoagulants, dementia, antidepressants, , Anti-malarial agent, anti-migraine agent, antimuscarinic agent, anti-neoplastic agent, immunosuppressive agent, antibiotic agent, anti-thyroid agent, anti-thyroid agent, anxiolytic agent, sedative agent, hypnotic agent, neuroleptic agent, A cytotoxic agent, a cell adhesion inhibitor, a corticosteroid, a cytokine receptor activity modulating agent, a diuretic agent, a Parkinson's disease agent, a gastrointestinal agent, a histamine H-receptor antagonist, a keratolytic agent, a lipid modulating agent, a muscle relaxant, , Nutrients, sex hormones, stimulants, erectile dysfunction agents, narcotics, antihistamines, decongestants, cough suppressants, It may contain a control, an expectorant, a derivative thereof, a combination thereof, and mixtures thereof, without being limited thereto.

In some embodiments, pharmaceutical compositions for use with some embodiments of the present invention include, but are not limited to, water ephedrine, phenylpropanolamine, phenyleprine, ephedrine, dextromethophen, chlorphedianol, carbbetapentane, But are not limited to, carnitine, caprine, diphenhydramine, codeine, menthol, hydrocodone, hydromorphone, phominobenz, glyceryl guaiacolate, terpine hydrate, ammonium chloride, N- acetylcysteine, bromhexine, , Bromopheniramine, dexchlorpenyramine, dexbropenyramine, tripolidine, azatadine, toxylamine, tripelene amine, cyproheptadiene, hydroxyzine, eleestin, carbinoxamine, phenindamine, bromodiphenhydra AHR-11325, astemizole, azelastine, cetirizine, evastin, ketotifen, rodsoxamide, laurethidine, levocabastine, mequitazine, oxathomide, But are not limited to, corticosteroids, corticosteroids, corticosteroids, corticosteroids, corticosteroids, corticosteroids, corticosteroids, But are not limited to, benzocaine, hexylresorcinol, dichlonin, derivatives thereof, combinations thereof, pharmaceutically acceptable salts thereof, and mixtures thereof.

The present invention provides a kit for the detection of an analyte comprising a reporter molecule coated with a coating comprising a substituted cellulose acetate of the present invention.

Reporter molecules for use with some embodiments of the present invention may include, but are not limited to, antibodies, proteins, enzymes, peptides, hexanes, small molecules, fluorophores, 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 reporter molecules from degrading (e.g., denatured, cleaved) during storage.

In some embodiments, the coated stent of the present invention comprises an outer coating layer comprising a substituted cellulose acetate of the invention, and a stent having an inner coating layer comprising the pharmaceutical composition.

In some embodiments, the stent comprises a shape memory material. Examples of shape memory materials suitable for use with some embodiments of the present invention include zinc alloy, copper alloy, gold alloy, iron alloy, copper-zinc-aluminum-nickel alloy, copper- But are not limited thereto.

In some embodiments, the stent comprises a polymer. Examples of polymers suitable for use with some embodiments of the present invention include, but are not limited to, fibrin, polylactic acid, silicone, polyurethane, polyester, vinyl homopolymer, vinyl copolymer, acrylate homopolymer, acrylate copolymer, But are not limited to, cellulosic, derivatives thereof, and combinations thereof.

In some embodiments, the pharmaceutical composition comprises a compound selected from the group consisting of glucocorticoids, heparin, hirudin, tocopherol, angiopectin, aspirin, growth factors, oligonucleotides, antiplatelet agents, anticoagulants, antimitotic agents, antioxidants, antimetabolites, ≪ / RTI >

In some embodiments, the nutrient composition for pollen of the present invention comprises an organic com- post, and an absorbent composition comprising a substituted cellulose acetate of the present invention. Optionally, the potting soil composition may further comprise at least one component selected from the group consisting of loam, diatomaceous earth component, perlite component, and combinations thereof.

In some embodiments, the ROM comprises a component selected from the group consisting of sand, silt, clay, 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 composition of the present invention comprises a soil composition, and a moisture retaining additive comprising the inventive substituted cellulose acetate. Optionally, the modified soil composition may further comprise additives selected from the group consisting of sand, silt, clay and calcined clay, iron oxide, anhydrous resins, and combinations thereof.

Suitable anhydrous resins for use with some embodiments of the present invention may include, but are not limited to, acrylic polymers, polyvinyl acetate polymers, vinyl acetate copolymers, derivatives thereof, and combinations thereof.

In some embodiments, the drilling fluid of the present invention comprises a base fluid, and a viscosifier comprising the substituted cellulose acetate of the present invention. Optionally, the drilling fluid may further comprise an additive selected from the group consisting of a fluid loss control agent, a clay inhibitor, a lubricant, an extender, a thickener, and any combination thereof.

In some embodiments, the base fluid may be an aqueous fluid, a flowable fluid, a synthetic fluid, or an emulsion.

In some embodiments, the present invention provides an article comprising a nonwoven layer comprising fibers from a substituted cellulose acetate of the present invention.

Disposable slippers, disposable slippers, isolation gowns, surgical gowns, surgical drapes and covers, surgical gowns, caps, filters (e.g., HEPA filters), and the like. ; Water, coffee and tea bags; Liquid cartridge, vacuum bag; Geotextiles (e.g., geomembranes); Carpet backing; And envelopes, but are not limited thereto.

In some embodiments, the present invention provides a process for preparing a cellulose acetate film, comprising: spinning a dope comprising a solution of a cellulose diacetate, a substituted cellulose acetate of the invention and a solvent, taking a spun substituted cellulose acetate filament, , Crimping the tow, conditioning the crimped tow, and packaging the dried crimped tow. ≪ RTI ID = 0.0 > [0002] < / RTI > Optionally, the method may further comprise lubrication of the substituted cellulose acetate filaments.

In some embodiments, the solvent is selected from the group consisting of water, acetone, methyl ethyl ketone, methylene chloride, dioxane, dimethylformamide, methanol, ethanol, glacial acetic acid, supercritical CO ₂ , any suitable solvent capable of dissolving the above- Or any combination thereof. In a non-limiting example, the solvent for the cellulose acetate may be an acetone / methanol mixture.

In some embodiments, the substituted cellulose acetate is emitted in a spinnerette. In some embodiments, the spinnerette comprises a hole. These holes may be any shape compatible with one or more embodiments of the present invention. Spray design and / or radiation parameters affect the rate at which the solvent evaporates from the filament, which can affect the size, cross-sectional shape, strength and processability of the filament. In some embodiments, the spinnerette may include a plurality of holes spaced at least 0.070 inches apart. In some embodiments, the spinnerette for use with the present invention may include a plurality of donut-shaped extrusion holes. As used herein, a "donut shape" has a void at its center, where the cavity may be of any shape (circular, ovular, polygonal, triangular, etc.) do. As used herein, the terms "hole" and "extrusion hole" when used in conjunction with a spinnerette design generally can be used interchangeably to refer to the opening through which the dope is extruded. In some embodiments, the extrusion orifices may be tapered, for example, conically, in the capillary exit direction. The tapering may proceed at a constant angle or at an angle greater than one. In some embodiments, the extrusion holes in a single spinnerette can have different tapering angles. In some embodiments, the extrusion holes and / or the capillary exit may have a cross-sectional shape that produces the desired filament cross-sectional shape. Examples of extrusion holes and / or capillary exit cross-sectional shapes include, but are not limited to, circular, substantially circular, oval, substantial oval, crescent, multi-lobal, polygonal (e.g., but are not limited to, tripods, tetrapods, stars, triangles, squares, trapezoids, pentagons, hexagons, etc., polygons with rounded corners, and any hybrid bodies thereof. In some embodiments, the spinnerette may include extrusion holes and / or capillary outlets of at least two different cross-sectional shapes. In some embodiments, the spinnerette may include at least two different sized extrusion holes and / or capillary outlets. In some embodiments, the size and / or cross-sectional shape of the extrusion holes may be different from that of the corresponding capillary exit.

In some embodiments, the spin parameters can include extruding the filaments at a drawdown ratio (fiber exit rate to take-up speed) ranging from about 0.7 to about 1.6.

It should be understood by those skilled in the art that extrusion does not imply a single method or function for producing filaments and can be interchanged with at least radiation, expelling, and the like.

In some embodiments, the methods of the present invention comprise providing the substituted cellulose acetate of the present invention, and introducing the substituted cellulose acetate into the absorbent article. In some embodiments, the absorbent article can be any article (e.g., a garment, gel, furniture, etc.) that can utilize the absorbent material. Suitable examples of absorbent articles include, but are not limited to, diapers, incontinence garments, bandages, surgical pads, hot and cold therapy packs, water beds, artificial theories and combinations thereof. In some embodiments, the absorbent article is disposable and / or degradable.

In some embodiments, the substituted cellulose acetate may be introduced into the interior portion of the absorbent article. In some embodiments, the substituted cellulose acetate may be introduced into the outer portion of the absorbent article. In some embodiments, the substituted cellulose acetate may be part of the outer portion of the absorbent article. The term "introduction" is not intended to limit the invention to any particular mode of operation.

In some embodiments, the method of the invention comprises the step of coating the seed with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coating may further comprise at least one component selected from the group consisting of plasticizers, binders, waxes, stabilizers and colorants.

In some embodiments, the methods of the invention comprise coating a pharmaceutical composition with a coating comprising a substituted cellulose acetate of the present invention. Optionally, the coating may further comprise additives selected from the group consisting of plasticizers, annealing agents, emulsifiers, emulsion stabilizers, and combinations thereof.

In some embodiments, the annealing agent comprises a water-soluble polymer selected from the group consisting of hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, methylethylcellulose, polyvinylpyrrolidone, sodium carboxymethylcellulose, derivatives thereof, .

In some embodiments, the methods of the present invention comprise providing an adhesive comprising a substituted cellulose acetate of the invention, and applying the adhesive to a surface. In some embodiments, the surface can be selected from the group consisting of wood, plastic, paper, glass, paperboard, 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 can be a mixture, e. In some embodiments, the solvent may be present from about 40% to about 99% by weight of the adhesive.

In some embodiments, the adhesive is selected from the group consisting of polyvalent salts (e.g., zirconium salts such as zirconium carbonate), polyamide epichlorohydrin resins, aldehydes (e.g., glyoxal, glutaraldehyde, hydroxyadipaldehyde) Additives selected from the group consisting of formaldehyde crosslinking agents (e.g., zero-formaldehyde, low formaldehyde crosslinking agents), polyvinyl acetate, polyvinyl alcohol, polystyrene, polylactic acid, derivatives thereof and combinations thereof.

In some embodiments, the present invention provides a paint composition comprising a stabilizing film-forming agent comprising a pigment and a substituted cellulose acetate of the present invention, and comprises coating the surface with a paint. Optionally, the paint comprises at least one component selected from the group consisting of solvents, fillers, antifreeze additives, catalysts, thickeners, adhesion promoters, UV stabilizers, de-glossing agents, biocides, May be further included.

Suitable examples of solvents include, but are not limited to, aliphatic solvents, aromatic solvents, alcohols, ketones, hydrocarbons, esters, petroleum distillates, water, their derivatives and combinations thereof.

Suitable examples of pigments include pigments selected from the group consisting of clays, calcium carbonate, mica, silica, talc, titanium dioxide, their derivatives and combinations thereof.

Suitable examples of fillers include fillers selected from the group consisting of diatomaceous earth, talc, lime, barite, clay, their derivatives and combinations thereof.

In some embodiments, the present invention includes a pigment and a substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a non-metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the non- Providing a paint comprising a stabilizing film former present in at least about 0.01% by weight of the substituted cellulose acetate, and coating the surface with a paint.

The method of the present invention comprises the steps of providing a stabilized film former comprising the substituted cellulose acetate of the present invention, and adding stabilizing film former to the emulsion. Suitable examples of emulsions include, but are not limited to, cosmetics, hair styling products, photographic films, cutting fluids, skin ointments, pastes, balm, oils, waxes, detergents, beverages and combinations thereof.

The method of the present invention comprises the steps of providing a thickening agent comprising the substituted cellulose acetate of the present invention and adding the thickened agent to the food composition. Suitable food compositions may include, but are not limited to, soups, gravies, desserts, jellies, candies, and the like.

For a better understanding of the invention, embodiments of the following preferred embodiments are provided. The following examples should not be construed as limiting or limiting 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 to various substrates including wood and paperboard using a lap shear test. The results were compared with commercially available glue (e.g., ELMER'S GLUE ALL®). A summary of the results is shown below in Tables 1A and 1B.

<Table 1A>

<Table 1B>

Substituted cellulose acetate (Batch Cellulose Acetate Adhesives 1-5) with high sulfur content according to one or more embodiments of the present invention was prepared and used as a wood glue using the INSTRON (Model 3366) Lap Shear Test . The results, including the amount of sulfur in solution (mg of sulfur per kg of sulfur) are summarized in Tables 1A and 1B above. Two small wooden blocks were glued together using an aqueous solution of 10% glue and dried. The resulting block was difficult to separate (i. E., The block was not broken in the used tensile test setup). When sufficient blocks of force were applied, the wood fibers were broken, suggesting that the substituted cellulose acetate adhesive is as strong as wood fibers. A substituted cellulose acetate adhesive was also used to adhere the cardboard. The carton was also difficult to separate. The substituted cellulose acetate adhesive was optically clear and high gloss, which may be desirable for commercial applications. The substituted cellulose acetate adhesive was dried at ambient conditions for less than 30 minutes.

This example particularly shows that substituted cellulose acetate with high sulfur content is effective as an adhesive for various materials.

Example 2

This example illustrates the synthesis of the sulfate substituted cellulose acetate of the present invention. In the first step, the cellulose is acetylated in the presence of acetic anhydride and sulfuric acid. Preparations of cellulose, acetic acid, acetic anhydride and sulfuric acid are the same as those contained in standard grade 2 cellulose acetate diacetate products. Next, the reagent was compounded to initiate the acetylation reaction. This reaction was completed and then water was added to react with any excess anhydride. The reaction rate and temperature were closely monitored and varied to control specific polymer properties.

Next, the acetylated cellulose (i.e., cellulose acetate) was hydrolyzed in the presence of acetic acid, and the precipitation and subsequent remelting steps were not performed. By carefully controlling the reaction temperature and time, the cellulose acetate was reduced to the desired acetate DS level. Water was added if necessary to maintain polymer solubility. This produced sulfate-substituted cellulose acetate with an unexpectedly surprising high sulfur content.

Finally, the solid was precipitated from the solvent system using a suitable diluent. The product was washed, if necessary, to remove excess solvent and dried to the desired solid level.

Example 3

In this example, water swellable cellulose acetate (low sulfur content) and substituted cellulose acetate (high sulfur content) were tested for their water absorption capacity using thermogravimetric analysis (TGA). Each sample was introduced into a TGA system and applied at the following temperatures. The sample was raised from 20 캜 / min to 110 캜. This temperature was maintained at 110 DEG C for 30 minutes. The temperature was then raised from 20 [deg.] C / min to 650 [deg.] C. Subsequently, the sample gas was replaced with air, and the temperature was maintained at 650 DEG C for 30 minutes. In each test run, the cellulose acetate sample was limited to less than 100 mg.

Figures 2 to 5 show various TGA assays that measure the water absorption of sulfate-substituted cellulose acetate with a high degree of substitution and sulfate-substituted cellulose acetate with a low degree of substitution.

Figure 2 shows a TGA analysis of a water-saturated, water swellable cellulose acetate (WSCA) 1036 RT-16 dried sample. WSCA 1036 RT-16 is a high-substitution sulfated-substituted cellulose acetate particulate sample containing approximately 0.5% by weight of sulfur in the cellulose acetate. When the temperature is raised to 110 [deg.] C, the total weight of the water-saturated sample decreases as the water dries. Subsequently, the temperature of the TGA system was raised and maintained at 650 DEG C, so that the sulfate-substituted cellulose acetate having a high degree of substitution was decomposed. WSCA 1036 RT-16 was able to absorb approximately 1440% by weight of water as a dry sample or more than 14 times its weight in water.

Figure 3 shows two TGA repeats for two WSCA 1037 RT-16 dried samples. Compared to WSCA 1036 RT-16, WSCA 1037 RT-16 is a sulfur-substituted cellulose acetate with a low degree of substitution (DS of acetate is similar). The water absorptions detected for both samples were 76.91% and 81.31%, corresponding to a ratio of water to dry WSCA of 3.35 and 4.37, respectively.

Figure 4 shows two repeats of TGA for two saline (about 0.9%) saturated WSCA 1036 (high sulfate substitution) RT-16 samples. Both samples contained 87.05% and 92.14% brine, corresponding to a ratio of water to dry WSCA of 7.48 and 13.6, respectively.

Figure 5 shows two repeats of TGA for a saline (about 0.9%) saturated WSCA 1037 RT-16 sample. The two samples contained 78.31% and 83.91% brine, corresponding to a ratio of water to dry WSCA of 3.72 and 5.46, respectively.

This example shows in particular that substituted cellulose acetate having a high sulfur content can absorb several times its weight of water (both deionized and saline). Sulfur-substituted cellulose acetate with a high sulfur content showed excellent water (both DI and saline) absorption as compared to substituted cellulose acetate with a low sulfur content.

Example 4

Various additives were added to some adhesive compositions containing the substituted cellulose acetate of the present invention. The resulting composition was tested for its adhesive properties to wood substrates (1/4 "pine strip, width 1.5") using Instron® (Model 3366) lap shear test. A summary of the results is shown in Tables 2 and 3 below.

<Table 2>

<Table 3>

As shown in Table 2, the addition of zirconium can increase the strength needed to break the bond formed by the cellulose acetate adhesive composition (substituted cellulose acetate with high sulfur content). Table 3 shows the results of the lap shear test of cellulose acetate adhesives 7 and 8 with ammonium zirconium carbonate (0.08% Zr), MW 140,000 polyvinyl acetate (14% solids) and MW 150,000 polyvinyl alcohol . The sulfur contents of cellulose acetate adhesives 6, 7 and 8 are 620 mg / kg, 520 mg / kg, and 557 mg / kg, respectively.

Accordingly, the present invention is readily adapted to attain the objects and advantages mentioned herein as well as the inherent therein. The particular embodiments disclosed above are merely illustrative and the invention may be modified and practiced otherwise than as apparent to one skilled in the art having the benefit of the teachings of the invention. Further, the present invention is not limited to the details of the constitution or design shown in the present invention, other than those described in the claims. It is therefore evident that the specific exemplary embodiments disclosed above may be altered, combined, or modified, and all such modifications are to be regarded as included within the scope and spirit of the invention. The invention illustratively disclosed herein may be suitably practiced without any of the elements specifically disclosed herein and / or any of the elements disclosed herein. Compositions, and steps are also referred to as " comprising, "" containing, " or" including, " Can be ". All values and ranges disclosed above may vary to some extent. When a numerical range having a lower limit and an upper limit is disclosed, any numerical value included in the range and any included range are specifically disclosed. In particular, all ranges of values disclosed herein ("about a to about b" or equivalently, "about a to b" or equivalently "about a-b") are intended to include all numbers and ranges &Lt; / RTI &gt; Also, the terms of the claims have their ordinary meanings unless the patentee expressly and explicitly defines otherwise. Also, the indefinite article ("a" or "an") used in the claims is defined herein as meaning that it exceeds one or more of the inserted elements. If the use of words or terms in any one or more of the patents or other documents that may be included herein and hereby incorporated by reference, the terms consistent with this specification should be employed.

Claims (16)

Cellulose diacetate, and substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a nonmetal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the base metal is a substituted cellulose Lt; RTI ID = 0.0 &gt; 0.01% &lt; / RTI &
&Lt; / RTI &gt; The tobacco filter material of claim 1, wherein the base metal is present at about 25 weight percent or less of the substituted cellulose acetate. The tobacco filter material of claim 1, further comprising a plasticizer. The tobacco filter material of claim 3, wherein 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. The tobacco filter material of claim 1, wherein the substituted cellulose acetate is tow. Smoking material, and
Cellulose acetate diacetate, and substituted cellulose acetate filaments comprising a polar substituent comprising an oxygen atom covalently bonded to a base metal selected from the group consisting of sulfur, phosphorus, boron, and chlorine, wherein the base metal is selected from the group consisting of substituted cellulose acetate A tobacco filter present at least about 0.01 wt%
. 7. The smoking device of claim 6 wherein the base metal is present at about 25 weight percent or less of the substituted cellulose acetate. The smoking device according to claim 6, wherein the smoking article is a tobacco. The smoking device according to claim 8, wherein the tobacco leaves have undergone treatment including a treatment selected from the group consisting of drying, fermentation, curing, cutting, and any combination thereof. The smoking device according to claim 6, wherein the smoking device is a cigar, a pipe, a cigarette or a vaporizer. Cellulose diacetate; Substituted cellulose acetate comprising a polar substituent comprising an oxygen atom covalently bonded to a nonmetal selected from the group consisting of sulfur, phosphorus, boron, and chlorine; And a solution of a solvent, wherein the base metal is present in at least about 0.01% by weight of the substituted cellulose acetate,
Taking up the spun substituted cellulose acetate filaments,
Forming a tow from a substituted cellulose acetate filament,
Crimping the tow,
Conditioning the crimped tow, and
A method of making a substituted cellulose acetate tow comprising the step of baling a dried crimped tow. 12. The method of claim 11, wherein the base metal is present at about 25 weight percent or less of the substituted cellulose acetate. The method of claim 11, wherein that the solvent is selected from water, acetone, methyl ethyl ketone, methylene chloride, dioxane, dimethylformamide, methanol, ethanol, acetic acid, supercritical CO _2, and the group consisting of any combination thereof Way. 12. The method of claim 11, wherein the substituted cellulose acetate is spun in a spinneret. 15. The method of claim 14, wherein the spinnerette comprises a hole. 12. The method of claim 11, further comprising lubrication of the substituted cellulose acetate filaments.

Images