Patent Application
20240318380
The present embodiment relates generally to methods for improving mycelial leather replacement compositions and more particularly, to a method of treating mycelium material through a cationization process to achieve leather replacement composition product with increased homogeneity and reactivity.
Fungal-based composite materials have emerged as an alternative biomaterial in the fields of construction, manufacturing, agriculture, textile and biomedical. Mycelium is mainly composed of natural polymers, making it a perfect alternative to non-biodegradable materials such as synthetic leather and animal products. Mycelium leather can be produced with less energy and materials than conventional leather production and can be grown in a way that contributes to viable stewardship of renewable resources. After cellulose, chitin is the most abundant polymer in nature. A byproduct of many industries, such as commercial fishing, aquaculture and industrial processing of fish, this resource plays an important cooperative role with mycelium.
Chitosan is produced from chitin through demineralization, deproteinization, and deacetylation processes. Chitosan can be produced on an industrial level by chemical deacetylation of chitin with a strong alkaline solution, such as sodium hydroxide (NaOH). Chitosan can also be produced from the enzymatic deacetylation of chitin using lysozyme, snailase, neutral protease, chitin deacetylase, and the like. Chitosan is a non-toxic, biocompatible, and biodegradable polymer.
Some conventional methods teach the production of leather and leather-like materials using highly toxic chemicals such as chromium, *and various solvents. It can be difficult to recycle and dispose of such waste materials in an environmentally safe way. Another conventional method that describes the production of materials with synthetic plastic-based leather alternatives. Synthetic plastic-based leathers are conventionally made of various chemical and polymer ingredients, the tanning and production of which can also lead to hazards for the environment. To overcome this, numerous methods and systems have been used for the large-scale production of composites grown with mycelium.
Mycelium leather replacement like traditional leather is typically dyed. Traditional leather dyeing methods include acid dyes, direct dyes and fiber-reactive dyes, which are anionic in charge in aqueous solutions. These dyes typically form relatively weak hydrogen bonds with cellulose when applied under moderate temperature and pH conditions resulting in poor fastness. Fiber-reactive dyes can produce good fastness when more extreme application conditions are applied. Fiber-reactive dyes work when the molecules combine chromophores with a reactive group that forms strong covalent bonds with the substrate being dyed. These strong covalent bonds provide good wash fastness for the color. Traditional dyeing processes utilizing fiber-reactive dyes, however, require alkaline pH levels of the dye solution and significant amounts of electrolytes, or salts, such as sodium chloride or sodium sulfate (e.g., up to an amount equal to the weight of the substrate) to help screen the anionic dyes from the charge of the substrates. Currently, dyeing methods require a significant amount of energy, chemicals, and salt to transfer the dye molecules from the dye solution to the fiber as well as swelling the fiber to render it more receptive to dyeing. Even with the best processes, only a certain percentage of the dyes are transferred to the cellulose fabric and the excess must be washed out in subsequent steps, causing a significantly negative environmental impact.
There is thus a need for an efficient system and method for improving the mycelial leather replacement compositions and dying of the same. Such a method would minimize environmental problems in the manufacturing, recycling or disposal phase of the mycelium substrate. Such a method would deliver a product that has increased homogeneity and aesthetic performances. Further, such a method would exhibit improved properties like softness, flexibility, strength, fastness of color, lack of cracking over time, uniformity of color and reactivity. *Further, such a method would generate a strong positive charge on the mycelium material, enhancing its reactivity and affinity for subsequent treatments. In addition, such a method would maintain consistent performance parameters across different pH levels. Moreover, such a method would maintain a degree of control to manage chemical uptake and efficiency. Further, such a method would achieve full chemical penetration and homogeneous distribution of reactive sites with substantive fillers in creating a leather-like material that closely resembles traditional leather in terms of texture, appearance and performance characteristics. The present embodiment overcomes shortcomings in the field by accomplishing these critical objectives.
To minimize the limitations found in the prior art, and to minimize other limitations that will be apparent upon the reading of the specification, the preferred embodiment of the present invention provides a system for enhancing mycelial leather replacement compositions including a mycelium material substrate, a deacetylation unit, a cationization unit, an affinity enhancement mechanism to combine both deacetylation and cationization process, a homogeneity control unit, a bonding unit and a dyeing unit for improving dyeing efficiency in mycelial leather replacement composition.
In the system for enhancing mycelial leather replacement compositions the deacetylation unit is configured to enzymatically convert chitin to chitosan within the mycelium material substrate. The cationization unit cationizes the deacetylated mycelium material by applying cationic chlorohydrin. The deacetylation and cationization process is combined by an affinity enhancement mechanism to enhance the affinity of the mycelial material interaction by means of anionic aqueous treatment. The homogeneity control unit ensures uniform distribution of aqueous anionic treatment within the mycelial leather replacement compositions. Further, the bonding unit creates bonds between the cationized mycelial material substrate and cellulosic fibers resulting in a positively charged fiber that maintains its charge in aqueous solution. The dyeing unit maintains precise control over the temperature and pH levels during the dyeing process that impacts the dye uptake and color fastness of the mycelial leather replacement composition.
In the preferred embodiment, concentrated NaOH is used in the conversion of chitin to chitosan. The addition of cationic chlorohydrin improves the dyeing efficacy as compared to the same treatment without cationic chlorohydrin. The addition of cationic chlorohydrin results in reduction of water consumption, salt in the effluent and color in the effluent as compared to non-cationic chlorohydrin treated mycelium material substrate. The dyeing process allows for greater control over coloration and homogeneity resulting in improved color-matching with greater speed and accuracy.
The preferred embodiment provides a method for improving mycelial leather replacement compositions. The method commences by providing a substrate of mycelium material. Next, the method calls for deacetylating chitin within the mycelial material substrate to enzymatically convert it to chitosan in a deacetylating unit thereby improving reactivity of the mycelial material substrate. Next, the method cationizes the deacetylated mycelial material substrate using cationic chlorohydrin in a cationization unit. Then, improving the interaction with anionic aqueous treatment by combining the deacetylation and cationization processes through an affinity enhancement mechanism. Thereafter, the method calls for ensuring uniform distribution of aqueous anionic treatment within the mycelial leather replacement compositions with the implementation of a homogeneity control unit. Next, the method establishes bonding between the cationized mycelial material substrate and cellulosic fibers to create a positively charged fiber that maintains its charge in aqueous solution. Then, the method improves dyeing efficiency in mycelial leather replacement compositions through optimized dyeing processes in a dyeing unit.
It is a first objective of the present invention to provide a mycelium material that minimizes environmental problems in manufacturing, recycling or the disposal phase of the mycelium substrate.
A second objective of the present invention is to provide a method that would deliver a product that has increased homogeneity and aesthetic performances.
A third objective of the present invention is to provide a method that would exhibit improved properties like softness, flexibility, strength, fastness of color, lack of cracking over time, uniformity of color and reactivity.
A fourth objective of the present invention is to eliminate the need for plasticization.
A fifth objective of the present invention is to generate a strong positive charge on the mycelium material enhancing its reactivity and affinity for subsequent treatments.
A sixth objective of the present invention is to maintain consistent performance parameters across different pH levels.
Another objective of the present invention is to maintain a degree of control to manage chemical uptake and efficiency.
Yet another objective of the present invention is to achieve full chemical penetration and homogeneous distribution of reactive sites with substantive fillers in creating a leather-like material that closely resembles traditional leather in terms of texture, appearance and performance characteristics.
These and other advantages and features of the present invention are described with specificity so as to make the present invention understandable to one of ordinary skill in the art.
In order to enhance their clarity and improve the understanding of the various elements and embodiments, elements in the figures have not necessarily been drawn to scale. Furthermore, elements that are known to be common and well understood to those in the industry are not depicted in order to provide a clear view of the various embodiments of the invention, thus the drawings are generalized in form in the interest of clarity and conciseness.
In the following discussion that addresses a number of embodiments and applications of the present invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized, and changes may be made without departing from the scope of the present invention.
Various inventive features are described below that can each be used independently of one another or in combination with other features. However, any single inventive feature may not address any of the problems discussed above or only address one of the problems discussed above. Further, one or more of the problems discussed above may not be fully addressed by any of the features described below.
As used herein, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. “And” as used herein is interchangeably used with “or” unless expressly stated otherwise. All embodiments of any aspect of the invention can be used in combination, unless the context clearly dictates otherwise.
Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “wherein”, “whereas”, “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.
The description of embodiments of the disclosure is not intended to be exhaustive or to limit the disclosure to the precise form disclosed. While the specific embodiments of, and examples for, the disclosure are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the disclosure, as those skilled in the relevant art will recognize.
Referring to
In this embodiment, the molecular reaction representation 300 in deacetylation unit 202 is configured to enzymatically or chemically convert chitin 301 to chitosan 303 via concentrated NaOH 302 as shown in
In this preferred embodiment, the molecular reaction representation 400 shown in
A number of cationic chlorohydrin products have been developed to cationize mycelium material substrate 201 as shown in
In the preferred embodiment, the mycelial leather replacement composition 212 will have a chemistry over which we can maintain a degree of control to manage chemical uptake and efficiency. The resultant reactivity will be similar to the leather that leather technicians would be comfortable manipulating when striving to develop subsequent product aesthetics and performance. Chemical homogeneity is achieved by creating an overall positively (cationic) charged mycelium material substrate 201 as shown in
In this preferred embodiment, the addition of cationic chlorohydrin 204 improves the dyeing efficacy as compared to the same treatment without cationic chlorohydrin 204. The addition of cationic chlorohydrin 204 results in reduction of water consumption, salt in the effluent and color in the effluent as compared to non-cationic chlorohydrin 204 treated mycelium material substrate 201. The dyeing process allows for greater control over coloration and homogeneity resulting in improved color-matching with greater speed and accuracy. Also, full chemical penetration results in a leather-like material with a uniform cross-sectional softness/lubrication, producing a natural drape & flexibility. If the chemistry is not uniformly distributed, layers with differential stresses and strains are formed which results in unnatural drape and flex, which can lead to poor aesthetics & product failure at points of high or uneven stress. In this preferred embodiment, the conversion of chitin 301 to chitosan 303 uses more gentile enzymes like lysozyme, snailase, neutral protease and other enzymes to ameliorate their losses. Also, genetically engineered versions of the above-mentioned enzymes, such as fusion enzymes and enzymes that are post-translationally modified at the specific protein residues are used to convert chitin 301 to chitosan 303. Also, in the anionic aqueous treatment 208 the entire mycelium material substrate 201 is utilized, eliminating the hindrance of unreactive and hydrophobic chitin 301. This results in significantly reduced or even fully eliminated cracking of the mycelium material substrate 201. Mycelium material substrate 201 is also much more chemically homogenous, but still possesses low reactivity.
In this preferred embodiment, cationic chlorohydrin 204 with a single epoxide functional group or multiple epoxide functional groups upon activation may be used. Further, cationic chlorohydrin 204 can be used to carry a singular quaternary ammonium positive charge or multiple quaternary ammonium positive charges. Each of the above delivers its own characteristic impact on the fullness and feel of resulting mycelium based leather replacement composites 212. Also, cationic chlorohydrin 204 that have multiple chlorohydrin functional groups will both increase the positive charge on the overall mycelium material substrate 201 and composite matrix and create a degree of cross-linking that will have positive impacts on the stability of the matrix, leading to improved strength performance, improved ply adhesion, as well as more consistent dimensional stability. Improved mycelial leather replacement compositions 212 replaces plasticization by delivering a chemically stable and dry intermediate product that could be shipped to customers to dye and make further chemical alterations to, resulting in their individualized desired end product. Further, this technique could be applied to plasticized materials in customer facilities.
In the preferred embodiment, reaction with cationic chlorohydrin 204 looks to increase the longevity of physical and aesthetic performance over time, including softness, flexibility, strength, fastness of color, lack of cracking over time, uniformity of color, and maintenance of color value as a result of long-term durability being a consequence of chemical reactivity.
In another embodiment of the present invention, deacetylation is carried out first then the mycelium is washed to remove alkali-liberated glucans and then reacted with cationic chlorohydrin in the presence of additional NaOH. Next, highly activated mycelium and cotton O minus, high NaOH and highly reactive epoxide are applied under a vacuum setting. High reactivity between the substrate and cationic chlorohydrin with high cationic chlorohydrin concentration is then applied under a vacuum setting. Next, wet processing using aqueous chemistry in a drum under a vacuum is the primary process element to deliver the desired chemical penetration and distribution.
In another embodiment of the present invention, the use of a 10% solution of sodium hydroxide is added to fresh or plasticized mycelium at 30 deg C. and run in a vacuum drum until fully penetrated (2-3 hours) and left to stand overnight (20 hours). The NaOH deacetylates chitin to chitosan activate cellulose, D-glucose type polysaccharides OH to O minus to react with subsequent cationic chlorohydrin. Also, the addition of a 10% solution of cationic chlorohydrin is converted from a cationic chloro/alcohol into an epoxide by pH >12.0 and reacts aggressively with activated D-glucose O minus. Penetration may in an exemplary case require 2-3 hours. In some process trials, multiple steps take place in the drum at the same time. In other processes, there are two separate steps taking place sequentially with a drain of the liquid happening between the steps. In still other embodiments, other chlorohydrin or epoxide-based chemistries are disclosed. One such chemistry is disclosed in the formula below which is an oil base with a chlorohydrin reactive species. where R represents an oil wherein the chemical or a polymer variant thereof generates a plasticizing/fatliquor effect to create softness, lubrication of the mycelium matrix but with very high substantively. There are potentially polymer variants of the above where R is a polyacrylate, polyurethane, or a lubricating/hydrophobic oil that may be useful.
In still other embodiments, to avoid prematurely breaking the fatliquor emulsion in future steps, pH may be neutralized to approximately 5.0 using a combination of sodium formate and formic acid to give a system that buffers at pH 5.0. This is carried out by draining the drum after the addition of cationic chlorohydrin 104, washing twice with water at 30 degrees C. to reduce alkalinity, and adding formate and formic solution to the drum. This pH target may change, but most oil emulsions do not tolerate the pH environment of deacetylation and cationic chlorohydrin 104 activation, possibly leading to premature emulsion breakage without some neutralization of the alkalinity, resulting in a surface deposition of oil and a stiff end product. Also, for softening an anionic fatliquor emulsion is the final step before removing the substrate from the drum. Further, the mycelium substrate is dried after a standing period to allow the draining of water and completion of reactivity.
In still other embodiments, after the deacetylation treatment, positively charged mycelium material will exhibit an increased affinity for negatively charged or election-rich molecules, such as dyes (e.g., direct dyes and fiber-reactive dyes). In still other embodiments, the continuous dyeing method is carried out in a vacuum drum due to the need for penetration though the cross-section. In still other embodiments, dyeing, deacetylation, application of cationic chlorohydrin and plasticization can be carried out in the same vessel. In still other embodiments, deacetylation and activation of cationic chlorohydrin to epoxide can be carried out simultaneously. In several embodiments, a multiple-vessel approach may be used to carry out dyeing, deacetylation, application of cationic chlorohydrin and plasticization in different vessels.
In certain embodiments, anionic dyes (fiber reactive, acid, direct dyes) will be used to achieve the final product. In some embodiments involving traditional dye methods, direct dyes create a relatively weak hydrogen bond with cellulose forming a semi-durable attachment, which exhibits good lightfastness and is ideal for use on textiles that are seldom washed.
In other embodiments involving more traditional dye methods, fiber-reactive dyes work with molecules that combine chromophores with a reactive group that forms strong covalent bonds with the substrate being dyed, the strong covalent bonds providing improved wash fastness for the color.
In certain embodiments, the deacetylation using only sodium hydroxide produces a much more chemically uniform substrate without the hydrophobic elements that hinder wet chemical reactions. The liquid post-deacetylation is a dark tea color, and the dry deacetylated material is thin with an empty feeling. The weight of the material after deacetylation drops approximately 5-15%. Also, dyes are required to penetrate through the mycelium thickness in the wet process.
In certain embodiments, the first few processes involve deacetylation and the latter relate to reaction with commercially available cationic chlorohydrin. In certain other embodiments, both the deacetylation and treatment with cationic chlorohydrin promote a strong positive charge on the mycelium.
In another embodiment of the present invention, the conditions required for the dye penetration of aqueous chemistry into mycelium or composite substrate is the application of a vacuum (0.45-0.90 mbar), in a vacuum drum rotating at 1-5 rpm, where the water for reaction in the drum is 30-40% the volume of the drum and the use of a 2% solution of nonionic wetting agent allows for aqueous contact of some hydrophobic regions within the mycelium matrix.
Another embodiment of the present invention utilizes NaOH acts as a strong base to degrade glucans and proteins. Also, deacetylation with 10-30% NaOH in a vacuum drum occurs until the mycelium is uniformly penetrated. The mycelium is then left to stand overnight. The material is then drained and washed to remove the soluble mycelium chemistry. This alkaline treatment also serves to activate the mycelium, by stripping protons from Mycelium polysaccharide-OH to produce-O minus, which is the reaction site for the cationic chlorohydrin, once activated to an epoxide. The cationic chlorohydrin is combined with 10-30% NaOH to activate the cationic chlorohydrin to an epoxide and to generate as much Mycelium O minus as possible. The process generates a higher rate of cationic chlorohydrin and mycelium reaction and creates a significantly fuller and less empty feeling product.
The end result can in some embodiments be described as a mycelial leather replacement composition comprising:
In some embodiments homogeneity control unit ensures the uniform distribution of the anionic aqueous treatment, thereby preventing the formation of layers with differential stresses and ensuring a natural drape and flexibility of the mycelial leather replacement product.
The end result in another embodiment is a composition of matter, comprising:
In yet other embodiments the a chemically engineered mycelial material for use in leather replacement is disclosed, the material comprising:
In some embodiments of the composition, the mycelium material substrate, post-treatment, exhibits increased affinity for negatively charged or electron-rich molecules, improving the substrate's compatibility with a wide range of dyes and finishing treatments. In other embodiments, the composition of matter further comprises a bonding unit configured to create durable linkages between the cationized mycelium material substrate and cellulosic fibers, wherein the fibers are integrated into the substrate to enhance its structural integrity and maintain its charge in an aqueous solution. In still other embodiments, the enhanced mycelial leather replacement composition includes additional treatments for improving the hydrophobicity, color consistency, and physical properties akin to traditional leather.
In certain embodiments, full chemical penetration delivers a product that has both homogeneous physical and aesthetic performances. In some embodiments, chemical homogeneity is achieved by creating an overall positively charged chemical environment that is relatively consistent in charge across a wide range of pH conditions, rather than a pre-treatment environment, that is generally negatively charged and very variable in charge across a wide range of pH conditions. In still other embodiments, Zeta potential measurements confirm that treatment with cationic chlorohydrin is creating an increased positive charge on the substrate versus the original sequences of chemical addition.
In certain embodiments, a method for improving mycelial leather replacement compositions is disclosed, the method comprising the steps of:
In certain embodiments, the cationization treatment eliminates the need for plasticization by providing a chemically stable intermediate product. In certain embodiments the positive charge on the mycelium material substrate is independent of pH. In certain embodiments the cationization treatment enables a consistent reaction environment for subsequent reaction with anionic dyestuffs and oil emulsions. In certain embodiments the cationic chlorohydrin used in the cationization process has a single epoxide functional group or multiple epoxide functional groups upon activation providing flexibility in the cationization process. In still other embodiments the conversion of chitin to chitosan uses genetically engineered enzymes including fusion enzymes and post-translationally modified enzymes. In still other embodiments the deacetylation unit utilizes a concentration of NaOH for the conversion of chitin to chitosan.
The method for improving mycelial leather replacement compositions can also be described as:
In other embodiments the cationic chlorohydrin used in the cationization process has a single epoxide functional group or multiple epoxide functional groups upon activation providing flexibility in the cationization process, and in still further embodiments the conversion of chitin to chitosan uses genetically engineered enzymes including fusion enzymes and post-translationally modified enzymes.
It is to be understood that the above-described arrangements are only illustrative of the application of the principles of the disclosure. Numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the disclosure and the appended claims are intended to cover such modifications and arrangements. Thus, while the disclosure has been shown in the drawings and described above with particularity and detail, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made without departing from the principles and concepts set forth herein.
The foregoing description of the preferred embodiment of the present invention has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations and permutations are possible in light of the above teachings. It is intended that the scope of the present invention to not be limited by this detailed description, but by the claims and the equivalents to the claims appended hereto.
This application claims priority to U.S. provisional patent application No. 63/453,221, filed Mar. 20, 2023, which is incorporated by reference herein as if set out in full.
| Number | Date | Country | |
|---|---|---|---|
| 63453221 | Mar 2023 | US |
