Patent Application
20240198579
The present invention relates to cellulose-based filaments. More specifically, the present invention is concerned with cellulose-based filaments which can be washed and dried repeatedly, including methods of production thereof.
Global volumes of textile production currently exceed 100 million metric tons per year, of which 63% is produced from petroleum (mainly polyester). This manufacturing stream is linked to a non-renewable carbon deposit, and is marked by high-energy processing technologies that produce high-risk effluents. Of the remaining 37% of textile production, 31% is derived from cotton, which is characterized by high water and pesticide use and 1% is wool. Non-cotton, cellulose-derived filaments currently account for about 5 million tons (5%) per year and is a fast-growing market. The majority of these filaments are made by the “rayon” or “viscose” process, in which cellulose is modified with carbon disulfide into cellulose xanthate, which, when passing through an acid bath, is changed back into (regenerated) cellulose, releasing the carbon disulfide. Carbon disulfide has a recommended daily exposure limit of 10 ppm, representing an acutely toxic component of the current manufacturing pipeline that creates risk to worker health and safety in both processing and waste-mitigation phases of production. Post production filament modification, including coloration or the introduction of antimicrobials, presents an additional, chemically intensive step, which is largely conducted in developing nations (e.g. India, Bangladesh or China), where relaxed environmental regulations do not prevent effluent discharge into local water supplies.
Other solvents which are being used to make textile from regenerated cellulose are: MNNO (N-methylmorpholine N-oxide), deep eutectic solvents and ionic liquids. These solvents need to be recovered, which requires an additional step in the production of textile.
Usually dyes are used as coloring materials for yarns in the dyeing industries. Different types of black dyes are used to produce black textile materials. Generally, white yarns are manufactured first and then dyeing of these yarns is performed at a later stage. During dyeing of textile materials, not all dyes attach to the fabrics and always a portion of them get released with water to the environment. Each day, approximately 1000-3000 m3 of wastewaters are released to the environment after producing 12-20 tonnes of dyed textile materials. These wastewaters are highly concentrated with dyes and chemicals. Some of these dyeing chemicals are non-biodegradable, carcinogenic and can be a serious threat to health and the environment if they are not treated properly before discharging. Therefore, having an effluent treatment plant is a major requirement in current textile industries.
One of the most significant properties of textile filaments is their mechanical strength. Mechanical strength indicates the ability of filament resistance to external damage, which primarily determines the longevity of textile products. Textile filaments with high mechanical strength are in high demand for the manufacturing of high-quality textile products. Water absorbency is also an important property of textile filaments. Textile filaments with low water absorbency are preferred for high-quality textile applications.
On another related subject, polyethylene and polypropylene are neither renewable nor recyclable. The production of cellophane films (thin, transparent sheet made of regenerated cellulose) involves toxic CS2. These are produced from regenerating cellulose from cellulose xanthate and do not contain charged functional groups.
Renewable drinking straws are made from paper, PLA (polylactic acid), or aluminum, but these straws become soggy, are expensive, or difficult to clean. Renewable cups, made from paper are usually lined with a plastic non-renewable film; or made from biopolymers, like PLA, which are expensive and cannot hold hot drinks.
Most plastic products are made from a molten polymer solution by molding. Cellulose-based products cannot be made this way, because cellulose degrades before it melts.
In accordance with the present invention, there is provided:
In the appended drawings:
In a first aspect of the invention, there is provided a cellulose-based filament comprising a negatively charged cellulose derivative bearing anionic functional groups.
The present inventors discovered that cellulose-based filaments with a charge content of less than or equal to about 1.4 mEq/g of cellulose and with a diameter of at most about 50 μm (i.e. an appropriate size for textile production) are surprisingly not superabsorbent, meaning they can be repeatedly washed and dried. This means that said cellulose-based filaments can be used to make reusable textiles. The present inventors also discovered that when specific anionic functional groups are used, the resulting cellulose-based filaments can be endowed with various advantageous properties. In addition, the inventors demonstrated that by functionalizing cellulose to produce the negatively charged cellulose derivative bearing anionic functional groups, the cellulose is thereby modified at the stage of the dope, as opposed to after the filament has been extruded or woven into a textile.
In embodiments, in addition to the advantages previously discussed, the cellulose-based filaments of the present invention can present one or more of the following advantages:
The cellulose-based filaments of the present invention can be used in a variety of applications. In embodiments, the cellulose-based filaments of the present invention can be woven into textiles. Due to the non-superabsorbent properties of the cellulose-based filaments, the resulting textile can be repeatedly washed and dried, thereby making it reusable. In addition, the resulting textile will also comprise the other characteristics of the cellulose-based filament; for example, a textile made from a fire-retardant or fluorescent cellulose-based filament will itself have fire retardant or fluorescent qualities.
Accordingly, the applications of the cellulose-based filaments of the present invention are vast; they can be employed in any known application for non-superabsorbent filaments. Besides being woven into textiles, the cellulose-based filaments of the present invention can be used in non-wovens and used as fillers in composite materials or strength agents in papermaking.
In addition, the method for producing the filaments of the present invention can present one or more of the following advantages:
In a first aspect of the invention, a cellulose-based filament comprising a negatively charged cellulose derivative bearing anionic functional groups is provided, wherein said anionic functional groups are covalently bonded to the cellulose derivative wherein the cellulose derivative has a charge content of less than or equal to about 1.4 mEq/g of cellulose, and wherein the cellulose-based filament has a diameter of at most about 50 μm.
As noted above, the cellulose-based filament has a diameter of at most about 50 μm, preferably at most about 25 μm, more preferably at most about 15 μm, and most preferably has a dimeter of about 10 μm. In embodiments, such cellulose-based filament has been manufactured by extruding the negatively charged cellulose derivative through a spinneret. In preferred embodiments, the cellulose-based filament of the present invention can be made from a negatively charged cellulose derivative using the method described in more detail below. In embodiments, the cellulose-based filament has a diameter of between about 10 μm and about 50 μm.
The negatively charged cellulose derivative bearing anionic functional groups that is used to make the cellulose-based filament of the present invention is cellulose that has been modified in such a manner that said anionic functional groups are covalently bonded to the cellulose derivative, thereby resulting in a cellulose derivative with a negative charge. In embodiments, the anionic functional groups are covalently bonded at the C2, C3, and/or C6 positions of the glucose units of the cellulose, preferably at the C2 position. It is to be understood that the anionic functional groups are covalently bonded to the cellulose, as opposed to for example being ionically bonded to the cellulose or adsorbed to the cellulose.
In embodiments of the present invention, the negatively charged cellulose derivative is optionally crosslinked.
The anionic functional groups can be any anionic functional group known in the art that can covalently bond with cellulose. In preferred embodiments, said anionic functional groups are carboxyalkyl groups (preferably carboxymethyl groups), phosphoryl groups, amine functionalized carboxylated carbon nanotubes, reactive orange 5 dye, reactive red 2 dye, reactive green 19 dye, or combinations thereof.
The presence of certain anionic functional groups can provide the cellulose-based filament with various desirable characteristics. The following represent various anionic functional groups which can be used, along with the effect said anionic functional group has on the cellulose-based filament:
It is to be understood that the negatively charged cellulose derivative can bear a variety of anionic functional groups at once. For example, the negatively charged cellulose can bear both covalently bonded carboxymethyl groups, as well as f-CNTs cross-linking cellulose strands together. It is to be understood that when an anionic functional group cross-links cellulose strands together, the charge of the anionic functional group is only counted once when calculating the charge content of the cellulose-based filament. It is also to be understood that when an anionic functional group cross-links cellulose strands together, mechanical strength of the cellulose-based filament can be increased and water absorbency can be decreased. It should be noted that this cross-linking can be achieved with many types of dyes.
It is also understood that other functional groups (including neutral and cationic functional groups) may be used in addition to the aforementioned anionic functional groups, as long as the cellulose derivative has a charge content of less than or equal to about 1.4 mEq/g of cellulose. For example, neutral or cationic dyes can also be used, provided the cellulose derivative has a charge content of less than or equal to about 1.4 mEq/g of cellulose.
As mentioned, the charge content of the cellulose-based filament is less than or equal to about 1.4 mEq/g, preferably between about 0.8 and about 1.4 mEq/g, more preferably between about 1.0 and about 1.4 mEq/g.
The charge content of the cellulose-based filament refers to the number of ionic charges present in each mmol of anionic functional group per gram of cellulose. For example, if the anionic functional group is a carboxymethyl group, which has a charge of −1, then a charge content of 1.0 mEq/g would be equivalent to 1.0 mmol of anionic functional group (in this case, carboxymethyl groups) per gram of cellulose. Conversely, if the anionic functional group is a phosphoryl group, which has a charge of −2, a charge content of 1.0 mEq/g would be equivalent to 0.5 mmol of phosphoryl group per gram of cellulose.
It is to be understood that the charge content of the filament takes into consideration the fact that different anionic functional groups, each with different charges, may be used. For example, if both carboxymethyl groups (charge: −1) and phosphoryl groups (charge: −2) are used, then the combination of said groups must still result in a charge content of less than or equal to about 1.4 mEq/g of cellulose.
For clarity, a charge content of 1.0 mEq/g would mean that, on average, for around every 6.17 glucose units, there is a charge of −1. Naturally, if the anionic functional group has a charge of −1, then this means there would be an average of 1 anionic functional group for every 6.17 glucose units. If the anionic functional group has a charge of −2, then this would mean there would be an average of 1 anionic functional group for every 12.34 glucose units. The above was calculated as follows:
The inverse of the above results equals 6.1675 glucose units per charge. Similarly, a charge content of 1.4 mEq/g would mean that, on average, for around every 4.405 glucose units, there is a charge of −1.
It is to be understood that the grams of cellulose measured when calculating the charge content refers to the mass of the cellulose excluding the mass of any anionic functional groups that may be present.
As mentioned, the inventors discovered that, when the cellulose-based filament has a diameter of at most about 50 μm and a charge content of less than or equal to about 1.4 mEq/g of cellulose, certain advantages are observed. Indeed, it has surprisingly low water absorbency, such that it is not superabsorbent (as would be expected) and, as such, can be dried and reused after becoming wet with water. Typically, when filaments have a charge content of greater than about 1.4 mEq/g of cellulose, the filament cannot be reused once wet because it becomes too water absorbent (superabsorbent). When filaments are superabsorbent, they typically exhibit swelling behaviour when exposed to water, as they absorb such a large quantity of water. Such filaments also typically retain water for significant periods of time, making them extremely difficult to dry, especially under normal handling conditions (such as doing laundry).
In a preferred embodiment of the present invention, the cellulose-based filament consists of the negatively charged cellulose derivative bearing anionic functional groups.
In preferred embodiments, the cellulose-based filaments are free of bubbles. In preferred such embodiments, the negatively charged cellulose derivative bears carboxymethyl (—CH2COO—) groups as the anionic functional groups and further bears methyl groups. Such cellulose derivative can be obtained by partial decarboxylation of a cellulose derivative bearing carboxymethyl groups.
In a related aspect of the invention, a method of producing the above cellulose-based filaments is provided, the method comprising the steps of:
In embodiments, the negatively charged cellulose derivative bearing anionic functional groups is produced by functionalizing cellulose so as to add said anionic functional groups. For example, cellulose can be carboxymethylated, which would result in a negatively charged cellulose derivative bearing carboxymethyl groups.
The anionic functional group can be covalently added to the cellulose using any method known in the art, including the examples described in more detail below (see Examples 1, 2, and 3). The content of anionic functional groups in the negatively charged cellulose derivative depends on the reaction conditions, such as reactant concentration, reaction temperature and duration of reaction.
In embodiments, the charge content of the cellulose derivative provided at step a) is greater than or equal to about 1.0 mEq/g of cellulose, preferably greater than about 1.0 mEq/g of cellulose.
In preferred embodiments, carboxymethyl cellulose is used as the negatively charged cellulose derivative bearing anionic functional groups.
In embodiments, the method comprises reacting cellulose with sodium chloroacetate to produce carboxylated carboxymethyl cellulose. In more preferred embodiment, the method further comprises the step of partially decarboxylating the carboxymethyl cellulose. In embodiments, this is accomplished by exposing the carboxymethyl cellulose to a solution with a pH of less than about 4 (preferably of about 3.5), then increasing the pH to about 8 in about 15 minutes, and allowing the partial decarboxylation to occur. The decarboxylated cellulose with a pH 8 or above can be dried afterwards without cellulose degradation.
The cellulose used in the functionalization step can be obtained or prepared using commercial cellulose products, such as softwood kraft pulp. These cellulose products can be ground to small pieces of about 300 μm in size. This can be done by a Wiley grinder or any other type of grinder or apparatus which gives comparable particle sizes.
It is to be understood that a wide variety of methods can be used to obtain the cellulose used in the method of the present invention, such as the methods described in Examples 1, 2, and 3 below.
The step of providing a dope solution comprising the negatively charged cellulose derivative bearing anionic functional groups can be performed using any method known in the art (see Examples 1, 2, and 3 below for examples). In embodiments, dope solution (or gel) can be produced by dissolving the negatively charged cellulose derivative bearing anionic functional groups in an alkaline aqueous solution.
In embodiments, the dope has a cellulose derivative concentration between about 4 wt % and about 8 wt %, preferably about 7 wt %, based on the total weight of the dope.
In embodiments, the alkaline aqueous solution is an NaOH aqueous solution, preferably with a NaOH/cellulose derivative weight ratio of about 0.3 to about 1. The more the carboxyl charge, the less the NaOH amount is preferred.
The dope can then be filtered before the extrusion step to remove non-dissolved residues. In embodiments, the dope is filtered through a filter with holes that are less than or equal to around 100 microns, preferably less than or equal to around 70 microns, preferably around 40 microns. This is because typically, in order to extrude the cellulose-based filaments, the dope needs to pass through the holes of a spinneret, which can be as small as around 100 microns, or even 70 microns, which would yield filaments with a diameter of about 10 microns to about 50 microns, as the filaments shrink when they dry. It is to be understood that the aforementioned diameter range of about 10 microns to about 50 microns is preferable because these are the desired dimensions for filaments used for making textiles.
Doping solutions obtained from the negatively charged cellulose derivative with a charge content of less than about 0.8 mEq/g cellulose are highly viscous, which makes spinning difficult. This is one reason why the cellulose derivative should have a charge content of greater than or equal to about 0.8 mEq/g of cellulose. Preferably, during this providing step of the method of the present invention, the cellulose derivative has a charge content between about 0.8 and about 1.4 mEq/g of cellulose. In embodiments, during this providing step of the method of the present invention, the charge content of the cellulose derivative is greater than or equal to about 1.0 mEq/g of cellulose (preferably greater than about 1.0 mEq/g of cellulose); greater than or equal to about 1.1 mEq/g of cellulose; greater than or equal to about 1.2 mEq/g of cellulose; or greater than or equal to about 1.3 mEq/g of cellulose.
The extrusion step can be carried out using any known method in the art provided that this method can produce filaments of the required diameter. One technique that does not allow obtaining such filament is simple extrusion from a syringe or the like by hand or using another slow mechanism, particularly when using a large gage needle. Indeed, in such conditions, filaments with diameters of more than 50 μm (e.g. about 1 mm) are produced.
Such filaments are must too large for textiles production.
In preferred embodiments, the dope is extruded into an acid coagulation bath (for example, 10% H2SO4 aqueous solution) to regenerate the cellulose.
In embodiments, the dope is extruded through a spinneret plate (which can contain holes of, for example, 100 microns or 70 microns in diameter), into the acid coagulation bath. Because the negatively charged cellulose derivative is not soluble in the acid solution, as soon as the dope exits the spinneret plate, dissolved negatively charged cellulose derivative precipitates out in the form of filaments.
In preferred embodiments, the filaments are collected and washed to remove residual acid. In embodiments, the filaments are collected together and passed via drawing rolls into a washing bath to remove residual acid, and collected onto a reel.
More specific examples of the extrusion step are described below (see Examples 1, 2, and 3).
Step d1) Curing Treatment (if the Cellulose-Based Filaments have a Charge Content of Greater than about 1.4 mEq/g of Cellulose)
As mentioned, the cellulose-based filaments of the present invention have a charge content of less than or equal to about 1.4 mEq/g of cellulose when measured at a pH of about 6 or more. However, after the extrusion step, it is possible that the resulting cellulose-based filaments can have a charge content of greater than about 1.4 mEq/g of cellulose when measured at a pH of about 6 or more. This occurs when there are too many anionic functional groups covalently attached to the negatively charged cellulose derivative. When this occurs, the resulting filament will be superabsorbent, such that it can no longer be considered reusable.
Accordingly, if the resulting cellulose-based filaments have a charge content of greater than about 1.4 mEq/g of cellulose when measured at a pH of about 6 or more, an additional curing step must be performed. The curing step is performed by dipping the filament into a solution of curing agent. The curing agent results in chemical crosslinking of negatively charged cellulose derivative chains e.g. through ester bonds (—COO—) occurring in the post-cured filaments. The ester bond is produced from the reaction between —OH and anionic functional groups of the negatively charged cellulose derivative chains.
For example, if the anionic functional group is a carboxymethyl groups, the ester bond resulting from the curing step will be produced from the reaction between —OH and —COOH groups of the negatively charged cellulose derivative chains (see
In other words, the curing has the effect of reducing the number of anionic functional groups covalently bonded to the negatively charged cellulose derivatives. This has the result of reducing the charge content of the cellulose-based filaments.
The curing is performed so as to reduce the charge content of the cellulose-based filaments such that the resulting cellulose-based filament has a charge content of less than or equal to about 1.4 mEq/g of cellulose.
In preferred embodiments, the curing agent is NaPO2H2, preferably 5% NaPO2H2. In preferred embodiments, the curing step is performed at a pH of about 3.5.
As mentioned, the curing step causes the chemical cross-linking of the cellulose chains. Accordingly, the curing step will also improve the mechanical strength of the result filament, in addition to reduction the charge content thereof. In addition, the curing step further surprisingly decreases the water absorbency of the cellulose-based derivative and the swelling of the cellulose molecules caused by water.
Step d2) Optional Curing Treatment (if the Cellulose-Based Filaments have a Charge Content of Less than or Equal to about 1.4 mEq/g of Cellulose)
Even if the cellulose-based filaments have a charge content of less than or equal to about 1.4 mEq/g of cellulose, the curing step may still be performed, although it is optional. This is because the curing step, as mentioned, may improve the mechanical strength of the resulting filament and lower the water absorbency of the resulting filament.
The optional curing step can be performed in the same manner as the curing step described above. However, the optional curing step is performed in such a manner so as to maintain the charge content to less than or equal to about 1.4 mEq/g of cellulose.
In a second aspect of the invention, bubble-free films and 3D objects are provided. These films and objects comprise carboxymethyl cellulose,
These films and 3D objects are biorenewable, biodegradable, recyclable and low-cost plastic replacements.
In embodiments, the carboxymethyl groups are covalently bonded at C2, C3, or C6 positions of the glucose units of the cellulose, preferably at the C2 position.
In embodiments of the present invention, the carboxymethyl cellulose is crosslinked. It is also to be understood that when a carboxymethyl group cross-links cellulose strands together, mechanical strength of the film/object can be increased.
As mentioned, the charge content is less than or equal to about 1.4 mEq/g, preferably between about 0.8 and about 1.4 mEq/g, more preferably between about 1.0 and about 1.4 mEq/g.
In a preferred embodiment of the present invention, the film/object consists of the above carboxymethyl cellulose.
Bubble-free films and 3D objects are free of gas bubbles trapped within the films/objects. Such bubbles are undesirable since they typically decrease the mechanical strength and uniformity of the films/objects, for example making films appear hazy rather than clear and transparent.
The carboxymethyl cellulose being “partially decarboxylated” means that some of its carboxymethyl groups have been replaced by methyl groups:
In embodiments, up to about one third of the carboxymethyl groups (preferably from about 15% to about 33% of the carboxymethyl groups) have been replaced by methyl groups in the partially decarboxylated carboxymethyl cellulose.
In embodiments, the film of the invention has a thickness from about 1 μm to about 100 μm. In preferred embodiments, the film of the invention has a thickness from about 30 μm to about 100 μm, which makes them useful for packaging. In alternative embodiments, the film of the invention has a thickness in the range from about 1 μm to about 30 μm and the carboxymethyl cellulose is cross-linked.
In embodiments, the film/object contain a dye and are therefore colored.
In embodiments, the 3D object is made of a stack of films of the invention.
In embodiments, the 3D object is made of one or more films of the invention shaped into a 3D shape. In such embodiments, the 3D objection can be a cup, a bottle, a plate, a block, a glove, etc. Such cups can withstand temperatures well over 100° C. without degrading.
In embodiments, the 3D object is made of a film of the invention bent so a part of the film is into contact with another part of film. Preferably, the film is rolled onto itself in the shape of a tube. In such embodiments, the 3D object can be a straw.
In embodiments, the film and 3D object are free of glue.
In a related aspect of the invention, a method of producing the above films/objects is provided, the method comprising the steps of:
As shown in Example 4, since the carboxymethyl cellulose is partially decarboxylated, few if any bubbles are formed in the film or 3D object at step C).
The method of the invention has the advantage of now requiring toxic chemicals (such as CS2) and, when making 3D objects, not requiring glue.
In embodiments, step A) comprises carboxymethylating cellulose so as to add carboxyl groups and then, partially decarboxymethylating the carboxymethylated cellulose.
These carboxymethylation and decarboxymethylation can be achieved using any method known in the art, including the examples described in more detail below (see Examples 1 to 4). The content of carboxyl groups in the negatively charged cellulose derivative depends on the reaction conditions, such as reactant concentration, reaction temperature and duration of reaction.
In embodiments, the cellulose is carboxymethylated by reacting cellulose with sodium chloroacetate to produce carboxylated carboxymethyl cellulose.
In embodiments, the carboxymethylated cellulose is partially decarboxylated by exposing the carboxymethyl cellulose to a solution with a pH of less than about 4 (preferably of about 3.5), then increasing the pH to about 8 in about 15 minutes, and allowing the partial decarboxylation to occur.
In preferred embodiments, the carboxymethylated cellulose has a carboxyl group content of about 1.0 to about 2.5 mmol —COOH/g cellulose.
In embodiments, the charge content of the carboxymethylated cellulose provided at step a) is greater than or equal to about 1.0 mEq/g of cellulose, preferably greater than about 1.0 mEq/g of cellulose, said charge content being measured at a pH of about 6 or more.
The cellulose used as a starting material can be obtained or prepared using commercial cellulose products, such as softwood kraft pulp.
Other feedstock such as any form of biomass, such as (chemo-) thermomechanical pulp (TMP), sawdust, forest and agricultural waste, recycled papers, etc. can be used. In fact, it is an advantage of the invention that films and 3D object can be made from lignin-containing fibers. When performing the carboxylation reaction on such products, the cellulose, hemicellulose and lignin therein will all be carboxylated, allowing their solubilization in alkaline to produce the dope.
These cellulose products can be ground and then optionally screened, for example using a 0.25 mm sieve, yielding an average fiber particle length of about 0.125 mm. This can be done by a GlenMills-SM300 or any other type of grinder or apparatus which gives comparable particle sizes.
This step is carried out in the same way as step b) in the previous method.
Of course, when biomass is used as a starting material for carboxylation, the dope will be a lignocellulose dope. Non-dissolved substances can be readily separated from such dope. Furthermore, dispersed small colloidal material can be flocculated and separated. Since the properties of the dope are different from those of dopes made from cellulose as a raw material, which will result in objects with different properties. These properties can advantageously be tailored for specific applications.
In embodiments, the dope may further comprise a dye.
In embodiments, the dope may further comprise a crosslinker, preferably a biodegradable crosslinker, such as epichlorohydrine. In embodiments, the dope has a crosslinker concentration of about 5 to about 15 wt %, preferably about 10 wt %, based on the total weight of the dope. The use of such crosslinker is particularly useful when thin films, e.g., about 1 μm to about 10 μm thick, are desired.
In embodiments, step c) comprises extruding said dope solution into a coagulation bath, so as to obtain a film or a 3D object.
In alternative embodiments, step c) comprises depositing said dope onto a substrate and then immerging the substrate with the dope solution into a coagulation bath, so as to obtain a film or a 3D object.
In both cases, the dope comes into contact with the coagulation bath. In embodiments, the coagulation bath is an acid coagulation bath, preferably a bath containing a 10% H2SO4 solution.
When the dope is exposed to the coagulation bath, cellulose is regenerated forming an insoluble film in a few minutes. For films that are 0.5 mm thick (when wet) regeneration time in a 10% sulfuric acid bath is about 3 minutes. For 1, 2, 5, and 10 mm think films, regeneration times are about 5, 12, 25, and 60 minutes.
As shown in Example 4, regenerating cellulose from carboxymethylated cellulose in such a bath generates bubbles, causing non-uniformity within the films and 3D objects produced. However, when the carboxymethylated cellulose is partially decarboxylated, the production of bubbles is reduced or even eliminated.
In embodiments, step c) comprises extruding said dope solution through an extruder die into the coagulation bath, so as to obtain a film or a 3D object. The extrusion can be carried out using any known method in the art provided that this method can produce films.
In embodiments, the die is a slit. This allows making films. The slit may be for example about 0.5 to about 1 mm wide, and as long as desired. Because the negatively charged cellulose derivative is not soluble in acid, as soon as the dope exits the extruder, dissolved carboxymethyl cellulose precipitates out in the form of film.
In other embodiments, the die is a ring. This allows making tubular objects, such as straw.
Dies of any other shape can also be used.
Preferably, the film or 3D object is pulled or pushed away from the die. The film or 3D object can then be washed to reduce residual acid (e.g., by being passed via drawing rolls into a washing bath), and then optionally collected onto a reel.
In embodiments, the film is then dried.
In embodiments, the dope is deposited onto a substrate and then the substrate with the dope is immersed into a coagulation bath. Since the dope is very viscous, it holds its shape until immersion in the coagulation bath, where the cellulose will be regenerated thus yielding a film or a 3D object. To get a sufficiently viscous dope, it can be useful to have undissolved fiber particles in the dope, e.g. from about 5 to about 20 wt % undissolved fiber particles, based on the total weight of the dope. Another alternative is to increase the carboxymethylated cellulose concentration of the dope, for example to a level or about 8 to about 15 wt %, based on the total weight of the dope.
In embodiments in which the dope comprises a crosslinker, the dope on the substrate is heated, for example in an oven, for example at about 100° C., e.g., for about 15 minutes or until completely dry, to allow crosslinking of the carboxymethylated cellulose, before the substrate with the dope is immersed in the coagulation bath. This advantageously allows producing thin films, for example a ±1 μm thick film with a tensile stress of over about 200 MPa and an elastic modulus of about 11.6 GPa.
In embodiments, the dope is deposited to form a layer on the substrate. In preferred embodiments, this layer is about 20 μm to about 50 μm thick, preferably about 30 μm thick. If films are very thin, they are difficult to handle when further used. If films are very thick, washing out residual acid before using them can be difficult.
In embodiments, the substrate is planar, and the dope is deposited to form a layer on the substrate. This allows forming planar films.
In embodiments, the substrate is non-planar, and the dope is deposited to form a layer on the substrate.
This allows forming films having different conformations. In preferred embodiments, the substrate is a mold, and the dope is deposited to form a layer around the mold or inside the mold. Examples of objects that can be produced by these methods include cups, bottles, plates, blocks, gloves, etc. Tubes (such as straws) can be produced by depositing a layer of dope onto a rod (for example, by dipping the rod into the dope).
In embodiments, the film or 3D object is then washed, preferably with water, to remove residual acid. The films are then preferably left in water for about 15 minutes to about 30 minutes.
In embodiments, the film or 3D object is then dried.
These steps are carried out in the same way as step d1) and d2) in the previous method.
In embodiments, the method further comprises the step of shaping one or more films produced according to steps A) to C) into a 3D object. This step can be carried before or after steps D1) and D2).
In embodiments, step E) comprises at least partially overlaying two or more films produced according to steps A) to C) while said films are nearly dry, but still contain enough moisture to allow the films to stick together upon further drying, and then allowing the films to dry. The two or more films can be completely overlaid, thus forming a neat stack. However, they can also be partially overlaid to produce any desired shape, for example bags could be produced. The shapes could even be computer generated and the stacking automated, similar as in LOM (laminated object manufacturing). Furthermore, the films may be overlaid within a mold to form a 3D object of any given shape.
In principle films of any thickness can be produced using steps A) to D). However, when the thickness is more than 3 mm, some lumps can form on the surface of the film during regeneration, which reduces film smoothness. The thicker the dope, the rougher the surface of the film. Thus, for making a thick 3D object, making thin films and overlaying them is more advantageous. It not only reduces the regeneration time, but also creates a product with a smooth surface. Upon drying, film thickness decreases 10-15 folds (depending on the concentration of the dope).
In other alternative embodiments, step E) comprises the step of bending a film produced according to steps A) to C) onto itself so a part of the film comes into contact with another part of film, while said film is nearly dry, but still contains enough moisture to allow said parts of the film to stick together upon further drying, and then allowing the film(s) to dry. Preferably, the film is rolled onto itself one or more times, forming a tube. Drinking straws can be produced by this method.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
The terms “comprising”, “having”, “including”, and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All subsets of values within the ranges are also incorporated into the specification as if they were individually recited herein.
Similarly, herein a general chemical structure with various substituents and various radicals enumerated for these substituents is intended to serve as a shorthand method of referring individually to each and every molecule obtained by the combination of any of the radicals for any of the substituents. Each individual molecule is incorporated into the specification as if it were individually recited herein. Further, all subsets of molecules within the general chemical structures are also incorporated into the specification as if they were individually recited herein.
All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed.
No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Herein, the term “about” has its ordinary meaning. In embodiments, it may mean plus or minus 10% or plus or minus 5% of the numerical value qualified.
The term “reusable”, when referring to the filament or the textile composed from the filament, refers to the fact that the filament and the textile can be repeatedly immersed in water (for example, during washing), and subsequently dried. This is because the hydrophobicity of the filament and the textile are sufficient such that, when the filament is immersed in water, it can be easily dried and reused. This means that the cellulose-based filament of the present invention is not superabsorbent.
It is to be understood that the terms “filament” and “filament” are used as synonyms in the present application.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Other objects, advantages and features of the present invention will become more apparent upon reading of the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings.
The present invention is illustrated in further details by the following non-limiting examples.
More specifically, the following examples describe the production of various cellulose-based filaments comprising a negatively charged cellulose derivative bearing anionic functional groups. In Example 1, the anionic functional group is a carboxymethyl group. In Example 2, the anionic functional groups are carboxymethyl groups and amine functionalized carboxylated carbon nanotubes (f-CNTs). In Example 3a, the anionic functional groups are carboxymethyl groups and reactive orange 5 dye. In Example 3b, the anionic functional groups are carboxymethyl groups and reactive red 2 dye. In Example 3c, the anionic functional groups are carboxymethyl groups and reactive green 19 dye.
Bleached softwood kraft (BSWK) pulp was supplied by a kraft pulp mill in Canada. Sodium hydroxide (NaOH) and isopropyl alcohol (IPA) were received from Fisher Scientific, USA. Sodium chloroacetate (ClCH2COONa) and sodium hypophosphite (NaH2PO2) were purchased from Sigma Aldrich, Canada. H2SO4 and HCl were obtained from Caledon, Canada and Fluka, USA, respectively. Ethyl alcohol was purchased from Brampton, Canada. Milli-Q deionized (DI) water was used in all experiments.
7 g grinded BSWK pulp was mixed well with 88 g IPA and then a NaOH solution was added to the pulp/IPA mixture, again mixed very well under magnetic stirring for 1 h at 40° C. This reaction step was conducted several times with various NaOH solution concentrations. Each time 1.33, 1.75, 2.54, 3.08 and 3.50 g NaOH dissolved in 7 g DI water was added to the pulp (7 g) mixed with IPA (88 g). Next, an aqueous solution of sodium chloroacetate was added to the reaction mixture and kept for 2 h under magnetic stirring at 50-60° C. This reaction step was also conducted several times by changing the concentration of sodium chloroacetate solution. Each time 1.06 (for 1.33 g NaOH), 1.42 (for 1.75 g NaOH), 2.1 (for 2.54 g NaOH), 2.64 (for 3.08 g NaOH) and 2.99 (for 3.50 g NaOH) g sodium chloroacetate dissolved in 5 g DI water was added to the reaction mixture. After completing the reaction, the negatively charged cellulose derivative was washed 3 times with an ethanol/water mixture (70% ethanol and 30% water). During the third washing, a HCl solution was added to the negatively charged cellulose derivative mixture to reduce the pH below 3.5. Finally, the negatively charged cellulose derivative was washed with pure ethanol and then dried for 24 h at room temperature.
Preparation of Dope Solutions from the Modified Cellulosic Pulps
First, 7 g of modified cellulosic pulps was mixed well with 78 g DI water and then 15 g NaOH solution (6 g NaOH dissolved in 9 g water) was added to this mixture. This mixture was then mixed well by an automatic mixer to form a fine gel which was finally filtered through a 40 μm filter media. This filtered gel (dope solution) was ready for wet spinning to fabricate textile filaments.
The prepared dope solutions were placed inside a steel cylinder, of which one end was connected to a spinneret with multiple holes of 100 μm diameter each. The spinneret was immersed into a coagulation bath filled with a 10% H2SO4 solution. The otherend of the cylinder was connected to a nitrogen gas cylinder. During extrusion, 100 psi pressure was applied on the dope solution placed inside the cylinder from the gas cylinder causing the dope solution to pass through the holes of the spinneret plate, thus generating filaments in the coagulation bath. The generated filaments were collected by a roller from the coagulation bath. The extrusion process to fabricate filaments is shown schematically in
5 g of dried filaments were dipped into 20 mL of 5% NaH2PO2 aqueous solution for 5 min and then taken out and heated at 180° C. in an oven for 5 min; they were then cooled to room temperature. Finally, the filaments were washed by DI water and then dried at room temperature. The entire process for fabricating textile filaments from cellulosic pulps is shown in
A conductivity titration (using a METER pH/conductivity S470-KIT, Mettler-Toledo GmbH, Greifensee, Switzerland titrator) was performed to determine the —COOH group content in the negatively charged cellulose derivative. First, a fixed quantity of negatively charged cellulose derivative dried at 105° C. in an oven was dispersed very well in 140 mL of Milli-Q DI water under magnetic stirring followed by using a homogenizer. Then, 2.5 mL of a 0.02 M sodium chloride solution was added to the above mixture under magnetic stirring conditions to achieve a very well dispersed suspension. In order to adjust the pH at 3, a HCl solution (0.1 M) was added slowly to the above cellulose suspension. Finally, titration with the suspension was conducted by adding a 0.01 M NaOH solution at a rate of 0.1 mL/min until the pH of the suspension reached 11. The —COOH group content of the negatively charged cellulose derivative was determined from the conductivity curve by using the following equation:
where [COOH]g is the —COOH group content of the negatively charged cellulose derivative (mmol/g of cellulose), VNaOH is the volume of NaOH solution (mL) required for deprotonation of the —COOH group, MNaOH is the strength of NaOH solution (mol/L), and DWg is the weight of the dried negatively charged cellulose derivative in grams dissolved in DI water.
Scanning electron microscopy (SEM) (QUANTA FEG 450) with a platinum coating on the sample surface was performed to observe the surface morphology of the filaments prepared from the negatively charged cellulose derivative and the dyed negatively charged cellulose derivative.
Fourier transform infrared (FTIR) spectrum of the samples was conducted using a Bruker Tensor 37 instrument (Bruker, Ettlingen, Germany) with PIKE MIRacle diamond Attenuated Total Reflectance (ATR) accessory. Solid samples were placed directly on the ATR crystal and then maximum pressure was applied by lowering the tip of the pressure clamp using a ratchet-type clutch mechanism. All the spectra of measured samples from 32 scans were averaged from 400 to 4000 cm−1 with a resolution of 4 cm−1.
Solid-state 13C-NMR spectra of the samples were obtained on a Varian/Agilent VNMRS-400 instrument operating at 100.5 MHz. Samples were packed uniformly inside a 7.5 mm zirconium rotor and spun at 5,500 Hz. Spinning sidebands were suppressed using the TOSS sequence.
Mechanical strength of the filaments was determined by using a TMI Lab Master tensile machine (John Chatillon & Sons, New York, USA) at ambient conditions. The filament sample was taken at a length of 50 mm with the strain rate of 5 mm/min. Ten filaments were taken together for mechanical strength measurements of each filament (average value of ten filaments together).
The water absorbency value was measured by dispersing 0.5 g of dried filaments in DI water followed by soaking for 12 h, and then centrifuging them at 1000 g for 10 min placed in a tube with a porous screen at the bottom to separate water from the filaments. The centrifuged filaments were then weighed to obtain the wet weight (Wg). Next, the wet filaments obtained after centrifugation were dried in an oven at 105° C. and then re-weighed in dry condition (Wd). Finally, the water absorbency value was calculated by using the following equation
Chemical modification of cellulosic pulps through carboxymethylation was performed in order to prepare a gel/dope solution (used for fabrication of the cellulose-based filaments by spinning) from the negatively charged cellulose derivative pulps. It was not possible to make a gel from the unmodified cellulose mixed with a NaOH solution due to likely high interaction among the —OH groups attached to the cellulose chain. The entire modification process is exhibited in
The occurrence of the carboxymethylation reaction was confirmed by 13C solid-state NMR and FTIR investigations.
Morphology of the Filaments Made from Negatively Charged Cellulose Derivative Pulps
SEM images of non post-curing and post-curing cellulose-based filaments made from the negatively charged cellulose derivative with carboxyl group content of 1.3 mmol/g cellulose are shown in
Mechanical Properties and Water Absorbency of the Filaments without Post-Curing
The mechanical strength of textile filaments is usually expressed in terms of tenacity. The tenacity of both dried and wet filaments was determined. Tenacities of ethanol and water washed dried filaments fabricated from the negatively charged cellulose derivative with carboxyl group contents of 1.3 mmol/g cellulose were ˜0.8 cN/dtex, which decreased to ˜0.63 cN/dtex in wet condition of the filaments (
On the other hand, water absorbencies of ethanol washed filaments made from the negatively charged cellulose derivative with carboxyl group contents of 1.5 and 1.7 mmol/g cellulose were 1.61 and 3.2 g water/g filaments, respectively (
The filaments fabricated from negatively charged cellulose derivative with carboxyl group contents of 1.3, 1.5 and 1.7 mmol/g cellulose were post-cured by applying heat in an oven at 180° C. for 5 min in the presence of NaH2PO2. The chemical reaction that took place during post-curing of the filaments is exhibited in
FTIR spectra of the fabricated filaments without and with post-curing are exhibited in
Tenacities of ethanol and water washed dried filaments made from negatively charged cellulose derivative with carboxyl group content of 1.3 mmol/g cellulose increased 25% for the post-cured filaments (
Water absorbencies of ethanol and water washed filaments made from negatively charged cellulose derivative with carboxyl group content of 1.3 mmol/g cellulose decreased 28% for the post-cured filaments (
Mild chemical modifications through carboxymethylation of cellulose and then mixing of aqueous solution of NaOH with the negatively charged cellulose derivative for preparing dope solutions from which filaments were spun in an acid bath were performed in this Example. Post-curing of these filaments with the use of aqueous solution of NaH2PO2 was also accomplished to obtain the filaments with extremely good properties for textile applications. Isopropyl alcohol used as a solvent for carboxymethylation (with the use of aqueous solutions of NaOH and ClCH2COONa) of cellulose, ethanol/water mixture (70% ethanol and 30% water by volume) for washing of the negatively charged cellulose derivative and aqueous solution of NaH2PO2 used as a catalyst for the chemical reaction occurred at the time of post-curing of the filaments were employed during the above steps. After reaction, isopropyl alcohol separated from negatively charged cellulose derivative could be reused for carboxymethylation of cellulose. In this stage, it might not be required to add extra aqueous solutions of NaOH and ClCH2COONa in isopropyl alcohol, just mixing of cellulose into this solvent could be required. However, lower amount of cellulose must be mixed in this solvent in order to achieve the same amount of carboxyl group content obtained previously.
Ethanol/water mixture was used to wash the negatively charged cellulose derivative separated from isopropyl alcohol after the carboxymethylation reaction. This used ethanol/water mixture could be reused many times for the same purpose. Ethanol from the ethanol/water mixture used for many times for washing can be separated by thermal distillation for further using.
In post-curing, dried filaments were dipped into an aqueous solution of NaH2PO2 for a few min and then took it out and heated in an oven for a few min followed by cooled to room temperature. Finally, the filaments were washed by DI water and then dried at room temperature. This washed out water mixed with the aqueous solution of NaH2PO2 in which filaments were previously dipped could be reused continuously for the post-curing of filaments.
Currently available processes for production of cellulose-based textiles are encountered by certain techno-economic and environmental drawbacks. A novel economical and environment friendly process—wet spinning of aqueous alkaline solution of carboxymethylated cellulose in an acid bath and then washing and drying of the spun filaments followed by heating them in the presence of NaH2PO2— has been developed in this Example to overcome some of shortcomings of the existing technologies applied for production of cellulosic textiles. After extrusion in acid bath, filaments containing 1.3 mmol —COOH/g cellulose could be washed with both water and ethanol, however, the filaments with carboxyl group content of 1.5 or 1.7 mmol/g cellulose could only be washed with ethanol. Most of the chemicals could be reused, demonstrating economical viability of this process. Carboxymethylated cellulose containing at least 1.3 mmol —COOH group/g cellulose was able to produce filaments with this process. Filaments with this amount of carboxyl group content demonstrated extremely good properties in terms of tenacity and water absorbency for textile applications. However, quality in terms of tenacity and water absorbency of the filaments containing carboxyl group content higher than 1.3 mmol —COOH group/g cellulose deteriorated due to increase in charge content in the filaments. It was also observed that the filaments with 1.3 mmol —COOH group/g cellulose demonstrated ˜10% higher tenacity and ˜3.7 to 7.4 times lower water absorbency as compared to the literature values of rayon filaments.
Bleached softwood kraft (BSWK) pulp was supplied by a kraft pulp mill in Canada. Sodium hydroxide (NaOH), sodium azide (NaN3) and isopropyl alcohol (IPA) were received from Fisher Scientific, USA. Sodium chloroacetate (ClCH2COONa) and multiwalled carboxylated carbon nanotube were purchased from Sigma Aldrich, Canada. H2SO4 was obtained from Caledon, Canada. 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and HCl were received from Fluka, USA. N-Hydroxysuccinimide (NHS) and Ethyl alcohol were purchased from Thermo Scientific, Japan and Brampton, Canada, respectively. Milli-Q deionized (DI) water was used in all experiments.
The modification of cellulosic pulps was done using the same method as performed in the same step of Example 1. This reaction step was conducted several times with various NaOH solution concentrations (1.33, 1.75 and 2.54 g NaOH). In addition, the negatively charged cellulose derivative was washed 3 times with an ethanol/water mixture (60% ethanol and 40% water).
First, carboxylated CNT was dispersed in DI water under sonication for 5 min. As compared to CNT, a 5 times larger amount of H2SO4 was added to the CNT dispersion and the mixture was sonicated again for 5 min. Afterward, a 1.5 times larger amount of NaN3 (as compared to the amount of CNT) dissolved in DI water was added to the above CNT dispersion and kept for 12 h under magnetic stirring at room temperature. The CNT reaction mixture was then filtered through a0.1 μm filter followed by washing with DI water. Finally, the amine functionalized carboxylated CNT was dried in an oven at 105° C.
Preparation of Negatively Charged Cellulose Derivative Cross-Linked by f-CNT Composite Gel
First 0.022 g EDC and 0.016 g NHS were dissolved in 100 g DI water. Then 7 g negatively charged cellulose derivative obtained from the modification reaction with the use of the highest amount of NaOH (2.54 g) and sodium chloroacetate (2.1 g) was thoroughly mixed with the EDC/NHS solution and kept for 2 h at a pH of 5.5. Afterward, 0.07 g amine functionalized carboxylated CNT dispersed well in 50 g DI water was added to this mixture and magnetically stirred for 5 h at a pH of 5.5. After 5 h, the pH of the reaction mixture was reduced to below 3.5 and then washed with ethanol/water mixture (60% ethanol and 40% water) followed by drying at room temperature. Afterward, 78 g DI water was mixed well with the dried negatively charged cellulose derivative cross-linked by f-CNT followed by mixing 15 g NaOH solution (6 g NaOH dissolved in 9 g water) with the use of an automatic mixer to form a fine gel. This gel was finally filtered through a 40 μm filter and the filtered gel was ready for wet spinning to fabricate filaments.
The gels without f-CNT used for wet spinning were also prepared for the all types of negatively charged cellulose derivative obtained from the modification reaction with the use of different amounts of NaOH (1.33, 1.75 and 2.54 g) and sodium chloroacetate (1.06, 1.42 and 2.1 g). First, 7 g negatively charged cellulose derivative was mixed well with 78 g DI water and then 15 g NaOH solution (6 g NaOH dissolved in 9 g water) was added to this mixture. This mixture was then mixed well by an automatic mixer to form afine gel, which was finally filtered through a 40 μm filter media. This filtered gel was ready for wet spinning to fabricate filaments.
This step was performed in the same manner as in Example 1. The entire process to fabricate the negatively charged cellulose derivative cross-linked by f-CNT composite filaments are shown in
Field emission-scanning electron microscopy (FE-SEM) (QUANTA FEG 450) with a platinum coating on the sample surface was performed to observe the surface and cross-sectional morphology of the filaments prepared from the negatively charged cellulose derivative and the negatively charged cellulose derivative cross-linked by f-CNT.
This step was performed in the same manner as in Example 1.
Mechanical strength of the filaments was determined by using a TMI Lab Master tensile machine (John Chatillon & Sons, New York, USA) at the ambient condition. The filament sample was taken at a length of 50 mm with the strain rate of 5 mm/min. Ten filaments were taken together for mechanical strength measurement of each filament (average value of ten filaments together).
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
Color fastness of the fabricated filaments of negatively charged cellulose derivative cross-linked by f-CNT was investigated as per the method described in literature (BS 1006 1990). The washing, rubbing, light and perspiration fastness were measured according to the method of ISO 105-C02 (1989), ISO 105-X12(1987), ISO 105-B02 (1988) and ISO 105-E04 (1989), respectively.
This step was performed in the same manner as in Example 1.
The content of —COOH group as a function of NaOH and ClCH2COONa concentrations under constant cellulose content (7 g), temperature (1st step: 40° C., 2nd step: 50-60° C.) and reaction duration (1st step: 1 h, 2nd step: 2 h) is exhibited in Table 2. Table 2 demonstrates that increasing the contents of NaOH (from 1.33 to 2.54 g) and ClCH2COONa (from 1.06 to 2.1 g) increased the —COOH group content (from 0.6 to 1.3 mmol/g cellulose) in the negatively charged cellulose derivative.
The negatively charged cellulose derivative with various —COOH group content (0.6 to 1.3 mmol/g cellulose) were used to make gel for fabricating filaments through spinning (Table 2). The negatively charged cellulose derivative with a —COOH group content of 0.6 mmol/g cellulose was not able to form a gel (for spinning). The negatively charged cellulose derivative with a —COOH group content of 1.0 and 1.3 mmol/g cellulose was able to form gel; however, the gel obtained from the negatively charged cellulose derivative with 1.0 mmol/g cellulose was highly viscous likely due to high interaction created by hydrogen bond formation among the —OH groups residing in the cellulose chain, which is why it was not suitable for spinning. The other type of gel obtained from the negatively charged cellulose derivative with —COOH group content of 1.3 mmol/g cellulose was suitable for spinning to fabricate filaments. Therefore, the negatively charged cellulose derivative with a —COOH group content of 1.3 mmol/g cellulose was selected for fabrication of filaments produced from the negatively charged cellulose derivative cross-linked by f-CNT composite in this research.
The conversion of carboxylated CNT to amine functionalized carboxylated CNT and the cross-linking reaction between negatively charged functional groups and f-CNT are presented schematically in
Mechanical Properties and Water Absorbency of the Negatively Charged Cellulose Derivative Cross-Linked by f-CNT Composite Filaments
The mechanical strength of textile filaments is usually expressed in terms of tenacity. The tenacity of both dried and wet filaments was determined. The tenacity of the dried filaments fabricated from the negatively charged cellulose derivative was 0.8 cN/dtex, which was ˜21% higher than the tenacity of wet filaments (0.63 cN/dtex) (
Water absorbency is one of the major properties of textile filaments. This property demonstrates the swelling behaviour and the capacity to take up water. The water absorbency of the filaments made from the negatively charged cellulose derivative was 0.75 water/g filament, which is ˜19% higher than that of the filaments made from the negatively charged cellulose derivative cross-linked by f-CNT (0.61 water/g filament) (
Color Fastness Properties of the Negatively Charged Cellulose Derivative Cross-Linked by f-CNT Composite Filaments
The color fastness properties of the fabricated cellulose-based filaments filled with f-CNT are presented in Table 3. Color fastness is the ability provided by dyed filaments to retain dye on them under external effects such as washing with the use of soaps and detergents, rubbing, exposure to light, contact to acid and alkaline solutions etc. Color fastness of a textile material is indicated by the numbers of 1 (poor fastness), 2 (limited fastness), 3 (fair fastness), 4 (good fastness) and 5 (excellent fastness). In this research, f-CNT was used as a coloring material alternative to the commonly used black color dyes. The fabricated filaments exhibited excellent values of fastness, i.e., 5, to washing, rubbing, light and perspiration. These excellent fastness values indicate no loss of f-CNT due to covalent bond formation with the negatively charged cellulose derivative under external effects on the fabricated filaments.
Morphological Properties of the Cellulose-Based Filaments Comprising Negatively Charged Cellulose Derivative Cross-Linked by f-CNT
The morphologies of the filaments made from the negatively charged cellulose derivative and the negatively charged cellulose derivative cross-linked by f-CNT are shown in
No Release of CNT from the Filaments into Acid Bath During Extrusion of Gel
The negatively charged cellulose derivative formed covalent bonds with f-CNT in the dope solution used for extrusion in acid solution bath. Due to these covalent bonds, no CNT was released from the filaments into the acid solution utilized for regeneration of cellulose during extrusion. The acid solution used for regeneration of cellulose during extrusion is exhibited in
Black color textile filaments were fabricated successfully from negatively charged cellulose derivative cross-linked by f-CNT by an eco-friendly method. Functionalized carboxylated carbon nanotubes were covalently cross-linked with the negatively charged cellulose derivative in the dope solution from which black color textile filaments were fabricated by extrusion in an acid solution bath. Thus, no conventional dyeing step using any commonly used black color dye was performed for the fabrication of black filaments. Production of dyed wastewaters is a common scenario in the current textile industries, whereas no chance to produce dyed wastewater due to the absence of conventional dyeing step in this research. The incorporation of f-CNT increased the mechanical strength but decreased the water absorbency along with excellent color fastness of the fabricated filaments. The increase in mechanical strength, decrease in water absorbency and excellent color fastness could make the fabricated filaments promising candidates for high quality textile applications.
We prepared cellulose-based filaments comprising (a) a negatively charged cellulose derivative bearing carboxymethyl groups and reactive orange 5 dye; (b) a negatively charged cellulose derivative bearing carboxymethyl groups and reactive red 2 dye; (c) a negatively charged cellulose derivative bearing carboxymethyl groups and reactive green 19 dye
Bleached softwood kraft (BSWK) pulp was supplied by a kraft pulp mill in Canada. Sodium hydroxide (NaOH) and isopropyl alcohol (IPA) were received from Fisher Scientific, USA. Sodium chloroacetate (ClCH2COONa) was purchased from Sigma Aldrich, Canada. Reactive orange 5, reactive red 2 and reactive green 19 dyes were obtained from Alfa Chemistry, USA. H2SO4 and HCl were obtained from Caledon, Canada and Fluka, USA, respectively. Ethyl alcohol was purchased from Brampton, Canada. Milli-Q deionized (DI) water was used in all experiments.
This step was performed in the same manner as in Example 2.
Preparation of Negatively Charged Cellulose Derivative Gel Covalently-Linked with Dyes
First, 0.006 g dye (reactive orange 5/reactive red 2/reactive green 19) was dissolved in 78 g DI water and then mixed well with 7 g dried negatively charged cellulose derivative [obtained from the modification reaction with the use of the highest amount of NaOH (2.54 g) and sodium chloroacetate (2.1 g)] followed by mixing 15 g NaOH solution (6 g NaOH dissolved in 9 g water) with the use of an automatic mixer to form a fine gel. This gel was finally filtered through a 40 μm filter and the filtered gel was ready for wet spinning to fabricate filaments. This gel was kept for 12 h before wet spinning.
Gels without dyes used for wet spinning were also prepared for all types of negatively charged cellulose derivative obtained from the modification reaction with the use of different amounts of NaOH (1.33, 1.75 and 2.54 g) and sodium chloroacetate (1.06, 1.42 and 2.1 g). First, 7 g negatively charged cellulose derivative was mixed well with 78 g DI water and then 15 g NaOH solution (6 g NaOH dissolved in 9 g water) was added to this mixture. This mixture was then mixed well by an automatic mixer to form a fine gel, which was finally filtered through a 40 μm filter media. This filtered gel was ready for wet spinning to fabricate filaments.
This step was performed in the same manner as in Example 1.
The entire process to fabricate covalently-linked dyed negatively charged cellulose derivative textile filaments is shown in
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 1.
This step was performed in the same manner as in Example 2.
This step was performed in the same manner as in Example 2.
The content of —COOH groups as a function of NaOH and ClCH2COONa concentrations under constant cellulose content (7 g), temperature (1st step: 40° C., 2nd step: 50-60° C.) and reaction duration (1st step: 1 h, 2nd step: 2 h) is exhibited in Table 4. Table 4 demonstrates that increasing the contents of NaOH (from 1.33 to 2.54 g) and ClCH2COONa (from 1.06 to 2.1 g) increased the —COOH group content (from 0.6 to 1.3 mmol/g cellulose) in the negatively charged cellulose derivative. The negatively charged cellulose derivative with various —COOH group content (0.6 to 1.3 mmol/g cellulose) were used to produce gels for fabricating of filaments through spinning (Table 4). The negatively charged cellulose derivative with a —COOH group content of 0.6 mmol/g cellulose was not able to form a gel suitable for spinning. The negatively charged cellulose derivative with a —COOH group content of 1.0 and 1.3 mmol/g cellulose was able to form gels; however, the gel obtained from the negatively charged cellulose derivative with 1.0 mmol/g cellulose was highly viscous made spinning difficult. The other type of gel obtained from the negatively charged cellulose derivative with a —COOH group content of 1.3 mmol/g cellulose was suitable for spinning to fabricate filaments. Therefore, in this research, this negatively charged cellulose derivative was selected to fabricate dyed textile filaments in which covalent bonds were formed between cellulose chains and dyes.
Photographs of the filaments made from the negatively charged cellulose derivative and the negatively charged cellulose derivative covalently-linked with dyes are shown in
SEM images of the filaments made from the negatively charged cellulose derivative and the negatively charged cellulose derivative covalently-linked with dyes are shown in
Covalently-Linking of Dyes with the Negatively Charged Cellulose Derivative in the Textile Filaments
FTIR spectra of dried dope solutions and filaments made from negatively charged cellulose derivative and negatively charged cellulose derivative covalently-linked with dyes are exhibited in
The occurrence of the carboxymethylation reaction and covalent linkage between negatively charged cellulose derivative and dyes were also confirmed by 13C solid-state NMR, shown in
The existence of these dyes in the cellulose-based filaments comprising negatively charged cellulose derivative was also investigated by SEM-EDS shown in
The mechanical strength of textile filaments is usually expressed in terms of tenacity. The tenacity of both dried and wet filaments was determined. The tenacity of the dried filaments fabricated from the negatively charged cellulose derivative was 0.8 cN/dtex, which was ˜21% higher than the tenacity of wet filaments (0.63 cN/dtex) (
Water absorbency is one of the major properties of textile filaments. This property demonstrates the swelling behaviour and the capacity to take up water. The water absorbencies of the filaments made from the negatively charged cellulose derivative, and the negatively charged cellulose derivative covalently-linked with reactive orange 5 and reactive red 2 were ˜0.75 water/g filament, which is ˜16% higher than that of the filaments made from the negatively charged cellulose derivative covalently-linked with reactive green 19 (0.63 water/g filament) (
The color fastness properties of the fabricated cellulose-based filaments comprising negatively charged cellulose derivative covalently-linked with reactive orange 5, reactive red 2 and reactive green 19 dyes are presented in Table 5. Colorfastness is the ability provided by dyed filaments to retain dye on them under external effects such as washing with the use of soaps and detergents, rubbing, exposure to light, contact to acid and alkaline solutions etc. Color fastness of a textile material is indicated by the numbers of 1 (poor fastness), 2 (limited fastness), 3 (fair fastness), 4 (good fastness) and 5 (excellent fastness). The fabricated filaments exhibited excellent values of fastness, i.e., 5, to washing, rubbing, light and perspiration. These excellent fastness values indicate no loss of dyes due to covalent bond formation with the negatively charged cellulose derivative under external effects on the fabricated filaments.
No Release of Dyes from the Filaments into Acid Bath During Extrusion of Gel
The negatively charged cellulose derivative formed covalent bonds with the dyes in the dope solution used for extrusion in acid solution bath. Due to these covalent bonds, no dye was released from the filaments into the acid solution utilized for regeneration of cellulose during extrusion. Camera images of the acid solutions used for regeneration of cellulose during extrusion is exhibited in
Dyed textile filaments were fabricated successfully from negatively charged cellulose derivative covalently-linked with the dyes of reactive orange 5, reactive red 2 and reactive green 19 by an eco-friendly method. These three dyes were covalently-linked with the negatively charged cellulose derivative in the dope solution from which dyed textile filaments were fabricated by extrusion in an acid coagulation bath. Thus, no conventional dyeing step was performed for the fabrication of dyed textile filaments. Production of dyed wastewaters is a common scenario in the current textile industries, whereas no colored wastewater was produced in this research. Excellent color fastness properties of the fabricated textile filaments were obtained due to covalent-linkage between dyes and negatively charged cellulose derivative. The incorporation of reactive green 19 dye increased the mechanical strength but decreased the water absorbency of the fabricated textile filaments due to chemical crosslinking of negatively charged cellulose derivative chains through this dye. The increase in mechanical strength, decrease in water absorbency and excellent color fastness could make the fabricated filaments promising candidates for high quality textile applications.
The inventors have noticed that during regeneration of the alkaline dope of carboxylated cellulose in the acid bath as described above, variable amounts of an unknown gas were formed. Some of this gas would stay in the middle of the films or filaments as bubbles (see
The bubbles decreased the mechanical strength and uniformity of the product depending on the size of the bubbles and their rate of formation. In the case of thin filaments, a small number of bubbles inside the filaments generally did not present major problems, but in the case of thin films, bubbles caused visible defects which could be a serious problem. This was especially noticeable for films with thickness >30 μm, designed for packaging, or for films in the range 10-30 μm, which might have other applications.
Degassing the dope did not reduce the number of bubbles, indicating they were not caused by dissolved air.
After various tests, we finally showed that the amount of carboxyl groups on the cellulose had a direct influence on the rate of bubble formation. We also noted that a high viscosity and the presence of undissolved fiber fragments or microspherical particles in the dope reduced the number of bubbles in the film, likely because they would help to release the gas in the acid bath leaving less bubbles in the film. More specifically, we have shown that up to one third of carboxyl groups in mildly carboxylated cellulose fibers (CMF) are unstable under acidic conditions. When cellulose in a CMF dope, an alkaline carboxymethylated cellulose solution, is regenerated in an acid bath, the unstable carboxyl groups are being decarboxylated and form carbon dioxide, leaving an equivalent amount of methyl groups on the cellulose (
To determine the nature of gas inside the bubbles, we collected and analyzed the released gas and determined it was carbon dioxide, not air. We hypothesized that the carbon dioxide was formed due to partial decarboxylation of the dope.
In order to eliminate bubbles and produce a defect free film with desired carboxyl comprising a partial decarboxylation of the carboxymethyl fiber (CMF) before making the dope, therefore eliminating the unstable carboxyl groups in CMF.
We used two methods to accomplish this partial decarboxylation. Firstly, at the end of the carboxymethylation reaction, we drained most of the isopropyl alcohol (IPA) together with by-products of salts, present in the reaction mixture, and reduced the pH from about 11 to less than 4 (preferably 3.5) by adding a few drops of HCl and allowed the partial decarboxylation and formation of carbon dioxide to proceed. The other method we used was to reduce the pH after CMF was washed and partially drained.
When the unstable carboxyl groups were eliminated according to either of above, prior to dope making and regeneration in an acid bath, there was no decarboxylation and CO2 formation during cellulose regeneration and the films formed were uniform. See
The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
The present description refers to a number of documents, the content of which is herein incorporated by reference in their entirety. These documents include, but are not limited to, the following:
This application claims benefit, under 35 U.S.C. § 119(e), of U.S. provisional application Ser. No. 63/177,172, filed on Apr. 20, 2021. All documents above are incorporated herein in their entirety by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2022/050599 | 4/20/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63177172 | Apr 2021 | US |
