Patent Application
20230407055
Each year, the global production of plastics continues to increase. Over one-half of the amount of plastics produced each year are used to produce plastic bottles, containers, drinking straws, and other single-use items. The discarded, single-use plastic articles, including plastic drinking bottles, are typically not recycled and end up in landfills. In addition, many of these items are not properly disposed of and end up in streams, lakes, and oceans around the world.
In view of the above, those skilled in the art have attempted to produce plastic articles made from biodegradable polymers. Many biodegradable polymers, however, lack the physical properties and characteristics of conventional polymers, such as polypropylene and/or polyethylene terephthalate.
Cellulose esters have been proposed in the past as a replacement to some petroleum-based polymers or plastics. Cellulose esters, for instance, are generally considered environmentally friendly polymers because they are recyclable, degradable and derived from renewable resources, such as wood pulp. Problems have been experienced, however, in melt processing cellulose ester polymers, such as cellulose acetate polymers. The polymer materials are relatively stiff and have relatively poor elongation properties. In addition, the melt temperature of cellulose ester polymers is close to the degradation temperature of the polymer, which requires careful control over temperatures during melt processing. Consequently, cellulose esters are typically combined with a plasticizer in order to improve the melt processing properties of the material.
Adding substantial amounts of plasticizer to the cellulose ester polymer, however, can produce various drawbacks. For instance, adding the plasticizer lowers the melting temperature of the composition. Relatively large amounts of plasticizer can also reduce modulus and stiffness. In addition, the plasticizer can have a negative impact on the heat deflection temperature.
In view of the above, a need currently exists for a method of improving the melt processing characteristics of cellulose ester polymers. A need also exists for cellulose ester polymer compositions that can be formulated with higher melt flow rates and/or lower intrinsic viscosities. Such compositions may be melt processed without having to add significant amounts of plasticizer if desired.
Alternatively or in addition, a need also exists for an additive that can be blended with a cellulose ester polymer for producing molded articles that have at least one improved physical property, such as a property that is related to the appearance of the molded article. For example, a need exists for an additive capable of improving the surface appearance of molded articles made from cellulose ester polymers.
In general, the present disclosure is directed to a polysaccharide ester polymer composition, particularly a cellulose ester polymer composition, that has at least one improved property. In one aspect, for instance, a property enhancing agent is combined with a cellulose ester polymer in an amount sufficient to improve the melt flow properties of the resulting composition. The improved flow properties not only greatly facilitate melt processing of the polymer composition but can also produce molded articles having one or more improvements in physical properties. In one aspect, a cellulose ester polymer can be combined with a property enhancing agent that reduces the intrinsic viscosity of the cellulose ester polymer and increases its melt flow rate. The modified cellulose ester polymer composition can be combined with lower amounts of plasticizer in producing molded articles.
Alternatively, or in addition to improving the melt flow properties of the cellulose ester polymer composition, the property enhancing agent can be combined with the cellulose ester polymer in an amount sufficient to improve the surface appearance of molded articles made from the composition. For instance, the property enhancing additive can dramatically increase surface reflectance. In this manner, molded articles can be made from the polymer composition having enhanced gloss characteristics if desired. The property enhancing agent can also improve surface smoothness and/or decrease surface irregularities.
For example, in one embodiment, the present disclosure is directed to a polymer composition comprising a cellulose ester polymer. The cellulose ester polymer is present in the polymer composition in an amount greater than about 20% by weight, such as in an amount greater than about 40% by weight, such as in an amount greater than about 50% by weight, such as in an amount greater than about 60% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 90% by weight. The cellulose ester polymer is combined with a plasticizer and a property enhancing agent. The property enhancing agent comprises an acidic species. For example, the property enhancing agent can be an organic acid and/or a diprotic acid. The property enhancing agent, for example, can have a Pka value of from about 2 to about 6, such as from about 2.5 to about 5, such as from about 3 to about 5. In one particular embodiment, the property enhancing agent comprises tartaric acid.
In one embodiment, the property enhancing agent is present in the polymer composition in an amount sufficient to increase the melt flow rate of the composition by greater than about 10%, such as greater than about 20% in relation to the same composition without the property enhancing agent and at the same cellulose ester polymer levels.
For example, the property enhancing agent can increase the melt flow rate of the polymer composition by greater than about 30%, such as by greater than about 50%, such as by greater than about 100%, such as by greater than about 200%, such as by greater than about 300%, such as by greater than about 400%, such as by greater than about 500%, such as by greater than about 600%, such as by greater than about 700%, such as by greater than about 800%, and generally less than about 2,000%.
The property enhancing agent can lower the intrinsic viscosity of the cellulose ester polymer. For example, the cellulose ester polymer can have an initial intrinsic viscosity of greater than about 1.5, such as greater than about 1.6, and can have a final intrinsic viscosity after being combined with the property enhancing agent of less than about 1.4, such as less than about 1.3, and generally greater than about 1. For example, the intrinsic viscosity of the cellulose ester polymer can be decreased by greater than about 5%, such as greater than about 10%, such as greater than about 15%, such as greater than about 20%, and generally less than about 80%.
In one aspect, the property enhancing agent can be present in the polymer composition in an amount sufficient to increase a reflectance of an article formed from the composition. For example, the property enhancing agent can be present in the composition in an amount sufficient to increase an L* value of an article formed from the polymer composition. The L* value, for instance, can be increased by greater than about 3%, such as greater than about 5%, such as greater than about 8%, such as greater than about 10%. In one aspect, an article formed in accordance with the present disclosure may have a surface that displays an L* value of greater than about 62.
The property enhancing agent can be present in the polymer composition generally in an amount from about 0.01% by weight to about 10% by weight, such as from about 0.05% by weight to about 5% by weight, such as from about 0.08% by weight to about 1% by weight.
The cellulose ester polymer modified in accordance with the present disclosure can contain cellulose diacetate. The cellulose ester polymer can have a degree of substitution, in one aspect, of from about 2.0 to about 2.8.
The cellulose ester polymer can be present in the polymer composition generally in an amount from about 55% to about 95% by weight. One or more plasticizers can be incorporated into the polymer composition generally in an amount from about 5% to about 40% by weight. In various embodiments, the amount of plasticizer can be less than about 25% by weight, such as less than about 23% by weight, such as less than about 20% by weight, such as less than about 18% by weight, such as less than about 16% by weight, such as less than about 14% by weight, such as less than about 12% by weight, such as less than about 10% by weight. In one embodiment, the plasticizer can comprise polyethylene glycol. In another embodiment, the plasticizer can comprise triacetin. In still another embodiment, the plasticizer can comprise a biodegradable polymer, such as polycaprolactone or a polyhydroxyalkanoate, such as a polyhydroxybutyrate.
Other plasticizers that may be incorporated into the polymer composition include tris(clorisopropyl) phosphate, tris(2-chloro-1-methylethyl) phosphate, glycerin, monoacetin, triethyl citrate, acetyl triethyl citrate, a phthalate, an adipate, polyethylene glycol, diacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributyl-o-acetyl citrate, dibutyl tartrate, ethyl o-benzoylbenzoate, n-ethyltoluenesulfonamide, o-cresyl p-toluenesulfonate, aromatic diol, a substituted aromatic diol, an aromatic ether, tripropionin, tribenzoin, glycerin esters, glycerol tribenzoate, glycerol acetate benzoate, a polyethylene glycol ester, a polyethylene glycol diester, di-2-ethylhexyl polyethylene glycol ester, a glycerol ester, diethylene glycol, polypropylene glycol, a polyglycoldiglycidyl ether, dimethyl sulfoxide, N-methyl pyrollidinone, propylene carbonate, a C1-C20 dicarboxylic acid ester, di-butyl maleate, di-octyl maleate, resorcinol monoacetate, catechol, catechol esters, phenols, epoxidized soy bean oil, castor oil, linseed oil, epoxidized linseed oil, difunctional glycidyl ether based on polyethylene glycol, an alkyl lactone, a phospholipid, 2-phenoxyethanol, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanol amine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, glyceryl tribenzoate, neopentyl dibenzoate, triethylene glycol dibenzoate, trimethylolethane tribenzoate, butylated hydroxytoluene, butylated hydroxyanisol, sorbitol, xylitol, ethylene diamine, piperidine, piperazine, hexamethylene diamine, triazine, triazole, pyrrole, and mixtures thereof.
The cellulose ester polymer composition may also contain various other additives and components. For instance, the composition can further comprise an antioxidant, a stabilizer, an organic acid, an oil, filler particles, glass fibers, a bio-based polymer other than the cellulose ester, a biodegradable enhancer, a foaming agent, or mixtures thereof. The composition can also contain a mineral filler, such as talc, calcium carbonate, a metal oxide, mica, or mixtures thereof. The polymer composition can also contain a coloring agent which can be a dye, a pigment, or mixtures thereof.
In one embodiment, the polymer composition is combined in a heated extruder or mixer and then extruded into strands that can then be cut into pellets. The pellets can then be used to produce various different molded articles. As an example, the polymer composition can be used to produce beverage holders, drinking straws, hot beverage pods, interior automotive parts, consumer appliance parts, medical device components, packaging and the like.
Other features and aspects of the present disclosure are discussed in greater detail below.
A full and enabling disclosure of the present disclosure is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.
It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.
In general, the present disclosure is directed to polymer compositions containing a polysaccharide ester polymer, such as a cellulose ester polymer. The cellulose ester polymer is combined with a property enhancing agent that improves at least one physical property of the polymer composition or of articles molded from the composition. In one aspect, for instance, the property enhancing additive is incorporated into the composition in an amount sufficient to improve the melt processing characteristics of the composition. Alternatively, the property enhancing agent can be incorporated into the composition in an amount sufficient to improve at least one surface property of molded articles made from the composition. For example, the property enhancing agent can increase reflectivity, increase gloss characteristics, increase surface smoothness, and/or decrease surface imperfections.
The polymer composition of the present disclosure can be formulated to be sustainable and biodegradable, and thus environmentally friendly. The polymer composition can be used to form all different types of products using any suitable molding technique, such as extrusion, injection molding, rotational molding, and the like. The polymer composition of the present disclosure is particularly well formulated for use in any of the processes described above.
In general, the polymer composition of the present disclosure contains a cellulose ester polymer, such as a cellulose acetate polymer, in combination with a property enhancing agent and optionally a plasticizer. Although unknown, it is believed that the property enhancing agent is believed to react with the cellulose ester polymer and reduce the chain length of the polymer. In this manner, the property enhancing agent can lower the overall molecular weight of the cellulose ester polymer as can be measured through intrinsic viscosity. For example, the property enhancing agent can be added to the cellulose ester polymer in an amount sufficient to lower the intrinsic viscosity by greater than about 5%, such as by greater than about 10%, such as by greater than about 15%, such as by greater than about 20%, such as by greater than about 25%. The intrinsic viscosity is generally lowered by no more than about 80%, such as by no more than about 50%, such as by no more than about 30%, such as by no more than about 25%. Intrinsic viscosity may be measured by forming a solution of 0.20 g/dL cellulose ester in 98/2 wt/wt acetone/water and measuring the flow times of the solution and the solvent at 30° C. in a #25 Cannon-Ubbelohde viscometer. Then, the modified Baker-Philippoff equation may be used to determine intrinsic viscosity (“IV”), which for this solvent system is Equation 1.
t1=the average flow time of solution (having cellulose ester) in seconds, t2=the average flow times of solvent in seconds, k=solvent constant (10 for 98/2 wt/wt acetone/water), and c=concentration (0.200 g/dL).
By combining a property enhancing agent with a cellulose ester polymer in accordance with the present disclosure, relatively high molecular weight cellulose ester polymers can be more easily melt processed into molded articles. In the past, such cellulose ester polymers were combined with copious amounts of a plasticizer in order to increase the melt flow rate of the composition sufficient for use in molding processes, such as injection molding. Although the use of a plasticizer has provided great benefits and advantages, high plasticizer amounts can cause adverse effects on the material properties, such as reduced modulus and stiffness. In addition, the heat deflection temperature can be negatively impacted. Through the process of the present disclosure, the use of plasticizers may be reduced or eliminated if desired. In other applications, however, conventional amounts of plasticizer may be used and benefits still may be obtained related to the melt flow properties of the composition, related to the physical properties of molded articles formed from the composition, or related to the overall appearance of the molded articles.
Instead of or in addition to improving the melt flow properties of the polymer composition, the property enhancing agent can be combined with a cellulose ester polymer in an amount sufficient to improve at least one physical property of molded articles made from the composition. For example, molded articles made from the present disclosure can have increased reflectance and/or gloss characteristics.
In general, any suitable cellulose ester polymer can be incorporated into the polymer composition of the present disclosure. In one aspect, the cellulose ester polymer is a cellulose acetate.
Cellulose acetate may be formed by esterifying cellulose after activating the cellulose with acetic acid. The cellulose may be obtained from numerous types of cellulosic material, including but not limited to plant derived biomass, corn stover, sugar cane stalk, bagasse and cane residues, rice and wheat straw, agricultural grasses, hardwood, hardwood pulp, softwood, softwood pulp, cotton linters, switchgrass, bagasse, herbs, recycled paper, waste paper, wood chips, pulp and paper wastes, waste wood, thinned wood, willow, poplar, perennial grasses (e.g., grasses of the Miscanthus family), bacterial cellulose, seed hulls (e.g., soy beans), cornstalk, chaff, and other forms of wood, bamboo, soyhull, bast fibers, such as kenaf, hemp, jute and flax, agricultural residual products, agricultural wastes, excretions of livestock, microbial, algal cellulose, seaweed and all other materials proximately or ultimately derived from plants. Such cellulosic raw materials are preferably processed in pellet, chip, clip, sheet, attritioned fiber, powder form, or other form rendering them suitable for further purification.
Cellulose esters suitable for use in producing the composition of the present disclosure may, in some embodiments, have ester substituents that include, but are not limited to, C1-C20 aliphatic esters (e.g., acetate, propionate, or butyrate), functional C1-C20 aliphatic esters (e.g., succinate, glutarate, maleate) aromatic esters (e.g., benzoate or phthalate), substituted aromatic esters, and the like, any derivative thereof, and any combination thereof.
The cellulose acetate used in the composition may be cellulose diacetate or cellulose triacetate. In one embodiment, the cellulose acetate comprises primarily cellulose diacetate. For example, the cellulose acetate can contain less than 1% by weight cellulose triacetate, such as less than about 0.5% by weight cellulose triacetate. Cellulose diacetate can make up greater than 90% by weight of the cellulose acetate, such as greater than about 95% by weight, such as greater than about 98% by weight, such as greater than about 99% by weight of the cellulose acetate.
The cellulose acetate can have a degree of substitution of from about 2.0 to about 2.7, such as from about 2.1 to about 2.5 including all increments of 0.1 therebetween. In one embodiment, the cellulose acetate can have a degree of substitution of from about 2.15 to about 2.45.
In general, the cellulose acetate can have a molecular weight of greater than about 10,000, such as greater than about 20,000, such as greater than about 30,000, such as greater than about 40,000, such as greater than about 50,000. The molecular weight of the cellulose acetate is generally less than about 300,000, such as less than about 250,000, such as less than about 200,000, such as less than about 150,000, such as less than about 100,000, such as less than about 90,000, such as less than about 70,000, such as less than about 50,000. The molecular weights identified above refer to the number average molecular weight. Molecular weight can be determined using gel permeation chromatography using a polystyrene equivalent or standard.
The cellulose ester polymer or cellulose acetate can have an initial intrinsic viscosity (prior to being combined with the property enhancing agent) of generally of from about 0.5 dL/g to about 2 dL/g, including all increments of 0.1 dL/g therebetween. Cellulose ester polymers having an intrinsic viscosity of greater than about 1.5 dL/g, such as greater than about 1.55 dL/g, such as greater than about 1.6 dL/g, such as greater than about 1.65 dL/g, such as greater than about 1.7 dL/g, and generally less than about 2 dL/g are particularly well suited for use in compositions made according to the present disclosure. It should be understood, however, that cellulose ester polymers having a lower intrinsic viscosity may also be useful in many applications. For example, in other embodiments, the intrinsic viscosity of the cellulose ester polymer prior to being combined with the property enhancing agent can be less than about 1.4 dL/g, such as less than about 1.3 dL/g, and generally greater than about 0.6 dL/g, such as greater than about 0.8 dL/g, such as greater than about 1 dL/g, such as greater than about 1.2 dL/g.
After being combined with the property enhancing agent, the intrinsic viscosity of the cellulose ester polymer can be greater than about 0.3 dL/g, such as greater than about 0.8 dL/g, such as greater than about 1 dL/g, such as greater than about 1.2 dL/g, such as greater than about 1.4 dL/g, such as greater than about 1.5 dL/g. The intrinsic viscosity is generally less than about 2 dL/g, such as less than about 1.8 dL/g, such as less than about 1.7 dL/g, such as less than about 1.65 dL/g.
In general, the cellulose ester polymer is present in the polymer composition in an amount from about 15% by weight to about 95% by weight, including all increments of 1% by weight therebetween. The cellulose acetate is generally present in the polymer composition in an amount greater than about 15% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 35% by weight, such as in an amount greater than about 45% by weight, such as in an amount greater than about 55% by weight, such as in an amount greater than about 65% by weight, such as in an amount greater than about 75% by weight, such as in an amount greater than about 85% by weight. The cellulose acetate is generally present in the polymer composition in an amount less than about 90% by weight, such as in an amount less than about 85% by weight, such as in an amount less than about 75% by weight, such as in an amount less than about 70% by weight, such as in an amount less than about 65% by weight.
In accordance with the present disclosure, the polysaccharide ester polymer or cellulose ester polymer is combined with at least one property enhancing agent. The property enhancing agent is combined with the cellulose ester polymer in a manner that improves at least one property of the composition or of a polymer article made from the composition. For example, the property enhancing agent can improve the melt flow properties of the composition and is believed to alter the molecular weight distribution of the cellulose ester polymer that makes the composition better suited to producing molded articles. In addition, the property enhancing agent can produce molded articles with more uniform properties and enhanced surface characteristics. For instance, the property enhancing agent can increase the reflectivity of articles made from the composition, increase surface smoothness, and/or decrease surface irregularities.
In one aspect, the property enhancing agent is an acidic species, such as an organic acid. The property enhancing agent, for instance, may have a Pka value of from about 2 to about 6, including all increments of 0.1 therebetween. For instance, the Pka value can be greater than about 2.3, such as greater than about 2.5, such as greater than about 2.7, such as greater than about 2.85, and generally less than about 5.4, such as less than about 5.2, such as less than about 4.9, such as less than about 4.8.
In one embodiment, the property enhancing agent can be a diprotic acid. Diprotic acids have multiple Pka values. The diprotic acid, for instance, can have a first Pka value of from about 2 to about 3.5 and a second Pka value of from about 3.5 to about 5. For example, the first Pka value can be greater than about 2.5, such as greater than about 2.6, such as greater than about 2.7, such as greater than about 2.8, and generally less than about 3.4, such as less than about 3.3, such as less than about 3.2, such as less than about 3.1. The second Pka value, on the other hand, can be greater than about 3.7, such as greater than about 3.9, such as greater than about 4, such as greater than about 4.1, such as greater than about 4.2, and generally less than about 4.9, such as less than about 4.7, such as less than about 4.5, such as less than about 4.4.
Although it is believed that various different property enhancing agents may be incorporated into the polymer composition as described above, in one embodiment, the property enhancing agent is tartaric acid. The tartaric acid can be L-tartaric acid, DL-tartaric acid, meso-tartaric acid, or mixtures thereof. In one particular embodiment, L-tartaric acid is incorporated into the composition.
The amount of property enhancing agent incorporated into the polymer composition can depend upon various factors including the molecular weight of the polysaccharide ester polymer, the amount and type of plasticizer that may be incorporated into the composition, and the desired resulting melt flow rate of the composition. In general, one or more property enhancing agents can be present in the composition in an amount from about 0.01% to about 10% by weight, including all increments of 0.01% by weight therebetween. For example, one or more property enhancing agents can be present in the composition in an amount greater than about 0.05% by weight, such as in an amount greater than about 0.08% by weight, such as in an amount greater than about 0.1% by weight, such as in an amount greater than about 0.3% by weight, such as in an amount greater than about 0.5% by weight, such as in an amount greater than about 0.8% by weight, such as in an amount greater than about 1% by weight, such as in an amount greater than about 1.2% by weight, such as in an amount greater than about 1.5% by weight, such as in an amount greater than about 2% by weight, such as in an amount greater than about 2.3% by weight. One or more property enhancing agents are generally present in the composition in an amount less than about 8% by weight, such as in an amount less than about 6% by weight, such as in an amount less than about 5% by weight, such as in an amount less than about 4% by weight, such as in an amount less than about 3% by weight, such as in an amount less than about 2% by weight, such as in an amount less than about 1% by weight.
The polymer composition of the present disclosure can also optionally include one or more plasticizers. Plasticizers particularly well suited for use in the polymer composition include triacetin, monoacetin, diacetin, and mixtures thereof. Other suitable plasticizers include tris(clorisopropyl) phosphate, tris(2-chloro-1-methylethyl) phosphate, triethyl citrate, acetyl triethyl citrate, glycerin, or mixtures thereof. In an alternative embodiment, the plasticizer can be a polyethylene glycol. In still another embodiment, the plasticizer can be a polycaprolactone or a polyhydroxyalkanoate, such as a polyhydroxybutyrate.
Other examples of plasticizers include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, acetyl tributyl citrate, tributyl-o-acetyl citrate, dibutyl tartrate, ethyl o-benzoylbenzoate, n-ethyltoluenesulfonamide, o-cresyl p-toluenesulfonate, aromatic diol, substituted aromatic diols, aromatic ethers, tripropionin, tribenzoin, glycerin, glycerin esters, glycerol tribenzoate, glycerol acetate benzoate, polyethylene glycol esters, polyethylene glycol diesters, di-2-ethylhexyl polyethylene glycol ester, glycerol esters, diethylene glycol, polypropylene glycol, polyglycoldiglycidyl ethers, dimethyl sulfoxide, N-methyl pyrollidinone, propylene carbonate, C1-C20 dicarboxylic acid esters, dimethyl adipate (and other dialkyl esters), di-butyl maleate, di-octyl maleate, resorcinol monoacetate, catechol, catechol esters, phenols, epoxidized soy bean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, difunctional glycidyl ether based on polyethylene glycol, alkyl lactones (e.g., .gamma.-valerolactone), alkylphosphate esters, aryl phosphate esters, phospholipids, aromas (including some described herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy hydroxy acetophenone (acetovanillone), vanillin, and ethylvanillin), 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g., ethylene glycol diacetate), propylene glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanol amine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, glyceryl tribenzoate, neopentyl dibenzoate, triethylene glycol dibenzoate, trimethylolethane tribenzoate, butylated hydroxytoluene, butylated hydroxyanisol, sorbitol, xylitol, ethylene diamine, piperidine, piperazine, hexamethylene diamine, triazine, triazole, pyrrole, and the like, any derivative thereof, and any combination thereof.
In one aspect, a carbonate ester may serve as a plasticizer. Exemplary carbonate esters may include, but are not limited to, propylene carbonate, butylene carbonate, diphenyl carbonate, phenyl methyl carbonate, dicresyl carbonate, glycerin carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, isopropylphenyl 2-ethylhexyl carbonate, phenyl 2-ethylhexyl carbonate, isopropylphenyl isodecyl carbonate, isopropylphenyl tridecyl carbonate, phenyl tridecyl carbonate, and the like, and any combination thereof.
In still another aspect, the plasticizer can be a polyol benzoate. Exemplary polyol benzoates may include, but are not limited to, glyceryl tribenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, sucrose benzoate, polyethylene glycol dibenzoate, neopentylglycol dibenzoate, trimethylolpropane tribenzoate, trimethylolethane tribenzoate, pentaerythritol tetrabenzoate, sucrose benzoate (with a degree of substitution of 1-8), and combinations thereof. In some instances, tribenzoates like glyceryl tribenzoate may be preferred. In some instances, polyol benzoates may be solids at 25° C. and a water solubility of less than 0.05 g/100 mL at 25° C.
The plasticizer can also be bio-based. For example, using a bio-based plasticizer can render the polymer composition well suited for contact with food items. Bio-based plasticizers particularly well suited for use in the composition of the present disclosure include an alkyl ketal ester, a non-petroleum hydrocarbon ester, a bio-based polymer or oligomer, such as polycaprolactone, having a number average molecular weight of 1000 g/mol or less, or mixtures thereof. Another bio-based polymer or oligomer that may serve as a plasticizer is a polyhydroxyalkanoate, such as a polyhydroxybutyrate having a number average molecular weight of about 10,000 or less, such as about 8,000 or less, such as about 6,000 or less, and generally greater than about 1,000, such as greater than about 3,000, such as greater than about 5,000 (g/mol).
In one aspect, the bio-based plasticizer is an alkyl ketal ester having a chemical structure corresponding to Structure I as provided below:
wherein a is from 0 to 12; b is 0 or 1; each R1 is independently hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group; each R2, R3, and R4 are independently methylene, alkylmethylene, or dialkylmethylene, x is at least 1, y is 0 or a positive number and x+y is at least 2; R6 is a hydrocarbyl group or a substituted hydrocarbyl group and each Z is independently —O—, —NH— or —NR— where R is a hydrocarbyl group or a substituted hydrocarbyl group.
The plasticizer identified above corresponds to a reaction product of a polyol, aminoalcohol or polyamine and certain 1,2- and/or 1,3-alkanediol ketal of an oxocarboxylate esters. 1,2- and 1,3-alkanediols ketals of oxocarboxylate esters are referred to herein as “alkyl ketal esters”. Up to one mole of alkyl ketal ester can be reacted per equivalent of hydroxyl groups or amino groups provided by the polyol, aminoalcohol or polyamine. The polyol, aminoalcohol or polyamine is most preferably difunctional, but polyols, aminoalcohols and polyamines having more than two hydroxyl and/or amino groups can be used.
The values of x and y in structure I will depend on the number of hydroxyl groups or amino groups on the polyol, aminoalcohol or polyamine, the number of moles of the alkyl ketal ester per mole of the polyol, aminoalcohol or polyamine, and the extent to which the reaction is taken towards completion. Higher amounts of the alkyl ketal ester favor lower values for y and higher values of x.
In structure I, y is specifically from 0 to 2 and x is specifically at least 2. All a in structure I are specifically 2 to 12, more specifically, 2 to 10, more specifically, 2 to 8, more specifically, 2 to 6, more specifically, 2 to 4, and more specifically, 2. All R1 are specifically an alkyl group, specifically methyl. In some embodiments of structure I, all Z are —O—, y is 0 and x is 2; these products correspond to a reaction of two moles of an alkyl ketal ester and one mole of a diol. In some other embodiments, all Z are —O—, y is 1 and x is 1; these products correspond to the reaction of one mole of the alkyl ketal ester and one mole of a diol.
In one embodiment, all b are 0. In another embodiment, all b are 1.
Some specific compounds according to structure I include those having the structure:
or the structure
or the structure
particularly in which R6 is —(CH2)—m wherein m is from 2 to 18, especially 2, 3, 4 or 6. In one specific embodiment, R6 corresponds to the residue, after removal of hydroxyl groups, of 1,4-butane diol resulting in the structure (Ia)
In another specific embodiment, R6 corresponds to the residue, after
removal of hydroxyl groups, of diethylene glycol resulting in structure (Ib)
In another specific embodiment, R6 corresponds to the residue, after removal of hydroxyl groups, of 2-methyl. 1-3 propane diol resulting in structure (Ic)
Compounds according to structure I can be prepared in a transesterification or ester-aminolysis reaction between the corresponding polyol, aminoalcohol or polyamine and the corresponding alkyl ketal ester. Alternatively, compounds according to structure I can be prepared by reacting an oxocarboxylic acid with the polyol, aminoalcohol or polyamine to form an ester or amide, and then ketalizing the resulting product with a 1,2- or 1,3-alkane diol such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl, 1-3 propane diol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,3-hexanediol, and the like.
Alkyl ketal ester plasticizers are particularly well suited for use in conjunction with one or more other plasticizers. For example, in one aspect, an alkyl ketal ester plasticizer can be combined with a benzoate ester. The weight ratio between the two plasticizers can vary such as from about 1:10 to about 10:1, such as from about 1:4 to about 4:1.
Another bio-based plasticizer that may be incorporated into the polymer composition of the present disclosure is a non-petroleum hydrocarbon ester. For example, one example of a non-petroleum hydrocarbon ester is sold under the tradename HALLGREEN by the Hall Star Company of Chicago, Ill. Non-petroleum hydrocarbon ester plasticizers, for instance, can contain greater than about 50% by weight, such as greater than about 70% by weight, such as greater than about 99% by weight of bio-based content. The esters, for instance, can be derived primarily from agricultural, forestry, or marine materials and thus are biodegradable. In one aspect, the non-petroleum hydrocarbon ester plasticizer has a specific gravity at 25° C. of about 1.16 or greater, such as about 1.165 or greater, such as about 1.17 or greater, such as about 1.74 or greater, and generally about 1.19 or less, such as about 1.185 or less, such as about 1.18 or less, such as about 1.78 or less. The non-petroleum hydrocarbon ester plasticizer can have an acid value of from about 0.5 mgKOH/g to about 0.6 mgKOH/g, such as from about 0.53 mgKOH/g to about 0.57 mgKOH/g.
In one aspect, the plasticizer is phthalate-free. In fact, the polymer composition can be formulated to be phthalate-free. For instance, phthalates can be present in the polymer composition in an amount of about 0.5% or less, such as in an amount of about 0.1% or less.
In general, one or more plasticizers can be present in the polymer composition in an amount from about 3% to about 40% by weight, such as in an amount from about 8% to about 35% by weight. In the past, however, it was believed that relatively high amounts of plasticizer were needed in order to produce a cellulose acetate composition capable of being melt processed. However, the amount of plasticizer can be significantly and dramatically reduced without compromising the melt processing characteristics of the composition. For example, in one aspect, one or more plasticizers can be present in the polymer composition in an amount of about 19% or less, such as in an amount of about 17% or less, such as in an amount of about 15% or less, such as in an amount of about 13% or less, such as in an amount of about 10% or less. One or more plasticizers are generally present in an amount from about 3% or greater, such as in an amount of about 5% or greater.
The cellulose acetate can be present in relation to the plasticizer such that the weight ratio between the cellulose acetate and the one or more plasticizers is from about 60:40 to about 95:5, such as from about 70:30 to about 90:10.
As described above, the amount of the property enhancing agent that is incorporated into the polymer composition can be used to control the melt flow rate of the composition. For example, in one embodiment, one or more property enhancing agents can be incorporated into the composition in order to increase the melt flow rate by at least about 10%, such as by at least about 20%, such as by at least about 30%, such as by at least about 50%, such as by at least about 100%, such as by at least about 200%, such as by at least about 300%, such as by at least about 400%, such as by at least about 500%, such as by at least about 600%, such as by at least about 700%, such as by at least about 800%, and generally less than about 2,000%. Unless otherwise indicated, melt flow rate as used herein is determined at 210° C. and at a load of 2.16 kg according to ASTM Test D1238-13. Melt flow rates can also be determined at 190° C., at 200° C., at 220° C., at 230° C., and at 240° C. and at a load of 2.16 kg.
The melt flow rate of the polymer composition of the present disclosure can be from about 2 g/10 min to about 70 g/10 min. In one aspect, the melt flow rate is greater than about 7 g/10 min, such as greater than about 10 g/10 min, such as greater than about 12 g/10 min, such as greater than about 15 g/10 min, such as greater than about 18 g/10 min, such as greater than about 20 g/10 min, such as greater than about 22 g/10 min, and generally less than about 50 g/10 min, such as less than about 40 g/10 min, such as less than about 30 g/10 min.
In addition to improving the melt processing characteristics of the cellulose ester polymer composition, the property enhancing agent of the present disclosure can also improve one or more physical properties of molded articles made from the composition. For example, the property enhancing agent can be present in the polymer composition in an amount sufficient to increase surface reflectance.
In one aspect, the surface characteristics of molded articles made according to the present disclosure can be measured using the CIELAB color scale. Color and reflectivity measurements are performed using a DataColor 600 Spectrophotometer utilizing an integrating sphere with measurements made using the specular excluded mode. Similar results would be obtained using 45/0 or 0/45 geometry instruments as they also exclude the gloss component from the color measurement. Color coordinates are calculated according to ASTM D2244-11 under illuminant D65, 10° observer, using CIELAB units. This method defines three color coordinates L*, a*, and b*, which correspond to three characteristics of a perceived color based on the opponent theory of color perception and are defined as follows:
In one aspect, an improvement in surface properties, such as reflectivity, can be ascertained by an increase in luminosity (L*). For instance, the property enhancing agent can be combined with a cellulose ester polymer such that the resulting composition has an L* value that is greater than the L* value of the same composition without the property enhancing agent and with the cellulose ester polymer in the same amount. For example, the L* value can increase by greater than about 0.1%, such as greater than about 0.3%, such as greater than about 0.5%, such as greater than about 0.8%, such as greater than about 1%. It should be understood that even the slightest increase in the L* value is dramatic and unexpected. Molded articles made according to the present disclosure, for instance, can have an L* value of greater than about 62, such as greater than about 62.5, such as greater than about 62.9, such as greater than about 63, such as greater than about 63.2, such as greater than about 63.5, such as greater than about 63.7. The L* value is generally less than about 100, such as less than about 80.
In addition to a polysaccharide ester polymer, one or more property enhancing agents, and optionally one or more plasticizers, the polymer composition of the present disclosure can contain various other additives and ingredients. For example, cellulose acetate, the one or more plasticizers and the one or more property enhancing agents can also be combined with one or more bio-based polymers that are different than the cellulose acetate and the one or more plasticizers. As used herein, a “bio-based” polymer or plasticizer refers to a polymer, oligomer, or compound produced from at least partially renewable biomass sources, such as produced from plant matter or food waste. For example, a bio-based polymer can be a polymer produced from greater than 30% renewable resources, such as greater than about 40% renewable resources, such as greater than about 50% renewable resources, such as greater than about 60% renewable resources, such as greater than about 70% renewable resources, such as greater than about 80% renewable resources, such as greater than about 90% renewable resources. Bio-based polymers are to be distinguished from polymers derived from fossil resources such as petroleum. Bio-based polymers can be bio-derived meaning that the polymer originates from a biological source or produced via a biological reaction, such as through fermentation or other microorganism process. Although a cellulose ester polymer can be considered a bio-based polymer, the term herein refers to other bio-based substances that can be combined with cellulose ester polymers. The bio-based polymer can also be biodegradable.
In one aspect, the bio-based polymer can be a polyester polymer, such as an aliphatic polyester. Particular bio-based polymers that may be incorporated into the polymer composition include polyhydroxyalkanoates, polylactic acid, polycaprolactone, or mixtures thereof.
In one aspect, the at least one bio-based polymer combined with the cellulose acetate is a polyhydroxyalkanoate. The polyhydroxyalkanoate can be a homopolymer or a copolymer. Polyhydroxyalkanoates, also known as “PHAs”, are linear polyesters produced in nature by bacterial fermentation of sugar or lipids. More than 100 different monomers can be combined within this family to give materials with extremely different properties. Generally, they can be either thermoplastic or elastomeric materials, with melting-points ranging from 40 to 180° C. The most common type of PHAs is PHB (poly-beta-hydroxybutyrate). Poly(3-hydroxybutyrate) (PHB) is a type of a naturally occurring thermoplastic polymer currently produced microbially inside of the cell wall of a number of wild bacteria species or genetically modified bacteria or yeasts, etc. It is biodegradable and does not present environmental issues post disposal, i.e., articles made from PHB can be composted.
The one or monomers used to produce a PHA can significantly impact the physical properties of the polymer. For example, PHAs can be produced that are crystalline, semi-crystalline, or completely amorphous. For example, poly-4-hydroxybutyrate homopolymer can be completely amorphous with a glass transition temperature of less than about −30° C. and with no noticeable melting point temperature. Polyhydroxybutyrate-valerate copolymers also can be formulated to be semi-crystalline to amorphous having low stiffness characteristics.
Examples of monomer units that can be incorporated in PHAs include 2-hydroxybutyrate, glycolic acid, 3-hydroxybutyrate (hereinafter referred to as 3HB), 3-hydroxypropionate (hereinafter referred to as 3HP), 3-hydroxyvalerate (hereinafter referred to as 3HV), 3-hydroxyhexanoate (hereinafter referred to as 3HH), 3-hydroxyheptanoate (hereinafter referred to as 3HH), 3-hydroxyoctanoate (hereinafter referred to as 3HO), 3-hydroxynonanoate (hereinafter referred to as 3HN), 3-hydroxydecanoate (hereinafter referred to as 3HD), 3-hydroxydodecanoate (hereinafter referred to as 3HDd), 4-hydroxybutyrate (hereinafter referred to as 4HB), 4-hydroxyvalerate (hereinafter referred to as 4HV), 5-hydroxyvalerate (hereinafter referred to as 5HV), and 6-hydroxyhexanoate (hereinafter referred to as 6HH). 3-hydroxyacid monomers incorporated into PHAs are the (D) or (R) 3-hydroxyacid isomer with the exception of 3HP which does not have a chiral center.
In some embodiments, the PHA in the methods described herein is a homopolymer (where all monomer units are the same). Examples of PHA homopolymers include poly 3-hydroxyalkanoates (e.g., poly 3-hydroxypropionate (hereinafter referred to as P3HP)), poly 3-hydroxybutyrate (hereinafter referred to as P3HB) and poly 3-hydroxyvalerate, poly 4-hydroxyalkanoates (e.g., poly 4-hydroxybutyrate (hereinafter referred to as P4HB)), poly 4-hydroxyvalerate (hereinafter referred to as P4HV)) or poly 5-hydroxyalkanoates (e.g., poly 5-hydroxyvalerate (hereinafter referred to as P5HV)).
In certain embodiments, the PHA can be a copolymer (containing two or more different monomer units) in which the different monomers are randomly distributed in the polymer chain. Examples of PHA copolymers include poly 3-hydroxybutyrate-co-3-hydroxypropionate (hereinafter referred to as PHB3HP), poly 3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter referred to as P3HB4HB), poly 3-hydroxybutyrate-co-4-hydroxyvalerate (hereinafter referred to as PHB4HV), poly 3-hydroxybutyrate-co-3-hydroxyvalerate (hereinafter referred to as PHB3HV), poly 3-hydroxybutyrate-co-3-hydroxyhexanoate (hereinafter referred to as PHB3HH) and poly 3-hydroxybutyrate-co-5-hydroxyvalerate (hereinafter referred to as PHB5HV).
An example of a PHA having 4 different monomer units would be PHB-co-3HH-co-3HO-co-3HD or PHB-co-3-HO-co-3HD-co-3HDd. Typically where the PHB3HX has 3 or more monomer units, the 3HB monomer is at least 70% by weight of the total monomers, such as greater than 90% by weight of the total monomers.
When present, one or more PHAs can be contained in the polymer composition in an amount of about 2% or greater, such as about 3% or greater, such as about 5% or greater, such as about 7% or greater, such as about 10% or greater, such as about 12% or greater, such as about 15% or greater, such as about 18% or greater. One or more PHAs are generally present in the polymer composition in an amount of about 30% or less, such as in an amount of about 25% or less, such as in an amount of about 20% or less, such as in an amount of about 15% or less.
In addition to one or more PHAs, the polymer composition can contain various other bio-based polymers, such as a polylactic acid or a polycaprolactone. Polylactic acid also known as “PLAs” are well suited for combining with one or more PHAs. Polylactic acid polymers are generally stiffer and more rigid than PHAs and thus can be added to the polymer composition for further refining the properties of the overall formulation.
Polylactic acid may generally be derived from monomer units of any isomer of lactic acid, such as levorotory-lactic acid (“L-lactic acid”), dextrorotatory-lactic acid (“D-lactic acid”), meso-lactic acid, or mixtures thereof. Monomer units may also be formed from anhydrides of any isomer of lactic acid, including L-lactide, D-lactide, meso-lactide, or mixtures thereof. Cyclic dimers of such lactic acids and/or lactides may also be employed. Any known polymerization method, such as polycondensation or ring-opening polymerization, may be used to polymerize lactic acid. A small amount of a chain-extending agent (e.g., a diisocyanate compound, an epoxy compound or an acid anhydride) may also be employed. The polylactic acid may be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acid and monomer units derived from D-lactic acid. Although not required, the content of one of the monomer units derived from L-lactic acid and the monomer units derived from D-lactic acid is preferably about 85 mole % or more, in some embodiments about 90 mole % or more, and in some embodiments, about 95 mole % or more. Multiple polylactic acids, each having a different ratio between the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid, may be blended at an arbitrary percentage.
In one particular embodiment, the polylactic acid has the following general structure:
The polylactic acid typically has a number average molecular weight (“Mn”) ranging from about 40,000 to about 160,000 grams per mole, in some embodiments from about 50,000 to about 140,000 grams per mole, and in some embodiments, from about 80,000 to about 120,000 grams per mole. Likewise, the polymer also typically has a weight average molecular weight (“Mw”) ranging from about 80,000 to about 200,000 grams per mole, in some embodiments from about 100,000 to about 180,000 grams per mole, and in some embodiments, from about 110,000 to about 160,000 grams per mole. The ratio of the weight average molecular weight to the number average molecular weight (“Mw/Mn”), i.e., the “polydispersity index”, is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments, from about 1.2 to about 1.8. The weight and number average molecular weights may be determined by methods known to those skilled in the art.
Polylactic acid can be present in the polymer composition in an amount of about 1% or greater, such as in an amount of about 3% or greater, such as in an amount of about 5% or greater, and generally in an amount of about 20% or less, such as in an amount of about 15% or less, such as in an amount of about 10% or less, such as in an amount of about 8% or less.
As described above, another bio-based polymer that may be combined with cellulose acetate alone or in conjunction with other bio-based polymers is polycaprolactone having a molecular weight higher than a polycaprolactone plasticizer. Polycaprolactone, similar to PHAs, can be formulated to have a relatively low glass transition temperature. The glass transition temperature, for instance, can be less than about 10° C., such as less than about −5° C., such as less than about −20° C., and generally greater than about −60° C. The polymers can be produced so as to be amorphous or semi-crystalline. The crystallinity of the polymers can be less than about 50%, such as less than about 25%.
Polycaprolactones can be made having a number average molecular weight of generally greater than about 5,000, such as greater than about 8,000, and generally less than about 15,000, such as less than about 12,000.
Polycaprolactones can be contained in the polymer composition in an amount of about 2% or greater, such as about 3% or greater, such as about 5% or greater, such as about 7% or greater, such as about 10% or greater, such as about 12% or greater, such as about 15% or greater, such as about 18% or greater. Polycaprolactones are generally present in the polymer composition in an amount of about 30% or less, such as in an amount of about 25% or less, such as in an amount of about 20% or less, such as in an amount of about 15% or less.
Other bio-based polymers that may be incorporated into the polymer composition include polybutylene succinate, polybutylene adipate terephthalate, a plasticized starch, other starch-based polymers, and the like. In addition, the bio-based polymer can be a polyolefin or polyester polymer made from renewable resources. For example, such polymers include bio-based polyethylene, bio-based polybutylene terephthalate, and the like.
In one aspect, an acid scavenger can also be present in the polymer composition. The acid scavenger can be a carbonate, an oxide, a hydroxide, an amine, or mixtures thereof. Examples of acid scavengers include zinc oxide, magnesium oxide, magnesium hydroxide, aluminum sodium carbonate, an aluminum silicate, a hydrotalcite, or mixtures thereof. One or more acid scavengers can be present in the polymer composition generally in an amount greater than about 0.1% by weight, such as greater than about 0.5% by weight, such as greater than about 1% by weight, and generally less than about 2.5% by weight, such as less than about 2% by weight, such as less than about 1.5% by weight.
The polymer composition may also contain antioxidants, pigments, lubricants, softening agents, antibacterial agents, antifungal agents, preservatives, flame retardants, and combinations thereof. Each of the above additives can generally be present in the polymer composition in an amount of about 5% or less, such as in an amount of about 2% or less, and generally in an amount of about 0.1% or greater, such as in an amount of about 0.3% or greater.
Flame retardants suitable for use in conjunction with a cellulose ester plastic described herein may, in some embodiments, include, but are not limited to, silica, metal oxides, phosphates, catechol phosphates, resorcinol phosphates, borates, inorganic hydrates, aromatic polyhalides, and the like, and any combination thereof.
Antifungal and/or antibacterial agents suitable for use in conjunction with a cellulose ester plastic described herein may, in some embodiments, include, but are not limited to, polyene antifungals (e.g., natamycin, rimocidin, filipin, nystatin, amphotericin B, candicin, and hamycin), imidazole antifungals such as miconazole (available as MICATIN® from WellSpring Pharmaceutical Corporation), ketoconazole (commercially available as NIZORAL® from McNeil consumer Healthcare), clotrimazole (commercially available as LOTRAMIN® and LOTRAMIN AF® available from Merck and CANESTEN® available from Bayer), econazole, omoconazole, bifonazole, butoconazole, fenticonazole, isoconazole, oxiconazole, sertaconazole (commercially available as ERTACZO® from OrthoDematologics), sulconazole, and tioconazole; triazole antifungals such as fluconazole, itraconazole, isavuconazole, ravuconazole, posaconazole, voriconazole, terconazole, and albaconazole), thiazole antifungals (e.g., abafungin), allylamine antifungals (e.g., terbinafine (commercially available as LAMISIL® from Novartis Consumer Health, Inc.), naftifine (commercially available as NAFTIN® available from Merz Pharmaceuticals), and butenafine (commercially available as LOTRAMIN ULTRA® from Merck), echinocandin antifungals (e.g., anidulafungin, caspofungin, and micafungin), polygodial, benzoic acid, ciclopirox, tolnaftate (e.g., commercially available as TINACTIN® from MDS Consumer Care, Inc.), undecylenic acid, flucytosine, 5-fluorocytosine, griseofulvin, haloprogin, caprylic acid, and any combination thereof.
Preservatives suitable for use in conjunction with a cellulose ester plastic described herein may, in some embodiments, include, but are not limited to, benzoates, parabens (e.g., the propyl-4-hydroxybenzoate series), and the like, and any combination thereof.
Pigments and dyes suitable for use in conjunction with a cellulose ester plastic described herein may, in some embodiments, include, but are not limited to, plant dyes, vegetable dyes, titanium dioxide, silicon dioxide, tartrazine, E102, phthalocyanine blue, phthalocyanine green, quinacridones, perylene tetracarboxylic acid di-imides, dioxazines, perinones disazo pigments, anthraquinone pigments, carbon black, metal powders, iron oxide, ultramarine, calcium carbonate, kaolin clay, aluminum hydroxide, barium sulfate, zinc oxide, aluminum oxide, CARTASOL® dyes (cationic dyes, available from Clariant Services) in liquid and/or granular form (e.g., CARTASOL® Brilliant Yellow K-6G liquid, CARTASOL® Yellow K-4GL liquid, CARTASOL® Yellow K-GL liquid, CARTASOL® Orange K-3GL liquid, CARTASOL® Scarlet K-2GL liquid, CARTASOL® Red K-3BN liquid, CARTASOL® Blue K-5R liquid, CARTASOL® Blue K-RL liquid, CARTASOL® Turquoise K-RL liquid/granules, CARTASOL® Brown K-BL liquid), FASTUSOL® dyes (an auxochrome, available from BASF) (e.g., Yellow 3GL, Fastusol C Blue 74L), and the like, any derivative thereof, and any combination thereof.
In some embodiments, pigments and dyes suitable for use in conjunction with a cellulose ester plastic described herein may be food-grade pigments and dyes. Examples of food-grade pigments and dyes may, in some embodiments, include, but are not limited to, plant dyes, vegetable dyes, titanium dioxide, and the like, and any combination thereof.
Antioxidants may, in some embodiments, mitigate oxidation and/or chemical degradation of a cellulose ester plastic described herein during storage, transportation, and/or implementation. Antioxidants suitable for use in conjunction with a cellulose ester plastic described herein may, in some embodiments, include, but are not limited to, anthocyanin, ascorbic acid, glutathione, lipoic acid, uric acid, resveratrol, flavonoids, carotenes (e.g., beta-carotene), carotenoids, tocopherols (e.g., alpha-tocopherol, beta-tocopherol, gamma-tocopherol, and delta-tocopherol), tocotrienols, tocopherol esters (e.g., tocopherol acetate), ubiquinol, gallic acids, melatonin, secondary aromatic amines, benzofuranones, hindered phenols, polyphenols, hindered amines, organophosphorus compounds, thioesters, benzoates, lactones, hydroxylamines, butylated hydroxytoluene (“BHT”), butylated hydroxyanisole (“BHA”), hydroquinone, and the like, and any combination thereof.
In some embodiments, antioxidants suitable for use in conjunction with a cellulose ester plastic described herein may be food-grade antioxidants. Examples of food-grade antioxidants may, in some embodiments, include, but are not limited to, ascorbic acid, vitamin A, tocopherols, tocopherol esters, beta-carotene, flavonoids, BHT, BHA, hydroquinone, and the like, and any combination thereof.
In one embodiment, the polymer composition contains an antioxidant comprising a phosphorus compound, particularly a phosphite. For instance, in one embodiment, the antioxidant can be a diphosphite. For example, in one embodiment, the antioxidant is a pentaerythritol diphosphite, such as bis(2,4-dicumylphenyl)pentaerythritol diphosphite. The antioxidant can be present in the polymer composition generally in an amount less than about 2% by weight, such as in an amount less than about 1% by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.3% by weight. The antioxidant can be present in the polymer composition generally in an amount greater than about 0.05% by weight, such as in an amount greater than about 0.08% by weight, such as in an amount greater than about 0.1% by weight, such as in an amount greater than about 0.13% by weight.
The polymer composition of the present disclosure can be formed into any suitable polymer article using any technique known in the art. For instance, polymer articles can be formed from the polymer composition through extrusion, injection molding, blow molding, and the like.
In one aspect, the polymer composition containing the cellulose acetate can be formulated such that the polymer composition has properties very comparable to petroleum-based polymers, such as polypropylene. By matching the physical properties of a petroleum-based polymer, the polymer composition of the present disclosure is well suited to replacing those polymers in many different end use applications.
Polymer articles that may be made in accordance with the present disclosure include drinking straws, beverage holders, automotive parts, knobs, door handles, consumer appliance parts, and the like.
For instance, referring to
Referring to
In still another embodiment, the polymer composition can be used to produce a hot beverage pod 30 as shown in
Referring to
The polymer composition is also well suited to producing cutlery, such as forks, spoons, and knives. For example, referring to
In still another embodiment, the polymer composition can be used to produce a storage container 90 as shown in
In still other embodiments, the polymer composition can be formulated to produce paper plate liners, eyeglass frames, screwdriver handles, or any other suitable part.
The cellulose ester composition of the present disclosure is also particularly well-suited for use in producing medical devices including all different types of medical instruments. The cellulose ester composition, for instance, is well suited to replacing other polymers used in the past, such as polycarbonate polymers. Not only is the cellulose ester composition of the present disclosure biodegradable, but the composition has a unique “warm touch” feel when handled. Thus, the composition is particularly well suited for constructing housings for medical devices. When held or grasped, for instance, the polymer composition retains heat and makes the device or instrument feel warmer than devices made from other materials in the past. The sensation is particularly soothing and comforting to those in need of medical assistance and can also provide benefits to medical providers. In one aspect, the cellulose ester composition used to produce housings for medical devices includes a cellulose ester polymer combined with a plasticizer (e.g. triacetin) and optionally another bio-based polymer. In addition, the composition can contain one or more coloring agents.
Referring to
During use, the inhaler 130 administers metered doses of a medication, such as an asthma medication to a patient. The asthma medication may be suspended or dissolved in a propellant or may be contained in a powder. When a patient actuates the inhaler to breathe in the medication, a valve opens allowing the medication to exit the mouthpiece. In accordance with the present disclosure, the housing 132, the mouthpiece 134 and the plunger 136 can all be made from a polymer composition as described above.
Referring to
The medical injector 140 as shown in
The polymer composition of the present disclosure can also be used in all different types of laparoscopic devices. Laparoscopic surgery refers to surgical procedures that are performed through an existing opening in the body or through one or multiple small incisions. Laparoscopic devices include different types of laparoscopes, needle drivers, trocars, bowel graspers, rhinolaryngoscopes and the like.
Referring to
A cellulose ester polymer was combined with a plasticizer and different amounts of tartaric acid. Pellets were extruded. The resulting formulations were formulated:
The cellulose ester polymer incorporated into the above compositions contained primarily cellulose diacetate and had a degree of substitution of from about 2.45 to about 2.6. Sample Nos. 1 and 2 were tested for melt flow rate and the following results were obtained:
As shown, the melt flow rate increased as the amount of tartaric acid was increased.
The samples were also tested according to the CIELab color scale and compared to samples containing no acid and samples containing citric acid. The following additional samples were formulated:
As used herein, CIELab color values L*, a*, and b* are measured according to the color space specified by the International Commission on Illumination. The L*a*b* colourimetric system was standardized in 1976 by Commission Internationale de l'Eclairage (CIE). The CIELab L* value, utilized herein to define the darkness/lightness of the polymer composition, is a unit of colour measurement in the afore-mentioned CIELab system. A colour may be matched according to CIELab. In the L*a*b* colourimetric system, L* refers to lightness expressed by a numerical value. The following results were obtained:
As shown above, the cellulose ester polymer compositions containing tartaric acid actually increased in L* value in comparison to the compositions only containing a plasticizer. In contrast, citric acid caused a decrease in the L* value. These results are surprising and unexpected.
These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention so further described in such appended claims.
The present application is based upon and claims priority to U.S. Provisional Application Ser. No. 63/352,830, having a filing date of Jun. 16, 2022, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63352830 | Jun 2022 | US |
