KR20230170990A - Carbohyrate-based polymeric materials - Google Patents

Abstract

Described herein are articles comprising carbohydrate-based polymeric materials, and methods of forming such articles. Such articles may exhibit improved sustainability, biodegradability, increased strength, and/or various other beneficial characteristics. Carbohydrate-based polymeric materials can be formed from one or more starch, a plasticizer (e.g., glycerin), and water. Carbohydrate-based polymeric materials may exhibit very low crystallinity characteristics such that they are substantially amorphous (e.g., having a crystallinity of less than 20%, less than 10%, less than 10%, etc.). Carbohydrate-based polymeric materials can be blended with non-biodegradable plastics to make these plastic materials now biodegradable, which can impart increased strength to films or other articles, and increased sustainability, e.g. ) can be blended with sustainable polymer materials (e.g. bio-PE, etc.).

Description

CARBOHYRATE-BASED POLYMERIC MATERIALS}

Cross-reference to related applications

This application is related to U.S. Application No. 15/481,806 (21132.1) filed on April 7, 2017; U.S. Application No. 15/481,823 (21132.2), filed April 7, 2017; U.S. Application No. 15/691,588 (21132.7), filed August 30, 2017; U.S. Application No. 15/836,555, filed December 8, 2017 (21132.4.1); U.S. Application No. 62/610,615 (21132.9), filed December 27, 2017; U.S. Application No. 62/610,618 (21132.12), filed December 27, 2017; U.S. Application No. 62/440,399 (21132.10) filed on December 29, 2016, and U.S. Application No. 62/442,432 (21132.11) filed on January 4, 2017, and U.S. Application No. 62/442,432 (21132.11) filed on January 4, 2017. Priority is claimed for No. 62/483,219 (21132.4). The entire contents of each of the above applications are incorporated herein by reference.

U.S. Application No. 14/853,725 (21132.6), filed September 14, 2015; U.S. Application No. 14/853,780 (21132.8), filed September 14, 2015; and U.S. Provisional Application No. 62/187,231, filed June 30, 2015, each of which is also incorporated herein by reference.

Conventional petrochemical-based plastics are formulated to be strong, lightweight, and durable. However, these plastics are typically not biodegradable, and as a result, hundreds of millions of tons of plastic end up in landfills or floating in the ocean. In an attempt to reduce the amount of plastic waste, some items typically produced using petrochemical-based plastics are now produced using biodegradable materials.

Petrochemical-based plastic materials, such as large quantities of polyethylene and polypropylene, as well as many other plastics (polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon, etc.) are typically readily biodegradable. don't do it This is also true for so-called “green” plastics, where these materials can be sourced from renewable or sustainable sources, rather than petrochemical feedstocks.

UV and/or OXO additives such as PDQ-M, PDQ-H, BDA, and OxoTerra ^TM from Willow Ridge Plastics, OX1014 from LifeLine, or organic additives such as Restore® from Enso, EcoPure from Bio-Tec Environmental ®, ECM Masterbatch Pellets 1M from ECM Biofilms, or BioSphere®), there have been more recent efforts to make these plastic materials compostable, but their biodegradability and biodegradation rates are often too slow, and OXO additives are generally Rather than the desired actual conversion of plastics back to natural substances such as carbon dioxide (CO ₂ ), water (H ₂ O), and methane (CH ₄ ), it promotes the physical degradation of these plastic materials into smaller fragments of the underlying base plastic material. The use of these additives has generally been disapproved of by plastics industry associations (e.g. SPC, APR, FPA, and/or BPI) because they simply initiate structural fragmentation or degradation.

For example, these substances serve to accelerate the destruction of the macrostructure of the plastic article itself simply due to exposure to UV light (from sun exposure) and/or exposure to oxygen. These special plastics cannot actually biodegrade to any significant extent within a given period of time (e.g., 5 years, 3 years, or 1 year), but simply lose strength, crack, and break into small pieces. The result is a pile or small pieces of polyethylene or other basic plastic material, which the bottle, film, or other article physically decomposes over time due to the addition of UV and/or OXO additives. The weight fraction remains substantially the same and no substantial biodegradation actually occurs. Decomposition is merely physical, so the article breaks, cracks, and breaks into small pieces, leaving behind many small fractions of polyethylene or other basic plastic material. Since complete biodegradation of the polymeric material itself may not occur in practice (e.g., if a substantial fraction of the plastic can decompose into CO ₂ , CH ₄ , H ₂ O, etc.), “biodegradable” does not mean that The application of the term is inappropriate.

Furthermore, most plastics used today are not formed from renewable or sustainable resources (i.e., starting materials that can be recycled within about 100 years). The terms renewable and sustainable are used interchangeably herein. Rather, polyethylene (PE), polyethylene terephthalate (PET) and other typical plastics used in large quantities in bottles, bags and other packaging are made from petroleum product starting materials that are not renewable or sustainable.

In an effort to increase sustainability, there have been some recent efforts to develop processes to make these plastic materials utilizing renewable raw materials such as sugar cane, corn, or other plant products made from sustainable plant materials. For example, these renewable materials can be used to produce ethanol, ethylene glycol, or other chemical building block materials that can be further reacted to produce monomers that can be polymerized. These efforts are aimed at creating premium-priced products that allow these "green" plastic resins to be blended with conventional petrochemical-based resins (to produce bottles or other packaging in which fractions of the material (e.g., 30%) are sustainable). The product is starting to show some promise. In fact, some products can now be made from 100% “green” plastic resins.

Blends of these “green” materials and conventional petrochemical plastics are starting to become available, but in terms of processing, cost, and other considerations, replacing the remaining conventional petroplastic materials with all sustainable materials There are still practical difficulties in doing so.

Moreover, although replacing some materials with sustainable plastic materials reduces the use of conventional non-sustainable plastic materials, the resulting plastic packaging is still not biodegradable. For example, even plastic packaging made of 100% “green” plastic or containing a fraction of “green” PE or green “PET” is not biodegradable. This lack of biodegradability continues to present a huge problem. If biodegradable items could be provided, it could be a significant advance in the related field of technology. Increased strength would also be desirable. A further advance could be made if these items were formed entirely (or almost entirely) from sustainable materials.

Moreover, recent efforts have been made to reduce the use of these non-renewable petrochemical-based plastic materials. Some of these efforts have attempted to source resins for producing plastic materials from renewable sources, such as sugar cane or other plant products. Although available to some extent, these renewable sourced plastics are much more expensive to produce than their petrochemical-based non-renewable counterparts.

Additionally, plastic materials have specific strength characteristics associated with them, depending on the specific material(s) used to form the plastic film or other material and the physical characteristics of the film or other article itself. For example, when forming plastic films, the use of non-renewable petrochemical-based plastic resin materials can be reduced by forming thinner films, but this reduction in material usage results in weaker films.

For example, WO 2014/0190395 by Leufgens describes the formation of films from blends of polyethylene and thermoplastic starches (particularly Cardia BL-F), but these films are weaker than comparable films formed from polyethylene alone, and are less effective than conventional thermoplastic starches. Because of the difficulty of processing blends containing , the films produced therein must be very thick (e.g., 3 mils). These very thick films may not result in a practical reduction in the use of petrochemical-based plastic resin materials, as forming thin films is not realistically possible and/or the inclusion of these thermoplastic starches would weaken the overall film, thereby achieving the desired level of strength. A thick film is needed to maintain the

When using renewable sourced plastic materials, it may be advantageous to provide associated manufacturing methods and films that can increase strength for any given film thickness, for example by adjusting the manufacturing parameters used in the manufacturing process. . Using these methods, it may be possible to produce films with higher strength at a given thickness, or to produce films with a thinner thickness but the same strength. This method can simultaneously substantially reduce the amount of petrochemical plastic material used, some of which is replaced with renewable sourced plastic material, and the overall thickness does not need to be increased.

Moreover, although replacing some of the petrochemicals with starches or starch-based materials offers some promise regarding increased sustainability, one problem posed by the addition of these starches or starch-based materials is that the starch or starch-based materials in the plastic compositions The incorporation of significant fractions of the base material may cause articles formed from such blends to have a distinct odor associated with such inclusions. For example, the material may emit a slightly burnt starch-like odor, a popcorn-like odor, or a caramel corn-like odor. Some people may find the odor to be pleasant, or even desirable, while others prefer that this odor not be present, such as in plastics formed without starch or starch-based materials (e.g., polyethylene or another polymer resin, formed alone). can do.

In light of the above, many problems remain to be solved in related technical fields.

The present disclosure relates to various concepts that can be implemented in manufacturing and/or manufacturing methods of articles. In one embodiment, the present disclosure relates to articles that exhibit increased strength and/or biodegradability. In some cases, the article is made of one or more polymeric materials (e.g., petrochemical-based or otherwise synthetic), and has low crystallinity (i.e., they are substantially amorphous), glass transition temperature, heat distortion temperature, Vicat softening temperature, etc. It can be produced from a mixture of one or more carbohydrate-based polymeric materials with specific characteristics. In certain examples, the one or more carbohydrate-based polymeric materials may include one or more starch-based polymeric materials. For example, the carbohydrate-based polymeric material can be substantially amorphous with a crystallinity of less than 20%, it can have a Young's modulus of at least 1.0 GPa, and/or it can have a glass transition temperature or thermal strain of 70°C to 100°C. temperature or Vicat softening temperature. Other features of the carbohydrate-based materials will be described further herein.

A method of producing an article may include providing one or more polymeric materials and one or more substantially amorphous carbohydrate-based polymeric materials. The one or more polymeric materials and the one or more carbohydrate-based polymeric materials can be mixed and heated. The resulting mixture can be extruded into a number of plastic products using plastic processing equipment such as injection molding machines, blow molding machines, and thermoforming machines. A film can be formed by injecting gas into the extruded mixture. These films can be processed into bags or another type of article. Other articles may be extruded plastic products, injection molded plastic products, blow molded plastic products, extruded or molded sheet or film, thermoformed plastic products, etc.

The article may exhibit increased strength and/or biodegradability. For example, in one embodiment, blending the substantially amorphous carbohydrate-based polymeric material with the other polymeric material makes the other polymeric material biodegradable to the other polymeric material even if the other polymeric material on its own is not otherwise biodegradable. Grants. For example, it is well known that polyethylene is not biodegradable on its own. Applicants have demonstrated the ability to impart biodegradability to plastic materials such as polyethylene that are not otherwise biodegradable. Other examples of such materials may include, but are not limited to, polypropylene, other polyolefins, polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon, and polycarbonate. For example, the amount of the article that biodegrades within 5 years or another given period of time under simulated disposal conditions (e.g., simulated landfill conditions) may be greater than the amount of carbohydrate-based polymeric material contained in the article. These simulated disposal conditions may include simulated landfill conditions (e.g., under any typical ASTM standard such as, but not limited to, D-5511 and/or D-5526), simulated industrial compost conditions (e.g., ASTM D-5338), or simulated marine conditions. May include conditions (e.g. ASTM D-6691). In other words, some of the polymeric materials that are not otherwise biodegradable are now somehow biodegrading as well as biodegrading the carbohydrate-based materials. For example, if the article is formed from a blend that includes 25% of the carbohydrate-based polymer material, the amount of the article that biodegrades under these conditions is greater than 25% (i.e., some of the other polymer material is also degrading). These other polymeric materials may not decompose on their own under similar conditions).

Third-party test results obtained by Applicant indicate that such degradation occurs relatively quickly, e.g., not within 5 years, but sometimes within about 180 days (6 months), within about 1 year, within about 2 years, or about It is suggested that this may occur within 3 years.

In addition to or alternatively to biodegradability, the articles and methods may have increased strength (e.g., a dart strength of at least 5%) compared to the strength the article would have if made only from other polymer materials and without carbohydrate-based polymer materials. strength) or an increase in other strength characteristics.

Another aspect of the present disclosure relates to renewable or sustainable “green” plastic materials and articles formed from such carbohydrate-based (e.g., starch-based) polymeric materials. For example, in one embodiment the other polymeric material may also be a sustainable, “green” polymeric material, sourced from sustainable sources (e.g., plants such as sugar cane, corn, etc.). In one embodiment, sustainable polymer materials may be engineered into polymers that exhibit similar but not identical characteristics to otherwise petrochemical-based polymers (e.g., they may be "green" polyethylene, "green" polypropylene, "green" polyethylene terete). may be phthalates (PET), etc.). These “green” polymers may have similar but not identical chemical and physical properties compared to identical polymers formed from petrochemical feedstocks (e.g., polyethylene). The carbohydrate-based polymeric materials may in fact impart biodegradable characteristics to blended or otherwise formed sustainable polymeric materials, which may not otherwise exhibit such biodegradable characteristics (or such characteristics may not otherwise be present in sustainable polymeric materials). If the material already exhibits some biodegradability, this can be improved).

In addition to or alternatively to biodegradability, such articles may exhibit increased strength compared to otherwise similar articles, but are formed comprising the above carbohydrate-based polymeric materials. For example, one embodiment is an article comprising one or more carbohydrate-based polymeric materials (e.g., those described above) and one or more sustainable polymeric materials sourced from sustainable plant sources, wherein the strength of the article is determined by the carbohydrate-based polymeric material. It relates to an article having at least 5% more than what the article would have if made without the polymeric material. For example, Applicants have shown that the inclusion of such carbohydrate-based polymeric materials in the article (e.g., as a blend of two polymeric materials) can provide increased strength compared to what the sustainable polymeric materials alone can provide. Found it.

Another aspect of the present disclosure is manipulating the blow up ratio and/or die gap used in the film manufacturing process to increase the strength of films produced from such blends of a carbohydrate-based polymer material and another polymer material. It's about how to do it. In particular, Applicants note that the strength of most plastic films blown from various resin materials (e.g., polyethylene and/or polypropylene) is not affected by changes in blowup ratio, but that certain amorphous features, such as certain glass transitions, as described herein, When the renewable carbohydrate-based (e.g., starch-based) polymeric material having a temperature characteristic, a Vicat softening temperature characteristic, or a heat distortion temperature characteristic, and/or a specific elastic modulus characteristic is included in a resin blend from which a film is blown, the strength is determined by the blowup ratio. and/or die gap, and it has been discovered that extremely narrow gauge films can be blown. It is believed that Applicants have actually blown films as thin as 0.1 mil and of considerable strength, such thin film blowing having not previously been possible with any known resin or production method.

The blowup ratio refers to the maximum diameter of the blown film divided by the diameter of the die of the film blowing device. Typically, there is some increase in diameter as the molten resin material exits the die and begins to move upward through the "frost line" toward the portion of the blown film bubble where the resin material is no longer molten but solidifies. there is. Solidification and crystallization typically occur at the frost line, which is the location where opacity or a "frost appearance" begins to become visible in the blown bubble film. Applicants have observed that when using certain renewable carbohydrate-based polymer materials as described herein, increases in strength beyond those achieved when blowing otherwise similar plastic films (but without carbohydrate-based polymer materials) can be obtained. . This increase is achieved by choosing a high blowup ratio and/or narrow die gap. This is believed to result in alignment, orientation, and/or stretching of the molecular structure of the carbohydrate-based polymer material that is uniformly distributed throughout the resin blend from which the film is formed. This alignment and orientation of the amorphous renewable carbohydrate-based polymer material within the film is believed to be at least partially responsible for the observed increase in strength.

In other words, as described herein, a particular renewable carbohydrate-based polymer material can be used under certain described processing conditions to improve the strength of a given film, while retaining a portion of the other polymer content of the film. Not to mention the sustainable benefits associated with replacing .

In particular, typical conventional films are blown at a blowup ratio of about 1.5. Applicant seeks to increase the blowup ratio to at least 2.0, e.g., 2.2 to 2.8 (e.g., about 2.5), to allow renewable carbohydrate-based polymer materials, such as NuPlastiQ or Eco Starch Resin "ESR", available from Applicant, to form a film. It was found that when included in a resin blend, there was a significant increase in film strength at higher blowup ratios. For example, a blend of NuPlastiQ or ESR and a typical polymer resin (e.g., polyethylene and/or polypropylene) is otherwise identical, but exhibits strength characteristics at a blowup ratio of 1.5 that are substantially the same as the strength of a film without NuPlastiQ or ESR. It can be expressed.

These films (NuPlastiQ or no ESR) did not show a significant increase in strength when the blowup ratio was increased, so there is no reason to manipulate this value when blowing these films. Applicants have discovered that when including NuPlastiQ or ESR in the resin blend, as mentioned above, the strength is significantly increased when using high blowup ratios (e.g., at least 2.0).

Moreover, NuPlastiQ or ESR have many of the problems of alternative thermoplastic starch materials that inhibit their ability to be used in the formation of relatively thin films (e.g., 2 mils or less, typically 1.5 mils or less, such as 0.1 mil to 1.5 mils). There is not. The combination of the above findings allows applicants to demonstrate that a given thickness of film exhibits increased strength compared to films formed from the same materials but without NuPlastiQ or ESR (or compatibilizers - i.e. other polymer materials such as polyethylene, formed alone). A film was allowed to form. This discovery also allows for the production of films with the same strength but reduced thickness when using NuPlastiQ or ESR in the blend. These results are surprising and advantageous, allowing the production of films containing a significant fraction of renewable resins, but at the same time increasing their strength. This is achieved by manipulating the blowup ratio and/or die gap. The applicant has also discovered that increased strength is also possible by ensuring that the die gap used in the film blowing device is relatively narrow. Additionally, narrow die gaps are not possible, a practical problem with many conventional thermoplastic starch blends, as demonstrated by Leufgens (the die gap used is 1.6 to 1.8 mm). The present invention may utilize die gaps of 1000 microns or less, more typically 500 microns or less. Accordingly, blowup ratios and/or die gaps can be used in accordance with the present invention to provide increased film strength.

For example, one embodiment provides a method for film blowing a plastic film, wherein the film is blown from a blend comprising a first polymer material (e.g., polyethylene, another polyolefin, or another conventional polymer material) and a renewable carbohydrate-based polymer material. It may relate to a method of providing increased strength to a blown plastic film comprising blowing using an apparatus. The renewable carbohydrate-based polymeric material may be substantially amorphous with a crystallinity of less than 20%, may have a Young's modulus of at least 1.0 GPa, and/or may have a glass transition temperature of 70° C. to 100° C., Vicat softening. It may have a temperature or heat distortion temperature. The film blowing device may operate at high blowup ratios and/or narrow die gaps, for example, a blowup ratio of at least 2.0 when blowing plastic films, or the die gap may be less than 500 microns. High blowup ratios and/or narrow die gaps can provide blown plastic films with increased strength (e.g., compared to lower blowup ratios and/or larger die gaps, all else being equal).

Another embodiment includes blowing a plastic film using a film blowing device, wherein the plastic film is a film blown from a blend comprising a first polymer material and a second polymer material comprising a renewable carbohydrate-based polymer material. It may be about a method of increasing the strength of blown plastic films by manipulating the up ratio. The renewable carbohydrate-based polymeric material may be substantially amorphous with a crystallinity of less than 20%, have a Young's modulus of at least 1 GPa, and have a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70°C to 100°C. . The method includes manipulating the blowup ratio of the film blowing device to select a high blowup ratio of at least 2.0 to increase the strength of the film (e.g. compared to a lower blowup ratio, all else being equal), i.e. , specifically selecting steps) may be additionally included. In addition to or alternatively to manipulating the blowup ratio, the method is operated such that the die gap of the film flowing device is operated to select (i.e., specifically selected) a narrow die gap of 500 microns or less, The die gap and/or higher blowup ratio may include increasing the strength of the film (e.g., comparing all else being equal but at a higher die gap and/or lower blowup ratio).

Another aspect of the present disclosure relates to methods of reducing characteristic odors that may be due to the inclusion of starch-based polymeric materials, or other carbohydrate-based polymeric materials, as well as articles comprising such reduced odors. The carbohydrate-based polymer materials described herein, as well as other similar carbohydrate-based polymer materials, exhibit a characteristic slightly burnt starch, popcorn, or caramel corn-like odor. Although typically not very strong, this odor may be present in some articles formed from blends of materials comprising the above carbohydrate-based polymeric materials, particularly where the geometry of the finished article may be relatively "closed" (e.g., within a cup, for example). This is typically evident in, or other enclosed structures whose volume is limited by plastic material on two, three or more sides. These characteristic odors may tend to accumulate within these enclosed volumes such that they become noticeable to the consumer or other users (e.g., when a user sticks his nose into such a cup and sniffs).

Applicant wishes to eliminate or minimize these characteristic odors, which may be similar to or identical to the (typically odorless) odors that would be present if the article were instead formed from standard (e.g. petrochemical-based) polymeric materials. there is. For example, articles according to the invention may be formed from blends of these standard “other polymer materials” and carbohydrate-based polymer materials, as described previously and elsewhere herein. The applicant has discovered that the characteristic odor can be substantially eliminated or minimized by adding very small fractions of odor reducers, especially organic odor reducers.

Although some attempts have previously been made by others to reduce odors produced from ethanol distiller (DDG) materials, for example as described in WO2009058426, these treatments are relatively inexpensive compared to activated carbon or steam activated anthracite materials. A high fraction addition was required. Although probably effective to some extent, the concentrations of these materials required are high and the cost of these materials is prohibitively high, making commercial application of this embodiment not particularly feasible. Moreover, the addition of high fractions of dark activated carbon or activated anthracite materials may be undesirable, taking into account their tendency to act as pigments and color plastic materials under certain conditions. This can be particularly problematic when high definition films, brightly colored articles, or other similar articles are desired.

Accordingly, one embodiment of the present invention relates to a sustainable plastic material comprising the above carbohydrate-based polymeric material, another polymeric material, as described above, but also comprising an odor reducer. Without the use of odor reducers, carbohydrate-based polymer materials can impart a characteristic burnt carbohydrate odor to the sustainable plastic material. In one embodiment, the odor reducing agent may be organic and includes an aromatic compound (e.g., containing a benzene ring), such as a benzaldehyde compound, a benzyl ketone compound, or another benzene derivative. In one embodiment, the organic odor reducer may include freeze-dried or other extracts of fruits or vegetables, such as vanillin. The organic odor reducers may in fact be extracted from such fruits, vegetables, or other plants, or are typically found in such extracts, but synthetically produced aromatic compounds, such as synthetic vanillin or another synthetic aromatic compound, may also be suitable. may include). Vanillin is an aromatic benzaldehyde compound, also known as 4-hydroxy-3-methoxybenzaldehyde.

Applicants have surprisingly found that a very small fraction of this aromatic odor reducer is sufficient to substantially eliminate any characteristic odor that could otherwise be attributed to the carbohydrate-based polymeric material included in the blend that makes up the sustainable plastic material. Found it. For example, the weight ratio of odor reducing agent to carbohydrate-based polymeric material that substantially eliminates the odor is approximately 1:1000 or less of the odor reducing agent. For example, levels below 100 ppm, 50 ppm, or even 20 ppm are sufficient to eliminate any realistic sign of a characteristic odor.

This is especially surprising considering that only very small amounts of odor reducers are needed to eliminate odors. It is believed that the mechanism of action may not be simply masking the characteristic carbohydrate odor, as little is required and the odor does not appear to be replaced or masked by any odor typically provided by the odor reducer. . Although the mechanisms of any of the above are probably not fully understood, there is a connection between these aromatic or other organic odor reducers and the characteristic odorous compounds produced when heating carbohydrate-based polymer materials during melting and forming thermoplastic blends into desirable articles. There may be chemical interactions.

The odor reducing agent may, for example, be included together with the carbohydrate-based polymer material in its masterbatch. Accordingly, one embodiment may relate to such a sustainable thermoplastic carbohydrate-based polymeric material exhibiting reduced odor comprising the organic odor reducer pre-blended with the carbohydrate-based polymeric material. The weight ratio of the organic odor reducer to the carbohydrate-based polymeric material may be 1:1000 or less (i.e., the amount of carbohydrate-based polymeric material is at least 1000 times greater than the amount of odor reducer). In one embodiment, the ratio of odor reducer to carbohydrate based polymeric material can be diluted even further, for example 1:50,000.

The present disclosure also encompasses related methods, e.g., methods of removing the characteristic odor of a blend of materials comprising a carbohydrate-based polymer material, e.g., by including a small fraction of an organic odor reducer within the blend. It will be clear. When the carbohydrate-based polymeric material is provided as a masterbatch, the odor reducing agent may be provided in the masterbatch already blended with the carbohydrate-based polymeric material. As such, when the masterbatch is then blended with a polymer resin material (e.g., PE, PP, other polyolefins, polyester, polystyrene, PBAT, polycarbonate, or many other various plastic resins), the blended material This also includes the above odor reducer blended therein.

Summary of example concepts to be claimed

1. One or more substantially amorphous carbohydrate-based polymeric materials ( e.g. starch-based polymeric substances); and one or more polyolefin-based polymeric materials, wherein the article has a dart drop impact test value of at least about 140 grams per mil of thickness.

2. The article of claim 1, wherein the at least one starch-based polymeric material is formed from at least one starch and at least one plasticizer.

3. The article of clause 2, wherein the one or more starches comprise one or more of potato starch, corn starch, tapioca starch, and the plasticizer comprises glycerin.

4. The article of clause 1, wherein the at least one polyolefin based polymer material comprises polyethylene.

5. The article of clause 1, wherein the article is a bag having a thickness of about 0.01 mm to about 0.1 mm, and wherein the bag comprises a cavity having a volume of about 1 L to about 100 L.

6. The method of clause 1, wherein said one or more starch-based polymeric materials comprise from about 20% to about 40% by weight of said article; wherein the one or more polyolefin-based polymeric materials make up about 60% to 80% by weight of the article; has a thickness of about 0.02 mm to about 0.05 mm; An article having a dart drop impact test value of about 265 g to about 330 g per mil of thickness.

7. The article of claim 1 further comprising a compatibilizer present in the article in an amount of not more than 8% by weight.

8. A crystallinity of less than 20%, less than 10%, a specific glass transition temperature, Vicat softening temperature or heat distortion temperature, formed from a mixture of starch comprising a first amount of the first starch and a second amount of the second starch, Substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) having a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR; and an article comprising a polyolefin-based polymeric material, wherein the article (i) lands a first dart of the first article comprising a first starch-based polymeric material formed from a single starch comprised of the polyolefin-based polymeric material and the first starch. an impact test value, and (ii) a dart drop impact greater than the second dart drop impact test value of a second article comprising a second starch-based polymeric material formed from a single starch comprised of said polyolefin-based polymeric material and said second starch. An article having a test value.

9. The article of clause 8, wherein the starch-based polymeric material is formed from one or more plasticizers.

10. The method of clause 8, wherein the first starch comprises or is derived from one of potato starch, corn starch, or tapioca starch; Wherein the second starch comprises or is derived from another of potato starch, corn starch, or tapioca starch.

11. The method of clause 8, wherein the starch-based polymeric material is present in an amount of about 20% to about 30% by weight of the article, and the polyolefin-based polymeric material is present in an amount of about 65% to about 75% by weight of the article. An article existing in an amount of .

12. The method of clause 11, wherein the first starch comprises from about 10% to about 50% by weight of the mixture of starches from which the starch-based polymeric material is formed, and wherein the second starch comprises the starch-based polymeric material. An article comprising about 50% to 90% of the mixture of starches from which it is formed.

13. The method of clause 12, wherein the mixture of starches from which the starch-based polymer material is formed comprises a third starch; wherein the third starch comprises from about 10% to about 35% by weight of the mixture of starches from which the starch-based polymer material is formed; wherein the dart drop impact test value of the article is greater than the third dart drop impact test value of a third article comprising a third starch-based polymeric material formed from a single starch comprised of the polyolefin-based polymeric material and the third starch. article.

14. The method of clause 8, wherein the article has a tensile elongation at break in the machine direction that is greater than the tensile elongation at break in the machine direction of the additional article formed from the polyolefin-based polymeric material without the starch-based polymeric material. , goods.

15. The article of claim 9 further comprising a compatibilizer present in an amount of not more than 8% by weight of the article.

16. Providing one or more petrochemical-based polymeric materials; One or more substantially amorphous carbohydrate-based polymeric materials having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR, e.g. providing a starch-based polymer material); mixing the one or more petrochemical-based polymer materials and the one or more carbohydrate-based polymer materials to produce a mixture of materials; heating the mixture of materials to a temperature ranging from about 120° C. to about 180° C.; and using the mixture of materials to produce a film having a dart drop impact test value of about 250 grams to about 350 grams per mil of thickness.

17. The method of clause 16, wherein producing the film using the mixture of materials comprises extruding the mixture of materials to produce an extruded object; and injecting gas into the extruded object.

18. The method of clause 16, wherein said at least one carbohydrate-based polymeric material is formed from a first starch and a second starch; wherein the film has (i) a first dart drop impact test value of a first article comprising a first carbohydrate-based polymeric material formed from a single starch comprised of the at least one petrochemical-based polymeric material and the first starch, and (ii) having a dart drop impact test value greater than a second dart drop impact test value of a second article comprising a second carbohydrate-based polymeric material formed from a single starch comprised of said one or more petrochemical-based polymeric materials and said second starch. method.

19. The method of clause 16, wherein the mixture of materials further comprises one or more compatibilizers; From about 10% to about 40% by weight of said one or more carbohydrate-based polymeric materials, from about 60% to about 89% by weight of said one or more petrochemical-based polymeric materials; and from about 1% to up to 8% by weight of the one or more compatibilizers.

20. The method of clause 16, comprising a film having a thickness of about 0.02 mm to about 0.05 mm.

1. Substantially amorphous, formed from at least the first starch, having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR. phosphorus carbohydrate based polymeric materials (e.g. starch based polymeric materials); and

An article comprising a polymer content comprising another polymer material,

The amount of polymer content that biodegrades after 91 days is based on the results of a biomethane potential test conducted at a temperature of about 52°C using an inoculum containing about 55% by weight water and about 45% by weight organic solids. An article comprising greater than or equal to an amount of starch-based polymeric material.

2. The biomethane potential test of claim 1, wherein substantially all of the starch-based polymer material is conducted at a temperature of about 52° C. using an inoculum containing about 55% by weight water and about 45% by weight organic solids. An article that is biodegradable after 91 days when measured according to .

3. The article of clause 1 further comprising a biodegradation enhancing additive present in an amount of from about 0.5% to about 2.5% by weight.

4. The article of claim 1, wherein the article is substantially free of biodegradation improving additives.

5. The starch-based polymer material of clause 4 based on the results of a biomethane potential test conducted at a temperature of about 52° C. using an inoculum containing about 55% by weight water and about 45% by weight organic solids. An article having a biodegradability amount of the article after 91 days that is about 5% to about 60% greater than the amount of.

6. The article of claim 1, wherein the starch-based polymeric material is formed from a material comprising one or more plasticizers.

7. The method of clause 1, wherein the starch-based polymeric material is formed from a first starch and a second starch, wherein the first starch comprises or is derived from one of potato starch, corn starch, or tapioca starch; Wherein the second starch comprises or is derived from another of potato starch, corn starch, or tapioca starch.

8. The method of clause 7, wherein the first amount of the first starch comprises from about 10% to about 50% by weight of the mixture of starches from which the starch-based polymer material is formed, and the second amount of the second starch An amount comprising from about 50% to about 90% by weight of the mixture of starches from which the starch-based polymer material is formed.

9. The article of claim 1 further comprising a compatibilizer present in an amount of not more than 8% by weight of the article.

10. One or more substantially one or more polymers formed from one or more carbohydrates, having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR. amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials); and

An article comprising a polymer content comprising one or more petrochemical-based polymer materials,

The amount of polymer content that biodegrades after 91 days is obtained at a temperature of about 40°C to about 50°C using an inoculum containing from about 50% to about 60% water by weight and from about 40% to about 50% organic solids by weight. An article, wherein the amount of one or more carbohydrate-based polymeric materials is greater than that based on the results of a biomethane potential test performed in the article.

11. The article of clause 10 comprising from about 20% to about 40% by weight of said one or more carbohydrate-based polymeric materials and from about 65% to about 85% by weight of said one or more petrochemical-based polymeric materials.

12. The biomethane of clause 11, wherein the amount of polymer content that biodegrades after 91 days is carried out at a temperature of about 52° C. using an inoculum containing about 55% by weight water and about 45% by weight organic solids. The article is about 30% to about 50% based on the results of the potential test.

13. The method of clause 10, wherein the amount of polymer content that biodegrades after 62 days is determined by biomethane potentialing performed at a temperature of about 52° C. using an inoculum containing about 55% by weight water and about 45% by weight organic solids. The article is about 25% to about 35% based on the results of the sex test.

14. The article of clause 10, wherein the one or more petrochemical-based polymeric materials comprise a first petrochemical-based polymeric material and a second petrochemical-based polymeric material that is compostable according to the ASTM D-6400 standard.

15. Providing one or more petrochemical-based polymeric materials;

One or more substantially amorphous carbohydrates formed from one or more carbohydrates, having a crystallinity of less than 20%, less than 10%, a certain glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a certain Young's modulus and/or other physical characteristics of NuPlastiQ or ESR. providing a base polymeric material (e.g., a starch-based polymeric material);

mixing one or more petrochemical-based polymer materials and one or more carbohydrate-based polymer materials to produce a mixture of materials;

heating the mixture of materials at a temperature comprised between about 120°C and about 180°C;

A step of forming a film using a mixture of the above materials,

the film comprising a polymer content comprised of one or more petrochemical-based polymer materials and one or more carbohydrate-based polymer materials; and

The amount of polymer content that biodegrades after 91 days is based on the results of a biomethane potential test conducted at a temperature of about 52°C using an inoculum containing about 55% by weight water and about 45% by weight organic solids. A method comprising steps greater than or equal to an amount of carbohydrate-based polymer material.

16. According to paragraph 15,

wherein the one or more carbohydrate-based polymeric materials are formed from a first starch and a second starch;

Based on the results of a biomethane potential test conducted at a temperature of about 52° C. using an inoculum containing about 55% by weight water and about 45% by weight organic solids, substantially all of the one or more carbohydrate-based polymeric materials were 91 How to biodegrade after 1 day.

17. The method of claim 15, wherein the mixture of said substances

Not more than 8% by weight of one or more compatibilizers;

About 10% to about 40% by weight of one or more carbohydrate-based polymeric materials; and

A method comprising from about 60% to about 90% by weight of one or more petrochemical-based polymeric materials.

18. The method of clause 15 further comprising producing a bag from the film.

19. The method of clause 15, wherein the bag has a thickness of about 0.02 mm to about 0.05 mm and comprises a cavity having a volume of about 5 L to about 20 L.

20. According to paragraph 15,

The mixture of materials is heated in multiple chambers of the extruder;

the first chamber of the extruder is set to a first temperature;

wherein the second chamber of the extruder is set to a second temperature that is different from the first temperature.

21. Substantially amorphous, formed from at least a first starch, having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR. phosphorus carbohydrate based polymeric materials (e.g. starch based polymeric materials); and

An article comprising a polymer content comprising a synthetic polymer material, comprising:

An article wherein the amount of polymer content that biodegrades after about one year under simulated landfill conditions, simulated compost conditions, or simulated ocean conditions is greater than the amount of the starch-based polymer material.

22. The article of clause 21, wherein at least 25% of the synthetic polymer material biodegrades within about 3 years.

23. The method of clause 21, wherein the starch-based polymer material is formed from a first starch and a second starch, and wherein the first starch comprises or is derived from one of potato starch, corn starch, or tapioca starch; Wherein the second starch is derived from another of potato starch, corn starch, or tapioca starch.

24. The method of clause 23, wherein the first amount of first starch comprises from about 10% to about 50% by weight of the mixture of starches from which the starch-based polymer material is formed, and the second amount of second starch wherein the starch-based polymer material comprises from about 50% to about 90% by weight of the mixture of starches from which the starch-based polymer material is formed.

25. The article according to item 21, further comprising a compatibilizer.

1. A crystallinity of less than 20%, less than 10%, a certain glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a certain Young's modulus and/or other physical properties of NuPlastiQ or ESR, configured to provide other materials of the article with biodegradability. Substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) having the following characteristics; and

An article comprising sustainable polymeric materials sourced from sustainable plant sources, comprising:

An article wherein the amount of the article that biodegrades within 5 years under simulated landfill conditions is greater than the amount of the carbohydrate-based polymer material.

2. The article of clause 1, wherein the carbohydrate-based polymeric material comprises a starch-based polymeric material.

3. The article of clause 1, wherein the sustainable polymeric material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from sustainable plant sources.

4. The article of clause 3, wherein the sustainable polymeric material is formed from one or more of sugarcane or corn.

5. The article of clause 2, wherein the starch-based polymer material is formed from one or more starches including one or more of potato starch, corn starch, or tapioca starch.

6. The method of claim 5, wherein the starch-based polymer material comprises two or more starches, a first starch comprising at least one of potato starch, corn starch, or tapioca starch, and another one of potato starch, corn starch, or tapioca starch. An article formed from a second starch comprising the above.

7. In paragraph 6,

The amount of the first starch comprises from about 50% to about 90% by weight relative to the combined weight of the first starch and the second starch, and the amount of the second starch comprises the first starch and the second starch. comprising from about 10% to about 50% by weight of the combined weight of starch;

wherein the amount of carbohydrate-based polymeric material comprises from about 10% to about 40% by weight of the combined weight of the carbohydrate-based polymeric material and the sustainable polymeric material, and wherein the amount of sustainable polymeric material comprises the carbohydrate-based polymeric material and about 60% to about 90% by weight of the combined weight of the sustainable polymeric materials.

8. The article of clause 7, wherein the article has a strength that is at least about 5% greater than what the article would have if made solely from the sustainable polymeric material and without the carbohydrate-based polymeric material.

9. The article of clause 1, wherein at least 90% of the polymer content of the article is sourced from sustainable sources.

10. The article of claim 1 comprising a film.

11. The article of claim 1 comprising at least one of a bottle or a sheet.

12. A crystallinity of less than 20%, less than 10%, a certain glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a certain Young's modulus and/or other physical properties of NuPlastiQ or ESR, configured to provide other materials of the article with biodegradability. One or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) having the following characteristics; and

An article comprising one or more sustainable polymeric materials sourced from sustainable plant sources, comprising:

The strength of the article is at least about 5% greater than what the article would have if made only from the sustainable polymeric material, without the carbohydrate-based polymeric material.

13. The article of clause 12 comprising a film and having a dart drop impact strength of at least about 100 g/mil thick.

14. The article of clause 12, wherein the sustainable polymeric material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from sustainable plant sources.

15. The article of clause 14, wherein the sustainable polymeric material is formed from one or more of sugar cane or corn.

16. The article of clause 12, wherein the carbohydrate-based polymeric material comprises a starch-based polymeric material.

17. The article of clause 16, wherein the starch-based polymer material is formed from one or more starches including one or more of potato starch, corn starch, or tapioca starch.

18. The method of clause 17, wherein the starch-based polymer material comprises two or more starches, a first starch comprising at least one of potato starch, corn starch, or tapioca starch, and another one of potato starch, corn starch, or tapioca starch. An article formed from a second starch comprising the above.

19. According to paragraph 18,

The amount of the first starch comprises from about 50% to about 90% by weight relative to the combined weight of the first starch and the second starch, and the amount of the second starch comprises the first starch and the second starch. comprising from about 10% to about 50% by weight of the combined weight of starch;

wherein the amount of carbohydrate-based polymeric material comprises from about 10% to about 40% by weight of the combined weight of the carbohydrate-based polymeric material and the sustainable polymeric material, and wherein the amount of sustainable polymeric material comprises the carbohydrate-based polymeric material and about 60% to about 90% by weight of the combined weight of the sustainable polymeric materials.

20. The article of clause 12, wherein the article has a strength that is at least 10% greater than what the article would have if made solely from the sustainable polymeric material and without the carbohydrate-based polymeric material.

21. The article of clause 12, wherein at least 90% of the polymer content of the article is sourced from sustainable sources.

22. The article of claim 12 comprising a film.

23. The article of clause 12 comprising at least one of a bottle or a sheet.

1. Providing a plastic material that is not itself biodegradable;

One or more substantially amorphous carbohydrate-based polymeric materials having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR, e.g. starch-based polymeric material), wherein one or more carbohydrate-based polymeric materials are selected for their ability to impart biodegradability to a plastic material that is not itself biodegradable; and

comprising blending the carbohydrate-based polymer material with the plastic material,

A method of imparting biodegradability to plastic materials that are not otherwise biodegradable.

2. The method of claim 1, wherein the one or more carbohydrate-based polymeric materials comprises one or more starch-based polymeric materials.

3. The method of clause 2, wherein the at least one starch-based polymer material is formed from at least one starch and at least one plasticizer.

4. The method of clause 3, wherein the one or more starches comprise one or more of potato starch, corn starch, or tapioca starch, and the plasticizer comprises glycerin.

5. The method of clause 3, wherein the starch-based polymeric material is formed from a blend of at least two different starches.

6. The method of paragraph 5, wherein the two different starches from which the starch-based polymer material is formed are (i) one of potato starch, corn starch, or tapioca starch, and (ii) potato starch, corn starch, or tapioca. A method comprising another one of starches, wherein (ii) is selected to be different from (i).

7. The method of clause 6, wherein the two different starches from which the starch-based polymeric material is formed are selected from one of the rows of the table below:

8. The method of claim 1, wherein the plastic material comprises polyolefin.

9. The method of clause 1, wherein the plastic material comprises polyethylene.

10. The method of claim 9, wherein the plastic material comprises a polyethylene film, which is a film formed from a blend of carbohydrate-based polymer materials and polyethylene.

11. The method of clause 1, wherein the plastic material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, or polycarbonate.

12. The method of clause 1, wherein blending at least 5% by weight of the carbohydrate-based polymer material with the plastic material is sufficient to render the plastic material biodegradable.

13. The method of claim 1, wherein the blend of carbohydrate-based polymeric material and plastic material comprises at least 5% by weight carbohydrate-based polymeric material.

14. The method of claim 1, wherein the blend of carbohydrate-based polymeric material and plastic material comprises 5% to 50% by weight carbohydrate-based polymeric material.

15. The method of claim 1, wherein the blend of carbohydrate-based polymeric material and plastic material comprises from 10% to 50% by weight carbohydrate-based polymeric material.

16. The method of claim 1, wherein the blend of carbohydrate-based polymeric material and plastic material comprises from 20% to 40% by weight carbohydrate-based polymeric material.

17. The method of claim 1, wherein the blend of carbohydrate-based polymeric material and plastic material further comprises a compatibilizer.

18. The method of clause 17, wherein the compatibilizer comprises up to 10% by weight of the blend.

19. Providing a plastic material that is not itself biodegradable;

One or more substantially amorphous carbohydrate-based polymeric materials having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and/or other physical characteristics of NuPlastiQ or ESR, e.g. starch-based polymeric material), wherein one or more carbohydrate-based polymeric materials are selected for their ability to impart biodegradability to a plastic material that is not itself biodegradable; and

Blending the carbohydrate-based polymer material with the plastic material, wherein the carbohydrate-based polymer material renders the plastic material biodegradable,

A method of imparting biodegradability to plastic materials that are not otherwise biodegradable.

1. Blowing a plastic film, the film blown from a blend comprising a first polymer material and a renewable starch-based polymer material, with a film blowing device, wherein the renewable starch-based polymer material is (i) 20% or less; is substantially amorphous with a degree of crystallinity, (ii) has a Young's modulus of at least 1.0 GPa, and/or (iii) has a glass transition temperature, Vicat softening temperature or heat distortion temperature of 70°C to 100°C, ,

(A) the film blowing device operates at a high blowup ratio of at least 2.0 when blowing a plastic film, and/or the high blowup ratio provides a blown plastic film with increased strength;

(B) the die gap of the film blowing device is selected to be a narrow die gap of 500 microns or less, the narrow die gap providing a blown plastic film with increased strength; How to provide.

2. The method of claim 1, wherein the first polymeric material comprises a polyolefin.

3. The method of clause 1, wherein the first polymeric material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, or polycarbonate.

4. The method of claim 1, wherein the first polymeric material comprises at least one of polyethylene or polypropylene.

5. The method of claim 1, wherein the blown plastic film has a thickness of 0.1 mil to 10 mils.

6. The method of clause 1, wherein the blowup ratio is 2.2 to 2.8.

7. The method of clause 1, wherein the blowup ratio is about 2.5.

8. The method of claim 1, wherein the renewable starch-based polymeric material is formed from a blend of at least two different starches.

9. Blowing a plastic film with a film blowing device, wherein the plastic film is a film blown from a blend comprising a first polymer material and a second polymer material comprising a renewable starch-based polymer material, wherein the renewable starch-based polymer material (i) is substantially amorphous, having a crystallinity of 20% or less, (ii) has a Young's modulus of at least 1.0 GPa, and (iii) has a glass transition temperature, Vicat softening temperature or heat distortion temperature of 70°C to 100°C. Phosphorus phase;

Manipulating the blowup ratio of the film blowing device to select a high blowup ratio of at least 2.0 such that the strength of the blown plastic film is increased.

A method of increasing the strength of blown plastic films by manipulating the blowup ratio.

10. The method of clause 9, wherein the intensity is increased by at least 1% by selecting a high blowup ratio.

11. The method of claim 9, wherein the intensity is increased by at least 10% by selecting a high blowup ratio.

12. The method of clause 9, wherein the blowup ratio is 2.2 to 2.8.

13. The method of clause 9, wherein the blowup ratio is about 2.5.

14. The method of claim 9, wherein the blown plastic film has a thickness of 0.1 mil to 10 mil.

15. Blowing a plastic film with a film blowing device, wherein the plastic film is a film blown from a blend comprising a first polymer material and a second polymer material comprising a renewable starch-based polymer material, wherein the renewable starch-based polymer material is (i ) has a crystallinity of 20% or less, is substantially amorphous, (ii) has a Young's modulus of at least 1.0 GPa, and/or (iii) has a glass transition temperature, Vicat softening temperature or heat distortion temperature of 70°C to 100°C. A step having a;

Manipulating the die gap of the film blowing device to select a narrow die gap of 500 microns or less;

manipulating the blowup ratio when blowing a plastic film to a value of at least 2.0, wherein the high blowup ratio and/or narrow die gap provide the blown pilastic film with increased strength. doing,

A method of increasing the strength of blown plastic films by manipulating blowup ratio and die gap.

16. The method of clause 15, wherein the blowup ratio is at least 2.0.

17. The method of clause 15, wherein the blowup ratio is 2.2 to 2.8.

18. The method of clause 15, wherein the blowup ratio is about 2.5.

19. The method of clause 15, wherein the die gap is between 250 microns and 500 microns.

20. The method of claim 15, wherein the blown plastic film has a thickness of 0.1 mil to 10 mil.

1. Polymer resin;

Organic odor reducer; and

A sustainable plastic material exhibiting reduced odor comprising a carbohydrate-based polymeric material that, in the absence of the organic odor reducer, can impart a characteristic burnt carbohydrate odor to the sustainable plastic material.

2. The material of claim 1, wherein the organic odor reducer is a freeze-dried powder.

3. The substance of claim 1, wherein the organic odor reducer comprises vanilla extract.

4. The material of clause 1, wherein the organic odor reducer comprises vanillin.

5. The substance according to clause 1, wherein the organic odor reducer has the following chemical structure:

6. The material of claim 1, wherein the organic odor reducer consists essentially of 4-hydroxy-3-methoxybenzaldehyde.

7. The material of clause 1, wherein the organic odor reducer comprises no more than 1% plastic material.

8. The material of claim 1, wherein the organic odor reducer comprises no more than 0.1% plastic material.

9. The material of clause 1, wherein the organic odor reducer comprises no more than 0.01% plastic material.

10. The material of claim 1, wherein the organic odor reducer comprises less than 1000 ppm of plastic material.

11. The material of claim 1, wherein the organic odor reducer comprises less than 100 ppm of plastic material.

12. The material of clause 1, wherein the organic odor reducer comprises no more than 50 ppm of plastic material.

13. The material of clause 1, wherein the organic odor reducer comprises no more than 20 ppm of plastic material.

14. The material of claim 1, wherein the organic odor reducer is present in a ratio of 1:1000 to 1:100,000 to the carbohydrate based polymeric material.

15. The material of claim 1, wherein the organic odor reducer is present in a ratio of 1:25,000 to 1:75,000 to the carbohydrate based polymer material.

16. The substance of claim 1, wherein the organic odor reducer comprises a fruit extract.

17. The method of claim 16, wherein the organic odor reducer is a freeze-dried organic fruit extract selected from extracts of vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, raspberry, or combinations thereof. Containing substances.

18. The material of claim 16, wherein the freeze-dried organic fruit extract is present in the plastic material in a ratio of less than 1:1000 to the carbohydrate-based polymeric material.

19. The material of clause 1, wherein the carbohydrate-based polymeric material is a starch-based polymeric material.

20. Organic odor reducer; and

A sustainable thermoplastic carbohydrate-based polymeric material exhibiting reduced odor, comprising:

A material wherein the weight ratio of the organic odor reducer to the carbohydrate-based polymeric material is less than or equal to 1:1000 such that the carbohydrate-based polymeric material is at least 1000 times greater than the organic odor reducer.

21. The material of clause 20, further comprising a thermoplastic polymer resin blended with the sustainable thermoplastic carbohydrate-based polymer material, wherein when blending the sustainable thermoplastic carbohydrate-based polymer material with the thermoplastic polymer resin at a high temperature, the organic A substance in which a burnt carbohydrate odor would be present were it not for the presence of an odor reducer.

22. The material of clause 21, wherein the thermoplastic polymer resin comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, or polycarbonate.

23. The material of claim 22, wherein the blend of the carbohydrate-based polymeric material and the thermoplastic polymer resin comprises 5% to 50% by weight of the carbohydrate-based polymeric material.

1. Providing one or more other polymeric materials (e.g., petrochemical-based polymeric materials);

providing one or more carbohydrate-based polymeric materials;

mixing the one or more other polymeric materials and the one or more carbohydrate-based polymeric materials to produce a mixture;

heating the mixture to a temperature ranging from about 120° C. to 180° C.; and

Using the mixture to produce a film having a thickness of about 1 to about 6 microns and a dart drop impact test value of about 40 g to about 100 g.

1. Providing at least one carbohydrate-based polymeric material;

providing one or more other polymeric materials (including, for example, PBAT or bio-PE);

mixing the one or more other polymeric materials and the one or more carbohydrate-based polymeric materials to produce a mixture;

heating the mixture to a temperature ranging from about 120° C. to 180° C.; and

Using the mixture to produce a film having a thickness of about 10 to about 100 microns and a dart drop impact test value of about 200 g to about 600 g.

These and other advantages and features of the invention will become more fully apparent from the following detailed description and appended claims, or may be learned by practice of the invention as set forth hereinafter.

For the purposes of how the above-cited and other advantages and objects of the invention may be obtained, a more specific description of the invention briefly described above will be presented with reference to specific embodiments of the invention illustrated in the accompanying drawings. With the understanding that these drawings illustrate only exemplary embodiments of the invention and therefore should not be considered limiting its scope, the invention will be described and explained with further specificity and detail through the use of the accompanying drawings, in which:
1 illustrates a flow diagram of an exemplary method of forming an article according to the present disclosure.
1A illustrates a flow diagram of an exemplary method for increasing the strength of blown plastic films by manipulating the blowup ratio.
1B illustrates a flow diagram of an exemplary method of including an odor reducer in a blend of materials comprising the carbohydrate-based polymer material and another polymer material.
1C is an illustration of forming a carbohydrate-based polymeric material comprising an odor reducing agent that counteracts the characteristic odor of the carbohydrate-based polymeric material, and then using the carbohydrate-based polymeric material comprising an odor reducing agent to produce an article. A flowchart of the method is illustrated.
2A illustrates components of an example manufacturing system for producing articles according to the present disclosure.
FIG. 2B illustrates a close-up schematic diagram of the film blowing apparatus of FIG. 2A showing the die, die gap, blown film bubble with high blowup ratio, and frost line of the bubble.
Figure 2C illustrates a close-up schematic cross-section through a portion of the die of Figure 2B, showing a narrow die gap.
Figure 3 presents modulus and elongation at break data for a variety of petrochemical plastics (labeled standard plastics) that are typically neither biodegradable nor compostable, as well as a variety of plastics that are more "environmentally friendly" in one or more respects.
4 shows an X-ray for an exemplary NuPlastiQ or “ESR” carbohydrate-based polymer material commercially available from BiologiQ compared to the The diffraction pattern is presented.
Figure 5 presents the dart strength for different thickness films based on the percentage of carbohydrate based polymer material in the film.
Figure 6 shows the dart strength for different thickness films (from about 0.1 mil up to 2 mil) formed from a blend of 25% carbohydrate-based polymeric material, about 5% compatibilizer, and about 70% PE, compared to a 100% PE film. It also presents a comparison of existing shopping cart bags, carrying bags, and potato bags.
Figure 7 presents dart strengths for different thickness films for various blended films including NuPlastiQ or ESR, as well as comparative films formed from virgin or recycled materials.
Figures 8A-8B present biodegradation rates measured over 349 days according to testing conducted under ASTM D-5511 for three samples formed in accordance with the present disclosure.
Figure 9 presents biodegradation rates measured over 843 days according to testing conducted under ASTM D-5526 for potato bags made with 25% NuPlastiQ or ESR, 70% PE, and 5% compatibilizer under simulated landfill conditions.
Figures 10A-10B present biodegradation rates measured over 370 according to testing conducted under ASTM D-5338 for various samples made in accordance with the present disclosure, as well as comparative controls.
Figure 11 presents biodegradation rates measured over 205 days according to ASTM D-6691, meant to simulate marine conditions, for various samples made in accordance with the present disclosure, as well as comparative controls.
Figure 12a presents the dart strength for films made from blends of NuPlastiQ or ESR carbohydrate-based polymer materials and biopolyethylene or “green” PE. Dart strength is presented as a function of NuPlastiQ or ESR percentage, for films of various thicknesses.
Figure 12B shows similar data to Figure 12A for blends containing various percentages of NuPlastiQ or ESR, but presents dart intensity as a function of film thickness.
Figure 13 shows the dart strength for a polyethylene film containing 25% NuPlastiQ or ESR material and the remainder formed entirely from polyethylene, showing no strength dependence on blowup ratio, with compatibilizer and polyethylene at a blowup ratio of 2.5. presents the dart strength for films formed from the blend.

I. Definition

All publications, patents, and patent applications cited herein, whether supra or infra, are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. It is included as

The term "comprising," which is synonymous with "comprising," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional uncited elements or method steps.

The term "consisting essentially of" limits the scope of the claim to the specified materials or steps "and which do not materially affect the basic and novel feature(s)" of the claimed invention.

As used herein, the term “consisting of” excludes any element, step, or ingredient not specified in the claims.

As used in connection with describing the features of the invention (and especially in connection with the claims below), the singular terms and similar referents include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. It should be interpreted as Thus, for example, reference to “starch” may include one, two or more starches.

As used herein, “film” refers to a thin, continuous article comprising one or more polymeric materials that can be used to separate areas or volumes, retain items, act as a barrier, and/or as a printable surface.

As used herein, “bag” refers to a container made of relatively thin, flexible film that can be used to contain and/or transport merchandise.

As used herein, “bottle” refers to a container that may be made of the plastics disclosed herein, typically of greater thickness than film, and typically includes a relatively narrow neck proximal to the mouth. These bottles can be used to hold a wide variety of products (eg, beverages, personal care products such as shampoos, conditioners, lotions, soaps, cleansers, etc.).

Unless otherwise stated, all percentages, ratios, parts, and amounts used and described herein are by weight.

Numbers, percentages, ratios, or other values mentioned herein may include those values, and also other values that are approximately or approximately the stated value, as would be understood by a person of ordinary skill in the art. there is. Accordingly, stated values should be interpreted broadly enough to encompass values that are at least sufficiently close to the stated value and/or rounded to the stated value to perform the desired function or achieve the desired result. The stated values include at least the variation expected in a typical manufacturing process and may include values that are within 25%, 15%, 10%, within 5%, within 1%, etc. of the stated value. Moreover, as used herein, the terms “substantially,” “similarly,” “about,” or “approximately” refer to an amount or state that is close to the stated amount or state that still performs the desired function or achieves the desired result. For example, the terms "substantially," "about," or "approximately" may refer to an amount that is within 25%, within 15%, within 10%, within 5%, or within 1% of the stated amount or value. You can.

Some ranges are disclosed herein. Additional ranges may be defined between any of the values disclosed herein as examples of specific parameters. All such ranges are considered within the scope of this disclosure. Additionally, references to ranges of values herein are intended to serve as a shorthand way of individually referring to each individual value that falls within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.

All numbers indicating quantities of ingredients, components, conditions, etc. used in the specification and claims are to be understood as being modified in all cases by the term “about.” Although the numerical ranges and parameters set forth in the broad scope of the invention are approximations, the numerical values set forth in specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that inevitably arise due to the standard deviation found in its respective test measurements.

As used herein, the phrase 'free' or similar phrases means that the composition contains 0% of the stated ingredient, i.e., that the ingredient was not intentionally added to the composition. However, it will be understood that such constituents may, under appropriate circumstances, form incidentally and may exist incidentally within other incorporated constituents, for example, incidental contaminants, etc.

As used herein, the phrase 'substantially free' or similar phrases means that the composition preferably comprises 0% of the stated constituents, but without, for example, incidental formation, incidental contamination, or even It will be understood that very small concentrations may exist due to intentional addition. These components, if any, may be present in amounts of less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0.01%, less than 0.005%, less than 0.001%, or less than 0.0001%. .

II. introduction

The present disclosure relates, inter alia, to articles formed from blends comprising a renewable or sustainable carbohydrate-based polymer material in combination with another polymer material. In addition to increased sustainability, such articles may exhibit biodegradability and/or increased strength. An article may be prepared by mixing one or more carbohydrate-based polymeric materials and one or more other polymeric materials (e.g., petrochemical-based or “green” sustainable polymer versions of these plastic resins), heating the mixture, and forming a polymer therefrom, e.g. It can be formed by forming the article by extrusion, injection molding, blow molding, blow forming, etc. In various embodiments, the carbohydrate-based polymeric material is a starch-based polymer that is substantially amorphous and/or exhibits other specific characteristics related to glass transition temperature, heat distortion temperature, Vicat softening temperature, Young's modulus, low crystallinity, etc., as described herein. May contain substances.

The articles described herein may be produced in the form of any conceivable structure, including but not limited to bottles, boxes, other containers, cups, plates, utensils, sheets, films, bags, etc. Thin films for bags and film wraps (e.g. for wrapping around or on products) can be easily made using blown film equipment. Other processes that may be used to form articles may include, but are not limited to, injection molding, blow molding, thermoforming, and other plastic manufacturing processes.

Examples of suitable carbohydrate-based or starch-based polymeric materials for use in forming such articles are available from BiologiQ under the trade names NuPlastiQ or ESR (“Eco Starch Resin”). Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. Specific features of these NuPlastiQ or ESR materials will be described in greater detail herein. Other carbohydrate-based or starch-based polymeric materials that exhibit similar properties may also be suitable for use, with NuPlastiQ or ESR, available from BiologiQ, being only non-limiting examples of suitable carbohydrate-based or starch-based polymeric materials.

In one embodiment, the “other” polymeric materials (other than carbohydrate-based polymeric materials) included in the blend may be sustainable polymeric materials, for example, formed from plants or other renewable sources (e.g., bacterial products). As such, all or substantially all (e.g., at least 90%, at least 95%, at least 97%, at least 98%, at least 99%) of the polymer content of the article may be formed from polymers sourced from plants or other renewable sources. there is. These features are particularly advantageous from a sustainability perspective. As described herein, a small fraction of compatibilizer may be present in addition to the polymer content to increase compatibility between the “other” polymer resin material and the carbohydrate based polymer material. In some embodiments, these compatibilizers may be the only ingredients that are not sourced or derived from sustainable sources. In other embodiments, such compatibilizers may be sustainable, such that 100% of the article can potentially be sustainably sourced.

In addition to desirable sustainability characteristics, the carbohydrate-based polymer materials can be blended to be biodegradable (“green” sustainable polymer materials such as “green” PE (or biopolyethylene), “green” PP, or bioPET). It can be configured to provide. In other words, even if the “green” sustainable polymeric material itself is not biodegradable, it can actually become biodegradable when included in an article that also includes the carbohydrate-based polymeric material. This result is also a huge advantage.

Moreover, many articles (e.g., especially thin films) do not have particularly good strength when formed from conventional plastic materials (e.g., petrochemical-based polymer materials), such that increased strength at a given thickness may be desirable. Because "green" plastic materials exhibit similar physical characteristics to their corresponding conventional petrochemical-based counterparts, these "green" plastic materials also do not have particularly superior strength, and it is difficult to increase strength without increasing article thickness. A method may be desirable. When blended with carbohydrate-based polymeric materials as described herein, these increased strength results are achievable. For example, polyethylene films (such as biopolyethylene (“green” PE) or metallocene petrochemical-based PE) can have a dart impact strength of approximately 150 g for a 1 mil thick film, but do not increase film thickness. It may be advantageous if the strength can be increased without This embodiment can provide this increased strength. For example, when blended with carbohydrate-based polymer materials as described herein, strength can be increased by at least 5%. Typical results of some embodiments can result in strength increases of 20% or more.

The article is made by mixing the carbohydrate-based polymer material and the sustainable polymer material, heating the mixture, molding the mixture (e.g., injection molding), extruding the mixture, blow molding the mixture, and It can be produced by blowing the mixture and thermoforming the mixture. A variety of other plastic manufacturing processes will be apparent to those skilled in the art in light of this disclosure.

With respect to biodegradability, the methods and articles are directed to plastics that are not otherwise biodegradable on their own by blending such plastic materials with carbohydrate-based (e.g., starch-based) polymeric materials that have specific characteristics, including low crystallinity, as described herein. It can give biodegradability to a substance. This embodiment is particularly advantageous in that it allows many discarded plastic products to readily biodegrade in landfills or similar environments, rather than continuing to exist in a polymer stable state indefinitely.

Moreover, Applicant asserts that biodegradation of said articles will not readily occur if said articles are stored in typical storage and use environments (e.g., stored in homes, offices, warehouses, etc.), but that they may not be disposed of in landfills or composted or otherwise disposed of. It has been observed that biodegradation generally only begins to occur when typical disposal conditions are simulated or placed in such an environment. For example, these conditions are often (i) slightly elevated temperatures above normal ambient “use” or “storage” temperatures, (ii) exposure to elevated moisture levels, and (iii) landfill or compost and similar Includes exposure to certain classes of microorganisms that are vulnerable to disposal environments. Elevated temperature and moisture will not cause decomposition of these articles unless the necessary microorganisms are also present. The combination of the above conditions causes articles formed from the blend of these materials to begin to biodegrade. Third party testing as described herein confirms that not only are the carbohydrate-based polymer materials biodegradable, but that otherwise non-biodegradable plastic materials are actually biodegradable.

Although the mechanisms by which such biodegradation becomes possible when blended with the carbohydrate-based polymeric material may not be fully understood, blending the two plastic materials together coupled with the specific characteristics of the carbohydrate-based polymeric material makes them non-biodegradable. It is believed that by somehow breaking the moisture absorption barrier associated with the plastic material, microorganisms capable of biodegrading the carbohydrate-based polymer material not only biodegrade the carbohydrate-based polymer material, but also biodegrade adjacent plastic molecules. Carbon bonds are broken and biodegradation is confirmed based on third-party testing that captures and measures released carbon dioxide and methane. These results are surprising, unexpected, and particularly advantageous.

Another aspect of the present disclosure relates to methods of providing increased strength to blown plastic films by manipulating the blowup ratio and or die gap, at least in some embodiments. Such methods may include blowing a plastic film with a film blowing device, wherein the film is formed from a blend comprising a polymeric material (e.g., polyethylene, etc.) and a renewable carbohydrate-based (e.g., starch-based) polymeric material described herein. Once blown, the renewable carbohydrate-based polymeric material is substantially amorphous, for example, has a crystallinity of 20% or less, and/or includes other specified characteristics. For example, the renewable carbohydrate-based polymeric material may have a Young's modulus of at least 1.0 GPa and/or may have a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70°C to 100°C. The film blowing device is specifically operated at high blowup ratios of at least 2.0 and/or with narrow die gaps (e.g. less than 500 microns) when blowing plastic films. These features surprisingly show an increase in the strength of plastic films when using the carbohydrate-based polymer materials discovered by the applicant, compared to the strength that can be provided at lower, more typical blow-up ratios (e.g. 1.5) or wider die gaps. Provides strength. This comparison, showing increased strength while simply varying the blowup ratio or die gap, can be performed with the same materials. This increased strength also allows the film to be blown using the "other" polymeric material (e.g., polyethylene) alone, without NuPlastiQ or ESR, or other renewable carbohydrate-based polymeric materials with specific characteristics as identified herein. It can be expressed by comparing it to the strength that can be provided when. When blowing PE alone, blowup ratio and die gap do not significantly affect strength.

This method may be used to provide increased strength to the resulting blown film, as opposed to any other purpose for which the blowup ratio can be plausibly manipulated (e.g., perhaps manipulating the unfolded flat width of the resulting film). This may include specifically selecting a high blowup ratio and/or narrow die gap.

For example, applicants have discovered that when blowing films from “other” polymer materials, such as polyethylene alone, there is no significant effect on strength as the blowup ratio is manipulated. Moreover, Applicants note that when adding renewable carbohydrate-based polymeric materials such as NuPlastiQ or ESR to the blend from which the film is blown, at the same typical 1.5 blowup ratio typically used in blown films, compared to 100% polyethylene or other polymeric material films. It was found that there was no significant decrease in strength for these blended films when blown. Applicants have shown that when blowing blended films containing renewable carbohydrate-based polymer materials such as NuPlastiQ or ESR by increasing the blowup ratio, for example, to at least 2.0, preferably 2.2 to 2.8 (e.g., 2.5), the increase in strength is actually achieved. It was further discovered that this can be achieved.

It is not fully understood why strength increases at higher blowup ratios when these effects other than strength do not occur in films formed from the "other" polymer materials alone, but as the blowup ratio increases, the amorphous or other structural properties of the molecules in the blend may change. There may be some type of aligned orientation, stretching, or regular arrangement, which is believed to increase strength. In any event, although perhaps not fully understood, Applicant has observed and measured increased strength under the conditions and methods described herein.

The article is made by mixing a renewable carbohydrate-based polymer material with another polymer material (e.g., a polyolefin such as polyethylene, or another plastic), heating the mixture, and melting the molten mixture at a high blowup ratio and/or a narrow die gap. It can be produced by feeding it into a film blowing device operated at The blown film can be further processed into a wide variety of conceivable structures, including but not limited to plastic bags, film wraps, etc.

Another aspect of the present disclosure is an embodiment in which the characteristic burnt carbohydrate odor produced during typical heating and molding or other formation of the plastic material is counteracted by including a very small fraction of an odor reducer, preferably an organic odor reducer. It's about. In one embodiment, an odor reducing agent may be included with the carbohydrate-based polymeric material (e.g., as part of a masterbatch of the carbohydrate-based polymeric material).

In one embodiment, the carbohydrate-based polymeric material may be present in a much larger fraction than the odor reducer. For example, the carbohydrate-based polymer material may be at least 1000 times, 10,000 times, or 50,000 times more abundant than the odor reducer. Even at very small concentrations (e.g., 1 odor reducer to 50,000 carbohydrate-based polymer material), effective control (i.e., substantially complete elimination) of popcorn, caramel corn, or slightly burnt starch odors can be achieved. It is surprising that such a small fraction of odor reducer is sufficient to achieve the above results.

Masterbatches containing the odor control agent and the carbohydrate-based polymeric material can be blended with virtually any conceivable polymeric resin material and used to produce desirable plastic articles. For example, an article may be prepared by mixing a carbohydrate-based polymer material (including an odor reducer) with a polymer resin, heating the mixture, molding the mixture (e.g., injection molding), extruding the mixture, and forming the mixture. It can be produced by blow molding, blow forming the mixture (e.g., forming a blown film), and thermoforming the mixture. The above listing of plastic manufacturing processes is of course not complete, and various other plastic manufacturing processes will be apparent to those skilled in the art.

A small portion of the odor reducer may be included within the carbohydrate-based polymeric material, incorporated with the polymeric resin with which the carbohydrate-based polymeric material is blended, or otherwise incorporated into the blend. In one embodiment, the masterbatch of carbohydrate-based polymeric material may be provided with an odor reducing agent already incorporated therein. In another embodiment, the odor reducing agent may be added separately from the carbohydrate-based polymeric material and/or separately from the polymeric resin included in the blend from which the article is formed. It will be clear that, in addition to NuPlastiQ or ESR available from BiologiQ, other carbohydrate-based or starch-based polymeric materials may also benefit from the addition of small fractions of odor reducers as described herein.

III. Exemplary Articles and Methods

1 illustrates an exemplary “basic” method 100 according to the present invention. Odor reducers, if said “other” polymeric materials include sustainable resins themselves (e.g. “green” PE, bio PET, etc.), or specific choices when blowing the film, with regard to blow-up ratio and/or die gap. It will be apparent from this disclosure that various details can be added, such as the inclusion of . At 102, method 100 may be used to prepare one or more “other” polymeric materials, such as materials that are typically, but not necessarily, non-biodegradable (e.g., polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyesters). , polystyrene, ABS, polyvinyl chloride, nylon, or polycarbonate). At 104, method 100 includes providing one or more substantially amorphous carbohydrate-based polymeric materials exhibiting a crystallinity of less than 20% (e.g., more typically less than 10%). Other characteristics may alternatively or additionally be present (e.g., Young's modulus of at least 1.0 GPa, glass transition temperature of at least 70°C, at least 80°C, or 80°C to 100°C, Vicat softening temperature or heat distortion temperature). The one or more carbohydrate-based polymeric materials may include starch-based polymeric materials. The carbohydrate-based polymeric materials and the other polymeric materials may be provided in any desired form, such as pellets, powders, nurdles, slurries, and/or liquids. In specific embodiments, the material may be in the form of pellets. The method further includes blending another polymeric material with the carbohydrate-based polymeric material.

Such blends may be formed and manufactured into the desired articles by any conceivable method. An example of such a method may be an extrusion method. For example, the other polymeric material and the carbohydrate-based polymeric material can be fed into an extruder (eg, into one or more hoppers of the extruder). Different materials may be introduced into the same chamber of the extruder, into different chambers, at approximately the same time (e.g., through the same hopper), or at different times (e.g., through different hoppers, one being introduced into the extruder earlier along the axis than the other). etc. can be supplied. It will be clear that many, many possibilities are possible.

In some cases, the other polymeric materials may include polyolefins. For example, such plastic or polymer materials may include, but are not limited to, polyethylene polypropylene polyethylene terephthalate, other polyolefins, polyesters, polystyrene, ABS, polyvinyl chloride, nylon, polycarbonate, etc. These plastic materials may be sourced from petrochemical sources or from so-called “green” or sustainable sources (e.g. “green” PE, bio PET, etc.).

In some cases, the “other” polymeric material may itself be sustainable, for example a sustainable polyolefin. For example, these sustainable polymer materials may include “green” polyethylene (bio-PE), “green” polypropylene (bio-PP), bio-PET, or other plastic materials that can be formed from sustainable plant sources. It is not limited to this. As a non-limiting example, “green” PE may be derived from ethanol, which may be formed from sugar cane, other sugar crops (e.g., sugar beets), or grains (e.g., corn, wheat, etc.). “Green” PE (also sometimes referred to as “bio-PE”) has a similar chemical structure to PE formed from petrochemical feedstocks, but the ethanol, or ethylene monomer used in the polymerization, is from sustainable sources, rather than petrochemical feedstocks. It is derived from “Green” PP can similarly be formed from propylene, which can be derived from propanol (or perhaps isopropanol) derived from sugar cane, other sugar crops, or grains (e.g. corn). Another example of a “green” sustainable polymer material is bio-PET, for example, in bio-PET the monomers used to form poly(ethylene terephthalate) (e.g. typically ethylene glycol and terephthalic acid) come from plant sources such as candy. It may similarly be derived from sorghum, other sugar crops, or grains. PET is the most common thermoplastic of the polyester family. Another polyester that can be similarly formed from sustainable plant sources is polybutyrate adipate terephthalate (bio-PBAT). PBAT can be formed as a copolyester of adipic acid, 1,4 butanediol, and dimethyl terephthalate. One or more of these starting materials may be derived from sustainable plant sources. Another possible "green" polymer resin material that could be used is poly(lactic acid). PLA, as understood by those skilled in the art, is typically produced from monomers of lactic acid and/or lactide esters. One or more starting materials for PLA production may be derived from sustainable plant sources. Other possible "green" polymers that will be familiar to those skilled in the art that could be used include PBS (polybutylene succinate) or PCL (polycaprolactone).

Those skilled in the art will be familiar with methods for synthesizing such polymers. One or more of the ingredients used to prepare such polymers may be derived from suitable renewable plant-based or other renewable biological sources (e.g., bacterially produced). “Green” PE is available from Braskem, bio PET is available from Coca Cola ^TM 's Plant Bottle ^TM and is also available from other plastic manufacturers. Although PE, PP, PET, and PBAT are examples of “green” bioplastics that can be formed from materials derived from sustainable plant sources, numerous other “green” plastics are also made at least in part from sustainable materials (e.g. plant sources). It will be understood that as long as it can be formed as, it may be suitable for use. Additionally, sugar cane, other sugar crops, corn, wheat and other grains are illustrative, non-limiting examples of plant materials from which these “green” polymer materials may be derived, although numerous other plants and materials may also be suitably used. This will be understood.

The carbohydrate-based polymeric material may be formed from a plurality of materials (eg, a mixture) comprising one or more starches. For example, one or more starches can be produced from one or more plants, such as corn starch, tapioca starch, cassava starch, wheat starch, potato starch, rice starch, sorghum starch, etc. In some embodiments, mixtures of different types of starch can be used, which the applicants have found results in a synergistic increase in strength. Plasticizers are also present in the mixture of ingredients from which the carbohydrate-based polymer material is formed. Although water may also be used to form the carbohydrate-based polymeric material, only small to negligible amounts of water are present in the finished carbohydrate-based polymeric material.

It will be appreciated that in some embodiments thereafter the entire polymer content (or substantially the entire polymer content) of the article may be derived from plant material. While "green" polymeric materials typically utilize polymerizable monomers or other small molecule polymerizable constituents, which may be derived from ethanol (etc.) formed from desirable plant materials, carbohydrate-based (or starch-based) polymeric materials may be derived from such starches or Rather than processing other plant materials to form smaller polymerizable monomers, they can be formed from starch (and glycerin or other plasticizers). Accordingly, the molecular weight of the starch(s) used to make starch-based polymer materials can typically be much greater than the molecular weight of the relatively small molecule monomers produced for use in making “green” sustainable polymer materials. For example, monomers or other polymerizable constituents derived from plant sources used to make “green” sustainable polymer materials typically have a molecular weight of less than about 500 daltons, less than 400 daltons, less than 300 daltons, less than 200 daltons, or 100 daltons. Although the molecular weight of the starch(s) used to make starch-based polymer materials can be significantly higher, typically exceeding 500 Daltons, it can often be measured in the thousands, tens of thousands, or even higher (e.g., 500 Daltons). exceeding a dalton, at least 1000 daltons, at least 10,000 daltons, at least 25,000 daltons, at least 40,000 daltons, etc.). In other words, the starch materials (e.g., natural starches) used to form starch-based materials are typically more complex molecules than the monomers or other polymerizable components used to make “green” sustainable polymer materials. For example, corn starch may have a molecular weight of about 693 daltons. Potato starch can have a molecular weight that can vary widely, for example, from about 20,000 Daltons to about 400,000,000 Daltons (e.g., amylose can range from about 20,000 Daltons to about 2,000,000 Daltons, while amylopectin can range from about 65,000 Daltons to about 400,000,000 Daltons). may be in the range of approximately 400,000,000 daltons). Tapioca starch can have a molecular weight ranging from about 40,000 daltons to about 340,000 daltons. Glycerin used to form starch-based polymer materials can also be derived from sustainable sources. Glycerin, of course, has a molecular weight of 92 Daltons.

Referring back to the characteristics of carbohydrate-based polymeric materials, one or more carbohydrate-based polymeric materials may be formed predominantly from starch. For example, at least 65%, at least 70%, at least 75%, or at least 80% by weight of the carbohydrate-based polymeric material can be attributed to one or more starches. In one embodiment, 65% to 90% by weight of the finished carbohydrate-based polymeric material can be attributed to one or more starches. Aside from the negligible water content, the remainder of the finished carbohydrate-based polymer material can be attributed to plasticizers (e.g., glycerin). The percentage may represent the starch percentage relative to the starting material from which the carbohydrate-based polymer material is formed, or it may represent the corresponding fraction of the finished carbohydrate-based polymer material that may be derived from or attributable to the plasticizer (e.g., carbohydrate-based polymer material at least 65% of can be attributed to (can be formed from) starch(s) as starting material. Although some water may be used to form the carbohydrate-based polymer material, substantially the remainder of the carbohydrate-based polymer material may be attributed to glycerin, or another plasticizer. Very little residue (e.g., less than 2%, typically less than about 1%) may be present in the finished carbohydrate-based polymer material.

For example, the material from which the one or more carbohydrate-based polymer materials are formed may comprise at least 12%, at least 15%, at least 18%, at least 20%, at least 22%, up to 35%, 32% by weight of plasticizer. It may include less than or equal to 30% by weight, less than or equal to 28% by weight, or less than or equal to 25% by weight. These percentages may represent the corresponding fraction of the finished carbohydrate-based polymeric material that is derived from or can be attributed to the plasticizer (e.g., at least 12% of the carbohydrate-based polymeric material can be attributed to the plasticizer as a starting material (to be formed therefrom). can)).

Exemplary plasticizers include glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, hydrogen bond forming organic compounds without hydroxyl groups, anhydrides of sugar alcohols, animal proteins, vegetable proteins, aliphatic acids, phthalate esters, dimethyl and diethylsuccinate. and related esters, glycerol triacetate, glycerol mono and diacetate, glycerol mono, di, and tripropionate, butanoate, theearate, lactic acid ester, citric acid ester, adipic acid ester, stearic acid ester, oleic acid ester, Including, but not limited to, other acid esters, or combinations thereof. Glycerin may be preferred.

The finished carbohydrate-based polymeric material contains no more than 5%, no more than 4%, no more than 3% by weight, no more than 2%, no more than 1.5%, no more than 1.4%, no more than 1.3%, no more than 1.2%, and no more than 1.1% by weight of water. % or less, or 1% by weight or less. The NuPlastiQ or ESR materials available from BiologiQ are examples of such finished carbohydrate-based polymer materials, but it will be understood that other materials available elsewhere (e.g., at some time in the future) may also be suitable for use.

In some embodiments, mixtures of different starches can be used to form carbohydrate-based polymeric materials. The use of mixtures of these different starches (e.g. originating from different crops) has surprisingly been found to be associated with a synergistic increase in strength in articles comprising these carbohydrate-based polymeric materials. In such mixtures of starches, the starch is present in an amount of at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15% by weight relative to the combined weight of the plurality of starches. %, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, up to 95% by weight, up to 90% by weight, up to 85% by weight, up to 80% by weight, 75% by weight Hereinafter, it may be present in the mixture in an amount of up to 70% by weight, up to 65% by weight, up to 60% by weight, up to 55% by weight, up to 50% by weight, or from 10% to 50% by weight. Some non-limiting exemplary mixtures include 90% first starch, and 10% second starch, or 30% first starch and 70% second starch, or 50% first starch and 50% second starch. May contain starch. Blends of more than two starches (e.g. using three or four different starches) may also be used.

Examples of suitable carbohydrate-based (e.g., starch-based) polymeric materials for use in forming films and other articles are available from BiologiQ, Idaho Falls, Idaho, under the trade names NuPlastiQ or ESR (“Eco Starch Resin”). Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. NuPlastiQ or ESR can be provided in pellet form. Physical characteristics for GS-270 and GS-300 are presented in Table 1 below.

The above characteristics presented for GS-270 and GS-300 are examples of other NuPlastiQ or ESR products available from BiologiQ, but values may vary slightly. For example, NuPlastiQ or ESR products from BiologiQ generally have temperatures of at least 70°C, at least 75°C, at least 80°C, up to 200°C, up to 150°C, up to 125°C, up to 110°C, or about 70°C to about 100°C. , or may have a glass transition temperature, Vicat softening temperature, or heat distortion temperature ranging from 80° C. to 100° C. Those skilled in the art will understand that glass transition temperature, Vicat softening temperature and heat distortion temperature can be indicative of the degree of crystallinity. The values for melt temperature range, density, Young's modulus, and water content may be the same or similar to the values set forth above in Table 1. Some characteristics may vary somewhat (e.g., ±25%, or ±10%) from the values presented for GS-270 and GS-300. NuPlastiQ or ESR has an amorphous structure (i.e. more amorphous than typical raw starch). For example, a typical raw starch powder has a predominantly crystalline structure (e.g., greater than 50% crystalline), whereas NuPlastiQ or ESR has a predominantly amorphous structure (e.g., less than 10% crystalline). Any suitable standard can be used to measure the glass transition temperature, heat distortion temperature, Vicat softening temperature or any other physical characteristic. For example, the glass transition temperature can be determined according to ASTM D-3418, the heat distortion temperature according to ASTM D-648, and the Vicat softening temperature according to ASTM D-1525.

NuPlastiQ or ESR has a low water content as described. NuPlastiQ or ESR absorbs moisture, so it exhibits plastic behavior and becomes flexible. When removed from the humid environment, the material dries and becomes stiff again (i.e. again exhibiting a water content of less than about 1%). Moisture present in NuPlastiQ or ESR (e.g. in pellet form) may be released in the form of vapor during processing, as shown in Figure 1. As a result, films or other articles produced from starch-based polymer materials such as NuPlastiQ or ESR blended with non-biodegradable plastic materials may exhibit much lower water content, as non-biodegradable plastic materials typically retain water. It will contain no or negligible water, as water in NuPlastiQ or ESR typically can be released during manufacture of the desired article.

The low water content in the carbohydrate-based polymer materials can be important, as significant water content can lead to incompatibility with non-biodegradable plastic materials, especially if the article requires the formation of a thin film. Because. For example, because water evaporates, this can lead to cavities within the film or other article, as well as other problems. When blowing thin films, the carbohydrate-based polymer material used may preferably contain up to about 1% water.

The low water content in NuPlastiQ or ESR materials is not achieved through conventional esterification in some conventional TPS materials, which may contain relatively low water content. Such esterifications can be expensive and complex to perform. The same may be true for etherification. Moreover, since the starting materials of NuPlastiQ or ESR or other carbohydrate-based polymeric materials have been chemically reacted and/or altered, the NuPlastiQ or ESR materials that are exemplary carbohydrate-based polymeric materials available herein also typically contain any such material. Contains virtually no identifiable starch or identifiable glycerin. The X-ray diffraction patterns of exemplary carbohydrate-based polymeric materials, such as those described below (e.g., and shown in Figure 4), are evidence of such chemical modifications, and indicate that the finished polymeric material may be substantially free of this identifiable, native form of starch. suggests that there is In other words, carbohydrate-based polymer materials are not simply perceived as a mixture containing starch and glycerin. It is believed that the low water content achievable in carbohydrate-based polymeric materials is due, at least in part, to the chemical modification of the starch and plasticizer materials to thermoplastic polymers that do not retain water, such as native starches or conventional thermoplastic starches.

Referring back to Figure 1, processing at relatively high temperatures may result in some release of volatilized glycerin (e.g., visible as smoke). If necessary (e.g. if stored pellets may have absorbed additional water), drying of the pellets can be accomplished by blowing sufficient warm dry air to remove any absorbed water, for example at 60°C for 1 to 4 hours. This can be done by simply introducing it. Pellets should be dried to a moisture content of less than about 1% prior to processing, especially if forming films. NuPlastiQ or ESR pellets can simply be stored in a sealed container containing a desiccant in a dry location away from heat to minimize water absorption and prevent undesirable decomposition.

In addition to NuPlastiQ or ESR being thermoplastic, NuPlastiQ or ESR may also be thixotropic, meaning that the material is solid at ambient temperature but flows as a liquid when heat, pressure and/or frictional motion is applied. Advantageously, the pellets of NuPlastiQ or ESR can be used identically to petrochemical-based pellets (any typical non-biodegradable plastic resin pellets) in standard plastic production methods. NuPlastiQ or ESR materials and products made therefrom may exhibit gas barrier characteristics. Products (e.g., films) made using these NuPlastiQ or ESR pellets exhibit oxygen gas barrier characteristics (e.g., see examples in Applicant's prior applications, already incorporated by reference). NuPlastiQ or ESR materials are non-toxic and edible, made using all edible raw materials. NuPlastiQ or ESR and products made therefrom are water resistant, but may be water soluble. For example, NuPlastiQ or ESR may resist swelling under moist heat conditions to the extent that their pellets (e.g., 3-4 mm in size) will not completely dissolve in boiling water within 5 minutes, but the pellets will be released from the mouth within about 10 minutes. It will dissolve. NuPlastiQ or ESR can be stable in the sense that they cannot show any significant retrogradation even when left in relatively high humidity conditions, a feature that makes them different from many other thermoplastic starch materials. Of course, products made with NuPlastiQ or ESR can also exhibit these characteristics. If NuPlastiQ or ESR is stored in humid conditions, excess absorbed water can simply evaporate and, once the water content is below about 1%, can be used to form films or other articles.

NuPlastiQ or ESR materials also do not undergo biodegradation under typical storage conditions, even relatively humid conditions, since other conditions typical of landfills, composts or similar disposal environments containing certain desired microorganisms are typically absent. Of course, when these conditions exist, not only is NuPlastiQ or ESR biodegradable, but the otherwise non-biodegradable plastic materials it is blended with are also surprisingly biodegradable. Evidence of these surprising results is included in the Examples section included herein.

NuPlastiQ or ESR is manufactured at a cost competitive with traditional polyethylene plastic resins, making it cost-competitive. NuPlastiQ or ESR can be blended with other polymers, including but not limited to PE, PP, PET, polyester, polystyrene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride, nylon, etc. The non-biodegradable polymers can be made biodegradable by blending them with NuPlastiQ or ESR, although NuPlastiQ or ESR can also be used to prepare polymers that are already biodegradable and/or compostable, such as polylactic acid (PLA), poly(butylene adipate-co). -Terephthalate (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), other so-called thermoplastic starches, as well as a variety of others. It will be. PBS, PCL, and PHA are polyesters. EcoFlex ^TM is another example of a plastic material that can be blended with NuPlastiQ or ESR carbohydrate based polymer materials. For example, the present method is not limited to blending carbohydrate-based polymeric materials (e.g., NuPlastiQ or ESR) with only non-biodegradable plastic materials; biodegradable plastics (other than NuPlastiQ or ESR) may also be blended, if desired. It will be understood that mixing may occur.

By way of further explanation, PLA is compostable, meaning that it can decompose under elevated temperature conditions (i.e., composting conditions), but is not technically “biodegradable.” Some of the materials listed above, such as PBS, PCL, and PHA, may be biodegradable and compostable. EcoFLEX ^TM is certified compostable. The FTC's green guidelines state that plastics cannot be recklessly claimed to be "degradable" unless they decompose "after normal disposal" within a "reasonably short period of time" (most recently defined as no more than five years).

In some embodiments, NuPlastiQ or ESR may be provided in a masterbatch formulation that may include an amount of carbohydrate-based polymeric material as described above, and one or more compatibilizers. The masterbatch may also contain one or more non-biodegradable plastic materials. These masterbatch formulation pellets may be mixed with pellets of non-biodegradable plastic materials at the time of processing. Any conceivable ratio may be used to mix these different pellets, depending on the desired percentage of NuPlastiQ or ESR and/or compatibilizer and/or conventional non-biodegradable plastic material in the finished product.

NuPlastiQ or ESR contains very low water content. For example, although raw starch (e.g. used to form ESR) may typically contain about 13% water by weight, finished NuPlastiQ or ESR pellets available from BiologiQ contain less than about 1% water. do. NuPlastiQ or ESR materials are biodegradable, and as described herein, starch-based NuPlastiQ or ESR materials are biodegradable as well as other polymers such as PE, PP, PET, polyester, polystyrene, ABS, polyvinyl, which are not biodegradable. When blended with chloride, nylon, and other non-biodegradable plastic materials, the blended material also becomes substantially entirely biodegradable. These results are quite surprising and particularly advantageous. The examples herein provide evidence of these surprising results. Typical thermoplastic starch materials do not claim or exhibit these characteristics when blended with other plastic materials.

NuPlastiQ or ESR materials may exhibit some elasticity, but their elasticity may be less than that of many other polymers (e.g., especially "green" sustainable polymers that mimic their petrochemical-based polymer families). Films and other articles can be formed from blends of NuPlastiQ or ESR with any other desired polymer(s), which provides elastic results that exhibit increased strength at a given article thickness compared to the other polymers alone. Although films are described and often used in embodiments herein where strength is often of paramount importance, increased strength may also be provided to articles other than films (e.g., bottles, sheets, boxes, cups, plate utensils, or other forms). It will be clear that there is. Table 2 below presents for comparison elongation at break and modulus values for various standard plastic (“SP”) materials, various “green” plastic materials, and NuPlastiQ or ESR. “Environmentally friendly” means that a material is at least partially derived from sustainable materials, is compostable, and/or can have one or more environmentally desirable characteristics, such as being biodegradable. NuPlastiQ or ESR in Table 2 has a tensile strength of 40 MPa.

Figure 3 presents similar data to Table 2 in chart form. Of course, some of the products listed in the table as standard plastics and shown in Figure 3 are "green" strains that may be derived from sustainable sources, such as, but not limited to, bio PET, "green" PP, "green" PE, and Has a bio PBAT. PLA is compostable, meaning it can decompose under elevated temperature conditions (i.e. composting conditions), but is not technically “biodegradable.” Other exemplary materials listed above, such as EcoFlex, PBS, PCL, and PHA, may be biodegradable and compostable. The FTC's environmental guidelines state that plastics cannot make indiscriminate claims that they are "degradable" unless they decompose "after normal disposal" within a "reasonably short period of time" (most recently defined as no more than five years).

NuPlastiQ or ESR materials described herein as suitable for use as carbohydrate-based (e.g., starch-based) polymeric materials are substantially amorphous. For example, raw starch powders (such as those used to make NuPlastiQ or ESR and various other thermoplastic starch materials) have an approximately 50% crystalline structure. NuPlastiQ or ESR materials available from BiologiQ differ from many other commercially available thermoplastic starch (TPS) materials in their degree of crystallinity compared to their amorphous character. For example, pages 62-63 of Kris Frost's PhD thesis (September 2010) "Thermoplastic Starch Composites and Blends" states that "Among the specific concerns in TPS are the integrity of gelatinization during processing, and type V amylose. “There is a random subsequent tendency towards aging to form crystals,” he notes. Frost further notes, "Gelatinization involves the loss of the granular and crystalline structure by heating with water and often including other plasticizers or modifying the polymer. Aging is due to the recoiling of the amylose helical coils that are crushed during gelatinization. "The starch molecules slowly recoil into their natural helical configuration, or a new single helical configuration known as the V-shape, causing the TPS film to rapidly break and lose its bright clarity." Therefore, conventional TPS tends to reform its crystalline structure after the gelatinization process used to produce TPS from raw starch. In contrast, NuPlastiQ or ESR materials available from BiologiQ do not revert to a predominantly crystalline structure. Moreover, it is stable and can maintain relatively high optical clarity, which may be useful for forming relatively optically clear films (e.g., especially by sandwiching NuPlastiQ or ESR containing layers between layers of polyethylene or other polyolefins).

In contrast to typical TPS materials, NuPlastiQ or ESR materials, which are suitable examples of starch-based polymer materials for use in forming the articles described herein, have an amorphous microstructure and physical characteristics as shown in Table 1. The difference in molecular structure between conventional TPS and NuPlastiQ or ESR materials is due to the fact that the NuPlastiQ or ESR materials as described herein are much less crystalline than the conventional thermoplastic starch-based materials, as shown by the X-ray diffraction shown in Figure 4. Demonstrated, Figure 4 compares the diffraction pattern results for the NuPlastiQ or ESR material available from BiologiQ (Sample 1) compared to the blend of natural raw corn starch and natural raw potato starch from which the NuPlastiQ or ESR of Figure 4 was formed. The diffraction pattern of NuPlastiQ or ESR as shown in Figure 4 is much less crystalline (e.g., less than about 10% crystallinity) than the diffraction pattern of the native starch blend (about 50% crystallinity). The difference in diffraction patterns demonstrates that substantial chemical changes have occurred in the material due to processing of native starch into NuPlastiQ or ESR. For example, natural starch has a prominent diffraction peak between 20-25°, but this peak does not appear with NuPlastiQ or ESR. Native starch additionally exhibits a strong peak at about 45° (intensity of 0.5 to 0.6), which is greatly reduced in NuPlastiQ or ESR (only about 0.25 to 0.3). Throughout almost the entire spectrum except from about 18° to about 22°, the diffraction intensity is higher for native starch than for NuPlastiQ or ESR as shown. The elevated diffraction intensity across a broad spectrum indicates greater crystallinity of native starch compared to NuPlastiQ or ESR. As indicated, numerous other differences also exist.

For example, the carbohydrate-based (e.g., starch-based) polymeric material used to make the film according to the present disclosure may be less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, It may have a crystallinity of less than about 15%, less than about 10%, less than about 8%, less than about 6%, less than about 5%, or less than about 3%. Any suitable testing mechanism for determining crystallinity may be used, including, but not limited to, FTIR analysis, X-ray diffraction methods, and symmetric reflection and transmission techniques. A variety of suitable test methods will be apparent to those skilled in the art.

In addition to the differences in the microstructure of starting materials and finished NuPlastiQ or ESR, films, bottles, sheets, disposable utensils, plates, cups, or other articles produced from blends containing carbohydrate-based polymer materials may differ from those of conventional TPS and starch powders. , or formed solely using plastic materials that are not biodegradable, but are otherwise different from similar articles. For example, articles formed by blending a carbohydrate-based polymeric material such as NuPlastiQ or ESR as described herein with a non-biodegradable plastic material can produce "sea-island" conditions common when blending conventional TPS materials with polymeric materials such as polyethylene. )" does not have the characteristic. The properties of different films can be viewed by comparing the physical properties of the films as shown in Table 11 of Example 5 of Applicant's US Patent Application No. 15/481,806, already incorporated by reference. In particular, this table compares the physical properties of films made by blending carbohydrate-based polymer materials as considered herein with non-biodegradable polyethylene to conventional TPS blended with PE (Cardia BL-F). In addition to the differences in properties shown in Table 11 of Example 5 of Applicant's U.S. Patent Application No. 15/481,806, films based on conventional TPS materials such as Cardia BL-F, blended with PE, are neither biodegradable nor compostable. not.

As described herein, blending a carbohydrate-based polymer material as described herein with a non-biodegradable plastic material not only renders the carbohydrate-based material biodegradable, but also renders the non-biodegradable plastic material actually biodegradable ( Non-biodegradable plastic materials (even if the material alone is not biodegradable). This result does not occur when blended with typical TPS materials. This difference in biodegradability results in significant structural and/or chemical effects in the resulting films and other articles because the entire composite structure (i.e., film or other structure) is now biodegradable, as shown by the various examples below. It clearly demonstrates that there is a difference.

Without wishing to be bound by any particular theory, the carbohydrate-based polymer resin reduces the crystallinity of the blended product, which may cause water or bacteria to orient and link the otherwise non-biodegradable plastic molecules of the blend with the carbohydrate-based polymer resin material. It is believed that it disrupts the crystallinity and/or hygroscopic barrier properties of polyethylene or other non-biodegradable plastic materials in a way that causes them to decompose. In other words, long polymer chains of polyethylene or other non-biodegradable plastic materials, when blended with carbohydrate-based polymer materials as contemplated herein, are more susceptible to chemical and mechanical forces present in environments rich in bacteria and microorganisms. is completely destroyed. Subsequently, microorganisms naturally present in waste environments (e.g. landfills) can consume the remaining smaller molecules so that they are converted back to their natural constituents (e.g. CO ₂ , CH ₄ , and H ₂ O). there is.

For example, actual biodegradable plastics break down into natural elements or compounds such as carbon dioxide, methane, water, inorganic compounds, or biomass through microbial assimilation (e.g., enzymatic action of microorganisms on plastic molecules). Biodegradation of plastics may be possible by first breaking the polymer chains through chemical or mechanical action, but can only be fully accomplished through the breakdown of the molecules by microbial assimilation.

Plastics made from petrochemical feedstocks or derived from plant sources begin their life as monomers (i.e., single small molecules that can react chemically with other small molecules). When monomers are joined together, they become polymers ("many parts") known as plastics. Before being conjugated together, many of the monomers are already biodegradable, but after being linked together through polymerization, the molecules become so large and conjugated in such arrangements and linkages that microbial assimilation by microorganisms is not feasible within any reasonable period of time.

Polymers are formed in both crystalline (regularly packed) and amorphous (randomly arranged) structures. Many polymers contain a high degree of crystallinity, with some amorphous regions randomly arranged and intertwined throughout the polymer structure.

NuPlastiQ or ESR materials available from BiologiQ are formed from highly crystalline starting starch materials, but the finished NuPlastiQ or ESR plastic resin materials exhibit low crystallinity (substantially amorphous). These starch-based polymer materials are used as starting materials in the production of articles as described herein. Therefore, NuPlastiQ or ESR is a plastic made from starch. Because of its natural, starch-based origin and carefully controlled linkage type, the molecules (size and linkage) of plastics made from NuPlastiQ or ESR are sensitive to humidity (water) and moisture, as evidenced by experimental test results included herein. It is highly susceptible to biodegradation by enzymatic reactions resulting from the introduction of bacteria or other microorganisms.

Polyolefins, such as rigid forms of polyethylene and polypropylene, have a high degree of crystallinity and are made by converting monomeric molecules (whether derived from petroleum, ethanol or other small building block molecules from plant sources) into long-chain polymers. The bonds created when linking monomers to form long polymer chains are strong and difficult to break. Films and other articles formed from these polymeric materials are not biodegradable. Even if a given article is formed from a blend of conventional non-biodegradable plastic materials and conventional TPS, it usually cannot suddenly acquire biodegradable characteristics (except for the starch portion of the blend, which is sometimes biodegradable).

Applicants have developed a method of imparting biodegradability to otherwise non-biodegradable plastic materials by blending these plastic materials with carbohydrate-based polymer materials with low crystallinity (e.g. NuPlastiQ or ESR). Typically, plastic materials that are not biodegradable (eg especially in the case of PE or PP) have a higher degree of crystallinity.

In addition to being biodegradable, the resulting blend may additionally or alternatively have a higher modulus (stiffness, or strength) than polyethylene or other non-biodegradable plastic materials, such as plastic films or pure polyethylene or other pure non-biodegradable plastics. It can be used to make other items that are stronger than the same item made from the material. This increased strength feature is previously described in US patent application Ser. No. 15/481,806, which is incorporated herein by reference.

Referring back to Figure 1, at 106, method 100 includes mixing the one or more carbohydrate-based polymeric materials with the one or more other polymeric materials to produce a mixture of materials. In some cases, mixing of the one or more other polymeric materials and the one or more carbohydrate-based materials may be performed using one or more mixing devices. In certain implementations, a mechanical mixing device can be used to mix the one or more other polymeric materials and the one or more carbohydrate-based polymeric materials. In one implementation, at least some of the components of the mixture of materials may be combined in an apparatus such as an extruder, injection molding machine, etc. In other implementations, at least some of the components of the mixture of substances may be combined before being supplied to the device.

The one or more carbohydrate-based polymeric materials can be present in a mixture of materials over a wide variety of materials depending on the characteristics desired. In one embodiment, such inclusions are used to impart biodegradability to otherwise non-biodegradable “other” polymeric materials included in the blend, to increase strength to a desired extent, or to provide a given level of “sustainable” content. , or may be sufficient for another purpose. For example, the carbohydrate-based polymeric material may comprise at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, or at least of the mixture of substances. 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45% by weight, up to 99% by weight, up to 95% by weight, up to 90% by weight, 80% by weight Weight % or less, 70 weight % or less, 60 weight % or less, 50 weight % or less, 2 weight % to 98 weight %, 20 weight % to 40 weight %, 10 weight % to 40 weight %, 20 weight % to 30 weight % , may be included in an amount of 50% by weight to 80% by weight, or 40% by weight to 60% by weight. More than one carbohydrate-based polymer material, and/or more than one other plastic material, may be included in the blend, if desired.

The other polymeric materials may comprise at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, or at least of the mixture of materials. 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 45% by weight, at least 50% by weight, up to 99% by weight, up to 95% by weight, up to 90% by weight, 85 wt.% or less, 80 wt.% or less, 75 wt.% or less, 70 wt.% or less, 65 wt.% or less, or 60 wt.% or less, 2 wt.% to 98 wt.%, 50 wt.% to 90 wt.%, 65 wt.% to It may be present in the mixture of substances in an amount of 75%, 20% to 50%, or 40% to 60% by weight.

Compatibilizers may be present in the mixture of the above materials. The compatibilizer can be mixed with the other polymeric material, the carbohydrate-based polymeric material, mixed with both, or provided separately. Often the compatibilizer may be provided, for example, with at least one of the polymeric substances included in the masterbatch formulation. The compatibilizer may be a modified polyolefin or other modified plastic, such as maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted polybutene, or combinations thereof. The compatibilizer may also include an acrylate-based copolymer. For example, the compatibilizer may include ethylene methyl acrylate copolymer, ethylene butyl-acrylate copolymer, or ethylene ethyl acrylate copolymer. Additionally, the compatibilizer may include a poly(vinylacetate)-based compatibilizer. In one embodiment, the compatibilizer is a grafted version of another polymer material (e.g., maleic anhydride grafted polyethylene where the other polymer material is polyethylene) or a copolymer where one of the blocks is the same monomer as the other polymer material (e.g. : block copolymer) (e.g. a styrene copolymer where the other polymer material is polystyrene or ABS).

The mixture of substances may comprise at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, at least 5% by weight, up to 50% by weight, up to 45% by weight, up to 40% by weight. or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight. Hereinafter, it may be included at 0.5% by weight to 12% by weight, 2% by weight to 7% by weight, or 4% by weight to 6% by weight.

Although certainty is not required, and in at least some embodiments it may be best to avoid such inclusion, any of a variety of UV and OXO degradable additives, such as PDQ-M, PDQ-H, BDA from Willow Ridge Plastics, are within the scope of the present invention. , and OxoTerra ^TM , OX1014 from LifeLine, or organic additives such as Restore® from Enso, EcoPure® from Bio-Tec Environmental, ECM Masterbatch Pellets 1M from ECM Biofilms, or Biodegradable 201 and/or Biodegradable 302 BioSphere®. Other additives may be included, for example for increased strength (e.g. Biomax® Strong from Dupont), or otherwise.

One or more additives may be present in at least 0.5%, at least 1%, at least 1.5%, at least 2%, at least 2.5%, at least 3%, at least 4%, of not more than 10%, not more than 9%, not more than 8%, not more than 7% of the mixture. , may be included in the mixture of substances in an amount of 6% or less, 5% or less, 0.2% to 12%, 1% to 10%, 0.5% to 4%, or 2% to 6% by weight.

Although described primarily in terms of mixtures of thermoplastic materials that can be melted together to form a desirable blend in some embodiments, blending a carbohydrate-based polymeric material with another polymeric material that is not thermoplastic (e.g., thermoset, such as a silicone) It may be possible. For example, a resin component that is a precursor to such non-thermoplastic “other” polymeric material may be blended with a carbohydrate-based polymeric material, wherein polymerization or other formation of the non-thermoplastic “other” polymeric material results in the formation of the carbohydrate-based polymeric material. Occurring in the presence, it can result in a finished product that is a blend of carbohydrate-based polymeric materials and thermoset or other non-thermoplastic plastic materials. The carbohydrate-based polymeric materials, when the two are blended together, can impart any of the same benefits (e.g., increased sustainability, biodegradability, increased strength, etc.) to non-thermoplastic materials as described herein.

Referring to Figure 1, at 108, method 100 may include heating the mixture of materials, especially if the materials are thermoplastic. In one embodiment, the mixture of substances has a temperature of at least 100°C, at least 110°C, at least 115°C, at least 120°C, at least 125°C, at least 130°C, at least 135°C, at least 140°C, below 200°C, below 190°C, below 180°C. It can be heated to a temperature of 175°C or less, 170°C or less, 165°C or less, 160°C or less, 155°C or less, 150°C or less, 95°C to 205°C, 120°C to 180°C, or 125°C to 165°C. there is.

A mixture of materials comprising carbohydrate-based polymer materials and other polymer materials may be heated in one or more chambers of the extruder. In some cases, one or more chambers of the extruder may be heated at different temperatures. The speed of one or more screws of the extruder may be any desired speed.

At 110, the article is produced using a mixture of substances. In some cases, the article may include a film. In other cases, the article may be formed from a film. In other embodiments, the article may have a shape based on a design such as a mold (eg, injection molded). Any conceivable article formed of plastic can be formed from a mixture including, but not limited to, films, bags, bottles, caps, lids, sheets, boxes, plates, cups, utensils, etc. If the article is a film, the film may be formed by using a die to inject gas into a heated mixture of materials to form the film (i.e., by blowing the film). The film may be sealed and/or otherwise transformed into the form of a bag or other article.

When the article is a film, the film may be comprised of a single layer or multiple layers. The film or any individual layer has a thickness of at least 0.001 mm, at least 0.002 mm, at least 0.004 mm, at least 0.01 mm, at least 0.02 mm, at least 0.03 mm, at least 0.05 mm, at least 0.07 mm, at least 0.10 mm, not more than 2 mm, not more than 1 mm. , may have a thickness of 0.5 mm or less, 0.1 mm or less, about 0.05 mm to about 0.5 mm, or 0.02 mm to 0.05 mm. Some specific examples may include films less than 0.005 mm, such as 0.002 mm to 0.004 mm, or 0.0025 mm (0.1 mil) to 0.25 mm (10 mil). Although there may be some overlap in thickness values for film and sheet articles, it will be understood that sheet materials of greater thickness than these film values may of course be provided, produced by any desirable plastic manufacturing process.

The ability to blow very thin films of 0.0025 mm (0.1 mil) has been demonstrated by Applicant using blends as described herein, with very thin films having significant strength (e.g., for 0.1 mil films, at least a dart effect). The drop impact test shows a dart strength of at least 40 g, i.e., for these very thin films, eg 40 g to 110 g, or 40 g to 100 g dart strength. The ability to even blow these very thin films is believed to be unique to the applicant using the blend and other parameters (e.g. blowup ratio, die gap, etc.) as described herein.

Films or other articles may be subjected to the dart drop impact test (ASTM D-1709), tensile strength at break test (ASTM D-882), tensile elongation at break test (ASTM D-882), secant modulus test (ASTM D-882), and/or have strength characteristics characterized through tests such as the Elmendorf tear test (ASTM D-1922). The film is at least 150 g, at least 175 g, at least 200 g, at least 225 g, at least 250 g, at least 275 g, at least 300 g, at least 400 g, at most 375 g, at most 350 g, or at least 325 g, at least 140 g. It may have a dart drop impact test value of 425 g, 200 g to 400 g, 250 g to 350 g, and 265 g to 330 g. In one implementation, these values can be obtained whatever the thickness of the film. In another implementation, these values may be for a 1 mil thick film formed from a mixture of materials.

The article has a pressure of at least 3.5 kpsi, at least 3.7 kpsi, at least 3.9 kpsi, at least 4.1 kpsi, at least 4.3 kpsi, or at least 4.5 kpsi, not more than 5.5 kpsi, not more than 5.3 kpsi, not more than 5.1 kpsi, not more than 4.9 kpsi, or not more than 4.7 kpsi, not more than 3.5 kpsi. It may have a tensile strength test value at break in the machine direction of from 4.1 kpsi to 4.9 kpsi, or from 4.1 kpsi to 4.9 kpsi.

The article has a temperature of at least 3.2 kpsi, at least 3.4 kpsi, at least 3.6 kpsi, at least 3.8 kpsi, at least 4.0 kpsi, at least 4.2 kpsi, below 5.7 kpsi, below 5.5 kpsi, below 5.3 kpsi, below 5.1 kpsi, below 4.9 kpsi, below 4.7 kpsi, It may have a tensile strength test value at break in the transverse direction of 4.5 kpsi or less, 3.2 kpsi to 5.7 kpsi, or 3.6 kpsi to 5.0 kpsi.

The article has at least 550%, at least 560%, at least 570%, at least 580%, at least 590%, at least 600%, at least 610%, at least 620%, at least 725%, at least 710%, at least 700%, at least 680%, It may have a tensile elongation at break test value in the machine direction of 665% or less, 650% or less, 635% or less, 550% to 750%, or 600% to 660%.

The article is at least 575%, at least 590%, at least 600%, at least 615%, at least 630%, or at least 645%, not more than 770%, not more than 755%, not more than 740%, not more than 725%, not more than 710%, not more than 695%. , may have a tensile elongation test value at break in the transverse direction of 680% or less, 575% to 775%, or 625% to 700%.

If applicable, the article has a weight of at least 280 g/mil, at least 300 g/mil, at least 320 g/mil, at least 340 g/mil, or at least 360 g/mil, not more than 450 g/mil, not more than 430 g/mil, not more than 410 g/mil. Elmendorf tear strength test value in the machine direction of g/mil or less, 390 g/mil or less, or 370 g/mil or less, 275 g/mil to 475 g/mil, or 325 g/mil to 410 g/mil. You can have it.

If applicable, the article has a weight of at least 475 g/mil, at least 490 g/mil, at least 500 g/mil, at least 525 g/mil, at least 540 g/mil, or at least 550 g/mil, not more than 700 g/mil, or less than 680 g/mil. g/mil or less, 650 g/mil or less, 625 g/mil or less, 600 g/mil or less, 580 g/mil or less, or 570 g/mil or less, 475 g/mil to 725 g/mil, or 490 g/mil It can have an Elmendorf tear strength test value in the transverse direction from mil to 640 g/mil.

Where applicable, the article has a temperature of at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, up to 40 kpsi, up to 38 kpsi, up to 36 kpsi, up to 34 kpsi, or up to 32 kpsi. Hereinafter, it may have a secant coefficient of elasticity test value in the machine direction of 20 kpsi to 40 kpsi, or 25 kpsi to 35 kpsi.

Where applicable, the article has a temperature of at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, up to 40 kpsi, up to 38 kpsi, up to 36 kpsi, up to 34 kpsi, or up to 32 kpsi. Hereinafter, it may have a secant coefficient of elasticity test value in the transverse direction of 20 kpsi to 40 kpsi, or 25 kpsi to 35 kpsi.

In some cases, articles comprising carbohydrate-based polymeric materials formed from a mixture of two or more starches have greater values of strength properties than articles comprising carbohydrate-based polymeric materials formed from a single starch. For example, an article comprising a carbohydrate-based polymeric material formed from a mixture of two or more starches may have at least about 5% more carbohydrate-based polymeric material than an article formed from a single starch, or more than 10% more carbohydrate-based polymeric material than an article formed from a single starch. A dart drop impact test value ( Units: grams or g/mil thickness). A detailed description of this increased strength is set forth within the examples herein and in US patent application Ser. Nos. 14/853,725 and 15/481,806, already incorporated by reference.

1A, 1B, and 1C further illustrate specific examples of methods according to the present disclosure. Accordingly, these drawings generally cover the more general steps of Figure 1 and are provided together with generally applicable explanations. For example, Figure 1A presents similar steps 102, 104, 106, 108, but where the article produced at 110' is specifically a blown film and the film blowing device has a blowup ratio of at least 2.0; It operates so that the die gap is less than 500 microns. In other words, Figure 1A increases the strength of blown plastic films by ensuring that renewable carbohydrate-based polymer materials are included in the blend from which the plastic films are blown, and by specifically selecting high blowup ratios and/or narrow die gaps. illustrates an exemplary method 100' that can be used to do so. At 102, method 100 includes, for example, one or more "other" polymeric materials, including any plastic resin that can be blown into a film, such as polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyester. , nylon, polystyrene, ABS, polyvinyl chloride, etc. The “other” polymeric material may be a petrochemical based polymeric material. It may also be a “green” version of such petrochemical-based polymer materials (e.g., “green” polyethylene available from Braskeem, etc.). It will be clear that a wide variety of polymers may be suitable for use as “other” polymer materials.

At 104, method 100 includes one or more carbohydrates that may be specifically selected to be included in the blend, for example, for their perceived ability to increase strength when blown at high blowup ratios and/or narrow die gaps. providing a base polymeric material. The renewable carbohydrate-based polymeric material may be substantially amorphous, with a crystallinity of less than 20%. Various other characteristics relating to elastic modulus (i.e., Young's modulus), glass transition temperature, heat distortion temperature, Vicat softening temperature or other characteristics may additionally or alternatively be made with respect to NuPlastiQ or ESR materials available from exemplary BiologiQ as described herein. It may be present as described. At 106, the materials may be mixed together at 106 to form a blend of materials. (108), they may be heated (e.g. melted in the case of thermoplastics) during manufacture in order to blow films therefrom. At 110', a plastic film is blown using a film blowing device using a mixture of materials. During such film blowing, the blowup ratio used may be at least 2.0. As described herein, Applicants have discovered that using carbohydrate-based polymer materials in the blend and using a blowup ratio of 2.0 or higher leads to a significant increase in strength to the film, especially when accompanied by a narrow die gap. .

A multilayer film formed from a blend of Cardia BL-F and PE is described in WO 2014/0190395 by Leufgens, which due to the different TPS materials used, as well as the choice of specific blowup ratio and/or selected die gap characteristics. It is significantly weaker than currently described films. For example, Leufgens' blown film is 80 microns thick (i.e., greater than 3 mils) and exhibits a strength that is actually less than that of a 100% PE film. In contrast, certain selections described herein allow for a substantial increase in strength at any given thickness compared to a 100% “other polymer material” (e.g., PE) control. Moreover, the present method allows the production of films with desirable levels of strength at much lower thicknesses. Such ability to achieve desirable levels of strength at significantly lower thicknesses also reduces the amount of material used in the film layer, leading to further cost savings and greater sustainability.

As described herein, a particular carbohydrate-based polymer material as described herein is blended with another polymer material and then the mixture of materials is used with a blowup ratio of at least 2.0 and/or a narrow die gap (e.g., 500 microns or less). Blowing the plastic film with a film blowing device thus produces a thin film (e.g., less than 2 mils, e.g., 0.1 to 1.5 mils) that exhibits substantially greater strength than an otherwise similar film blown with only the first polymeric material (e.g., PE). It has been revealed by the applicant that it provides mils).

Without wishing to be bound by any particular theory, certain substantially amorphous renewable carbohydrate-based polymer resins, when blown at such high blow-up ratios and/or narrow die gaps, have a tendency to increase the strength of the resulting blended plastic films. It is believed that this facilitates the desired alignment, orientation, and/or stretching of the different polymer molecules of the blend.

For example, polymers are formed in both crystalline (regularly packed) and amorphous (randomly arranged) structures. Many polymers (such as polyethylene) have a high degree of crystallinity, although they contain some amorphous regions that are randomly arranged and intertwined throughout the polymer structure. The particular renewable carbohydrate-based polymeric material utilized is not highly crystalline and is substantially amorphous. Without being bound by any particular theory, the combination of a first polymer material that is crystalline and a renewable carbohydrate-based polymer material that is amorphous ensures that the components of the blend are homogeneously blended together but directed in a direction that results in increased strength. It is believed that the components are oriented, aligned, and stretched in a direction that allows them to be aligned and stretched. Such increases can be observed in both the machine direction (MD) and transverse direction (TD), so the observed phenomenon does not simply cancel out the strength in one direction versus the other. This is evident from the dart drop impact data, which illustrates the intensity in both directions.

Such increased strength, through selection of specific amorphous carbohydrate-based materials and, for example, selection of high blow-up ratios, and/or use of narrow die gaps, is often advantageously achieved with other TPS-containing blends, such as Cardia BL-F. Provides increased strength in thinner films than would otherwise be possible. In some cases, the film can be blown as thin as is possible when blowing the first polymer material alone, as described herein, or even thinner. For example, Applicants are seeking the ability to blow films from polyethylene or blends of renewable carbohydrate-based polymer materials as thin as the thinnest film that can be blown with polyethylene alone, or even thinner (e.g., the ability to blow a 0.1 mil film). ) was observed.

As described herein, an article comprising a carbohydrate-based polymeric material having low crystallinity and/or other characteristics as described herein, and another polymeric material formed at the high blowup ratio and/or narrow die gap described herein is referred to as “another polymeric material” “Can have greater strength property values than articles formed from the polymeric material alone. Such an increase in strength is advantageous and surprising compared to, for example, those in the related art. For example, Leufgens describes a film blown from a blend of polyethylene with a starch-based polymer material (Cardia BL-F), but the resulting film has a lower tensile strength compared to an otherwise similar film formed from polyethylene alone (Leufgens' Figure 2), and lower dart drop impact strength (Figure 5 from Leufgens). This is true even when the blend of Cardia BL-F and polyethylene is blown at a blowup ratio of 3:1. It is clear that, at least under the specific conditions used in Leufgens (which also involve a relatively wide die gap of 1.6 to 1.8 mm), an increase in strength cannot occur with just any renewable carbohydrate-based polymer material. As shown in the Examples, increased strength occurs when using renewable carbohydrate-based polymer materials of the invention with low crystallinity and/or other specific characteristics associated with NuPlastiQ or ESR.

An increase in strength (e.g., tensile strength, dart drop impact strength, or other measured strength) is an otherwise identical article formed from a “different” polymeric material alone (i.e., without a renewable carbohydrate-based polymeric material or compatibilizer). At least about 1%, at least about 2%, at least about 3%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, 1% to 50%, 1% to 40%, Or it may be 10% to 40%.

Figures 1b and 1c illustrate a particular method of counteracting the characteristic odor provided by the inclusion of carbohydrate-based polymeric materials in the blend. As will be apparent to those skilled in the art, any of the methods described herein can be used in conjunction (e.g., while blowing the film at high blowup ratios and/or narrow die gaps while also including odor reducers). 1B illustrates an exemplary method 100'' according to the present invention for producing an article comprising carbohydrate-based polymeric materials, organic odor reducers, and polymeric resins. At 102, method 100 may include providing one or more “other” polymer resins. Such resins can be any of the vast number traditionally used in plastic manufacturing, as described herein. In each of (103) and (104), method 100 includes providing an organic odor reducer and a carbohydrate-based polymeric material.

In one embodiment, the odor reducing agent may be included with the carbohydrate-based polymeric material (e.g., included in its masterbatch). In other embodiments, the odor reducing agent may be added via another route, for example, together with the polymer resin, separately from both the polymer resin and the carbohydrate-based polymer. It will be clear that a variety of routes for such addition are contemplated and possible. Odor reducers are specifically selected for inclusion in the blend for their ability to counteract odors otherwise imparted to the final product by the carbohydrate-based polymer materials. For example, carbohydrate-based polymer materials produce a slightly burnt carbohydrate odor (e.g., a slightly burnt starch, popcorn, or caramel corn-like odor) that develops during thermal processing of the blend (e.g., during injection molding, blow molding, film blowing, etc.). Alternatively, the mixture of components at 102, 103, and 104 is melted together and formed in a heated state.

The odor reducing agent in 103 may be in any such desirable form (e.g., pellets, powders, nurdles, slurries, and/or liquids). In one embodiment, the odor reducing agent may comprise a lyophilized powder that can be mixed into a masterbatch of the carbohydrate-based polymeric material either initially during or after manufacturing the carbohydrate-based polymeric material. For example, if the carbohydrate-based polymeric material is formed from a mixture of starch powder(s), glycerin, and water, the odor reducer (e.g., as a lyophilized powder) may simply be added to the mixture with the starch powder(s); Alternatively, it may be added to and mixed with water, or a plasticizer (e.g., glycerin). The carbohydrate-based polymeric material can then be prepared by the same method by which it is normally produced, with the odor reducing agent incorporated into the carbohydrate-based polymeric material as a component dispersed therein (e.g., homogeneously dispersed therein).

In another embodiment, the powdered or other odor reducing agent can simply be mixed with the carbohydrate-based polymer, so that it is melted and prepared for combination with other components included in the masterbatch (e.g., compatibilizers). It will be clear to those skilled in the art that numerous possibilities exist for adding odor reducing agents to any of the components forming plastic articles from blends of carbohydrate-based polymer materials with another polymer resin. A variety of such alternative routes for incorporation of organic odor reducers may also be suitable for use.

Regardless of the route chosen to introduce the odor reducer in the blend, the blend of ingredients in (102, 103, and 104) can be prepared by any conceivable method, such as those described above and elsewhere herein. It can be formed through any possible method.

The odor reducer may be organic. Those skilled in the art of chemistry will understand that organic compounds are carbon based, but exclude simple carbon compounds such as carbides, carbonates, oxides of carbon (e.g. CO and CO ₂ ), and cyanides. In one embodiment, the organic odor reducer may include a benzyl group containing aromatic compound. Various aromatic derivatives of benzene may be suitable for use, such as benzaldehyde and/or benzyl ketone. In one embodiment, the organic odor reducer may be a compound containing only carbon, oxygen, and hydrogen atoms (eg, no heteroatoms). In other embodiments, compounds containing one or more heteroatoms may prove suitable for use. In one embodiment that has proven to be particularly effective, the odor reducer includes a benzaldehyde compound, such as 4-hydroxy-3-methoxybenzaldehyde. Such aromatic compounds are also known as vanillin, which has the chemical structure shown below.

Very small fractions of organic odor reducers have been found to be sufficient to cancel out odors associated with carbohydrate-based polymeric materials. In addition to the fact that very little odor reducer is required, it is also surprising that the problems associated with the addition of organic components (carbohydrate based polymeric materials) can be solved by the addition of even more organic component(s). For example, those skilled in the art will recognize that additional organic components, especially those having an aromatic chemical structure, are released by the blend upon thermal processing rather than reducing or substantially eliminating such odors. It can be expected that it will add to the smell.

In one embodiment, inorganic or other odor reducing agents are not included in the composition. For example, in one embodiment, activated carbon, zeolites, or other ingredients known to contain active sites to which odorous volatile molecules can bind are not included in the composition. For example, the inclusion of such odor reducers operating in a mechanism requiring binding at the active site may somehow inhibit the ability of benzaldehyde or other organic odor reducers to perform their intended function (e.g. The active site may simply serve to bind benzaldehyde or other organic odor reducers).

The odor reducer may be comprised of not more than 1%, but not more than 0.5% of either the blended plastic material or the carbohydrate-based polymer material comprising the odor reducer provided therein (e.g., as a masterbatch when blended with another polymer resin). Hereinafter, it may include 0.25% or less, 0.1% or less, 0.05% or less, 0.01% or less, 1000 ppm or less, 500 ppm or less, 250 ppm or less, 100 ppm or less, 50 ppm or less, or 20 ppm or less. When blending such carbohydrate-based polymer materials with another polymer resin, the concentration of the odor reducer may of course be further diluted. For example, the concentration of such odor reducer in a plastic blended article may be 15 ppm or less, 10 ppm or less, 5 ppm or less, or even 1 ppm. Such small fractions have surprisingly been found by the applicants to be effective in counteracting and substantially eliminating the characteristic odor of plastics comprising carbohydrate-based polymeric materials.

In addition to vanillin, other extracts from various fruits and/or vegetables may also be suitable for use as organic odor reducers. Possible non-limiting examples include freeze-dried extracts from vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, or raspberry. Combinations may also be suitable for use.

As noted above, in one embodiment, the odor reducing agent may be added to (e.g., dissolved or dispersed in) the water and/or glycerin used to form the carbohydrate-based polymeric material, which It is particularly advantageous to ensure homogeneous mixing of a very small fraction of the odor reducer throughout the polymeric material. For example, a powdered odor reducer can be added to another powdered material (e.g. starch(s)) to make a carbohydrate-based polymer material, but the amount of odor reducer added may be too small (e.g. 20% in a masterbatch). ppm), it may be easier to ensure homogeneous dispersion of the odor reducer by mixing it with the liquid component(s) rather than mixing it with the solid powder(s).

The addition of an odor reducing agent to a carbohydrate-based polymer material alters the odor characteristic by substantially eliminating any tendency of the blend of the carbohydrate-based polymer material and another thermoplastic polymer resin from exhibiting an otherwise characteristic caramel corn or popcorn-like odor. , such inclusions do not substantially alter any physical or other properties of the NuPlastiQ or ESR material, as described herein. As mentioned, the odor reducer is a carbohydrate-based polymer NuPlastiQ or "ESR" material at levels below 1000 ppm, 500 ppm, 250 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 25 ppm, 20 ppm, It may be present in a range of 5 ppm to 50 ppm, 10 ppm to 50 ppm, or 15 ppm to 25 ppm. Applicants have found that a level of 20 ppm is particularly effective for NuPlastiQ or ESR materials. When diluted with polymeric resin material(s), it will be apparent that the concentration of odor reducer in articles formed from such blends is even lower (e.g., levels of 20 ppm in NuPlastiQ or ESR masterbatch compared to only 10 ppm in the finished product). may drop to just 5 ppm, or to just 1 ppm).

In some embodiments, NuPlastiQ or ESR may be provided in a masterbatch formulation that may include a carbohydrate-based polymeric material as described above, an odor reducer, and a significant amount of one or more compatibilizers. The masterbatch may also include one or more “other” polymer resins already included therein (e.g., the same polymer resin that is blended with the carbohydrate-based polymer resin to form the target article). Such masterbatch formulation pellets may be mixed with pellets of “other” polymeric resin materials at the point of processing. Any conceivable ratio may be used to mix such different pellets, depending on the desired percentages of NuPlastiQ or ESR and/or compatibilizer and/or conventional polymer resin in the finished product.

As mentioned above, odor reducers typically contain carbohydrate-based polymeric substances at very low levels, such as less than 1%, less than 0.1%, less than 0.01%, less than 1000 ppm, less than 100 ppm, less than 50 ppm, or less than 20 ppm. can exist in When a carbohydrate-based polymer material containing an odor reducer is mixed with a polymer resin, the level of odor reducer in the resulting blended plastic article is reduced, depending on the mixing ratio of the carbohydrate-based polymer material to the polymer resin material. As mentioned herein, a wide variety of mixing ratios are suitable. As an example, at a 1:1 mixing ratio, if the initial level of odor reducer in the carbohydrate-based polymeric material masterbatch is 20 ppm, it now drops to just 10 ppm in the finished plastic article formed from the blend. At a blend ratio of 25% carbohydrate based polymer material and 75% polymer resin material, the initial 20 ppm level for the odor reducer now drops to 5 ppm.

It will be apparent that although the concentration of odor reducer is reduced, the ratio of odor reducer to carbohydrate based polymer material does not change due to such blending. For example, the weight ratio of odor reducer to carbohydrate based polymer can be 1:1000, or even diluted further. For example, the above ratios are 1:1000, 1:2000, 1:5000, 1:10,000, 1:15,000, 1:20,000, 1:25,000, 1:30,000, 1:35,000, 1:40,000, 1:45,000, It may be 1:50,000, 1:60,000, 1:70,000, 1:80,000, 1:90,000, or 1:100,000. The ratio can be within a range between any of the two values (eg, 1:1000 to 1:100,000, or 1:10,000 to 1:80,000, or about 1:50,000). A level of 20 ppm for odor reducers in carbohydrate-based polymeric materials may correspond to a ratio of about 1:50,000. Even when blended with polymeric resin materials, these ratios can remain substantially constant since the addition of polymeric resin materials does not change the amount of odor reducer or carbohydrate-based polymeric materials in the blend.

It will also be clear that while the odor reducer may be organic, it may be important to ensure that these components are not volatile so that they are not simply released during high temperature processing of the article (with a residual water content in the carbohydrate based polymer material). For example, the odor reducer may be a solid rather than a liquid at ambient temperature (e.g., 25° C.) and pressure (e.g., 1 atm). If liquid, the odor reducer may exhibit less volatility than that of water (e.g., as measured for vapor pressure at a given temperature and pressure (e.g., STP as noted above)). In one embodiment, the odor reducer may have a boiling point greater than any temperature associated with processing at (108 and 110''). The odor reducer may have a melting point that is less than the temperature associated with processing, at (108 and/or 110''). For example, the odor reducer may be solid at ambient temperature (e.g., 25° C.), but may be liquid at the elevated temperature at which processing occurs (e.g., 125° C. to 165° C.). 4-Hydroxy-3-methoxybenzaldehyde is an example of such an odor reducer.

For example, the odor reducer may be used at a temperature of at least 30°C, at least 50°C, below 200°C, below 190°C, below 180°C, below 175°C, below 170°C, below 165°C, below 160°C, below 150°C, below 145°C. Below, below 140°C, 135°C, below 130°C, below 125°C, below 120°C, below 115°C, below 120°C, below 115°C, below 110°C, 100°C, 50°C to 180°C, 50°C to 150°C °C, or may have a melting point of 60°C to 100°C. The odor reducer is used at temperatures above 150°C, above 160°C, above 170°C, above 180°C, above 200°C, above 225°C, above 250°C, between 150°C and 500°C, between 200°C and 400°C, or between 250°C and 300°C. It can have a boiling point of . For example, vanillin melts at 81°C to 83°C and boils at 285°C.

Figure 1B illustrates how an article can be produced from a polymer resin (at 102), an odor reducer (at 103), and a carbohydrate-based polymeric material (at 104), and Figure 1C illustrates how an odor reducer is contained within the carbohydrate-based polymeric material. Examples of ways in which mixing can occur (100''') are provided. For example, an odor reducer may be provided at 103, a carbohydrate based polymer material may be provided at 104, and they are mixed together at 106''. By way of example, this may be the case if an organic odor reducer is mixed into the carbohydrate-based polymer material when formulating the masterbatch (e.g., when a compatibilizer or other ingredients to be included in the masterbatch are also added). may occur if added). In another embodiment, the odor reducing agent may be mixed with the starting material(s) from which the carbohydrate-based polymeric material is formed (e.g., with one or more of the water, glycerin, or starch constituents from which the carbohydrate-based polymeric material is formed). by mixing odor reducers). In any case, the method chosen results in a carbohydrate-based polymeric material containing the odor reducer dispersed therein. The concentration can be very low (eg, 20 ppm), as described herein. In (110'''), such carbohydrate-based polymeric materials (including odor reducers) are prepared by blending with a polymeric resin (e.g., typically involving the application of heat to melt and blend with a thermoplastic material) to form an article. It can be used to produce

Referring back to standard features applicable to any of the embodiments described herein, biodegradation testing (e.g., biomethane potential test), or any applicable ASTM standard, such as ASTM D-5511, ASTM D-5526, ASTM D -5338, or ASTM D-6691) can be characterized. Under such testing, and within a given period of time (e.g., 30 days, 60 days, 90 days, 180 days, 365 days (1 year), 2 years, 3 years, 4 years, or 5 years), the article has a total polymer content of , and/or any non-biodegradable “other” polymer inclusions (excluding carbohydrate-based polymer inclusions). Biomethane potential testing is typically performed over 30 or 60 days, but sometimes up to 90 days. Longer duration testing is more typically performed under any of the above-mentioned ASTM standards. For example, an article that may be free or substantially free of biodegradation enhancing additives may exhibit greater biodegradation than its carbohydrate-based polymer material content, indicating that other plastic material(s) are also biodegradable (or have biomethane potential). Indicates potential for biodegradation under test).

In particular, the article simulates biodegradation under landfill or other disposal and/or decomposition conditions (e.g., composting conditions, or marine conditions) for 180 days, 200 days, 365 days (1 year), 2 years, 3 years, or 5 years. When conducting tests, biodegradation can be greater than the weight percent of carbohydrate-based polymeric material in the article. In other words, the inclusion of the described carbohydrate-based polymeric material may result in at least some biodegradation of the “other” polymeric material that is not otherwise biodegradable.

For example, an article formed from a blend of carbohydrate-based polymeric material and PE may exhibit biodegradation greater than the weight fraction of the carbohydrate-based polymeric material in the film after such a period of time, compared to the PE (not previously considered biodegradable). indicates that it is indeed biodegradable along with carbohydrate-based polymer materials. Such results are surprising and particularly advantageous.

The biomethane potential test determines the potential for anaerobic biodegradation based on methane production as a percentage of total methane production potential. The biomethane potential test can be used to predict the biodegradability of samples tested according to the ASTM D-5511 standard, and the biomethane potential test can be performed using one or more conditions from the ASTM D-5511 standard. For example, biomethane potential testing can be performed at a temperature of about 52°C. Additionally, the biomethane potential test may have some conditions that differ from those of ASTM D-5511, for example, to accelerate such testing, which would typically be completed within 30, 60 days, or sometimes up to 90 days. The biomethane potential test can utilize an inoculum having 50% to 60% water and 40% to 50% organic solids by weight. For example, the inoculum used in a biomethane potential test may have 55% water and 45% organic solids by weight. Biomethane potential testing can also be performed at different temperatures, such as 35°C to 55°C or 40°C to 50°C.

When performing biodegradation testing, articles having significant amounts of carbohydrate-based polymeric materials as described herein and "other" polymeric materials with up to about 2% by weight of biodegradation enhancing additives (or preferably without them) may be: As a result of the introduction of carbohydrate-based polymeric materials within the article, enhanced degradation may be exhibited. For example, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40% of non-carbohydrate based polymeric material (e.g., “other” polymeric material) %, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or even at least 95% is landfill. , composting, and/or biodegradation over a period of at least about 1 year, at least about 2 years, at least about 3 years, or at least about 5 years when subjected to marine conditions (or conditions simulating the same). Such biodegradation is particularly noteworthy and advantageous. Thus, not only are carbohydrate-based polymeric materials biodegradable, but "other" polymeric materials are also biodegradable, even if they themselves are not otherwise biodegradable.

Embodiments may be such that substantially the entire article biodegrades over an increased amount of time (e.g., within 180 days, or 200 days, or 365 days (1 year), within 2 years, within 3 years, within 5 years). biodegradation of at least about 85%, at least about 90%, or at least about 95% within a certain period of time), suggesting that the amount of biodegradation can be very high.

2A illustrates components of an example manufacturing system 200 for producing articles according to the present disclosure. In some cases, manufacturing system 200 may be used in method 100 of Figure 1, or any of Figures 1A-1C. In an illustrative example, manufacturing system 200 is an extruder, such as a single screw extruder or a twin screw extruder.

In one implementation, one or more non-biodegradable plastic materials and one or more carbohydrate-based polymer materials are provided through first hopper 202 and second hopper 204. Compatibilizers may be included (e.g. in their masterbatch) with one or both substances.

One or more carbohydrate-based polymeric materials and one or more non-biodegradable plastic materials may be mixed in the first chamber 206 to produce a mixture of materials. In some cases, the mixture of materials includes 5% to 40% by weight of one or more carbohydrate-based polymeric materials, 60% to 94% by weight of one or more non-biodegradable plastic materials, and 1% to 9% by weight of one or more non-biodegradable plastic materials. It may contain the above compatibilizers. As described herein, minor amounts of odor reducing agent may also be present. The range may, of course, vary beyond the above range depending on the desired characteristics.

In the example implementation shown in Figure 2A, the mixture of materials is stored in a plurality of chambers, such as first chamber 206, second chamber 208, third chamber 210, fourth chamber 212, fifth chamber ( 214), and an optional sixth chamber 216. The mixture of substances may be heated in chambers 206, 208, 210, 212, 214, and 216. In some cases, the temperature of one of the chambers may be different from the temperature of another one of the chambers. In an illustrative example, first chamber 206 is heated to a temperature between 120° C. and 140° C.; The second chamber 208 is heated to a temperature of 130° C. to 160° C.; The third chamber 210 is heated to a temperature of 135° C. to 165° C.; The fourth chamber 212 is heated to a temperature of 140° C. to 170° C.; The fifth chamber 214 is heated to a temperature of 145° C. to 180° C.; The optional sixth chamber 216 is heated to a temperature of 145°C to 180°C.

The heated mixture may then be extruded using die 218 to form an extruded object, such as a film, sheet, etc. Injection molding, thermoforming, or other plastic production methods can be used to produce a variety of articles such as utensils, plates, cups, bottles, caps, or lids. In film blowing, gas is injected into an extruded object so that the object can expand to a pressure of 105 bar to 140 bar. The resulting tube 220 may be pulled through rollers 222 to produce a film 224 typically having a thickness of 0.02 mm (about 0.8 mil) to 0.05 mm (about 2 mil). For example, even thinner films, with thicknesses as low as 0.1 mil (0.0025 mm), can be made using blends as described herein. Of course, thicknesses greater than 2 mil may also be achieved. In some cases, film 224 may be comprised of a single layer. In other cases, film 224 may be comprised of multiple layers. If multiple layers are present, at least one of the layers may include a carbohydrate-based polymeric material. In some embodiments, carbohydrate-based polymeric materials may be present in one or more outer layers. In another embodiment, carbohydrate-based polymeric materials may be present in the inner layer. If carbohydrate-based polymeric materials are not included in the outer layer(s), biodegradation of the outer layer(s) may not occur.

2B and 2C schematically illustrate the formation of die 218 and bubble 220, which provide additional details for the blown film device of FIG. 2, particularly the blowup ratio and die gap characteristics. It is presented how they can be selected specifically for increased strength. As shown in FIGS. 2B and 2C, die 218 may include an outer member 218a and an inner member 218b, and a die gap 226 defined therebetween. As described herein, die 218 may have a particularly narrow die gap, e.g., less than 1000 microns, less than 900 microns, less than 800 microns, less than 700 microns, less than 600 microns, or less than 500 microns (e.g., less than 200 to 500 microns). microns). This narrow die gap contrasts sharply with the wide die gap used (and possibly required) in the state of the art when blowing films containing other thermoplastic starch components. For example, Leufgens lists a die gap of 1.6 to 1.8 mm (i.e., 1600 to 1800 microns). Even at high blowup ratios, the use of such large die gaps can make it impossible to achieve the increases in strength described herein.

Figure 2B further illustrates the relatively high blowup ratio, defined as the ratio of the maximum diameter of the bubble (D _B ) divided by the diameter at the die gap (D _D ). In other words, with respect to the unfolded flat width of the film, the blowup ratio is 0.637*(unfolded flat width)/D _D. Frost lines 228 are also shown in FIG. 2B where previously molten material in the bubble begins to crystallize, giving frost lines 228 a more translucent appearance compared to those crystallization areas. As described herein, the blowup ratio is at least 2.0, e.g., 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 2.2 to 2.8, or about 2.5. Applicants have observed that the strength for the film is increased by simply increasing the blowup ratio from a typical blowing formation blowup ratio of 1.5 to at least 2, such as 2.5. The intensity has been observed to increase up to values of about 3, after which no significant further increase in intensity has been observed, with values of 2-3, 2.2 to 2.8, or about 2.5 being particularly appropriate. As described herein, the die gap can be maintained at a narrow value, especially when blowing blends comprising the described renewable carbohydrate-based polymer materials, which may also contribute to the described increase in strength.

By way of example, blowing films from such blends with a die gap of less than 500 microns and a blowup ratio of at least 2 (e.g., 2.2 to 2.8, or about 2.5), especially with a thickness of up to 1.5 mil (e.g., 0.1 mil to 1.5 mil). It is very suitable for doing this. To blow thicker films (if thicker films were needed), the die gap may need to be increased to accommodate the flow of molten material through it. For example, to blow very thick films, 10 mil, or even 5 mil, the die gap may need to be increased slightly (but the value may still be less than 1000 microns, or even less than 500 microns).

The concepts described herein will be further illustrated in the examples below.

Example

Example 1

Eleven starch-based polymers were formed from 27% tallow glycerin (99% pure glycerin) and 73% starch, excluding water. Each finished starch-based polymer represented <about 1% water and was mixed with LLDPE and anhydride-modified LLDPE at proportions of 25%, 70%, and 5% by weight, respectively. The resulting mixture was then extruded and blown into films. 70% of each film was LLDPE, 25% was a starch-based polymer, and 5% of each film was anhydride-modified LLDPE. The film was then tested using the drop dart impact test according to ASTM D-1709. The combination of starches tested and strength test results (in grams) are presented in Table 3. The results in Table 3 suggest that samples formed from a mixture of starches have dart drop impact test values that are greater than those of samples formed from a single starch.

Figure 5 reports dart impact test strengths for different thickness films (0.5 mil, 1 mil, 1.5 mil, 2.0 mils) based on the percentage of starch-based NuPlastiQ or "ESR" in the film. NuPlastiQ or ESR used in the formed films shown in Figure 5 were formed from a blend of starches including 90% corn starch and 10% potato starch. Figure 5 shows how the strength of the film increases with increasing NuPlastiQ or ESR percentage, from about 20% to a maximum strength at about 25% NuPlastiQ or ESR. The remainder of the blend includes polyethylene and a suitable compatibilizer, as described herein.

Figure 6A shows different thickness films (about 0.1 mil) for a film comprising 25% carbohydrate-based polymeric material, with the remainder being a small fraction of compatibilizer (e.g., about 5%) and PE (about 70%) as described herein. Record the dart impact test strength for up to 2 mil). Figure 6 also presents comparative strengths for 100% PE films, which are in all respects smaller than the blends according to the present disclosure. Figure 6 shows cart bags (e.g., bags provided to consumers in supermarket produce aisles to hold merchandise), various "carrying" bags (e.g., grocery and other plastic bags provided for carry-out), and potato bags (supermarket Various other tested reference points (plastic bags typically used to hold 5, 10, or 20 pounds of potatoes in the produce section) are additionally presented. Example 8 presents results for a similar, but blend where the “other” polymer material is biopolyethylene rather than synthetic LLDPE derived from petroleum sources.

7 shows darts for different thickness films (from less than 0.5 mil up to about 2 mil) for various blended films according to the present disclosure, as well as comparative films (e.g., 100% LLDPE, 100% recycled LLDPE (rLLDPE)). Record the impact test strength. In addition to presenting strength characteristics for films formed from virgin material (labeled 25% NuPlastiQ or ESR, 70% LLDPE, 5% compatibilizer (25% NuPlastiQ or ESR/75% LLDPE), Figure 7 It also occurs when such recycled material (rLDESR) is subsequently blended with virgin material (labeled 25% NuPlastiQ or ESR/25% rLDESR/50% LLDPE), or when recycled LLDPE (rLLDPE) is used in the blend ( (labeled with 25% NuPlastiQ or ESR/25% rLLDPE/50% LLDPE). The strength results show that in addition to the increased recyclability and biodegradability features previously described, the use of PE polymer materials, as shown, It is improved compared to .

Example 2

Three samples were tested for 349 days to determine biodegradability characteristics according to ASTM D-5511. The test was intended to replicate the conditions of a full-scale anaerobic digester (landfill). Results for three samples (referred to as 1342, 1343, and 1344) are presented in Figures 8A-8B and Table 4. Figure 8A presents results for all samples 1343, 1343, and 1344, compared to the control. Figure 8B presents results for sample 1344 alone, compared to the control. Sample 1342 was formed from 30% NuPlastiQ or ESR (a substantially amorphous carbohydrate-based polymer material with less than 10% crystallinity), 67% PBAT, and 3% compatibilizer, and had a thickness of 1.1 mil. Sample 1343 was formed from 27.5% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer and had a thickness of 1.0 mil. Sample 1344 was formed from 40% NuPlastiQ or ESR, 56% LLDPE, and 4% compatibilizer and had a thickness of 1.0 mil.

Figures 8A-8B show that after 204 days the negative control was 2.5% degraded, the positive control was 86.5% degraded, sample 1342 was 43.3% degraded, sample 1343 was 53.9% degraded, and sample 1344 was 77.2% degraded. . At day 349, the degradation values are as shown in Table 4.

Biodegradation is particularly excellent after 349 days. For example, samples containing PBAT (1342 and 1343) show very good biodegradation, with biodegradation rates much greater than the fraction of carbohydrate-based polymer material contained in the film, but sample 1344 (see Figure 8b) is even more surprising. , showing almost 96% biodegradation (higher than the positive control), where the non-biodegradable plastic material is polyethylene, which of course is not biodegradable under normal circumstances (e.g. see the negative control which was 100% polyethylene in Table 4). Such biodegradation results are notable and particularly advantageous.

Example 3

Made with a blend of 25% NuPlastiQ or ESR, 70% LLDPE, and 5% compatibilizer for anaerobic biodegradation according to ASTM D-5526 after 60, 107, 202, 317, 439, 573, and 834 days. Potato packaging bags were tested. The test was intended to replicate the conditions of a full-scale anaerobic digester (landfill). Tests were performed under various conditions with inoculums having approximately 35%, 45%, and 60% organic solids and the remainder being water. Results for the inoculum containing 35% organic solids (and 65% water) are presented in Figure 9 and Table 5A. Table 5B presents results for different inoculum values, and different samples. The potato bag had a thickness of 1.35 mil. These bags are referred to as sample 1072.

[Table 5a]

Potato bags made of 25% NuPlastiQ or ESR, and 70% LLDPE showed a notable 81% biodegradation over 834 days under simulated landfill conditions. NuPlastiQ or ESR is homogeneously blended with polyethylene, advantageously the long carbon chains of polyethylene are broken and digested by the same microorganisms that consume the carbohydrate-based polymer NuPlastiQ or ESR material. Those results suggest that the entire bag, including polyethylene, biodegrades to carbon dioxide, methane, and water. The results are surprising and particularly advantageous.

Tests conducted with 45% organic solids and 60% organic solids also showed that biodegradation rates exceeded those of NuPlastiQ or ESR contained in potato bags. Tests were also conducted with a similar potato bag containing 1% biodegradation enhancing additive (Sample 1073), and another similar potato bag containing EcoFLEX™ compostable resin, and metallocene LLDPE (Sample 1075).

[Table 5b]

Example 4

Films made from NuPlastiQ or a blend of ESR and LLDPE were tested for anaerobic biodegradation after 201 and 370 days according to ASTM D-5338. Conditions simulated aerobic digestion and/or industrial composting conditions. The films tested are labeled 1345 and 1346 in Table 6 and Figures 10A-10B, which present results after 370 days. At day 201, samples 1345 and 1346 gave adjusted biodegradation values of 74.2% and 72.4%, respectively, while the negative control gave -3.3% and the positive control gave 100%. Figures 10A-10B plot the actual biodegradation rates. Sample 1345 contained 25% NuPlastiQ or ESR, 72.5% LLDPE, and 2.5% compatibilizer. Sample 1346 contained 40% NuPlastiQ or ESR, 56% LLDPE, and 4% compatibilizer. Both films had a thickness of 1.0 mil.

Biodegradation is particularly good after 370 days, especially for sample 1345. This sample (see Figure 10b) shows over 97% biodegradation, where the non-biodegradable plastic material is polyethylene, which of course is not biodegradable under normal circumstances (e.g. see negative control in Table 6 which was 100% polyethylene). Such biodegradation results are notable and particularly advantageous.

Example 5

Films made from NuPlastiQ or a blend of ESR and PBAT were tested for anaerobic biodegradation after 205 days according to ASTM D-6691, intended to simulate marine conditions. The films tested are labeled 1439 and 1440 in Table 7 and Figure 11. At day 205, samples 1439 and 1440 gave adjusted biodegradation values of 49.6% and 53.6%, respectively. Sample 1439 contained 30% NuPlastiQ or ESR, 67% PBAT, and 3% compatibilizer. Sample 1440 contained 27% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer. Sample film 1439 had a thickness of 1.1 mil and sample film 1440 had a thickness of 1.0 mil.

Example 6

Additional prepared films were tested for biodegradability. Table 8 below summarizes the results of such tests, some of which are detailed above. Such tests provide excellent biodegradability results over a wide range of carbohydrate-based polymeric materials and fractions of different polymeric materials, under a variety of simulated conditions (e.g., landfill, composting, marine environments).

Example 7

According to the present invention, further tests were performed to evaluate the biodegradability of different loading levels of carbohydrate-based polymeric materials. Testing followed ASTM D5511. The levels of carbohydrate-based polymeric material in the samples tested were 0% (control), 1%, 5%, 10%, and 20% by weight of the blend. Table 9 below summarizes the results of such tests. Even for 1% loading, the biodegradation rate after 65 days (2.7%) is greater than the loading amount (only 1%), meaning that the polyethylene included in the blend is also degrading. This trend continues in the data shown at 95 days, where the biodegradation rate continues to increase (e.g. 5% at 95 days). More accelerated results are seen at higher loadings of carbohydrate-based polymer material of 5%, 10%, and 20%. In all samples loaded with carbohydrate-based polymer material that imparts biodegradability, the total non-biodegradable plastic content is reduced within a reasonable period of time under such disposal conditions, e.g., 1 year, 2 years, 3 years, 4 years, or within 5 years) is expected to decompose.

Example 8

Films were prepared from a blend of bio-polyethylene (supplied from Braskem), NuPlastiQ or ESR, and Bynel® compatibilizer. Once formed, the resulting film was tested for dart strength (e.g., according to ASTM D-1709). Films were blown at various thicknesses from 0.5 mil up to 2 mil and with various percentages of starch-based polymeric material (NuPlastiQ or ESR) ranging from 0 to 35% by weight NuPlastiQ or ESR. The results are presented in Figures 12A and 12B.

As evident from Figure 12A, biopolyethylene alone (without NuPlastiQ or ESR) has a dart strength of about 120 g for a thickness of 0.5 mil, a dart strength of about 155 g for a thickness of 1 mil, and a dart strength of about 1.5 g for a thickness of 1.5 mil. Provides a dart strength of 200 g, and a dart strength of approximately 270 g for a thickness of 2 mil. Approximate dart strengths are given in Table 10A. Table 10B presents the strength increase compared to pure biopolyethylene film. It is clearly evident that there is an increase for all thicknesses of NuPlastiQ or ESR in the film, and for all percentages tested. The increase in strength is particularly high as the film becomes thicker (i.e., the rate of increase is more dramatic for thicker films compared to thinner films).

[Table 10a]

[Table 10b]

In forming and testing such films, Applicants have observed that the results of increased strength generally agree well with the results seen using synthetic petrochemical polyethylenes. As mentioned above, when using biopolyethylene materials in the blend, it was observed that the improvement in strength increased more rapidly with increasing thickness (i.e., the percentage increase was most dramatic for thicker films compared to thinner films). lim).

It was also observed that the sweet spot for starch-based NuPlastiQ or ESR with biopolyethylene may be at about 15%, rather than about 25% observed with petrochemical-sourced polyethylene. Nonetheless, a similar increase in intensity was observed when blending the base resin with NuPlastiQ or ESR.

Finally, the film formed according to Example 8 contains a raw content well in excess of 40%, which is particularly advantageous, including base resins (e.g., any of the "green" sustainable polymer materials such as those described herein) and carbohydrates. This is because both NuPlastiQ or ESR materials, either starch-based or starch-based, are derived from sustainable materials. The only component of the film not included in the raw content is the compatibilizer (where available, sustainable compatibilizers may be used). Accordingly, the raw content is at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, by weight of the film or other product. It may be 80% by weight, at least 85% by weight, at least 90% by weight, or even at least 95% by weight. The film of Example 8, in addition to the Bynel® compatibilizer, consists of a raw content, such that it contains more than 90% by weight of the raw content.

Finally, the film of Example 8 is substantially fully biodegradable, in a similar manner as described for the various other tested polyethylenes tested in the examples described above. The present invention therefore provides very high biocontent polymer films and other products that are not only sustainable but also biodegradable.

Example 9

This example illustrates the effect of blowup ratio and/or die gap. Dart impact test strengths are measured for a variety of films, including films formed from polyethylene alone, and films formed from a blend of NuPlastiQ or ESR, polyethylene, and a compatibilizer. The film formed from the blend contains 25% renewable carbohydrate-based polymer material, 5% compatibilizer, and 70% polyethylene. All films are blown at a blowup ratio of approximately 2.5. Applicants have observed that an increase in strength is observed when blowing films into blends at increased blowup ratios, but that the blowup ratio does not have any significant effect on strength when blowing films from polyethylene alone. In other words, using polyethylene alone, the strength is virtually the same whether the blowup ratio is 1.5, 3, or anywhere in between. Table 11 below presents approximate dart impact values (in grams) for various thickness films of the invention compared to the control, as well as the percent increase in strength for various blends compared to the control.

13 shows additional comparisons for 100% polyethylene films at various film thicknesses compared to films formed from blends of polyethylene and 25% NuPlastiQ or ESR renewable carbohydrate-based polymer materials, for example, at a blowup ratio of about 2.5. Impact strength data is presented. Figure 13 presents the ability to produce films with thicknesses as small as 0.1 mil. As described herein, there can be considerable difficulty in forming such thin films from polyethylene materials alone. As shown in Figure 13, the strength of a 100% polyethylene film is substantially independent of the blowup ratio (i.e., the strength is substantially the same at a blowup ratio of 1.5, or at a blowup ratio of 2.0, or 2.5, or 3.0). . In all respects, the strength of films formed from 25% NuPlastiQ or ESR renewable carbohydrate based polymer material blends is greater than that of films formed from polyethylene alone.

Example 10

Examples 10-14 illustrate the addition of odor reducers. Example 10 is a comparative example. Samples are prepared from a blend of a carbohydrate-based polymer material and another polymer resin (selected as polyethylene), as well as a maleic anhydride modified PE compatibilizer. The compatibilizer is included in an amount of 5% by weight. The amount of carbohydrate-based polymer material varies from 5% to up to 50% by weight, with the remainder being polyethylene polymer resin. These samples do not contain any odor reducers and exhibit a slightly characteristic odor of carbohydrate-based polymeric materials that can be described as a popcorn-like odor, a caramel corn-like odor, or a slightly burnt starch odor. Odor is virtually unobservable when the geometry of the article is relatively open (e.g. a flat sheet or film of material), but odor can be observed when the geometry is relatively closed (e.g. in the shape of a cup, or when a film is rolled into a roll). (if wrapped in) becomes more noticeable.

Example 11

The sample was prepared identical to that of Example 10, but containing a small fraction of 4-hydroxy-3-methoxybenzaldehyde (vanillin) therein as an odor reducer. Odor reducers are provided as powders, for example as freeze-dried powders. The powder is mixed with the liquid ingredients used to make the carbohydrate-based polymer material (e.g. water and/or glycerin) to obtain a homogeneous dispersion of the odor reducer therein. The carbohydrate-based polymeric material was then formed from water, glycerin, and starch in the same manner as Example 10 (and Example 1), such that the finished carbohydrate-based polymeric material was dispersed therein at a level of 20 ppm (0.002% by weight). Contains odor reducers. In each sample, the ratio of carbohydrate-based polymeric material to odor reducer (NuPlastiQ or ESR to ORA ratio) is 50,000:1.

Characteristics of the sample are presented in Table 12.

In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slightly characteristic odor described in Example 10. Differences in odor are particularly evident in relatively closed geometries, such as when the blend is molded into the shape of a cup. By comparison, cups formed from such blends shown in Table 12 exhibit no discernible odor similar to cups formed from 100% polyethylene. It is surprising that a small amount of odor reducer is sufficient to counteract the characteristic odor typically associated with carbohydrate-based polymer content.

Example 12

The sample is identical to that of Example 10, but is prepared to include a small fraction of freeze-dried strawberry powder as an odor reducer. The powdered odor reducer is dispersed in the carbohydrate-based polymer material at a level of 20 ppm (0.002% by weight).

The article was formed in the same manner as Example 10, but with a small fraction of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slightly characteristic odor described in Example 10. Differences in odor are particularly evident in relatively closed geometries, such as when the blend is molded into the shape of a cup. By comparison, cups formed from such blends as shown in Table 13 exhibit no discernible odor similar to cups formed from 100% polyethylene. It is surprising that a small amount of odor reducer is sufficient to counteract the characteristic odor typically associated with carbohydrate-based polymer content.

Example 13

The sample is identical to that of Example 10, but is prepared to include a small portion of freeze-dried blueberry powder as an odor reducer. The powdered odor reducer is dispersed in the carbohydrate-based polymer material at a level of 20 ppm (0.002% by weight).

The article was formed in the same manner as Example 10, but with a small fraction of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slightly characteristic odor described in Example 10. Differences in odor are particularly evident in relatively closed geometries, such as when the blend is molded into the shape of a cup. By comparison, cups formed from such blends as shown in Table 14 exhibit no discernible odor similar to cups formed from 100% polyethylene. It is surprising that a small amount of odor reducer is sufficient to counteract the characteristic odor typically associated with carbohydrate-based polymer content.

Example 14

Samples were prepared in a similar manner to Example 10, but containing various small fractions of lyophilized vanillin powder as an odor reducer. The powdered odor reducer is dispersed in the carbohydrate-based polymeric material at a level of 5 ppm (0.0005% by weight) to 100 ppm (0.01% by weight).

The article was formed in the same manner as Example 10, but with a small fraction of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slightly characteristic odor described in Example 10. Differences in odor are particularly evident in relatively closed geometries, such as when the blend is molded into the shape of a cup. By comparison, cups formed from such blends as shown in Table 15 exhibit no discernible odor similar to cups formed from 100% polyethylene. It is surprising that a small amount of odor reducer is sufficient to counteract the characteristic odor typically associated with carbohydrate-based polymer content. At relatively higher levels of vanillin (e.g. above 100 ppm) it may begin to contain a characteristic pleasant vanilla odor.

IV. conclusion

In conclusion, although various implementations may be described in language specific to structural features and/or methodological acts, it should be understood that the subject matter defined in the accompanying presentation is not necessarily limited to the specific features or acts described. Rather, specific features and acts are disclosed in the form of examples that embody the claimed subject matter.

In conclusion, it should be understood that the embodiments of the invention disclosed herein illustrate the principles of the invention. Other variations that may be employed are within the scope of the invention. Accordingly, by way of example, but not limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the invention is not limited to exactly as shown and described.

It will be understood that the scope of the disclosure extends to rewrite any claim to be dependent on any other claim, to include multiple dependent claims from any combination of other claims, and/or to combine together multiple claims. will be. This also extends to the "Summary of Exemplary Concepts to Be Claimed" as set forth in the Summary section. The scope of the present disclosure also extends to inserting and/or removing any combination of features from any claim, inserting into another claim, or introducing new features including any combination of such features from any other claim(s). Extended for drafting claims.

Claims (27)

Starches containing one or more of potato starch, corn starch, or tapioca starch and glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, anhydrides of sugar alcohols, aliphatic acids, phthalate esters, dimethyl or diethylsuccinate, glycerol triacetate, An amorphous starch-based polymer formed from a plasticizer comprising one or more of glycerol mono or diacetate, glycerol mono, di, or tripropionate, lactic acid ester, citric acid ester, adipic acid ester, stearic acid ester, or oleic acid ester. As a material, the amorphous starch-based polymer material has a crystallinity of less than 20%, the amorphous starch-based polymer material does not revert to a crystalline structure, and the amorphous starch-based polymer material has a water content of less than 2% by weight. an amorphous starch-based polymer material comprising: and
An article comprising another polymeric material blended with said amorphous starch-based polymeric material,
Other polymeric materials include polyethylene, polypropylene, polyethylene terephthalate, polystyrene, acrylonitrile butadiene styrene (ABS), nylon, polyvinyl chloride, poly(butylene adipate-co-terephthalate) (PBAT), or polycarbohydrate. Contains one or more of the following:
the amorphous starch-based polymer material and other polymer materials do not have sea-island properties when blended together to form an article;
The dart impact strength of the article is at least 5% greater than what the article would have if it were made only of other polymer materials and without the amorphous starch-based polymer material; or
The amount (% by weight) of the article that is biodegradable within 5 years in accordance with ASTM D-5511 or ASTM D-5338 is greater than the loading (% by weight) of amorphous starch-based polymer material contained in the article.
An article characterized by at least one of: 2. The article of claim 1, wherein the other polymeric material comprises a polyolefin. 2. The article of claim 1, wherein the amorphous starch-based polymeric material has a crystallinity of less than 15%. 2. The article of claim 1, wherein the amorphous starch-based polymer material has a glass transition temperature, heat distortion temperature, or Vicat softening temperature of from 70°C to 100°C. 2. The article of claim 1, wherein the amorphous starch-based polymer material has a Young's modulus of at least 1.0 GPa. 2. The article of claim 1, wherein the other polymeric material comprises polyethylene. 7. The article of claim 6, wherein the article comprises a film, wherein the film is formed from a blend of an amorphous starch-based polymer material and polyethylene. 2. The article of claim 1, wherein the other polymeric material comprises one or more of polypropylene, or poly(butylene adipate-co-terephthalate) (PBAT). 2. The article of claim 1, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises at least 1% by weight of the amorphous starch-based polymeric material. 2. The article of claim 1, wherein the article comprises a film, the film having a thickness between 0.0025 mm (0.1 mil) and 0.25 mm (10 mil). 2. The article of claim 1, wherein the dart impact strength of the article is at least 10% greater than what the article would have if it were made solely of other polymeric materials and without the amorphous starch-based polymeric material. 2. The article of claim 1, wherein the other polymeric material comprises a sustainable polymeric material, and wherein at least 90% by weight of the polymer content in the article is sourced from sustainable sources. 2. The method of claim 1, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material further comprises an odor reducer,
The odor reducer is an organic odor reducer,
In the absence of an odor reducer, the amorphous starch-based polymer material can impart a burnt carbohydrate odor to the article;
The organic odor reducer is an article characterized in that it has the following chemical structure:
The combination of the following polymer materials with the amorphous starch- A method of providing at least one of increased dart impact strength or improved biodegradability to a plastic article formed from a blend of based polymer materials, the method comprising:
One or more of polyethylene, polypropylene, polyethylene terephthalate, polystyrene, acrylonitrile butadiene styrene (ABS), nylon, polyvinyl chloride, poly(butylene adipate-co-terephthalate) (PBAT), or polycarbonate. providing a polymeric material comprising;
Mixing an amorphous starch-based polymer material with the polymer material to form a mixture, wherein the amorphous starch-based polymer material is a starch comprising one or more of potato starch, corn starch, or tapioca starch and glycerin, polyethylene glycol, sorbitol. , polyhydric alcohol plasticizers, anhydrides of sugar alcohols, aliphatic acids, phthalate esters, dimethyl or diethylsuccinate, glycerol triacetate, glycerol mono or diacetate, glycerol mono, di, or tripropionate, lactic acid esters, citric acid esters, Formed from a plasticizer comprising one or more of an adipic acid ester, a stearic acid ester, or an oleic acid ester, the amorphous starch-based polymeric material has a crystallinity of less than 20%, and the amorphous starch-based polymeric material does not revert to a crystalline structure. and wherein the amorphous starch-based polymer material has a water content of less than 2% by weight;
melt blending the polymeric material with the amorphous starch-based polymeric material by heating the mixture to a temperature ranging from 95°C to 205°C; and
forming a plastic article from a blend of the polymeric material and an amorphous starch-based polymeric material, wherein the amorphous starch-based polymeric material and the polymeric material do not have sea-island properties when blended together to form the plastic article. Characterized by, comprising steps,
The dart impact strength of the article is at least 5% greater than what the article would have if it were made solely of the polymeric material, without the amorphous starch-based polymeric material; or
The amount (% by weight) of the article that is biodegradable within 5 years in accordance with ASTM D-5511 or ASTM D-5338 is greater than the loading (% by weight) of amorphous starch-based polymer material contained in the article.
A method, characterized in that at least one of. 15. The method of claim 14, wherein forming the plastic article includes blowing the plastic film with a film blowing device, wherein the film is blown from a blend of polymeric material and amorphous starch-based polymeric material,
A method characterized by providing at least one of the following:
(A) The film blowing device is operated at a blow-up ratio of at least 2.0 when blowing a plastic film, wherein the blow-up ratio is such that the blow-up ratio is at least 2.0 for a plastic film blown from the polymeric material alone without the amorphous starch-based polymeric material. providing blown plastic films from a blend of polymeric materials and amorphous starch-based polymeric materials having increased strength compared to; or
(B) The die gap of the film blowing device is selected to be a narrow die gap of 500 microns or less, which provides a blown plastic film with increased strength. 2. The article of claim 1, wherein the other polymeric material comprises polypropylene. 2. The article of claim 1, wherein the other polymeric material comprises polystyrene. 2. The article of claim 1, wherein the other polymeric material comprises poly(butylene adipate-co-terephthalate) (PBAT). Starches containing one or more of potato starch, corn starch, or tapioca starch and glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, anhydrides of sugar alcohols, aliphatic acids, phthalate esters, dimethyl or diethylsuccinate, glycerol triacetate, An amorphous starch-based polymer formed from a plasticizer comprising one or more of glycerol mono or diacetate, glycerol mono, di, or tripropionate, lactic acid ester, citric acid ester, adipic acid ester, stearic acid ester, or oleic acid ester. As a material, the amorphous starch-based polymer material has a crystallinity of less than 20%, the amorphous starch-based polymer material does not revert to a crystalline structure, and the amorphous starch-based polymer material has a water content of less than 2% by weight. an amorphous starch-based polymer material comprising: and
An article comprising another polymeric material blended with said amorphous starch-based polymeric material,
Other polymeric materials include polyethylene, polypropylene, polyethylene terephthalate, polystyrene, acrylonitrile butadiene styrene (ABS), nylon, polyvinyl chloride, poly(butylene adipate-co-terephthalate) (PBAT), or polycarbohydrate. Contains one or more of the following:
the amorphous starch-based polymer material and other polymer materials do not have sea-island properties when blended together to form an article;
An article characterized in that the dart impact strength of the article is at least 5% greater than what the article would have if it were made only of other polymeric materials and without the amorphous starch-based polymeric material. Starches containing one or more of potato starch, corn starch, or tapioca starch and glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, anhydrides of sugar alcohols, aliphatic acids, phthalate esters, dimethyl or diethylsuccinate, glycerol triacetate, An amorphous starch-based polymer formed from a plasticizer comprising one or more of glycerol mono or diacetate, glycerol mono, di, or tripropionate, lactic acid ester, citric acid ester, adipic acid ester, stearic acid ester, or oleic acid ester. As a material, the amorphous starch-based polymer material has a crystallinity of less than 20%, the amorphous starch-based polymer material does not revert to a crystalline structure, and the amorphous starch-based polymer material has a water content of less than 2% by weight. an amorphous starch-based polymer material comprising: and
An article comprising another polymeric material blended with said amorphous starch-based polymeric material,
Other polymeric materials include polyethylene, polypropylene, polyethylene terephthalate, polystyrene, acrylonitrile butadiene styrene (ABS), nylon, polyvinyl chloride, poly(butylene adipate-co-terephthalate) (PBAT), or polycarbohydrate. Contains one or more of the following:
the amorphous starch-based polymer material and other polymer materials do not have sea-island properties when blended together to form an article;
An article characterized in that the amount (% by weight) of the article that biodegrades within 5 years according to ASTM D-5511 or ASTM D-5338 is greater than the loading (% by weight) of amorphous starch-based polymer material contained within the article. 2. The article of claim 1, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises from 5% to 40% by weight of the amorphous starch-based polymeric material. 15. The article of claim 14, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises at least 1% by weight of the amorphous starch-based polymeric material. 15. The article of claim 14, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises from 5% to 40% by weight of the amorphous starch-based polymeric material. 20. The article of claim 19, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises from 5% to 40% by weight of the amorphous starch-based polymeric material. 21. The article of claim 20, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises at least 1% by weight of the amorphous starch-based polymeric material. 21. The article of claim 20, wherein the blend of the amorphous starch-based polymeric material and the other polymeric material comprises from 5% to 40% by weight of the amorphous starch-based polymeric material. 2. The method of claim 1, wherein at least 10% of the other polymeric materials are biodegradable within 5 years according to ASTM D-5511 or ASTM D-5338, and the other polymeric materials are less biodegradable or non-biodegradable under these conditions when used alone. An article characterized in that.