Polymer antioxidant stabilizers

Abstract

To provide the use of a herbaceous lignin and / or a hardwood lignin as an antioxidant stabilizer in polymers or polymer compositions, such as thermoplastic substances, thermoplastic composites, thermosetting substances, coatings, films, adhesives, personal care compositions, or any combinations thereof.SOLUTION: A composition comprises a thermoplastic polymer, and biomass that comprises a lignin. The lignin is present at a concentration from 0.5 wt.% to 1.5 wt.%. The composition contains cellulose and / or hemicellulose in an amount less than or equal to 20% based on the weight of the biomass. The lignin is preferably a hardwood lignin, and further preferably a herbaceous lignin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Cross-reference of related applications This application is U.S. Provisional Patent Application No. 62 / 555,642, filed on September 7, 2017. The interests of the party are asserted, and the entirety of which is incorporated herein by reference.

[0002] The present invention relates to herbaceous lignin and / as antioxidants in polymers or polymer compositions. Or relating to the uses of hardwood lignin. Specifically, polymers or polymer compositions, e.g. Examples include thermoplastics, thermoplastic composites, thermosetting materials, coatings, films, and adhesives. as an antioxidant stabilizer in personal care compositions, or any combination thereof. Uses of herbaceous lignin and / or broadleaf tree lignin are disclosed herein. [Background technology]

[0003] Due to the direct or indirect effects of heat and ultraviolet light, most polymers (e.g., thermoplastics) It has long been recognized that substances are susceptible to oxidative decomposition over time. This can occur early in the polymer compounding and processing stages, but the degradation of properties is more pronounced. This can lead to discoloration and a decrease in strength, flexibility, rigidity, scratch resistance, or gloss. It is more commonly recognized in the final product in which it occurs. The detailed mechanism of decomposition is complex, but Generally, they are considered to be free radicals found in nature, and are involved in initiation processes, such as polymer chains. It begins with the loss of hydrogen atoms (H.) from the polymer, resulting in reactive and unstable polymer free radicals. R.) remains. Free radical reaction propagation involves polymer free radical reaction with oxygen molecules. It includes various reactions, including the formation of peroxyl radicals (ROO·), and Hydroxy radicals move hydrogen atoms from another polymer chain to form hydroperoxides (RO). It can form an OH group and generate another polymer free radical (R·). The hydroperoxide then forms two new free radicals, (RO·) and (·OH). They can be broken down, and these will continue to propagate the reaction to other polymer molecules. Further reactions with adjacent polymer chains can lead to branching and crosslinking. - In some cases, the reaction may terminate spontaneously by combining radicals, but during this period Significant degradation of the polymer may occur. This technology may cause free radioactive contamination during the degradation process. "Mop up" the CAL, thereby bringing the radical reaction to a quicker end. We developed applications for the designed additives. Such additives are typically called antioxidant stabilizers. The stabilizing polymers include polypropylene, polyethylene, and polyvinyl chloride (PVC). Polyvinyl acetate (PVA), chlorinated polyethylene, polystyrene, acrylonitrile- Tadiene-styrene (ABS) copolymer, ethylene-vinyl acetate copolymer, PVC / ABS blend, polyethylene terephthalate (PET), polycarbonate, polyurethane This includes tannins, acrylics, styrene-acrylics, polyamides, nylons, elastomers, etc. , but not limited to these.

[0004] Known antioxidant stabilizers include metals, such as lead, barium, cadmium, tin, and more. Recently, heavy metal salts containing zinc, calcium, magnesium, and aluminum, and organometallic compounds have been used. This includes compounds and complexes, most of which are environmental and / or toxicological. It was phased out (or is being phased out) due to concerns. Other antioxidant stabilizers include: Organic phosphates and organic phosphonites, sterically hindered phenols, amines, and thioesters Steal is included.

[0005] Stabilization of free radicals (termination of decomposition reactions) and favorable environmental and toxicological processes. In addition to having a file, the stabilizer has good compatibility with the polymer and diffusion or immersion It must demonstrate resistance to migration from the polymer due to emission. The latter problem (antioxidant Additive migration and blooming can occur, especially with low molecular weight additives, particularly when they have poor compatibility with polymers. This is particularly troublesome for the agent. Many commercially available stabilizing additives have one of these properties. There are several shortcomings. What is needed is an economical stabilizer that provides all of these characteristics. It is an additive.

[0006] The methods and compositions of the present invention are directed toward these and other important purposes. [Overview of the project]

[0007] In one embodiment, a composition comprising a thermoplastic polymer and biomass is provided, and biomass It contains lignin, and the composition is less than 20% of the weight of the biomass, and Contains bi / or hemicellulose.

[0008] In one embodiment, one of broadleaf tree lignin, coniferous tree lignin, and herbaceous tree lignin A polymer or polymer composition comprising or a plurality of is provided. In a particular embodiment, The rimer or polymer composition may further contain acridine orange (AO). Therefore, in one embodiment, a polymer or polymer composition containing hardwood lignin is Provided. In another embodiment, a polymer or polymer composition containing coniferous lignin. is provided. In yet another embodiment, a polymer or polymer composition containing herbaceous lignin is provided.

[0009] In certain embodiments, a thermoplastic, thermoset material, composite material, coating, film, adhesive, personal care composition, or any combination thereof containing the disclosed polymer or polymer composition is provided. Thus, for example, the disclosed thermoplastic, thermo set material, composite, coating, film, adhesive, personal care composition, or combination thereof can be formed from or made with the disclosed polymer or polymer composition.

[0010] In certain embodiments, the oxidation onset temperature of a polymer or polymer composition containing herbaceous lignin is at least 10 °C higher than that of the same polymer or polymer composition containing kraft lignin or softwood lignin instead of herbaceous lignin.

[0011] In certain embodiments, the polymer or polymer composition containing herbaceous lignin has an oxidation onset temperature of from about 232 °C to about 250 °C. In such an embodiment, the polymer is polypropylene. In such an embodiment, the herbaceous lignin is switchgrass lignin.

[0012] In certain embodiments, the polymer is a thermoplastic.

[0013] In certain embodiments, the thermoplastic includes polyethylene, polypropylene, or a combination thereof.

[0014] In certain embodiments, the herbaceous lignin is switchgrass lignin.

[0015] Other advantages are some of which are described below, some of which are evident from that description, or The advantages can be acquired by implementing the present invention. The advantages are specifically described in the appended claims. It is realized and achieved through the elements and combinations mentioned above. Both the following detailed description and the description below are illustrative and descriptive only and do not limit the invention as described in the claims. Please understand that this is not a fixed rule. [Brief explanation of the drawing]

[0016] The accompanying figures incorporated herein and forming part thereof illustrate several embodiments and explain This helps to explain the principles of the present invention along with its clarity.

[0017] [Figure 1] Figure 1 shows the oxidation onset temperature (OOT), (°C) obtained for various antioxidant concentrations added to polypropylene. [Figure 2] Figure 2 shows an overview of the oxidation onset temperature (OOT) of an exemplary composition. [Figure 3A] Figure 3A shows the results of UV testing of an exemplary composition. [Figure 3B] Figure 3B shows the results of UV testing of an exemplary composition. [Figure 4A] Figure 4A shows the results of a thermal test of an exemplary composition. [Figure 4B] Figure 4B shows the results of a thermal test of an exemplary composition. [Figure 4C] Figure 4C shows the results of a thermal test of an exemplary composition. [Figure 5-1] Figure 5-1 shows the results of the reference oxidation onset temperature (OOT) test for exemplary compositions. [Figure 5-2] Figure 5-2 shows the results of the standard oxidation onset temperature (OOT) test for exemplary compositions. [Figure 5-3] Figure 5-3 shows the results of the reference oxidation onset temperature (OOT) test for exemplary compositions. [Figure 5-4] Figure 5-4 shows the results of the standard oxidation onset temperature (OOT) test for exemplary compositions. [Figure 6A] Figure 6A shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6B] Figure 6B shows the data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6C] Figure 6C shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6D] Figure 6D shows data corresponding to the Oxidation Onset Temperature (OOT) test for an exemplary compositional basis. [Figure 6E] Figure 6E shows data corresponding to the Oxidation Onset Temperature (OOT) test for an exemplary compositional basis. [Figure 6F] Figure 6F shows data corresponding to the Oxidation Onset Temperature (OOT) test for an exemplary compositional basis. [Figure 6G] Figure 6G shows data corresponding to the Oxidation Onset Temperature (OOT) test for an exemplary compositional basis. [Figure 6H] Figure 6H shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6I] Figure 6I shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6J] Figure 6J shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6K] Figure 6K shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Figure 6L] Figure 6L shows data corresponding to the Oxidation Onset Temperature (OOT) test based on an exemplary composition. [Modes for carrying out the invention]

[0018] The present invention relates to lignin, particularly thermoplastics, thermoplastic composites, thermosetting materials, and coatings. In addition to coatings, films, adhesives, personal care compositions, or any combination thereof, Specifically, acid-resistant polymers, polymer composites, or polymer compositions. Regarding the uses of herbaceous lignin as a chemical stabilizer.

[0019] However, the present invention is not limited to the use of lignin as an antioxidant additive for polymers, Herbaceous lignifolia as a filler for rimers or polymer compositions (e.g., polymer composite materials) The applications of the filler can include the effects of heat or light on the polymer composite. Therefore, it provides protection from the resulting degradation.

[0020] The present invention is described in the following detailed description, examples, and claims, as well as the preceding statements therein. This can be more easily understood by referring to the explanation below. However, Furthermore, unless otherwise specified, the present invention does not apply to any particular composition, article, apparatus, or system disclosed. And / or not limited to methods, and therefore understand that they may naturally change. The aspects of the present invention are described and asserted in a specific legal classification, for example, the legal classification of compositions. It is possible to classify each aspect of the present invention according to the legal classification, but this is for convenience only, and those skilled in the art will classify each aspect of the present invention according to the legal classification. You will understand that this can be explained and argued.

[0021] The following description of the present invention also enables the teaching of the present invention in the best known mode. It is provided as such. For this purpose, those skilled in the art can further obtain the beneficial results of the present invention. It is acknowledged that various aspects of the present invention described herein can be modified and altered. They will become aware of and understand. Furthermore, some of the advantages of the present invention are that it can be done without utilizing other features. It will be clear that this can be achieved by selecting some of the features of the invention. Therefore, those skilled in the art will be able to make numerous modifications and adaptations to the present invention. We recognize that this may be desirable in certain circumstances and is therefore part of the present invention. It is likely.

[0022] The present invention can be implemented in various forms, but the following description of some embodiments is This disclosure should be considered illustrative of the invention, and specific practices illustrating the invention should be considered illustrative of the invention. This is done with the understanding that it is not intended to be limited to form. Headings are for convenience only. This is provided and should not be construed as limiting the invention in any way. Embodiments illustrated in any heading or any part of this disclosure are subject to the same heading as this disclosure. Or embodiments as illustrated in part or in any other heading or part of this disclosure It can be combined with this.

[0023] Unless otherwise specified herein, or unless the context clearly contradicts it, this specification Any combination of any possible variation of the elements described in this document is included in the present invention.

[0024] All publications referenced herein are incorporated herein by reference and cited herein. The relevant methods and / or materials are disclosed and described.

[0025] The terms used herein are for the purpose of describing only specific aspects and are not limited to them. Please understand that this is not intended to be the case. Unless otherwise defined, the term used herein is used in this context. All technical and scientific terms used are understood by those skilled in the art to which this invention pertains. It has the same meaning as it is generally understood. In this specification and the following claims, this Refer to some terms defined in the specification.

[0026] A.Definition As used above and throughout this disclosure, the following terms mean the same as the following unless otherwise indicated. It shall be understood that it has meaning.

[0027] When used in the specification and attached claims, the singular forms "a", "an", and "The" is used to indicate multiple fingers unless the context clearly indicates otherwise. Includes the object being shown.

[0028] As used herein, the terms “any” or “as needed” are defined below. The event, condition, component, or situation may or may not occur. Furthermore, the description includes when the aforementioned events, conditions, components, or circumstances occur, and when they occur. This means that it includes cases where it does not happen.

[0029] When used herein, the phrase "sufficient" (for example, "sufficient conditions" or "sufficient") ) is a function or characteristic that can perform such a value or condition. "T" refers to a condition. As noted below, the exact value or specific condition required is Depending on the recognized variables, such as the materials and / or processing conditions used, each embodiment There may be differences.

[0030] The term "by weight," when used with ingredients, means that unless otherwise specified, the ingredients are included. It is based on the total weight of the compound or composition. For example, a specific compound or article When an element or component is said to be present in an amount of 8% by weight, this percentage represents 100% of the total composition. It is understood that this is relative to a percentage. In some cases, the weight percentage of the component is water. Based on the total weight of the composition, which is based on a "dry weight basis" indicating the weight of the composition not included (e.g.) For example, less than approximately 1% by weight, less than approximately 0.5%, less than approximately 0.1% by weight of the total weight of the composition. (Approximately less than 0.05%, or approximately 0% water).

[0031] Unless otherwise specified, the use of numerical values ​​for the various quantitative values ​​specified in this application is within the scope described. As if the word "approximately" were placed before both the minimum and maximum values ​​within the box, they are treated as approximate values. This is further described in the following way. In this way, a small deviation from the stated value is used This allows you to achieve essentially the same results as the values ​​listed. Furthermore, the disclosure of the range is for the columns. All values ​​between the minimum and maximum values ​​listed, and the possibilities formed by such values. It is intended as a continuous range that includes all ranges of a certain component. For example, a range where the component is between 2% and 10%. Disclosures indicating that it may be present in certain quantities include those for 2%-9%, 2%-8%, 3%-10%, and 3%. This will include percentages such as %~9%, 4%~5%, etc. Furthermore, in this specification, certain stated numerical values... All that can be formed by dividing all other listed numbers by The ratios (and the range of such ratios) are also disclosed. Therefore, those skilled in the art will find many of these Such ratios, ranges, and proportions can be clearly derived from the numerical values ​​presented herein. This is possible, and in all cases, such ratios, ranges, and proportions are in various embodiments of the present invention. They will understand how to express voice.

[0032] If we disclose a number here, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, then the following The sentence may follow such numbers. "The term "approximately" may precede each of the numbers mentioned above." You can add "at least approximately" or "less than approximately," and use one of the aforementioned numerical values. You can describe an open-ended scope on its own, or a closed-ended scope in combination with it. This sentence can be written. Each of the aforementioned numbers can be used individually (for example, 4). The word "approximately" (for example, approximately 8) is used to begin with the phrase "at least approximately" (for example, at least It can also begin with approximately 2, or with the phrase "approximately less than" (for example, less than approximately 7), or To define a range (for example, 2-9, approximately 1-4, 8-approximately 9, approximately 1-approximately 10, etc.), It can be used in any combination, with or without any of the preceding words or phrases. This means that. Furthermore, when the range is described as "approximately X or less" (where X is a number), this phrase... This is equivalent to a range that combines "approximately X" and "less than approximately X". For example, "approximately "10 or less" is the same as "about 10, or less than about 10." In this specification, such exchanges A description of interchangeable ranges is possible. Although other range formats are disclosed in this specification, differences in format This should not be interpreted as meaning that there is a difference in substance.

[0033] As used herein, the term "substantially free" means approximately 1 by weight of the total weight of the composition. Less than %, for example less than approximately 0.5% by weight, less than approximately 0.1% by weight, less than approximately 0.05% by weight, and This refers to a composition containing less than approximately 0.01% by weight of the listed material.

[0034] (Unless the phrase "substantially does not include") The term "substantially" as used herein When used in relation to composition, "qualitatively" means at least about 60% of the total weight of the composition. Weight percentage, for example, at least about 65%, at least about 70%, at least about 75%, less Approximately 80%, at least approximately 85%, at least approximately 90%, at least approximately 91%, and less Both approximately 92%, at least approximately 93%, at least approximately 94%, at least approximately 95%, less Both approximately 96%, at least approximately 97%, at least approximately 98%, at least approximately 99%, or It refers to approximately 100% of a specific characteristic or component.

[0035] As used herein, "continuous" means a process that is not interrupted during the process period or during that period. In contrast, this refers to a process that is only temporarily interrupted, paused, or stopped. The generating material (cellulose-containing composite material) is supplied into the apparatus without interruption or substantial interruption. If supplied, or if the processing of composite materials is not carried out in a batch process, the process is It is "continuous".

[0036] A supercritical fluid is a fluid that, at temperatures exceeding its critical temperature and pressures exceeding its critical pressure... A supercritical fluid is a fluid in which the liquid phase and the vapor (gas) phase are in a state of relative neutrality. It exists above the point of maximum temperature and pressure at which it can exist in equilibrium. (Critical pressure or critical temperature) In the above case, the distinction between the liquid phase and the gas phase disappears. A supercritical fluid possesses the solvent properties of a liquid and a gas simultaneously. It possesses almost the same penetration characteristics. Therefore, for supercritical fluid extraction, high penetration and good It has the advantage of solvation.

[0037] The reported critical temperature and pressure are as follows: For pure water, the critical temperature is approximately 374.2°C, and the critical temperature is approximately 374.2°C. The critical pressure is approximately 221 bar, and for carbon dioxide, the critical temperature is approximately 31°C, and the critical pressure is approximately 221 bar. The pressure is approximately 72.9 atmospheres (approximately 1072 psig). Near-critical water is water at temperatures above approximately 300°C. Temperatures below the critical temperature (374.2°C), and sufficient to ensure that all fluids are in the liquid phase. It has high pressure. Subcritical water is at a temperature of less than approximately 300°C, and all fluids are definitely in the liquid phase. It has a sufficiently high pressure despite this. The subcritical water temperature is higher than approximately 250°C and below approximately 300°C. Subcritical water can be full, and in most cases, it has a temperature of approximately 250°C to 280°C. In this specification, the term "high-temperature, high-pressure water" refers to near-critical water or subcritical water, or less At any temperature of at least about 50°C (preferably at least about 100°C, at least about 150°C) °C, at least about 200°C, at least about 250°C, at least about 300°C, or less At least around 350°C, but below supercritical (for example, below approximately 374°C), water (for example, It is defined as the pressure at which all water is in a liquid state.

[0038] As used herein, "supercritical" fluids (e.g., supercritical water, supercritical CO2) (d) indicates a fluid that is supercritical when it exists in its pure form under certain temperature and pressure conditions. For example, whether the water is pure water or a mixture (for example, water and ethanol, water and CO2) Whether it exists as (, etc.) or "supercritical water", it is at a temperature of at least approximately 374.2°C. This refers to water that exists at a pressure of at least approximately 221 bar. Therefore, for example, "subcritical" A mixture of water and supercritical carbon dioxide is defined regardless of whether any supercritical phase contains water. , and regardless of whether the aqueous phase contains any carbon dioxide, from the critical point of carbon dioxide At high temperatures and pressures, but below the critical point of water, it exhibits a mixture of water and carbon dioxide. For example, a mixture of subcritical water and supercritical CO2 is produced at temperatures of approximately 250°C to approximately 280°C and It can have a pressure of at least approximately 225 bar.

[0039] The term "supercritical hydrolysis" refers to the process of hydrolysis of one or more fluids under supercritical conditions (i.e., supercritical conditions This refers to a hydrolysis reaction brought about by a fluid.

[0040] Unless otherwise clearly indicated by the context, all pressures disclosed herein are gauge pressures.

[0041] In this specification, "fluid" means vapor, liquid, or both.

[0042] In this specification, “slurry” means a mixture of an insoluble or partially soluble solid and a fluid. A mixture that has fluidity with a body or can be pumped, for example, a suspension in water or a bio It refers to the particles of mass.

[0043] In this specification, "herbaceous lignin" refers to lignin derived from herbaceous biomass. Herbaceous biomass includes switchgrass, Japanese pampas grass (silvergrass), turfgrass, and ornamental plants. This includes grasses and grains, such as sorghum, barley, and wheat. Herbaceous lignin consists of three types. Nolignol (Lignin Syringyl-S, Lignin Iacyl-G, and Lignin Hy Composed of droxyphenyl-H subunits, and usually more H subunits than non-herbaceous plants. It contains (more coumaryl derivatives). Herbaceous lignin has ether bonds to the lignin. Large amounts of hydroxycinnamic acid units, such as ferulic acid and p-coumaric acid, are produced by Further distinctions are made.

[0044] In this specification, "composite material" refers to a material whose constituent components have different physical or chemical properties. An article or material made from two or more constituent components. The term "multiple" as used herein refers to an article or material made from two or more constituent components. "Composite material" includes lignin-containing composite materials, such as polymer-lignin composite materials.

[0045] "Synthetic polymers" are polymers that are not natural polymers but are artificially created. This refers to, for example, those that are artificial or mechanically produced. An example of synthetic polymers is homopoly. Polymers, such as polyethylene and polypropylene, and copolymers, such as ethylene Examples include vinyl acetate and styrene-butadiene. Terms used herein: Synthetic polymers include various types of polymers, such as thermosetting polymers and thermoplastic polymers. Structural forms of polymers, or synthetic polymers (e.g., isotactic, syndiotactic) Polypolymers (including tactic polymers), as well as polymers that are distinguished as high-density polymers or low-density polymers. Any or all of the remers (e.g., low-density polyethylene, high-density polyethylene, etc.) It includes.

[0046] As used herein, the term "polymer-lignin composite" refers to a composite containing a polymer and lignin. This means a composite, where each of these components is greater than 0% by weight relative to the weight of the dry composite, and at most It is present in amounts ranging from less than 100% by weight. The term "polymer-lignin" as used herein. A "complex" is a naturally occurring complex, such as wood, lignocellulosic biomass, or cell. Rose-hemicellulose composite, or derived from wood or lignocellulosic biomass. It does not contain any of the following components. Cellulose or hemicellulose, or even wood, (Po It may be present as an additional component (in addition to polymer and lignin components). --Specific examples of lignin complexes are described elsewhere in this specification and used herein. This represents the meaning of "cellulose-polymer composite."

[0047] As used herein, "grinding" refers to any mechanical means used to reduce the size of a solid. It refers to methods such as crushing, grinding, and impact crushing.

[0048] As used herein, the terms “ambient temperature” and “ambient pressure” refer to normal (typical, not necessarily) conditions. However, it refers to (unadjusted) room temperature and room pressure. These conditions can change. Because of their inherent properties, the term is used only to convey approximate temperature and approximate pressure. In this specification, ambient temperature is interpreted as meaning a temperature of 20°C ± 5°C, and ambient pressure is This is interpreted as meaning a pressure of 1 bar (1 atmosphere) ± 0.2 bar (0.2 atmospheres).

[0049] As used herein, the term "glass transition temperature" or Tg refers to the temperature at which a glassy polymer becomes glassy. - Temperatures above the temperature at which the chain segments undergo motion (and from a "glassy" state to melting or This refers to the transition to a rubbery state, and when used herein, using a heating rate of 10°C / min. This refers to the measurement Tg obtained by differential scanning calorimetry (DSC), which is the intermediate point in the heat flow-temperature transition. The point is used as the Tg value.

[0050] As used herein, "C1-05 alcohol" refers to an alcohol containing 1 to 5 carbon atoms. This indicates an alcohol. Examples of C1-05 alcohols include methanol, ethanol, and n-p Lopanol, isopropanol, n-butanol, s-butanol, t-butanol, i -Butanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl Examples include 2-2-butanol and 2,2-dimethyl-1-propanol, but These are not limited to these alcohols. One or more mixtures of these alcohols may be used.

[0051] B. Polymers and Polymer Compositions In one embodiment, a composition comprising a thermoplastic polymer and biomass is disclosed, and biomass It contains lignin, and the composition is less than 20% of the weight of the biomass, and Contains bi / or hemicellulose.

[0052] The present invention relates to lignin, for example, broadleaf tree lignin, coniferous tree lignin, herbaceous tree lignin, and This provides polymers or polymer compositions containing combinations thereof. Specific embodiments Therefore, the polymer or polymer composition further contains acridine orange (AO). This is possible. In certain embodiments, broadleaf lignin, coniferous lignin, and / or herbaceous lignin can be used. Lignin is prepared by the disclosed process.

[0053] While I don't want to be bound by any theory, the composition of lignin varies by species. They are different. To put it simply, the three monolignol monomers are precursors of lignin, and All of these are methoxylated to varying degrees. These include p-coumaryl alcohol, co It contains niferyl alcohol and cinapyl alcohol. These lignols are each Phenylpropanoids: p-hydroxyphenyl (H), guaiacyl (G), and syl It is incorporated into lignin in the form of ringil (S). Gymnosperms are almost entirely G and small amounts. It has lignin composed of H. Dicotyledonous angiosperms are usually a mixture of G and S. And H is almost nonexistent. Finally, monocotyledonous plants have all three types of lignin (i.e., H, G, O It is a mixture of (and S). Many herbaceous plants mainly have G, but some palms mainly have S. All lignins contain small amounts of incomplete or modified monolignols. Furthermore, non In woody plants, a different monomer is prominent.

[0054] In certain embodiments, the lignin is substantially cellulose-free. Therefore, for example, Lignin, based on the total weight of lignin, is less than approximately 20% by weight, less than approximately 15% by weight, and about 1% by weight. It may contain less than 0% by weight, less than approximately 5% by weight, or less than approximately 1% by weight of cellulose. Cut.

[0055] In certain embodiments, the lignin is substantially free of hemicellulose. Therefore, for example... For example, lignin is less than approximately 20% by weight, less than approximately 15% by weight, based on the total weight of lignin. Contains less than approximately 10% by weight, less than approximately 5% by weight, or less than approximately 1% by weight of hemicellulose. It is possible.

[0056] In certain embodiments, lignin is either cellulose or hemicellulose. It does not contain virtually any of the above. Therefore, for example, lignin is not a component of both cellulose and hemicellulose. Based on the total weight of lignin, the percentages are approximately less than 20% by weight, approximately less than 15% by weight, and approximately 10% by weight. It may contain less than % by weight, less than approximately 5% by weight, or less than approximately 1% by weight.

[0057] The present invention also relates to polymers or polymer combinations containing biomass essentially composed of lignin. To provide a product. Therefore, in a particular embodiment, the biomass is the total weight of the biomass. Based on that, at least about 60%, at least about 65%, at least about 70%, and at least Approximately 75%, at least approximately 80%, at least approximately 85%, at least approximately 90%, and at least Approximately 91%, at least approximately 92%, at least approximately 93%, at least approximately 94%, and at least Approximately 95%, at least approximately 96%, at least approximately 97%, at least approximately 98%, and at least It also contains approximately 99%, or even 100%, of lignin.

[0058] A polymer-lignin composite comprises at least one polymer and lignin. Each of the components and lignin components is greater than 0% by weight, based on the weight of the dry composite. , present in amounts ranging from less than 100% by weight at most. In one embodiment, at least two components Each of the minutes is within the range of at least 2% by weight and up to 98% by weight, based on the weight of the composite. It exists in a surrounding quantity. In one embodiment, each of at least two components is the weight of the composite. Based on this, it is present in amounts ranging from at least 5% by weight to a maximum of 95% by weight.

[0059] Lignin (e.g., herbaceous lignin or broadleaf tree lignin) is used in any suitable amount, poly It can be used in polymer or polymer compositions, such as thermoplastic polymers. The quantities are 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6 , 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 18 ,20,22,24,26,28,30,32,34,36,38,40,42,44, 46, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 (heavy The quantity can be expressed as %). The terms "about" or "at least about" can be placed before each of the aforementioned numbers. You can add "approximately less than" or any of the above numbers, and open it alone. You can specify the range of the end end, or combine it with the range of the closed end. For example, lignin may be present in a polymer or polymer composition at a concentration of 0.1 to 3.0% by weight. Alternatively, it can be used in amounts of 0.3–2.0% by weight, or 10–60% by weight. Lignin can be obtained from biomass as described elsewhere in this specification. Yes, it is possible. Suitable biomass includes switchgrass, Japanese pampas grass (silvergrass), turfgrass, and broadleaf grass. This includes leafy trees, ornamental grasses, and grains such as sorghum, barley, and wheat, but these Not limited to, however, lignin is a polymer or polymer composition as disclosed herein. The composition present in the coating, film, adhesive, or personal care composition It can be used in any composition for antioxidant purposes, including,

[0060] Therefore, in certain embodiments, the polymer or polymer composition is a thermoplastic, Thermosetting materials, composite materials, coatings, films, adhesives, personal care compositions, or any combination of those.

[0061] In certain embodiments, the oxidation initiation temperature of a polymer or polymer composition containing herbaceous lignin Except for containing kraft lignin or broadleaf tree lignin instead of herbaceous lignin. At least 10°C higher than the same polymer or polymer composition.

[0062] In certain embodiments, the polymer or polymer composition is subjected to an acid at a temperature of about 232°C to about 250°C. It has a polymerization initiation temperature. In one such embodiment, the polymer is polypropylene. In one embodiment, the herbaceous lignin is switchgrass lignin.

[0063] In certain embodiments, the polymer or polymer composition is a thermoplastic.

[0064] In certain embodiments, the thermoplastic material is polyethylene, polypropylene, or the same. This includes combinations.

[0065] Other suitable components of the polymer or polymer composition include fillers (e.g., talc, carbonate). Calcium, glass fiber, etc.), colorants (e.g., inorganic pigments, e.g., titanium dioxide, carbon Black, metal salts, or organic colorants (e.g., phthalocyanine blue), and others Additives, such as compatibilizers (e.g., graft-modified polymers, block copolymers, silanes) (etc.), processing aids (e.g., waxes, lubricants, zinc stearate, etc.), wear-resistant aids ( For example, lubricants such as polytetrafluoroethylene, PTFE, oils, and silicones. ), anti-blocking agent (e.g., talc), antistatic agent (for metals, e.g., stainless steel) Fibers, ionic salts, etc.), nucleating agents (e.g., sorbitol, minerals, metal salts, etc.), Flame retardants (bromine-containing compounds, phosphorus-containing compounds, magnesium hydroxide, etc.), Or it could be any combination of those.

[0066] The polymer to be stabilized (or polymer of the polymer-lignin complex) is any polymer —For example, thermosetting polymers, thermoplastic polymers, coatings, films, adhesives, This may be a personal care composition or a combination thereof. Specific Embodiments The polymer may be a synthetic polymer. In certain embodiments, the polymer is thermoplastic. It may be a polypolymer. In certain embodiments, the polymer is polyethylene, polypropylene, etc. Pyrene, polyester (for example, poly(ethylene terephthalate)), polyamide (for example) (including aliphatic, aromatic, or semi-aromatic polyamides), or any combination thereof It contains, essentially consists of, or comprises. The stabilizing polymer is polypropylene. Polyethylene, polyvinyl chloride (PVC), polyvinyl acetate (PVA), chlorinated polyethylene Tylene, polystyrene, acrylonitrile-butadiene-styrene (ABS) copolymer ethylene-vinyl acetate copolymer, PVC / ABS blend, polyethylene terephthalate PET, polycarbonate, polyurethane, acrylic, styrene-acrylic, This includes, but is not limited to, riamide, nylon, and elastomer. Any of the polymers described herein may be used alone or in any combination (e.g., with other synthetic polymers). The polymer may be present as a natural polymer, or both. The polymer may also be present in the solvent. It may exist as a bulk (dry) polymer that does not contain any rear liquid, or as a solvent solution. It may be present in a dispersion, or in an aqueous solution or dispersion, or dry film It may exist as a substance or a coating. Therefore, in various embodiments, stable The polymer being processed is subjected to a processing temperature lower than the scorching point of lignin (i.e., melting or softening). It can be a polymer having (chemical) properties. In various other embodiments, the stabilized polymer The polymer can be one that has a processing temperature of less than approximately 400°C.

[0067] The activity of antioxidants was measured by ASTM2009-02 (differential scanning calorimetry (DSC)). It can be evaluated using the standard test method for the oxidation onset temperature of hydrogen. Herbaceous lignin, For example, switchglass lignin is more resistant to the oxidative degradation of polymers compared to other lignins. It can provide excellent protection. For example, at a concentration of 1.0 wt%, switchglass lignin is Typically, polypropylene (Bapolene® 4012F, Bamberger Pol The oxidation onset temperature of (ymer, Inc., Houston, TX, USA) is (same polymer (Compared to hardwood lignin and kraft lignin at the same concentration and approximately 230°C) Raise the temperature from approximately 200°C to approximately 244°C.

[0068] In certain embodiments, the composition may contain kraft lignin or broadleaf lignin instead of herbaceous lignin. Except for containing tree lignin, it has an oxidation onset temperature at least 10°C higher than the same composition. do.

[0069] 1. Herbaceous lignin In certain embodiments, the lignin is herbaceous lignin. The lignin is switchgrass lignin. In certain embodiments, herbaceous lignin is lignin A large number of hydroxycinnamic acid units are ether-bonded to it, such as ferulic acid and p- It has a malic acid unit. For example, herbaceous lignin contains p-hydroxyphenyl, guai palm. It may contain a mixture of ru and syringyl units.

[0070] In certain embodiments, herbaceous lignin is less than approximately 600 μm as measured by light scattering, approximately Less than 550 μm, approximately less than 500 μm, approximately less than 450 μm, approximately less than 400 μm, approximately 350 μm Less than m, less than approximately 300 μm, less than approximately 250 μm, less than approximately 200 μm, less than approximately 150 μm, Less than approximately 125 μm, less than approximately 100 μm, less than approximately 75 μm, less than approximately 50 μm, less than approximately 25 μm Average particle diameter d is less than approximately 10 μm, or less than approximately 5 μm. (50) It has.

[0071] In certain embodiments, herbaceous lignin is hydrolyzed by fluids into herbaceous biomass, for example These are obtained by subcritical, nearcritical, or supercritical hydrolysis. Examples of fluids include water and melanin. Butanol, ethanol, propanol, butanol, carbon dioxide, sulfur dioxide, or this Any combination of these, but not limited to them, may be used. In certain embodiments, water may be added. The decomposition is supercritical hydrolysis. As will be further detailed herein, the preparation process is a pretreatment. While such pretreatment steps may be included, they are not mandatory. In certain embodiments, The process may include processing steps, as will be further detailed herein.

[0072] In certain embodiments, herbaceous lignin is obtained by hydrolysis, for example, supercritical hydrolysis. Hydrolysis occurs at pressures such as 1, 5, 10, 20, 30, 40, 50, 60, and 70 degrees Celsius. 80, 90, 100, 110, 120, 125, 130, 140, 150, 160, 17 0, 175, 180, 190, 200, 210, 220, 221, 225, 230, 24 0, 250, 260, 270, 275, 280, 290, 300, 310, 320, 32 5, 330, 340, 350, 360, 370, 375, 380, 390, 400, 42 0, 440, 450, 460, 475, 480, 500, 525, 550, 575, 60 0, 625, 650, 675, 700, 725, 750, 775, or 800 (bar) Hydrolysis can be carried out at temperatures such as 374, 375, 380, and 39°C. 0, 400, 410, 420, 430, 440, 450, 460, 470, 480, 49 0, 500, 510, 520, 530, 540, 550, 560, 570, or 575 This can be done in (°C). The word "about" or "at least" can be placed before each of the numbers above. You can add "approximately" or "less than approximately," and you can use either of the above numbers on their own. Specify the scope of the open end, or combine it with the scope of the closed end. Therefore, in certain embodiments, herbaceous lignin can reduce herbaceous biomass by approximately 3 A fluid with a temperature of 40°C to approximately 400°C and a pressure of approximately 225 bar to approximately 250 bar It is obtained by exposure.

[0073] Traditionally, antioxidants for polymers have been supplied as additives, typically in amounts of 0.05 to 10% by weight. Used in quantities within the range of (solid-based solids). Used as an antioxidant for polymers. Herbaceous lignins disclosed herein (e.g., switchgrass lignin) also have polymer additives. It can be used in this manner. However, as disclosed herein and further explained below... Similarly, herbaceous lignin also functions as an antioxidant polymer filler (or augmented polymer). It may be used as a dosage agent. Therefore, the herbaceous lignin content is high at 95% by weight. There are cases where this is the case.

[0074] The polymer-lignin complex comprises at least one polymer and herbaceous lignin. Each of the polymer component and the herbaceous lignin component is 0W based on the weight of the dry composite. It is present in amounts greater than a percent and less than 100% by weight at most. In one embodiment, Each of the two components is at least 2% by weight and up to 9% by weight of the composite. It is present in amounts in the range of 8% by weight. In one embodiment, each of at least two components is Based on the weight of the composite, it is present in an amount ranging from at least 5% by weight to a maximum of 95% by weight. .

[0075] Herbaceous lignin (e.g., switchgrass lignin) can be polymerized in any suitable amount. It can be used in polymer compositions, such as thermoplastic polymers. For example, the amount , 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1. 7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3. 6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7. 5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 18, 20 , 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 (by weight %) It is possible to add the terms "about," "at least about," and before each of the aforementioned numbers. The term "less than approximately" can be added, and using any of the aforementioned numerical values, open-ended You can specify the range of the "do" section, or combine them to specify the range of the "closed end" section. For example, herbaceous lignin may be present in a polymer or polymer composition at a concentration of 0.1 to 3.0% by weight. It can be used in amounts of 0.3-2.0% by weight, or 10-60% by weight. This lignin is obtained from herbaceous biomass as described elsewhere in this specification. Suitable biomass includes switchgrass, Japanese pampas grass (silvergrass), This includes grasses, ornamental plants, and grains such as sorghum, barley, and wheat, but these Not limited to, however, herbaceous lignin may be polymers or polymer compounds as disclosed herein. The composition in which the product is present in coatings, films, adhesives, or personal care compositions. It can be used in any composition containing antioxidants for antioxidant purposes.

[0076] Herbaceous lignin is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 , 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 40, 5 The average particle diameter, diameter / maximum dimension can be 0 (micrometers). You can add the terms "approximately," "at least approximately," or "less than approximately" before each word. You may use any of the above numerical values ​​to describe the open-end range on its own, or in combination with them. The scope of the closed end can also be specified. For example, herbaceous lignin is 1. Having an average particle size (micrometers) of 0-10.0 or 2-8 micrometers. It is possible.

[0077] Herbaceous lignin is 0.1, 0.5, 1.0, 1.5, 2.0, 5.0, 6.0, 7.0 , 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2 The carbohydrate content can be 0, 25, 30, 40, or 50%. You can add the terms "about," "at least about," or "less than about" before each of these. , using any of the above numerical values, you may describe the open-end range individually or in combination The closed-end range can also be specified. For example, herbaceous lignin is 1.0 It can have a carbohydrate content of ~15.0%, or 2-8%.

[0078] Biomass containing switchgrass biomass typically consists of cellulose, hemicellulose, and lignin. Herbaceous lignin is obtained, for example, by hydrolyzing herbaceous biomass in a fluid. It can be derived from herbaceous biomass by any preferred method, including the following. Hydrolysis involves one or more steps (2, 3, 4, 5, 6, 7, 8, or 9 steps). The above hydrolysis step is included. The temperatures, pressures, and times described herein are: It can be applied to any single process. For example, the hydrolysis process is implemented in two steps. The first step may be carried out, and the temperature, pressure, and residence time disclosed herein The second step has either of the following: the temperature, pressure, and time disclosed herein. It has.

[0079] The fluids are water, methanol, ethanol, propanol, butanol, carbon dioxide, and diacitol. Sulfur compounds, or any combination thereof, consisting of or essentially made from them. In the embodiment, the fluid consists of, or essentially consists of, water.

[0080] In certain embodiments, herbaceous biomass (e.g., switchgrass) is subcritical, near critical It is hydrolyzed or supercritically. This process involves herbaceous biomass being subjected to a first temperature and And pre-treat under a first pressure for a first period, thereby forming pre-treated biomass The pretreatment steps may include processing steps. The pretreatment steps used herein typically involve biomass This includes extracting hemicellulose (if present), while cellulose (if present) ) and leaving lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment bio (referred to as "mass"). The process involves the pre-treated biomass being subjected to a second temperature and a second pressure. The process may further include a processing step that is carried out under force for a second period. In some embodiments, The process includes processing steps but does not include pre-processing steps. In other words, as defined herein, Herbaceous biomass that has not undergone a pretreatment process undergoes a treatment process that includes fluids. Before the processing step, the herbaceous biomass may be crushed (for example, by mechanical means, e.g. This can be done by crushing, grinding, impact crushing, or by explosive decompression, such as steam explosion. (Reducing the size), this grinding is not considered a pretreatment step as used herein. Supercritical water When using a fluid containing supercritical water, the process can be performed without the pretreatment steps defined herein. This may also include treating herbaceous biomass using [a specific method / tool].

[0081] In some embodiments, if necessary, herbaceous biomass is typically about 600 micrometers. Average particle diameter d less than 1 meter or less than 500 micrometers (50) To manufacture Therefore, even if the above size reduction is performed before subcritical, near-supercritical, or supercritical hydrolysis, Good. In certain embodiments, the size reduction is achieved by reducing herbaceous biomass in the presence of ammonia. This includes causing an explosion. In certain embodiments, the size reduction is achieved by using grass in the presence of sulfur dioxide. This involves detonating the biomass. However, size reduction may not be necessary.

[0082] In certain embodiments, subcritical, near-supercritical, or supercritical hydrolysis, or as described herein. Herbaceous biomass that are hydrolyzed by any other means (e.g., by enzymes) is measured by light scattering. A defined average particle diameter d of less than approximately 600 μm or less than approximately 500 μm. (50) For example, average Particle size, d (50) The numbers are 5, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600 (micrometers) It may also be μm. The word "about", "at least about", before each of the above numbers. Alternatively, you can add "approximately less than," and use any of the aforementioned numbers to open it alone. You can specify the end range, or combine them to specify the closed end range. For example, the average particle diameter d (50) This ranges from approximately 50 μm to approximately 600 μm, and from approximately 50 μm to approximately 50 0 μm, approximately 50 μm to approximately 450 μm, approximately 25 μm to approximately 250 μm, or approximately 100 μm to It can be made approximately 400 μm thick.

[0083] In certain embodiments, preferably herbaceous biomass of reduced size as described herein. It is mixed with a fluid, such as water, which consists of or essentially consists of a fluid, and it A mixture is formed, and the mixture is hydrolyzed at a temperature of at least about 100°C. In this embodiment, the fluid in contact with the mixture or the mixture itself is 100, 120, 140°C 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃ 230℃, 240℃, 250℃, 260℃, 280℃, 300℃, 320℃, 340℃ 350℃, 360℃, 370℃, 374.2℃, 380℃, 390℃, 400℃, 41 0℃, 420℃, 440℃, 450℃, 460℃, 480℃, 500℃, 520℃, 54 It has a temperature (°C) of 0°C, 560°C, 580°C, or 600°C. The words "about," "at least about," or "less than about" can be placed before it, as described above. Use any of the numbers to specify the open-end range, either individually or in combination. The rose end range can be specified. For example, the mixture is 190°C to 374°C. Hydrolysis may occur with temperature. Alternatively, the mixture may be hydrolyzed at a temperature of 374°C to 500°C, Hydrolysis may be performed at temperatures exceeding 500°C. In certain embodiments, the mixture is 100 Hydrolysis occurs at temperatures ranging from ℃ to 500℃ under pressures sufficient to ensure all fluids remain in liquid form. In some such embodiments, the mixture is substantially free of exogenous acids. In some such embodiments, the mixture is substantially free of Ci-05 alcohol. If necessary, one or more preheating steps may also be used in each embodiment.

[0084] In certain embodiments, the herbaceous biomass consists of, for example, water, or from The essential fluid is mixed with the mixture to produce a mixture, the mixture is supercritically hydrolyzed, and the mixture The object is at least about 374°C, for example, at a temperature of about 374.2°C to about 575°C, and less At least 221 bar of pressure must be subjected to a period of time sufficient to produce at least one C6 sugar. When the mixture undergoes supercritical hydrolysis, the water in contact with the mixture must be at least approximately 374°C. It has a temperature. The water in contact with the mixture is 374, 375, 380, 390, 400, 41 0, 420, 430, 440, 450, 460, 470, 480, 490, 500, 51 It has temperatures of 0, 520, 530, 540, 550, 560, 570, and 575 (°C). Add the word "approximately," "at least approximately," or "less than approximately" before each of the aforementioned numbers. It is possible to use any of the above numerical values ​​to describe the open-ended range on its own, Alternatively, the range of the closed end can be described by combining them. Therefore, the mixture and The water in contact has a temperature bounded by any two of the aforementioned endpoints. It is possible. For example, water can be heated to approximately 374°C to approximately 575°C, approximately 374°C to approximately 450°C, and approximately It has a temperature of 400°C to approximately 520°C, or approximately 375°C to approximately 430°C, and in each case In this configuration, the pressure can be at least about 221 bar. In certain embodiments, Water can have a temperature higher than 575°C and be under a pressure of at least approximately 221 bar. In some such embodiments, the mixture is substantially free of exogenous acids. In some such embodiments, the mixture is substantially free of C1-05 alcohol. Depending on the requirements, additional preheating steps may also be used in each embodiment.

[0085] In embodiments in which the mixture is subjected to subcritical, near-supercritical, or supercritical hydrolysis, the hydrolysis is performed as follows: 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 1 20, 125, 130, 140, 150, 160, 170, 175, 180, 190, 2 00, 210, 220, 221, 225, 230, 240, 250, 260, 270, 2 75, 280, 290, 300, 310, 320, 325, 330, 340, 350, 3 60, 370, 375, 380, 390, 400, 420, 440, 450, 460, 4 75, 480, 500, 525, 550, 575, 600, 625, 650, 675, 7 The process is carried out at a pressure of 00, 725, 750, 775, or 800 (bar). You can put the words "about," "at least about," or "less than about" before each of these. , using any of the above numerical values, you may describe the open-end range individually or in combination The closed-end range can also be specified. For example, the pressure is approximately 221 bar. ~800bar, 230bar~500bar, 325bar~750bar , or it can be about 275 bar to about 350 bar. In certain embodiments, the pressure The force can be greater than 800 bar.

[0086] In certain embodiments in which the mixture is subjected to near-supercritical or supercritical hydrolysis, during the continuation of hydrolysis The intervals are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9 .0, 10.0, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1 20, 140, 160, 180, 200, 220, 240, 260, 280, or 30 It is 0 (seconds). The word "approximately", "at least approximately", or " The term "approximately less than" can be added, and any of the above numbers can be used to determine an open-ended term on its own. You can specify a range, or a combination of ranges, to specify a closed-end range. For example The duration is approximately 0.1 seconds to 10 seconds, approximately 0.1 seconds to 5 seconds, and approximately 0.1 seconds to 0.3 seconds. This can be approximately 1.1 seconds to approximately 5 seconds, or approximately 0.9 seconds to approximately 9 seconds. Specific Embodiments Then, the duration is greater than 10 seconds. In a preferred embodiment, the duration is approximately 1.4 seconds. For example, the interval is approximately 0.1 seconds to 1.4 seconds. The mixture will be exposed to a lower temperature (for example, sub (Critical hydrolysis) In certain embodiments, the duration of hydrolysis is 0.5, 1, 1.5, 2. 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30 , 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, Or 300 (minutes). The word "approximately" or "at least approximately" should be placed before each of the numbers above. You can add "approximately less than" or any of the above numbers, and open it alone. You can specify the range of the end end, or combine it with the range of the closed end. Cut.

[0087] In certain embodiments, a mixture containing herbaceous biomass that will be hydrolyzed later is C1-0 5. Substantially alcohol-free. In certain embodiments, the mixture substantially contains exogenous acids. No. If necessary, in each embodiment, one or more preheating steps are also performed before hydrolysis. It can be used for the following purposes. In another embodiment, the mixture is (disclosed elsewhere in this specification). (i) any C1-05 alcohol, exogenous acid, or any combination thereof.

[0088] In certain embodiments, the solid content of the mixture based on the total weight of the mixture is about 1% by weight or more, e.g. For example, 1% to 40% by weight. The solid content of the mixture is 1, 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 2 2, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40 (%) or more. The word "approximately" or "minus" may precede each of the numbers. You can add "approximately" or "less than approximately," and use one of the aforementioned numerical values. You can describe open-ended scopes individually, or close-ended scopes in combination. It is possible. For example, the solids content of the mixture is about 10% to 29% by weight, about 15% by weight. Quantity % to approximately 29% by weight, approximately 10% by weight to approximately 18% by weight, or approximately 24% by weight to approximately 27% by weight It can be done this way.

[0089] 2. Hardwood lignin In certain embodiments, lignin is hardwood lignin. For example, hardwood lignin is It may contain a mixture of guaiacil and syringyl units. In another specific embodiment, Therefore, broadleaf tree lignin cannot contain p-hydroxyphenyl.

[0090] In certain embodiments, hardwood lignin is less than approximately 600 μm as measured by light scattering. Less than approximately 550 μm, less than approximately 500 μm, less than approximately 450 μm, less than approximately 400 μm, approximately 350 Less than μm, less than approximately 300 μm, less than approximately 250 μm, less than approximately 200 μm, less than approximately 150 μm Approximately less than 125 μm, approximately less than 100 μm, approximately less than 75 μm, approximately less than 50 μm, approximately 25 μm Average particle diameter d is less than approximately 10 μm, or less than approximately 5 μm. (50) It has.

[0091] In certain embodiments, hardwood lignin is hydrolyzed by fluid biomass, for example sub It is obtained by critical, near-critical, or supercritical hydrolysis. Examples of fluids include water and methanol. ethanol, propanol, butanol, carbon dioxide, sulfur dioxide, or those Any combination of these, but not limited to them, may be used. In certain embodiments, hydrolysis This is supercritical hydrolysis. As will be further detailed herein, the preparation process is a pretreatment step. This may include, but such pretreatment steps are not essential. In certain embodiments, The process may include processing steps, as will be further detailed herein.

[0092] In certain embodiments, hardwood lignin is obtained by hydrolysis, for example, supercritical hydrolysis. Hydrolysis occurs under pressure, for example, 1, 5, 10, 20, 30, 40, 50, 60, 70 , 80, 90, 100, 110, 120, 125, 130, 140, 150, 160, 1 70, 175, 180, 190, 200, 210, 220, 221, 225, 230, 2 40, 250, 260, 270, 275, 280, 290, 300, 310, 320, 3 25, 330, 340, 350, 360, 370, 375, 380, 390, 400, 4 20, 440, 450, 460, 475, 480, 500, 525, 550, 575, 6 00, 625, 650, 675, 700, 725, 750, 775, or 800 (ba This can be carried out at r). Hydrolysis can be carried out at temperatures, e.g., 374, 375, 380, 3 90, 400, 410, 420, 430, 440, 450, 460, 470, 480, 4 90, 500, 510, 520, 530, 540, 550, 560, 570, or 57 It can be carried out at 5 (°C). The word "about", "at least about", or "less than about" can be attached before each of the above numbers, and any of the above numerical values can be used alone to describe an open-ended range or in combination to describe a closed-ended range. Therefore, in certain embodiments, hardwood lignin is exposed to a fluid having a temperature of about 34 0 °C to about 400 °C and a pressure of about 225 bar to about 250 bar to obtain. Conventionally, antioxidants for polymers are provided as additives and are generally used in amounts in the range of 0.05 to 10% by weight (based on solids for solids). The hardwood lignin disclosed herein can also be used as such as a polymer additive for use as an antioxidant for polymers. However, as disclosed herein and further described below, hardwood lignin may also be used as a polymer filler (or extender) that also functions as an antioxidant.

[0093] Therefore, the content of hardwood lignin may be as high as 95% by weight. (based on solids for solids). The hardwood lignin disclosed herein can also be used as such as a polymer additive for use as an antioxidant for polymers. However, as disclosed herein and further described below, hardwood lignin may also be used as a polymer filler (or extender) that also functions as an antioxidant. Therefore, the content of hardwood lignin may be as high as 95% by weight. (or extender) that also functions as an antioxidant. Therefore, the content of hardwood lignin may be as high as 95% by weight. (or extender) that also functions as an antioxidant. Therefore, the content of hardwood lignin may be as high as 95% by weight.

[0094] [[ID=3(]] A polymer-lignin composite includes at least one polymer and hardwood lignin. Each of the polymer component and the hardwood lignin component is present in an amount in the range of more than 0% by weight and up to less than 100% by weight based on the weight of the dry composite. In one embodiment, each of at least two components is at least 2% by weight and up to, based on the weight of the composite, at most It is present in an amount ranging from 0 to 98% by weight. In one embodiment, each of at least two components is present in an amount ranging from at least 5% to a maximum of 95% by weight based on the weight of the composite .

[0095] Hardwood lignin can be used in any suitable amount in a polymer or polymer composition, such as a thermoplastic polymer. For example, the amount can be 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 , 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 55, 60, 65, 7 0, 75, 80, 85, 90, or 95 (wt%). The terms "about", "at least about", or "less than about" can be prefixed to each of the above numbers, and any of the above numerical values can be used to describe an open-ended range alone or in combination to describe a closed-ended range. For example, hardwood lignin can be present in a polymer or polymer composition in an amount of 0.1 to 3.0 wt%, or 0.3 to 2.0 wt%, or also in an amount of 10 to 60 wt%. Hardwood lignin can be obtained from biomass as described elsewhere in this specification. As disclosed herein, hardwood lignin can be used in a polymer or polymer composition for coating, film, adhesive as described elsewhere in this specification. As disclosed herein, hardwood lignin can be used in a polymer or polymer composition for coating, film, adhesive Any combination of antioxidants, including compositions present in adhesives or personal care compositions. It can be used in finished products.

[0096] The lignin content of broadleaf trees is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0. 8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1. 9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.5, 4.0, 4.5, 5. 0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10 , 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 40, The average particle diameter and diameter / maximum dimension can be 50 (micrometers). You can add the terms "approximately," "at least approximately," or "less than approximately" before each number. You may use any of the above numerical values ​​to describe the open-end range individually or in combination. By combining these, the closed-end range can be described. For example, hardwood lignin is, Average particle size (micrometers) of 1.0 to 10.0 or 2 to 8 micrometers It is possible to have.

[0097] The lignin content of hardwoods is 0.1, 0.5, 1.0, 1.5, 2.0, 5.0, 6.0, and 7. 0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, The carbohydrate content can be 20, 25, 30, 40, or 50%. You can add the terms "approximately," "at least approximately," or "less than approximately" before each word. You may use any of the above numerical values ​​to describe the open-end range on its own, or in combination with them. The closed-end range can also be specified. For example, hardwood lignin is 1 It can have a carbohydrate content of 0.0 to 15.0, or 2 to 8%.

[0098] Biomass typically includes cellulose, hemicellulose, and lignin. Hardwood Lignin can be derived from biomass by any suitable method, including, for example, hydrolyzing the biomass with a fluid. Hydrolysis can include one or more steps (2, 3, 4, 5, 6, 7, 8, or 9 or more hydrolysis steps). The temperatures, pressures, and times described herein can be applied to any single step. (2, 3, 4, 5, 6, 7, 8, or 9 or more hydrolysis steps). The temperatures, pressures, and times described herein can be applied to any single step. For example, the hydrolysis process can be carried out in two steps, where the first step has any of the temperatures, pressures, and residence times disclosed herein, and the second step has any of the temperatures, pressures, and times disclosed herein. For example, the hydrolysis process can be carried out in two steps, where the first step has any of the temperatures, pressures, and residence times disclosed herein, and the second step has any of the temperatures, pressures, and times disclosed herein. For example, the hydrolysis process can be carried out in two steps, where the first step has any of the temperatures, pressures, and residence times disclosed herein, and the second step has any of the temperatures, pressures, and times disclosed herein. For example, the hydrolysis process can be carried out in two steps, where the first step has any of the temperatures, pressures, and residence times disclosed herein, and the second step has any of the temperatures, pressures, and times disclosed herein.

[0099] The fluid consists of, or consists essentially of, water, methanol, ethanol, propanol, butanol, carbon dioxide, sulfur dioxide, or any combination thereof. In some embodiments, the fluid consists of, or consists essentially of, water. In some embodiments, the fluid consists of, or consists essentially of, water.

[0100] In certain embodiments, the biomass is hydrolyzed subcritically, near-critically, or supercritically. This process can include a pretreatment step of pretreating the biomass at a first temperature and a first pressure for a first period to form pretreated biomass. The pretreatment step used herein typically includes extracting hemicellulose (if present) from the biomass while leaving cellulose (if present) and lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment biomass"). The process is the pretreatment This process can include a pretreatment step of pretreating the biomass at a first temperature and a first pressure for a first period to form pretreated biomass. The pretreatment step used herein typically includes extracting hemicellulose (if present) from the biomass while leaving cellulose (if present) and lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment biomass"). The process is the pretreatment This process can include a pretreatment step of pretreating the biomass at a first temperature and a first pressure for a first period to form pretreated biomass. The pretreatment step used herein typically includes extracting hemicellulose (if present) from the biomass while leaving cellulose (if present) and lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment biomass"). The process is the pretreatment (2, 3, 4, 5, 6, 7, 8, or 9 or more hydrolysis steps). The temperatures, pressures, and times described herein can be applied to any single step. This process can include a pretreatment step of pretreating the biomass at a first temperature and a first pressure for a first period to form pretreated biomass. The pretreatment step used herein typically includes extracting hemicellulose (if present) from the biomass while leaving cellulose (if present) and lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment biomass"). The process is the pretreatment This process can include a pretreatment step of pretreating the biomass at a first temperature and a first pressure for a first period to form pretreated biomass. The pretreatment step used herein typically includes extracting hemicellulose (if present) from the biomass while leaving cellulose (if present) and lignin (i.e., the product of the pretreatment step is referred to herein as "pretreatment biomass"). The process is the pretreatment The process may further include a treatment step in which the biomass is treated for a second period under a second temperature and a second pressure. In some embodiments, the process includes a treatment step and does not include a pretreatment step. In other words, biomass that has not undergone the pretreatment step as defined herein undergoes a treatment step that includes a fluid. However, prior to the treatment step, the biomass may be ground (e.g., by mechanical means such as grinding, crushing, impact milling, or size reduction by explosive decompression such as steam explosion), but this grinding is not considered the pretreatment step as used herein. When using a fluid containing supercritical water, the process may include treating the biomass with supercritical water without the pretreatment step as defined herein.

[0101] In some embodiments, optionally, the biomass has an average particle size d less than typically about 600 micrometers, or less than 500 micrometers (50) in order to produce a size reduction of the above size may be performed prior to subcritical, near-supercritical, or supercritical hydrolysis. In certain embodiments, the size reduction includes exploding the biomass in the presence of ammonia. In certain embodiments, the size reduction includes exploding the biomass in the presence of sulfur dioxide. However, size reduction may not be necessary.

[0102] In certain embodiments, biomass that is subjected to subcritical, near-supercritical, or supercritical hydrolysis, or any other hydrolysis (e.g., enzymatic, etc.) disclosed herein has an average particle size d less than about 600 μm, or less than about 500 μm, measured by light scattering (50) , e.g., an average particle size , d (50)The numbers are 5, 10, 25, 50, 75, 100, 125, 150, 200, and 250. , 300, 350, 400, 450, 500, 550, 600 (micrometers, μm) ) may also be used. The word “about,” “at least about,” or “about” may be placed before each of the aforementioned numbers. You can add "approximately less than," and use any of the above numbers to make an open-end function on its own. The scope can be described, or combined to describe the closed-end scope. Example For example, the average particle diameter d (50) The range is approximately 50 μm to 600 μm, and approximately 50 μm to 500 μm. Approximately 50 μm to 450 μm, approximately 25 μm to 250 μm, or approximately 100 μm to 40 It can be set to 0 μm.

[0103] In certain embodiments, preferably the biomass whose size has been reduced as herein is a fluid. Mixed with a fluid consisting of, for example, water, or essentially consisting of, and thereby mixed A compound is formed, and the mixture is hydrolyzed at a temperature of at least about 100°C. Several implementations In terms of form, the fluid in contact with the mixture or the mixture itself is 100, 120, 140°C, 15 0℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 23 0℃, 240℃, 250℃, 260℃, 280℃, 300℃, 320℃, 340℃, 35 0℃, 360℃, 370℃, 374.2℃, 380℃, 390℃, 400℃, 410℃, 420℃, 440℃, 450℃, 460℃, 480℃, 500℃, 520℃, 540℃, It has a temperature (°C) of 560°C, 580°C, or 600°C. The words "approximately," "at least approximately," or "less than approximately" can be added to the aforementioned number. Use either one to describe an open-ended scope on its own, or in combination to describe a closed scope. The end range can be specified. For example, the mixture is at a temperature of 190°C to 374°C. It may be hydrolyzed. Alternatively, the mixture may be heated at a temperature of 374°C to 500°C, or 500°C. Hydrolysis may be performed at temperatures above 100°C. In certain embodiments, the mixture is hydrolyzed at 100°C to 5°C. At a temperature of 0°C, hydrolysis is performed under pressure sufficient to ensure that all fluids remain in liquid form. In some such embodiments, the mixture is substantially free of exogenous acids. In such embodiments, the mixture is substantially free of Ci-05 alcohol. Accordingly, in each embodiment, one or more preheating steps may also be used.

[0104] In certain embodiments, the biomass consists of, or essentially comprises, water, for example. It is mixed with a fluid to produce a mixture, the mixture is subjected to supercritical hydrolysis, and the mixture is A temperature of at least approximately 374°C, for example, from approximately 374.2°C to approximately 575°C, and at least The mixture is subjected to a pressure of approximately 221 bar for a sufficient amount of time to produce at least one C6 sugar. If the mixture undergoes supercritical hydrolysis, the water in contact with the mixture must be at a temperature of at least approximately 374°C. It has. The water that comes into contact with the mixture is 374, 375, 380, 390, 400, 410, 4 20, 430, 440, 450, 460, 470, 480, 490, 500, 510, 5 It has temperatures of 20, 530, 540, 550, 560, 570, and 575 (°C). You can put the word "approximately," "at least approximately," or "less than approximately" before each number. You may use any of the above numerical values ​​to describe the open-end range individually or in combination. The combined closed-end range can be described. Therefore, contact with the mixture The water has a temperature bounded by any two of the aforementioned endpoints. This is possible. For example, water can be heated to approximately 374°C to 575°C, approximately 374°C to 450°C, and approximately 400°C. It has a temperature of ℃ to approximately 520℃, or approximately 375℃ to approximately 430℃, in each case , can be under a pressure of at least about 221 bar. In certain embodiments, water, It can have a temperature higher than 575°C and be under a pressure of at least about 221 bar. In some such embodiments, the mixture is substantially free of exogenous acids. In such embodiments, the mixture is substantially free of C1-05 alcohol. In each embodiment, an additional preheating step may also be used.

[0105] In embodiments in which the mixture is subjected to subcritical, near-supercritical, or supercritical hydrolysis, the hydrolysis is performed as follows: 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 1 20, 125, 130, 140, 150, 160, 170, 175, 180, 190, 2 00, 210, 220, 221, 225, 230, 240, 250, 260, 270, 2 75, 280, 290, 300, 310, 320, 325, 330, 340, 350, 3 60, 370, 375, 380, 390, 400, 420, 440, 450, 460, 4 75, 480, 500, 525, 550, 575, 600, 625, 650, 675, 7 The process is carried out at a pressure of 00, 725, 750, 775, or 800 (bar). You can put the words "about," "at least about," or "less than about" before each of these. , using any of the above numerical values, you may describe the open-end range individually or in combination The closed-end range can also be specified. For example, the pressure is approximately 221 bar. ~800bar, 230bar~500bar, 325bar~750bar , or it can be about 275 bar to about 350 bar. In certain embodiments, the pressure The force can be greater than 800 bar.

[0106] In certain embodiments in which the mixture is subjected to near-supercritical or supercritical hydrolysis, during the continuation of hydrolysis The intervals are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9 .0, 10.0, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1 20, 140, 160, 180, 200, 220, 240, 260, 280, or 30 It is 0 (seconds). The word "approximately", "at least approximately", or " The term "approximately less than" can be added, and any of the above numbers can be used to determine an open-ended term on its own. You can specify a range, or a combination of ranges, to specify a closed-end range. For example The duration is approximately 0.1 seconds to 10 seconds, approximately 0.1 seconds to 5 seconds, and approximately 0.1 seconds to 0.3 seconds. This can be approximately 1.1 seconds to approximately 5 seconds, or approximately 0.9 seconds to approximately 9 seconds. Specific Embodiments Then, the duration is greater than 10 seconds. In a preferred embodiment, the duration is approximately 1.4 seconds. For example, the interval is approximately 0.1 seconds to 1.4 seconds. The mixture will be exposed to a lower temperature (for example, sub (Critical hydrolysis) In certain embodiments, the duration of hydrolysis is 0.5, 1, 1.5, 2. 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30 , 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, Or 300 (minutes). The word "approximately" or "at least approximately" should be placed before each of the numbers above. You can add "approximately less than" or any of the above numbers, and open it alone. You can specify the range of the end end, or combine it with the range of the closed end. Cut.

[0107] In certain embodiments, the mixture containing biomass that will be hydrolyzed later is C1-05 aluminum It is substantially free of kohl. In certain embodiments, the mixture is substantially free of exogenous acids. If necessary, in each embodiment, one or more preheating steps may also be used before hydrolysis. It can be done. In another embodiment, the mixture is (as disclosed elsewhere in this specification) This includes C1-05 alcohols, exogenous acids, or any combination thereof.

[0108] In certain embodiments, the solid content of the mixture based on the total weight of the mixture is about 1% by weight or more, e.g. For example, 1% to 40% by weight. The solid content of the mixture is 1, 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 2 2, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40 (%) or more. The word "approximately" or "minus" may precede each of the numbers. You can add "approximately" or "less than approximately," and use one of the aforementioned numerical values. You can describe open-ended scopes individually, or close-ended scopes in combination. It is possible. For example, the solids content of the mixture is about 10% to 29% by weight, about 15% by weight. Quantity % to approximately 29% by weight, approximately 10% by weight to approximately 18% by weight, or approximately 24% by weight to approximately 27% by weight It can be done this way.

[0109] C. Methods for producing polymers and polymer compositions This invention provides a method for producing a polymer or polymer composition, the method of which involves lignin For example, a process of combining herbaceous lignin or broadleaf tree lignin and a polymer carrier. Includes. Examples of polymer carriers include polypropylene, ethylene, and polyvinyl chloride (PVC). ), polyvinyl acetate (PVA), chlorinated polyethylene, polystyrene, acrylonitrile -Butadiene-styrene (ABS) copolymer, ethylene-vinyl acetate copolymer, PV C / ABS blend, polyethylene terephthalate (PET), polycarbonate, poly Urethane, acrylic, styrene-acrylic, polyamide, nylon, elastomer, and Any combination of these could be listed, but is not limited to them.

[0110] The method of the present invention includes a tubular reactor, a (vertical, horizontal, or inclined) digester, etc. This can be carried out in any suitable reactor, not limited to the following. Suitable digesters include the United States This includes the digester system described in Japanese Patent No. 8,057,639B, which is a digester It also includes a steam explosion unit.

[0111] Therefore, for example, in certain embodiments, lignin is (a)(i) cellulose and (ii) a lignocellulose system comprising a first solid component containing lignin and (ii) a first liquid component. (b) supplying biomass, and (b) mixing the first solid component with water to form a slurry. , and (c) (in a particular embodiment, when the residence time is about 20 seconds to about 45 seconds) about 225b The slurry is preheated to a temperature of approximately 340°C to 400°C at a pressure of approximately 250 bar. It is obtained by and .

[0112] In certain embodiments, lignin is obtained by hydrolysis, for example, supercritical hydrolysis. Hydrolysis occurs under pressures such as 1, 5, 10, 20, 30, 40, 50, 60, 70, 80 , 90, 100, 110, 120, 125, 130, 140, 150, 160, 170, 175, 180, 190, 200, 210, 220, 221, 225, 230, 240, 250, 260, 270, 275, 280, 290, 300, 310, 320, 325, 330, 340, 350, 360, 370, 375, 380, 390, 400, 420, 440, 450, 460, 475, 480, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, or 800 (bar) It can be carried out. Hydrolysis can be performed at temperatures such as 374, 375, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, or 575 (°C) ) can be done. The word "about" or "at least about" can be placed before each of the numbers mentioned above. You can add "approximately less than" or any of the above numbers, and open it alone. You can specify the range of the end end, or combine it with the range of the closed end. Therefore, in certain embodiments, lignin is used to heat biomass at approximately 340°C to approximately 40°C. By exposing it to a fluid with a temperature of 0°C and a pressure of approximately 225 bar to approximately 250 bar... It can be obtained.

[0113] In certain embodiments, the process includes hydrolysis (e.g., supercritical hydrolysis) and collection of the products. The methods disclosed herein are performed sequentially, but in other embodiments, they may be performed in batches or It can be run as a semi-batch process.

[0114] Herbaceous biomass (e.g., switchgrass) is used "as is" for hydrolysis. Also, for example, washing, mechanical preparation (e.g., grinding, shredding, pulverizing, etc.), Alternatively, any combination thereof may be suitably prepared.

[0115] Another process suitable for preparing the herbaceous lignin of the present invention may also be used.

[0116] The herbaceous lignin of the present invention is typically produced in the above processing step by using a suitable solvent. Extraction from the resulting solid (but not necessarily). Extraction with a suitable solvent. This is referred to herein as the “extraction step” or “extraction.” For example, the solvent is alkaline aqueous solution. The solution can be, for example, an aqueous solution of sodium hydroxide. The amount of base in the alkaline aqueous solution. This can be approximately 0.1% by weight or more, and the maximum amount is not particularly limited. Alkaline water-soluble The amount of base in the solution can be approximately 3% by weight or less, and the minimum amount is not particularly limited. The remainder usually contains or consists of water. For example, the amounts of base are 0.1, 0.3, 0.5, 0.7, 0.9, 1.2, 1.4, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3( The weight can be expressed as %). The word "about" or "at least about" can be placed before each of the numbers. You can add "" or "approximately less than", and you can use either of the above numbers on their own. You can specify the open-end range, or combine it with the closed-end range. Yes, it is possible. For example, the amount of base is approximately 0.9% by weight or more, approximately 1.7% by weight to approximately 2.6% by weight. It can be approximately 2.8% to 3% by weight, or approximately 0.9% to 1.2% by weight. Preferably, the alkaline aqueous solution is about 1% by weight.

[0117] Other suitable extraction solvents include aqueous organic solvents, such as dioxane, acetone, and ethanol. Contains at least one of methanol, propanol, or butanol aqueous solution Organic solvents in aqueous organic solvents (dioxane, acetone, ethanol, methanol, propane) The amount of (butanol, butanol, or a combination thereof) should be at least 80% by volume. This is possible, and there is no particular upper limit. The amount of organic solvent can be approximately 99.5% by volume or less. The minimum amount is not particularly limited. The remainder contains or consists of water. For example, aqueous organic solvents. The amounts of organic solvent inside are 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, It can be 99 or 99.5 (volume %). The word "approximately" should be placed before each of the above numbers. You can add "at least about" or "less than about," and use one of the aforementioned numerical values. You may describe an open-end scope on its own, or a closed-end scope in combination with it. This can be stated. For example, the amount of organic solvent in an aqueous organic solvent is approximately 86% by volume or less. Approximately 88% to 94% by volume, approximately 90% to 92% by volume, or approximately 94% to 94% by volume It can be 96% by volume. The preferred amount of organic solvent in water is about 90% by volume or about It is 96% by volume.

[0118] In certain embodiments, the yield of herbaceous lignin is at least 30% of the theoretical yield. In a specific embodiment, the yield (%) of the herbaceous lignin is 30, 35, 40, and 4% of the theoretical yield. 5, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% The words "approximately," "at least approximately," or "less than approximately" are placed before each of the aforementioned numbers. It is possible to use any of the above numerical values ​​to specify the open-end range independently. The scope of the closed end can be described by combining, or by combining. For example, a specific actual In application methods, the yield of herbaceous lignin is at least about 70% of the theoretical yield, or the theoretical yield. It is at least about 85%.

[0119] D. product In some embodiments, the present invention relates to the product produced by the method described herein. To relate to.

[0120] In some embodiments, the stabilizing polymer is polypropylene, ethylene, polyvinyl chloride. PVC, polyvinyl acetate (PVA), chlorinated polyethylene, polystyrene, acrylic Lilonitrile-butadiene-styrene (ABS) copolymer, ethylene-vinyl acetate copolymer Remar, PVC / ABS blend, polyethylene terephthalate (PET), polycarbonate Polyurethane, Acrylic, Styrene-Acrylic, Polyamide, Nylon, Elastomer This includes, but is not limited to, Tomar and any combination thereof.

[0121] In some embodiments, the stabilizing coating is one of the aforementioned polymers, or Architectural coatings and industrial coatings that may include any combination thereof. Includes.

[0122] In some embodiments, herbaceous lignin, such as switchgrass, is one or more It is used in combination with other antioxidants. A suitable antioxidant is IRGANOX 101. 0, IRGANOX B225, IRGAFOS 168, and other phosphates, Phosphates Honite, sterically hindered phenol, amine, thioester, or any combination thereof It includes se.

[0123] In some embodiments, herbaceous lignin (e.g., switchgrass lignin) is included. The oxidation onset temperatures (OOT) of the polymers are 150, 155, 160, 165, 170, and 1 75, 180, 185, 190, 195, 200, 205, 210, 215, 220, 2 22, 225, 227, 230, 231, 232, 233, 234, 235, 236, 2 37, 238, 239, 240, 241, 242, 243, 244, 245, 246, 2 47, 248, 249, 250, 252, 255, 257, 260, 262, 265, 2 67, 270, 275, 280, 285, 290, 295, 300, 305, 310, 3 15, 320, 325, 330, 335, 340, 345, 350, 355, 360, 3 65, 370, 380, 390, 400, 410, 420, 430, 440, or 45 It can be set to 0 (°C). The word "approximately" or "at least approximately" can be placed before each of the numbers mentioned above. You can add "" or "approximately less than", and you can use either of the above numbers on their own. You can specify the open-end range, or combine it with the closed-end range. can.

[0124] In some embodiments, herbaceous lignin (e.g., switchgrass lignin) is included. The oxidation onset temperature of the polymer is different for kraft lignin or broadleaf lignin instead of herbaceous lignin. Aside from containing gunin, the polymer is at least 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 3 8, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64 , 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, or 100°C higher.

[0125] E. Exemplary Clauses Some embodiments of the methods or products disclosed herein are described in the following clauses: Any combination of these clauses (or parts thereof) may be created and disclosed herein. Embodiments of the method or product shown can be defined.

[0126] Clause 1: A polymer or polymer composition containing herbaceous lignin.

[0127] Clause 2: Polymers or polymer compositions are thermoplastics, thermosettings, composites, Coatings, films, adhesives, personal care compositions, or any combination thereof A polymer or polymer composition as described in Clause 1.

[0128] Clause 3: The oxidation onset temperature of a polymer or polymer composition containing herbaceous lignin is the same as that of herbaceous lignin. The same polymer except that it contains kraft lignin or hardwood lignin instead of gunnin. - A polymer or polymer composition as described in Clause 1, which is at least 10°C higher than -

[0129] Clause 4: The polymer or polypropylene of Clause 1 having an oxidation onset temperature of approximately 232°C to approximately 250°C. A polymer composition. In one such embodiment, the polymer or polymer composition is a herbaceous rig. This is a polypropylene polymer containing nin. In such one embodiment, the polymer or The polymer composition is a polypropylene polymer containing switched glass lignin.

[0130] Clause 5: The polymer or polymer composition is a thermoplastic, according to Clauses 2, 3, or 4. The polymer or polymer composition described in any one of the following items.

[0131] Clause 6: Thermoplastic materials are polyethylene, polypropylene, or combinations thereof. The polymer or polymer composition described in Clause 5, including the polymer or polymer composition described in Clause 5.

[0132] Clause 7: The thermoplastic material contains polypropylene, and herbaceous lignin is 0.5-1.5% by weight. A polymer or polymer composition as described in Clause 5, present at a concentration of such a concentration. In this state, the thermoplastic material contains polypropylene, and herbaceous lignin is 0.5 to 1.5% by weight. This is switchglass lignin present at a specific concentration.

[0133] Clause 8: A coating composition containing herbaceous lignin at a concentration of 0.5 to 2.0% by weight or film.

[0134] Clause 9: A personal care composition containing herbaceous lignin at a concentration of 0.5 to 2.0% by weight.

[0135] Clause 10: The biomass must contain lignin, and the composition must be no more than 20% of the weight of the biomass. Thermoplastic polymers and biocellulose containing the following amounts of cellulose and / or hemicellulose A composition containing omas.

[0136] Clause 11: Thermoplastic polymers have a processing temperature of less than approximately 400°C, as described in Clause 10. The composition of.

[0137] Clause 12: Thermoplastic polymers are polyethylene, polypropylene, or combinations thereof. The composition described in Clause 10, which is a combination of the two.

[0138] Clause 13: The composition according to Clause 10, wherein the lignin is hardwood lignin.

[0139] Clause 14: The composition according to Clause 10, wherein the lignin is herbaceous lignin.

[0140] Clause 15: Lignin comprises a mixture of guaiacil units and syringyl units, Clause 1 The composition described in 0.

[0141] Clause 16: The composition according to Clause 10, having an oxidation onset temperature of approximately 232°C to approximately 250°C. .

[0142] Clause 17: Lignin has an average particle size of approximately 2 micrometers to approximately 8 micrometers. The composition described in Article 10.

[0143] Clause 18: The composition according to Clause 10, wherein lignin is prepared by supercritical hydrolysis.

[0144] Clause 19: Lignin is produced by heating biomass at a temperature of approximately 340°C to approximately 400°C and approximately 225b Prepared by exposing to a fluid with a pressure of approximately 250 bar, as described in Clause 10. The composition of the listed items.

[0145] Clause 20: The polymer is polypropylene, and the lignin content is approximately 0.5% by weight to approximately 1.5% by weight. The composition described in Clause 10, present in a concentration of %.

[0146] Clause 21: A coating composition or film comprising the composition of Clause 10.

[0147] Clause 22: A personal care composition comprising the composition of Clause 10.

[0148] Clause 23: The method is (a) to heat the biomass at a temperature of approximately 340°C to approximately 400°C and approximately 225°C Lignin is obtained by exposing it to a fluid with a pressure of approximately 250 bar, (b) a composition of clause 10 comprising the step of mixing lignin with a thermoplastic polymer. A method for manufacturing this product.

[0149] Clause 24: Thermoplastic polymers have a processing temperature of less than approximately 400°C, as described in Clause 23. method.

[0150] Clause 25: Thermoplastic polymers are polyethylene, polypropylene, or combinations thereof. The method described in Article 23, which is a combination of the above.

[0151] Clause 26: Lignin is hardwood lignin, as described in Clause 23.

[0152] Clause 27: Lignin is herbaceous lignin, as described in Clause 23.

[0153] Clause 28: The composition has an oxidation onset temperature of approximately 232°C to approximately 250°C, as described in Clause 23. The method.

[0154] Clause 29: Lignin has an average particle size of approximately 2 micrometers to approximately 8 micrometers. The method described in Article 23.

[0155] The present invention is further defined by the following embodiments, but unless otherwise specified, all proportions and parts -cent is by weight. These examples illustrate preferred embodiments of the present invention, It is given only as an example and should be interpreted as limiting in any way. It should be understood that there is no such thing. From the above description and these examples, those skilled in the art will understand the essential nature of the present invention. The features can be confirmed, and without departing from the spirit and scope thereof, the present invention can be described as follows. Various changes and modifications can be made to adapt it to a variety of uses and conditions. [Examples]

[0156] F. Examples 1. Example 1 This example demonstrates the effect of switched glass lignin as an antioxidant for polypropylene. Then, compare it to hardwood lignin and kraft lignin, as well as commercially available antioxidants. All samples were analyzed using ASTM 2009-02 (Differential Scanning Calorimetry (DSC) for carbonized water). It was evaluated using the standard test method for the oxidation onset temperature of the element, and in ASTM 2009-02, It is believed that the higher the oxidation onset temperature (OOT), the better the stability against oxidative decomposition. All samples are made of polypropylene, specifically Bapolene® 4012F (Bamb Prepared using Erger Polymer, Inc., Houston, TX, USA. Therefore, it is 12.0g / 10 minutes (ASTM D-1238, 230C / 2,160g) It is commercially available as melt-flow compounding / extrusion grade polypropylene. Live blend (polypropylene, lignin antioxidant or commercially available antioxidant, and processing) (0.5% by weight zinc stearate as an auxiliary agent), and a co-rotating 20mm twin screw - It was fed directly to the extruder. The sample was extruded to produce pellets, which were then made into small discs. The sample was cut into approximately 2.6 mg pieces and accurately weighed for the OOT test (performed 3 times). This is due to DSC in the air, Tzero aluminum pan (TA Instrument) The samples were tested separately at ts (New Castle, DE, USA) at a rate of 50 mL / min. The sample was brought to equilibrium at 50°C before the temperature was raised at a rate of 20°C / min with an airflow. The sample is shown in Figure 1. As shown, various amounts of each test antioxidant (0, 0.1, 0.3, 0.5, or 0.6) It contained , and 1.0% by weight.

[0157] Figure 1 shows the OOT (°C) obtained for each antioxidant concentration added. Referring to the legend in Figure 1, the antioxidants tested were:

[0158] Base - No added antioxidants (i.e., 0% by weight antioxidants)

[0159] EBS / Omno(50%) - Added antioxidant: 50% ethylenebistearate It contained 50% hardwood lignin.

[0160] Irg1010 / Omno(40%) - Added antioxidant: Irganox 10 It contained 60% 10 and 40% hardwood lignin.

[0161] The added antioxidant was Irganox 1010.

[0162] IrgB225 / Omno(30%) - The added antioxidant is IrgB2 It contained 70% 25% and 30% hardwood lignin.

[0163] Kraft – The added antioxidant was Kraft lignin.

[0164] The antioxidant added was broadleaf tree lignin.

[0165] The antioxidant added to Switchglass Omno was switchglass lignin.

[0166] [Irganox 1010 is pentaerythritol tetrakis(3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionate), sterically hindered phenol Irganox B225 = Solubility of Irganox 1010 and Irgafos 168 Melting blend; Irgafos 168 = Tris(2,4-ditert-butyl) phosphite [Enyl, Phosphite stabilizer]

[0167] Both hardwood lignin and switchgrass lignin are 5 micrometers in diameter / maximum The particles were pre-ground to an average particle size of large size.

[0168] OOT is higher than the base case (base: polypropylene that contains no antioxidants). Therefore, the data shows that at an additive concentration of 1.0% by weight, all lignin is antioxidant and stable. It shows some effectiveness as an agent. However, switchglass lignin is a kraft lignin. Compared to lin and hardwood lignin, it significantly improves OOT. For example, 1.0 wt% In terms of concentration, (at the same concentration in the same polymer, approximately) hardwood lignin and kraft lignin (Compared to 230℃) Switchglass lignin typically has an OOT of approximately 0. The temperature is raised from 200°C to approximately 244°C. Furthermore, extrapolation of the curve shows the lignin concentration (antioxidant). As the concentration (as an agent) increases, the concentration of improvement is likely to become much greater. vinegar.

[0169] Commercially viable performance is achieved at typical usage concentrations (0.3 wt%) with Irganox 10 This can be judged from the OOT achieved using 10, and such performance is slightly This should be achieved with high concentrations of switchglass lignin used in the industry. While these special chemicals are usually expensive, even a slight increase in their concentration is prohibited from a commercial standpoint. It may not happen.

[0170] 2. Example 2 Table 1 shows the components of the masterbatch (MB) AF. JPEG0007832990000001.jpg70165

[0171] The components of the exemplary composition are shown in Table 2 (weight %) and Table 3 (grams) (Note: 1 pellet (The net holds 500g). JPEG0007832990000002.jpg253147JPEG0007832990000003.jpg233158JPEG0007832990000004.jpg229158JPEG0007832990000005.jpg140154 JPEG0007832990000006.jpg232152JPEG0007832990000007.jpg229159JPEG0007832990000008.jpg229157JPEG0007832990000009.jpg229155

[0172] Table 4 shows the total amount (in grams) of each component used. JPEG0007832990000010.jpg152124

[0173] 3. Example 3 The components of an example composition are shown in Table 5 (weight %) and Table 6 (grams) (Note: one pellet (The net holds 500g). JPEG0007832990000011.jpg75169JPEG0007832990000012.jpg101169

[0174] Table 7 shows the total amount (in grams) of each component used. JPEG0007832990000013.jpg67153

[0175] The oxidation initiation temperatures of the composition in Example 3 are shown in Table 8 (approximately 2.5 mg of sample; air, 50 mL). (A gradient of 20°C per minute up to 310°C). JPEG0007832990000014.jpg92166

[0176] 4. Example 4 Table 9 and Figure 2 show an overview of the oxidation onset temperatures (OOT) for exemplary compositions. JPEG0007832990000015.jpg243144JPEG0007832990000016.jpg17398

[0177] 5. Example 5 The results of UV testing of exemplary compositions are shown in Tables 10 and 11 and Figures 3A and 3B. It will be shown. JPEG0007832990000017.jpg253149JPEG0007832990000018.jpg191152JPEG0007832990000019.jpg51148

[0178] 6. Example 6 The results of thermal tests on exemplary compositions are shown in Tables 12-14 and Figures 4A-C. JPEG0007832990000020.jpg225143JPEG0007832990000021.jpg222138JPEG0007832990000022.jpg206149 JPEG0007832990000023.jpg208137JPEG0007832990000024.jpg226148JPEG0007832990000025.jpg224129 JPEG0007832990000026.jpg211152JPEG0007832990000027.jpg214145JPEG0007832990000028.jpg222155 JPEG0007832990000029.jpg224127JPEG0007832990000030.jpg205154JPEG0007832990000031.jpg203130

[0179] 7. Example 7 Tables 15 and 16 show the results of the standard oxidation onset temperature (OOT) tests for exemplary compositions, and This is shown in Figure 5. JPEG0007832990000032.jpg246149JPEG0007832990000033.jpg244119JPEG0007832990000034.jpg253154

[0180] 8. Example 8 Table 17 shows the data corresponding to the Oxidation Onset Temperature (OOT) tests for the exemplary compositional criteria. These are shown in i-xii and Figures 6A-L. JPEG0007832990000035.jpg57165JPEG0007832990000036.jpg36165JPEG0007832990000037.jpg43165 JPEG0007832990000038.jpg51165JPEG0007832990000039.jpg87166JPEG0007832990000040.jpg54166 JPEG0007832990000041.jpg44166JPEG0007832990000042.jpg77168JPEG0007832990000043.jpg84167 JPEG0007832990000044.jpg50167JPEG0007832990000045.jpg43164JPEG0007832990000046.jpg63164

[0181] While preferred embodiments of the present invention have been disclosed, without departing from the spirit and scope of the invention, It is possible to make various changes and modifications to achieve some of the advantages of the present invention. This should be clear to the person concerned. Therefore, the attached claims express the true spirit of the present invention and The scope of this invention encompasses all such equivalent variations within the scope, and is as described in the attached claims. It shall be determined by the enclosure.

[0182] The scope of this specification includes physical properties, such as molecular weight, or chemical properties, such as chemical formula. When used, all combinations and partial combinations of the scope of a particular embodiment within it It is intended that a combination is included.

[0183] Each patent, patent application, and publication disclosure cited or described herein is, in whole, a public interest interest. This is incorporated herein by reference.

[0184] Without departing from the scope or spirit of the present invention, various modifications and variations may be made in the present invention. It will be obvious to those skilled in the art that this can be done. Another aspect of the present invention is disclosed herein. This will be apparent to those skilled in the art from the specification and consideration of the embodiment of the present invention. (Specification and Examples) These are illustrative examples only, and the true scope and spirit of the invention are provided in the appended claims. It is intended to be shown in this way.

Claims

1. A composition comprising a thermoplastic polymer and herbaceous lignin, wherein the herbaceous lignin is present at a concentration of 0.5% to 1.5% by weight, the herbaceous lignin has an average particle size of 2 micrometers to 8 micrometers as measured by light scattering, and the herbaceous lignin is (a) A step of exposing herbaceous biomass containing lignin to a fluid having a temperature of approximately 340°C to approximately 400°C and a pressure of approximately 225 bar to approximately 250 bar, (b) A step of mixing the herbaceous lignin with the thermoplastic polymer, It is obtained by a method that includes, The composition comprises cellulose and / or hemicellulose in an amount of 20% or less relative to the weight of the herbaceous lignin. A composition characterized by having an oxidation onset temperature at least 10°C higher than the same composition, except that it contains kraft lignin or broadleaf tree lignin instead of the aforementioned herbaceous lignin.

2. The composition according to claim 1, wherein the thermoplastic polymer has a processing temperature of less than 400°C.

3. The composition according to claim 1, wherein the thermoplastic polymer is polyethylene, polypropylene, or a combination thereof.

4. The composition according to claim 1, wherein the herbaceous lignin is switchgrass lignin.

5. The composition according to claim 1, wherein the lignin comprises a mixture of guaiacyl units and syringyl units.

6. The composition according to claim 1, having an oxidation onset temperature of 232°C to 250°C.

7. A coating composition or film comprising the composition of claim 1.

8. A personal care composition comprising the composition of claim 1.

9. A method for producing the composition of claim 1, wherein the method is: (a) A step of obtaining herbaceous lignin by exposing biomass to a fluid having a temperature of 340°C to 400°C and a pressure of 225 bar to 250 bar, (b) A step of mixing the herbaceous lignin with the thermoplastic polymer, Methods that include...

10. The method according to claim 9, wherein the thermoplastic polymer has a processing temperature of less than 400°C.

11. The method according to claim 9, wherein the thermoplastic polymer is polyethylene or polypropylene.

12. The method according to claim 9, wherein the herbaceous lignin is switchgrass lignin.

13. The method according to claim 9, wherein the composition has an oxidation onset temperature of 232°C to 250°C.

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