WO2022201519A1 - 共融混合物及び液状組成物 - Google Patents
共融混合物及び液状組成物 Download PDFInfo
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- WO2022201519A1 WO2022201519A1 PCT/JP2021/012964 JP2021012964W WO2022201519A1 WO 2022201519 A1 WO2022201519 A1 WO 2022201519A1 JP 2021012964 W JP2021012964 W JP 2021012964W WO 2022201519 A1 WO2022201519 A1 WO 2022201519A1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/14—Hemicellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/56—Non-aqueous solutions or dispersions
Definitions
- the present invention relates to a eutectic mixture and a liquid composition containing the same.
- a safe and inexpensive heat medium that is liquid in a wide temperature range is a useful material in various fields.
- oils, silicone oils, synthetic oils such as polychlorinated biphenyls (PCB), molten salts, and the like are known as heat carriers that can be used at high temperatures.
- Nitrite can be used at high temperatures close to 400°C, but when the temperature drops, it becomes solid, which may cause clogging of pipes.
- many of the oils used as heat transfer medium have a flash point and are flammable, which poses a safety problem. Oil with a high flash point has a problem of low fluidity due to its high viscosity and solidification at low temperatures.
- PCB is a synthetic oil with high thermal stability and low flow viscosity, but even a very small amount is harmful to the human body.
- silicone oils which are highly thermally stable, non-flammable, and less harmful to living organisms, are expensive and may be of limited industrial use.
- Non-Patent Document 1 describes that a mixture of choline chloride/urea has a solubility of cellulose of 0.2% or less, and hardly dissolves cellulose.
- urea is a substance that is produced in the human body, and its accumulation in high concentrations can have various adverse effects. For safety reasons, the use of urea is not preferred.
- Patent Documents 1 to 5 disclose deep eutectic solvents composed of combinations of various compounds.
- US Pat. No. 6,200,000 discloses a deep eutectic solvent comprising N,N,N-trimethylglycine and trifluoroacetamide for use in fixing and preserving biological material.
- WO 2005/010000 proposes a fire-fighting foam composition comprising a deep eutectic solvent of binary or ternary system.
- Patent Document 3 discloses the use of deep eutectic solvents combined with compounds having predetermined structures for immobilization of biomolecules.
- Patent Document 4 proposes a method of preparing a flavor composition using at least two compounds that are solid at 25°C and a deep eutectic solvent containing water and/or glycerol.
- Patent Document 5 a eutectic solvent containing choline chloride, aspartic acid and glutamic acid in a molar ratio of 2:0.5:0.5 to 2:1.5:1.5 is used to pretreat cornstalks.
- a recycling method of processing is disclosed.
- JP 2019-141098 A Japanese Patent Publication No. 2019-528814 Patent No. 6527616 Japanese translation of PCT publication No. 2016-538405 Chinese Patent Publication No. 106086106
- Patent Documents 1-5 The combinations of compounds disclosed in Patent Documents 1-5 are enormous, and all of them are selected for the purpose of applying them to specific uses. From these Patent Documents 1 to 5, it is not easy to select a combination of compounds that are safe and inexpensive heat carriers and are suitable as solvents for plant biomass.
- An object of the present invention is to provide a eutectic mixture and a liquid composition which are excellent in safety and workability and which are easy to produce.
- a eutectic mixture according to the present disclosure includes a first component and a second component as main components.
- the first component is a quaternary ammonium salt
- the second component is an aminocarboxylic acid and/or derivative thereof having a --COOH group and --NH-- group in the same molecule.
- the melting point Tm of the eutectic mixture is lower than the melting point T1 of the first component and the melting point T2 of the second component. This eutectic mixture exhibits a uniform liquid state at a temperature higher than the melting point Tm.
- the total content of the first component and the second component is 99% by weight or more of the entire eutectic mixture.
- the melting point Tm is greater than 0 and less than 50°C.
- the difference (T 1 ⁇ Tm) between the melting point T 1 and the melting point Tm of the first component is 100° C. or more.
- the first component is selected from quaternary ammonium salts represented by the following general formula (1).
- n is an integer of 1 to 3
- R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 5 carbon atoms
- X is a halogen group.
- the first component is choline chloride.
- the second component is an aminocarboxylic acid represented by the following general formula (2) and/or a derivative thereof.
- R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.
- the second component is an aminocarboxylic acid represented by the following general formula (3) and/or a derivative thereof.
- R 1 is a hydrogen atom or a hydrocarbon group which may have a substituent
- Y is a functional group containing a hetero atom
- Z is a carbon number of 5 or less which may have an unsaturated bond. It is an alkylene group.
- the second component is an aminocarboxylic acid and/or its cyclized derivative.
- the second component is selected from glutamine, glutamic acid and pyroglutamic acid.
- a liquid composition according to the present disclosure includes any of the eutectic mixtures described above and a third component dissolved in the eutectic mixture.
- the third component contains one or more selected from cellulose, hemicellulose and lignin.
- the third component preferably contains lignocellulose.
- the third component comprises one or more selected from wood, pulp and linter.
- the liquid composition is liquid at a temperature of 25°C or less.
- a molded article according to the present disclosure is formed from any of the liquid compositions described above.
- the eutectic mixture of the present disclosure can be easily produced by substantially mixing two components and heating.
- This eutectic mixture is liquid in a wide temperature range and has fluidity, so it is excellent in workability.
- This eutectic mixture uniformly dissolves the plant-based biomass containing cellulose, hemicellulose and lignin to form a liquid composition.
- FIG. 1 is a graph showing the relationship between the composition and the melting point of the eutectic mixture according to one embodiment of the present invention.
- FIG. 2 is a photograph showing that the molten state of the first component and the second component is good.
- FIG. 3 is a photograph showing a liquid composition according to one embodiment of the present invention, FIG. 3(a) before dissolution and FIG. 3(b) after dissolution.
- FIG. 4 is an electron micrograph of a liquid composition according to an embodiment of the present invention, FIG. 4(a) before dissolution and FIG. 4(b) after dissolution.
- the eutectic mixture of the present disclosure includes a first component that is a quaternary ammonium salt and a second component that is an aminocarboxylic acid and/or derivative thereof having —COOH groups and —NH— groups in the same molecule. Contains as a main component.
- This eutectic mixture has a melting point Tm lower than the melting point T1 of the first component and the melting point T2 of the second component.
- This eutectic mixture exhibits a uniform liquid state at a temperature higher than the melting point Tm.
- homoogeneously liquid means that there is no substantially solid component in the eutectic mixture.
- the eutectic mixture of the present disclosure can be readily produced by mixing and heating the first and second components.
- the eutectic mixture has high thermal stability at temperatures near the melting point T1 of the first component or the melting point T2 of the second component, and the melting point Tm of the eutectic mixture is It is sufficiently low compared to the melting point T1 and the melting point T2 of the second component.
- This eutectic mixture exhibits a uniform liquid state over a wide temperature range and has fluidity, so it is excellent in workability.
- this eutectic mixture does not contain urea, which is considered to be harmful to humans, and thus is excellent in safety.
- this eutectic mixture can uniformly dissolve plant-based biomass containing cellulose, hemicellulose and lignin.
- the term "main component” means that the first component and the second component constitute at least 50% by weight or more of the entire eutectic mixture.
- the total content of the first component and the second component in the eutectic mixture of the present disclosure is 90% or more, more preferably 99% or more by weight of the total eutectic mixture.
- the eutectic mixture of the present disclosure consists essentially of the first component and the second component.
- the melting point Tm of the eutectic mixture of the present disclosure is preferably greater than 0°C and less than 50°C.
- the eutectic mixture can exist as a flowable liquid up to at least 50°C. According to this eutectic mixture, problems such as clogging of pipes due to solidification during cooling can be avoided.
- the melting point Tm of this eutectic mixture is preferably 40° C. or lower, more preferably 30° C. or lower. In the eutectic mixture of the present disclosure, the melting point Tm may be greater than 0°C and 40°C or less, and may be greater than 0°C and 30°C or less.
- a eutectic mixture having a melting point Tm of room temperature (20° C. ⁇ 5° C.) or less, that is, a liquid state at room temperature is preferred.
- a known method such as a visual method according to JIS K0065 or a thermal analysis method can be used.
- the melting point and freezing point are the same for the same substance.
- the melting point Tm of the eutectic mixture of the present disclosure is lower than the melting point T1 of the first component and the melting point T2 of the second component.
- the difference (T 1 ⁇ Tm) between the melting point T 1 and the melting point Tm of the first component is preferably 100° C. or more, more preferably 110° C. or more. , more preferably 120° C. or higher.
- the difference (T 2 ⁇ Tm) between the melting point T 2 and the melting point Tm of the second component is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher.
- the upper limits of the difference (T 1 ⁇ Tm) and the difference (T 2 ⁇ Tm) are not particularly limited, but from the viewpoint of ease of production, the difference (T 1 ⁇ Tm) is preferably 250° C. or less, and the difference (T 2 ⁇ Tm) is preferably 200° C. or less.
- the first component is a quaternary ammonium salt.
- the quaternary ammonium salt There are no particular restrictions on the type of the quaternary ammonium salt.
- a quaternary ammonium salt is defined as a salt consisting of an ammonium cation having a substituent and an anion (counterion).
- Each substituent attached to N may be the same or different.
- Preferred substituents are aliphatic or aromatic hydrocarbon groups.
- a hydrocarbon group may have a substituent such as a hydroxyl group, a halogen group, an amino group, a nitrile group, or a carbonyl group.
- the number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 9 or less.
- the number of carbon atoms in the hydrocarbon group may be 1 or more and 10 or less, or 2 or more and 9 or less.
- Anions in the quaternary ammonium salts are typically halogen ions such as chloride and bromide ions.
- Other anions include organic carboxylate anions such as acetate anion, propionate anion and butyrate anion, organic sulfonate anions such as methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and paratoluenesulfonate anion. mentioned.
- quaternary ammonium salts include choline chloride, triethyl-2-hydroxyethylammonium chloride, triethyl-2-hydroxyethylammonium bromide, triethyl-2-hydroxyethylammonium iodide, tributyl-2-hydroxy ethylammonium chloride, tributyl-2-hydroxyethylammonium bromide, tributyl-2-hydroxyethylammonium iodide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, octyltrimethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide
- a preferred first component is one or more selected from quaternary ammonium salts represented by the following general formula (1).
- n is an integer of 1 to 3
- R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 5 carbon atoms
- X is a halogen group.
- a eutectic mixture in which the first component is choline chloride is preferable from the viewpoint of cost and availability.
- the melting point T1 of the first component is not particularly limited, but is preferably 400° C. or lower, more preferably 380° C. or lower, and more preferably 100° C. or higher from the viewpoint of ease of production and thermal stability.
- the melting point T1 may be 100 ° C. or higher and 400° C. or lower, and may be 100° C. or higher and 380° C. or lower.
- the second component is an aminocarboxylic acid and/or derivative thereof having --COOH and --NH- groups in the same molecule.
- Aminocarboxylic acid as long as it can be mixed with the first component and heated to form a eutectic mixture having a melting point Tm lower than the melting point T1 of the first component and the melting point T2 of the second component.
- the type of acid and/or derivative thereof is not particularly limited.
- Derivatives of aminocarboxylic acids include cyclized derivatives. A cyclized derivative of an aminocarboxylic acid may be formed by heating during eutectic preparation.
- the second component is preferably an aminocarboxylic acid represented by the following general formula (2) and/or a derivative thereof.
- R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent.
- aminocarboxylic acids represented by the general formula (2) include glutamine, glutamic acid, asparagine, aspartic acid, glycine, serine, phenylalanine, tryptophan, threonine, methionine, tyrosine, alanine, valine, leucine, isoleucine, and lysine. , arginine, histidine and the like.
- a more preferred second component is an aminocarboxylic acid represented by the following general formula (3) and/or a derivative thereof.
- R 1 is a hydrogen atom or a hydrocarbon group which may have a substituent
- Y is a functional group containing a hetero atom
- Z is a carbon number of 5 or less which may have an unsaturated bond. It is an alkylene group.
- aminocarboxylic acid represented by the general formula (3) examples include glutamine, glutamic acid, asparagine, aspartic acid, and the like.
- Preferred aminocarboxylic acids are glutamine and glutamic acid, and a preferred aminocarboxylic acid derivative is pyroglutamic acid. Eutectic mixtures in which the second component is selected from glutamine, glutamic acid and pyroglutamic acid are preferred.
- the melting point T2 of the second component is not particularly limited, it is preferably 400° C. or lower, more preferably 380° C. or lower, and preferably 100° C. or higher from the viewpoint of ease of production and thermal stability.
- the melting point T2 may be 100° C. or higher and 400° C. or lower, and may be 100° C. or higher and 380° C. or lower.
- the eutectic mixture of the present disclosure is obtained by mixing the first component and the second component to prepare a mixture and heating the mixture.
- the heating temperature and heating time are appropriately selected so that the first component and the second component melt and become a uniform liquid. From the viewpoint of preventing coloration, it is preferable to mix and heat under reduced pressure or in an inert gas atmosphere.
- inert gas include nitrogen gas and argon gas.
- FIG. 1 is a graph plotting the freezing point (melting point Tm) of a eutectic mixture obtained from choline chloride (first component) and glutamic acid (second component).
- the horizontal axis of the graph is the ratio (mol %) of glutamic acid (aminocarboxylic acid) in the mixture before heating, and the vertical axis of the graph is the freezing point of the obtained eutectic mixture.
- the molar ratio of the first component to the second component is in the range of 1:1 to 1:4 (50-80 mol % aminocarboxylic acid), and the homogeneous liquid at 25 ° C.
- a eutectic mixture of is formed.
- a preferred mixing ratio can be selected depending on the type of first and second components selected and to obtain the desired melting point Tm for the eutectic mixture.
- a solvent may be added to disperse the mixture when the first and second components are mixed to form a mixture and the mixture is heated.
- the use of this dispersing solvent improves agitation and enhances heat transfer when heating the mixture. As a result, heat is evenly transmitted to the entire mixture, so that it is possible to prevent coloration and thermal decomposition due to local heating or long-term heating.
- the type of dispersion solvent is not particularly limited, a solvent capable of dissolving the first component and the second component is preferable.
- the dispersion solvent is removed by concentration, and the boiling point is preferably 200° C. or lower, more preferably 120° C.
- the liquid composition of the present disclosure includes the eutectic mixture described above and a third component.
- the third component is dissolved in this eutectic mixture.
- dissolution means a state in which the eutectic mixture containing the third component forms a uniform phase.
- a preferred liquid composition exhibits a liquid state at 25° C. or lower. Liquid compositions that are liquid at room temperature (20° C. ⁇ 5° C.) or lower are more preferred.
- the third component is one or more selected from cellulose, hemicellulose and lignin.
- a third component may comprise lignocellulose.
- the third component may contain one or more selected from wood, pulp and linter.
- the content of the third component in the liquid composition is not particularly limited, but from the viewpoint of ease of production, it is preferably 50% by weight or less, more preferably 35% by weight or less, further preferably 20% by weight or less, and 10% by weight. The following are particularly preferred.
- the method for producing the liquid composition of the present disclosure is not particularly limited. Typically, it is obtained by mixing the above-mentioned eutectic mixture and the third component and heating by a conventionally known heating method. The heating conditions are appropriately adjusted according to the types and amounts of the eutectic mixture and the third component. From the viewpoint of preventing coloration, it is preferable to mix and heat under reduced pressure or in an inert gas atmosphere. Examples of inert gas include nitrogen gas and argon gas.
- the third component contained in the liquid composition of the present disclosure is also the main component of so-called plant-based biomass.
- the liquid composition of the present disclosure is a solution containing the major constituents of plant-based biomass. Molded articles formed from this liquid composition have excellent biodegradability due to plant biomass.
- a fourth solvent which is a poor solvent for the third component
- the cellulose, hemicellulose, and lignun, which are the third component are regenerated, resulting in film-like moldings and fibrous moldings. , particulate moldings and porous moldings can be obtained.
- Example 1-6 Choline chloride (melting point 302 ° C., manufactured by Tokyo Chemical Industry Co., Ltd., purity 98% or higher) and glutamic acid (melting point 225 ° C., manufactured by Nacalai Tesque, purity 99% or higher) are adjusted to the molar ratio shown in Table 1 below. were weighed under a nitrogen atmosphere, and put into a test tube with a diameter of 1 mm. Each test tube was then heated to 150° C. using an oil bath. At a temperature of 150 ° C., two straight lines (width 1 mm) drawn at an interval of 2 mm were visually observed through the test liquid in each test tube. A straight line could be clearly confirmed.
- Example 7-12 Test solutions of Examples 7 to 12 were prepared in the same manner as in Examples 1 to 6, except that the compositions shown in Table 2 below were used. All of the test liquids of Examples 7 to 12 uniformly melted at 150°C. Each test liquid was then cooled to 25°C at a rate of 5°C/min. After standing at 25° C. for 24 hours, two straight lines (width of 1 mm) drawn at an interval of 2 mm were visually observed through the test liquid in the test tube. The results obtained are shown in Table 2. In Table 2, the test solution (uniform melting) in which two straight lines were clearly visible is indicated by ⁇ . A test liquid (incomplete melting) in which the line cannot be visually recognized or is blurred and looks like a single line is indicated by x. Figure 2 is a photograph of Example 7 showing uniform melting at 25°C.
- Reference Example 1-3 In the same manner as in Examples 1-6, except that glutamic acid was changed to urea (melting point 133 ° C., manufactured by Nacalai Tesque, purity 99% or more) and the molar ratios shown in Tables 1 and 2 below were used. Test solutions 1-3 were prepared. All of Reference Examples 1-3 melted uniformly at 150° C., and as shown in Table 2, exhibited uniform melting after standing at 25° C. for 24 hours. The freezing point of each test liquid is shown in Table 1.
- Example 13-26 The choline chloride and glutamic acid described above were weighed in a nitrogen atmosphere so that the molar ratio was 1:1, put into a test tube with a diameter of 1 mm, and heated to 150 ° C. using an oil bath. A uniformly melted test solution was prepared. The third component was added to each test solution in the amount shown in Table 3 below, and heated at 110° C. for 5 hours using an oil bath. Table 3 shows the results of visual observation of the dissolution state of the third component. In Table 3, test liquids (uniform melting) in which powder sedimentation or fibers could not be visually recognized are shown as ⁇ .
- FIG. 3(a) is a photograph showing the state before heating
- FIG. 3(b) is a photograph after heating at 110° C. for 5 hours.
- Example 26 The resulting liquid composition of Example 26 was observed with an electron microscope (500x magnification). Results are shown in FIG. FIG. 4(a) is an image obtained for the third component (cotton linter) before dissolution, and FIG. 4(b) is an image of Example 26 (20.0% by weight). It was confirmed that almost no cellulose fibers were present in the liquid composition of Example 26.
- Example 27 A uniformly melted test solution was prepared in the same manner as in Example 14, except that the glutamine described above was used instead of glutamic acid. Table 3 below shows the results of evaluating the solubility of the third component at 110° C. in this test liquid.
- a uniform liquid eutectic mixture similar to the reference example was formed by a simple means of mixing and heating the materials without using urea as the material. can do. Furthermore, in Examples 7-8 and 10-12, a uniform liquid eutectic mixture can be formed in a wide temperature range from 150°C to 25°C.
- the eutectic mixtures of the examples can uniformly dissolve various celluloses to form liquid compositions having fluidity at a temperature of 110°C. Furthermore, it was confirmed that all examples exhibited a uniform liquid state at a temperature of 25°C. From these evaluation results, the superiority of the present invention is clear.
- the eutectic mixture described above can be applied as a highly safe heat-resistant solvent and a solvent for plant biomass. Moreover, the liquid composition described above can be applied to the use of various plant-based biomass.
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Abstract
Description
本開示の共融混合物は、第4級アンモニウム塩である第一成分と、同一分子内に-COOH基及び-NH-基を有するアミノカルボン酸及び/又はその誘導体である第二成分と、を主成分として含む。この共融混合物は、第一成分の融点T1及び第二成分の融点T2よりも低い融点Tmを有している。この共融混合物は、融点Tmより高い温度で均一な液状を呈するものである。ここで、「均一な液状」とは、共融混合物中に、実質的に固体である成分が存在しないことを意味する。
本開示の共融混合物の融点Tmは、0℃を超えて50℃未満であることが好ましい。換言すれば、この共融混合物は、少なくとも50℃まで、流動性を有する液体として存在しうる。この共融混合物によれば、冷却時の固化に起因する配管閉塞等のトラブルが回避されうる。この共融混合物の融点Tmは、40℃以下が好ましく、30℃以下がより好ましい。本開示の共融混合物において、融点Tmは、0℃を超えて40℃以下であってよく、0℃を超えて30℃以下であってよい。融点Tmが室温(20℃±5℃)以下、即ち、室温で液状である共融混合物が好ましい。融点Tmの測定方法としては、JIS K0065に準じた目視法、熱分析法等既知の方法を用いることができる。同一物質である場合、原則として、融点と凝固点とは等しい。
本開示の共融混合物において、第一成分は第4級アンモニウム塩である。後述する第二成分と混合して加熱されることにより、第一成分の融点T1及び第二成分の融点T2よりも低い融点Tmを有する共融混合物を形成することができる限り、第4級アンモニウム塩の種類は特に限定されない。
本開示の共融混合物において、第二成分は同一分子内に-COOH基及び-NH-基を有するアミノカルボン酸及び/又はその誘導体である。前述した第一成分と混合して加熱されることにより、第一成分の融点T1及び第二成分の融点T2よりも低い融点Tmを有する共融混合物を形成することができる限り、アミノカルボン酸及び/又はその誘導体の種類は特に限定されない。アミノカルボン酸の誘導体としては、環化誘導体が挙げられる。アミノカルボン酸の環化誘導体は、共融混合物製造時の加熱により形成されるものであってもよい。
本開示の共融混合物は、第一成分と第二成分とを混合して混合物を調整し、この混合物を加熱することにより得られる。加熱温度及び加熱時間は、第一成分及び第二成分が溶融して、均一な液状になるように適宜選択される。着色防止の観点から、減圧下又は不活性ガス雰囲気下で混合及び加熱されることが好ましい。不活性ガスとしては、窒素ガス、アルゴンガス等が例示される。
第一成分及び第二成分が溶融して、均一な液状を呈する限り、第一成分と第二成分との混合比は特に限定されない。例えば、図1は、塩化コリン(第一成分)とグルタミン酸(第二成分)とから得られる共融混合物の凝固点(融点Tm)がプロットされたグラフである。グラフの横軸は、加熱前の混合物中のグルタミン酸(アミノカルボン酸)の比率(モル%)であり、グラフの縦軸は得られた共融混合物の凝固点である。図示される通り、この実施形態では、第一成分と第二成分とのモル比が1:1~1:4(アミノカルボン酸が50-80モル%)の範囲で、25℃において均一な液状の共融混合物が形成される。選択される第一成分及び第二成分の種類に応じて、また、共融混合物について所望の融点Tmが得られるように、好ましい混合比が選択されうる。
第一成分と第二成分とを混合して混合物を調整しこの混合物を加熱するときに、混合物を分散させるために溶媒を添加することもできる。この分散溶媒を使用すると、混合物を加熱するときに、攪拌状態が改善され熱の伝達性が高まる。これにより、混合物全体に熱が均一に伝わるため、局所的な加熱あるいは長時間の加熱による着色や熱分解を防ぐことができる。分散溶媒の種類は特に限定されないが、第一成分及び第二成分を溶解可能な溶媒が好ましい。また、共融混合物を製造後、この分散溶媒を濃縮除去して、第一成分及び第二成分を所望の含有量に調節できるように、沸点が好ましくは200℃以下、より好ましくは120℃以下の溶媒が好ましい。具体的には、水、アセトン、メチルエチルケトン、メタノール、エタノール、ブタノール、テトラヒドロフラン等が挙げられる。
本開示の液状組成物は、前述した共融混合物と、第三成分とを含んでいる。第三成分は、この共融混合物に溶解している。ここで、「溶解」とは、第三成分を含む共融混合物が均一な相を形成している状態を意味する。好ましい液状組成物は、25℃以下で液状を示す。室温(20℃±5℃)以下で液状である液状組成物が、より好ましい。
本開示の液状組成物において、第三成分は、セルロース、ヘミセルロース及びリグニンから選択される1種又は2種以上である。第三成分が、リグノセルロースを含んでもよい。第三成分が、木材、パルプ及びリンターから選択される1種又は2種以上を含んでもよい。
本開示の液状組成物の製造方法は特に限定されない。典型的には、前述した共融混合物と第三成分とを混合し、従来既知の加熱方法により加熱することにより得られる。加熱条件は、共融混合物及び第三成分の種類及び量に応じて適宜調整される。着色防止の観点から、減圧下又は不活性ガス雰囲気下で混合及び加熱されることが好ましい。不活性ガスとしては、窒素ガス、アルゴンガス等が例示される。
塩化コリン(融点302℃、東京化成工業社製、純度98%以上)と、グルタミン酸(融点225℃、ナカライテスク社製、純度99%以上)とを、下表1に示されたモル比となるように、窒素雰囲気下で秤量して、それぞれ、直径1mmの試験管に投入した。その後、オイルバスを使用して、各試験管を150℃に加熱した。温度150℃において、各試験管中の試験液を通して、2mmの間隔をあけて記載された2本の直線(幅1mm)を、目視で観察したところ、いずれも、試験液を介して、2本の直線を明瞭に確認することができた。これにより、塩化コリン及びグルタミン酸は、いずれのモル比においても、150℃において完全に溶融することがわかった。続いて、各試験管を速度5℃/分で冷却し、目視観察により結晶の発生を確認した温度を凝固点として記録した。得られた結果が表1に示されている。各実施例におけるグルタミン酸(アミノカルボン酸)の比率に対する凝固点をプロットしたグラフが、図1に示されている。図1及び表1に示される通り、実施例1-6の凝固点(融点)は、塩化コリン及びグルタミン酸の融点より低い。
下表2に示される組成とした以外は、実施例1-6と同様にして、実施例7-12の試験液を作製した。実施例7-12の試験液は、いずれも150℃で均一に溶融した。続いて、各試験液を速度5℃/分で25℃まで冷却した。25℃で24時間静置後に、試験管中の試験液を通して、2mmの間隔をあけて記載された2本の直線(幅1mm)を目視で観察した。得られた結果が表2に示されている。表2中、2本の直線が明瞭に視認された試験液(均一溶融)が○として示されている。線が視認できない、又はぼやけて1本に見える試験液(溶融不良)が×として示されている。図2は、25℃で均一溶融を示した実施例7の写真である。
グルタミン酸を尿素(融点133℃、ナカライテスク社製、純度99%以上)に変更し、下表1及び2に示されたモル比にした以外は、実施例1-6と同様にして、参考例1-3の試験液を作製した。参考例1-3は、いずれも150℃で均一に溶融し、表2に示される通り、25℃で24時間静置後に均一溶融を示した。各試験液の凝固点が表1に示されている。
前述の塩化コリン及びグルタミン酸を、窒素雰囲気下で、モル比1:1となるように、秤量して、直径1mmの試験管に投入し、オイルバスを使用して150℃に加熱することにより、均一に溶融した試験液を作製した。各試験液に、下表3に示される量となるように、第三成分を投入し、オイルバスを用いて110℃で5時間加熱した。第三成分の溶解状態を目視で観察した結果が表3に示されている。表3中、粉末の沈殿又は繊維が視認できなかった試験液(均一溶融)が○として示されている。図3(a)が加熱前の状態を示す写真であり、図3(b)が110℃で5時間加熱後の写真である。
グルタミン酸に代えて、前述のグルタミンを使用した以外は実施例14と同様にして、均一に溶融した試験液を作製した。この試験液について、110℃における第三成分の溶解性を評価した結果が、下表3に示されている。
グルタミン酸に代えて、前述の尿素を使用した以外は実施例15と同様にして、均一に溶融した試験液を作製した。この試験液に第三成分を投入し、オイルバスを用いて110℃で6時間加熱したが、セルロース繊維はほとんど溶解しなかった。この結果が、下表3に×として示されている。
Avicel:旭化成工業社製の微結晶セルロース、重量平均重合度200-250、登録商標「Avicel」
パルプ:重量平均重合度1500-2000
テンセル:レンチング社製の精製セルロース、登録商標「テンセル」
Cotton linter:サザンセルロース社製のコットンリンター、重量平均重合度800-1800
Claims (15)
- 第一成分と、第二成分と、を主成分として含み、
上記第一成分が第4級アンモニウム塩であり、上記第二成分が同一分子内に-COOH基及び-NH-基を有するアミノカルボン酸及び/又はその誘導体であり、
上記第一成分の融点T1及び上記第二成分の融点T2よりも低い融点Tmを有しており、この融点Tmより高い温度では均一な液状を呈する、共融混合物。 - 上記第一成分と上記第二成分との合計含有量が、上記共融混合物全体の99重量%以上である、請求項1に記載の共融混合物。
- 上記融点Tmが0を超えて50℃未満である、請求項1又は2に記載の共融混合物。
- 上記第一成分の融点T1と上記融点Tmとの差(T1-Tm)が100℃以上である、請求項1から3のいずれかに記載の共融混合物。
- 上記第一成分が、塩化コリンである、請求項1から5のいずれかに記載の共融混合物。
- 上記第二成分が、上記アミノカルボン酸及び/又はその環化誘導体である、請求項1から8のいずれかに記載の共融混合物。
- 上記第二成分が、グルタミン、グルタミン酸及びピログルタミン酸から選択される、請求項1から9のいずれかに記載の共融混合物。
- 請求項1から10のいずれかに記載の共融混合物と、この共融混合物に溶解した第三成分と、を含み、
上記第三成分が、セルロース、ヘミセルロース及びリグニンから選択される1又は2種以上を含む、液状組成物。 - 上記第三成分がリグノセルロースを含む、請求項11に記載の液状組成物。
- 上記第三成分が木材、パルプ及びリンターから選択される1種又は2種以上を含む、請求項11又は12に記載の液状組成物。
- 温度25℃以下で液状である、請求項11から13のいずれかに記載の液状組成物。
- 請求項11から14のいずれかに記載の液状組成物から形成される成型品。
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