Method for producing a petroleum-derived polyhydric hydroxymonomer-containing phase, method for producing a urea-containing phase, method for producing recycled carbonate resin, and recycling method.

Abstract

To provide a novel production method of urea.SOLUTION: Provided is a production method of urea, comprising: the first step of depolymerizing a carbonate resin by means of ammonolysis by contacting the carbonate resin with ammonia; and the second step of recovering urea from a decomposition product generated by the first step. The carbonate resin is a copolymer in which structures based on two or more polyhydroxy monomers including one or more petroleum-derived polyhydroxy monomers are connected through carbonate bonds. The two or more polyhydroxy monomers, which correspond to the decomposition products, and urea respectively have n-octanol / water partition coefficients ((Log Pow) and acid dissociation coefficients (pKa), either or both of which are mutually different. Based on the differences, the respective compounds can be separated by carrying out liquid-liquid extraction for a plurality of times using water and an organic solvent in the second step.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing urea, a method for producing a fertilizer composition, a method for producing recycled carbonate resin, and a recycling method. [Background technology]

[0002] Polymer materials are widely used in various fields, including automobiles, civil engineering, construction, information and communication, food, and medicine. In recent years, with growing concern for environmental issues, there has been increasing interest in plant-derived polymer materials, which are renewable resources, and in the recycling of polymer materials.

[0003] Known recycling methods for polymer materials include thermal recycling, mechanical recycling, and chemical recycling. Of these, chemical recycling involves depolymerizing polymer materials into monomers and oligomers through thermal decomposition or chemical reactions, and then repolymerizing them to regenerate the original polymer material or reduce it to a new polymer material. Chemical recycling has the advantage of not causing a decrease in physical properties, as it remanufactures the polymer material from monomers.

[0004] Carbonate resins are one of the most commonly used polymer materials. Because of their excellent properties such as transparency, impact resistance, tensile strength, creep resistance, heat resistance, and low-temperature characteristics, carbonate resins using aromatic monomers, particularly bisphenol A, are widely used. The use of plant-derived monomers instead of petroleum-derived aromatic monomers is also being considered; for example, polyisosorbide carbonate, which uses the plant-derived monomer isosorbide, has been put into practical use.

[0005] Patent Document 1 describes a method for recovering useful materials from waste plastics mainly composed of polycarbonate resin. Non-Patent Document 1 describes a recycling system that converts plastic into fertilizer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2001-270961 [Non-patent literature]

[0007] [Non-Patent Document 1] "Development of a recycling system that converts plastic into fertilizer," [online], published October 28, 2021, Tokyo Institute of Technology, Internet <URL: https: / / www.titech.ac.jp / news / 2021 / 062173> [Overview of the project] [Problems that the invention aims to solve]

[0008] Under these circumstances, the inventor focused particularly on petroleum-derived carbonate resins (i.e., carbonate resins manufactured using petroleum-derived monomers) among the carbonate resins that can be considered as typical targets for recycling. Furthermore, after diligently studying how to improve conventional carbonate resins and construct an excellent recycling system centered on new petroleum-derived carbonate resins, the inventor discovered that it is possible to produce urea, fertilizer compositions, or recycled carbonate resins and their raw material monomers from petroleum-derived carbonate resins obtained by copolymerizing two or more monomers, and reuse them, leading to the present invention. In other words, the present invention provides a novel method for producing urea, a fertilizer composition, and recycled carbonate resin, as well as a novel method for recycling petroleum-derived carbonate resin, and the like. [Means for solving the problem]

[0009] The present invention has the following aspects. [1] A first step of depolymerizing the carbonate resin by ammonia by contacting the carbonate resin with ammonia, A second step of recovering urea from the decomposition products generated in the first step, including The carbonate resin is a copolymer in which structures based on two or more polyhydroxy monomers including one or more petroleum-derived polyhydroxy monomers are linked via carbonate bonds, The n-octanol / water partition coefficient (Log P ow ) and the acid dissociation constant (pK a ) of each of the two or more polyhydroxy monomers and urea that are the decomposition products have differences in either one or both, Each of the compounds can be separated by performing liquid-liquid extraction using water and an organic solvent a plurality of times based on the differences in the second step. A method for producing urea, characterized in that. [2] The two or more polyhydroxy monomers are weak acidic substances, The acid dissociation constant (pK a ) of the two or more polyhydroxy monomers is larger than the acid dissociation constant (pK a ) of urea. The production method according to [1] above. [3] The number of hydroxyl groups of the two or more polyhydroxy monomers is two. The production method according to [1] or [2] above. [4] The one or more petroleum-derived polyhydroxy monomers are monomers selected from the group consisting of compounds represented by the following formula (1). The production method according to any one of [1] to [3] above.

Chemical formula

[10] A method for producing a fertilizer composition containing urea as an active ingredient, A method for producing a fertilizer composition, comprising the step of granulating or blending a powdered or liquid raw material containing a urea component with water, either alone or together with other components, wherein the urea component is urea produced by the production method described in any of [1] to [9] above.

[11] The method for producing the fertilizer composition according to

[10] , wherein the other component is all or part of the one or more polyhydric hydroxy monomers containing plant growth promoting activity obtained by recovering one or more of the two or more polyhydric hydroxy monomers containing plant growth promoting activity from the decomposition product generated in the first step of the production method according to any one of [6] to [9].

[12] A method for producing a recycled carbonate resin, characterized by recovering two or more polyvalent hydroxy monomers from the decomposition products generated in the first step of the production method described in any of [1] to [9] above, and polymerizing one or more polyvalent hydroxy monomers containing all or part of the recovered two or more polyvalent hydroxy monomers as all or part of the raw material monomers to obtain a recycled carbonate resin.

[13] A recycling method characterized by comprising a step of reusing all or part of the urea recovered in the second step of the manufacturing method described in any of [1] to [9] above as a fertilizer component.

[14] A recycling method characterized by comprising the step of recovering two or more polyhydric hydroxy monomers from the decomposition products generated in the first step of the manufacturing method described in any of [1] to [9] above, and reusing all or part of the recovered two or more polyhydric hydroxy monomers as fertilizer components and / or monomers for carbonate resin.

[15] A recycling method characterized by comprising the step of recovering one or more polyhydric hydroxy monomers containing plant growth promoting activity from the decomposition product generated in the first step of the manufacturing method described in any of [6] to [9] above, and reusing all or part of the recovered urea and / or the one or more polyhydric hydroxy monomers containing plant growth promoting activity as a fertilizer component.

[16] A recycling method characterized by comprising a step of reusing all or part of the two or more polyhydric hydroxy monomers, excluding those to be used as fertilizer components, from the decomposition product generated in the first step of the manufacturing method described in any of [1] to [9] above, as monomers for a carbonate resin. [Effects of the Invention]

[0010] According to the present invention, a novel manufacturing method for producing urea, fertilizer compositions, or recycled carbonate resin from petroleum-derived carbonate resin can be provided, as well as a novel recycling method for petroleum-derived mocarbonate resin. [Brief explanation of the drawing]

[0011] [Figure 1] This figure shows the 1H NMR spectrum of P(BPAC-co-BDMC) obtained in Synthesis Example 1. [Figure 2] This figure shows the GPC elution curve of P(BPAC-co-BDMC) obtained in Synthesis Example 1. [Figure 3] This figure shows the 1H NMR spectra of the decomposition products of the aqueous and organic layers, respectively, recovered in Test Example 1. [Figure 4] This figure shows a magnified portion of the 1H NMR spectrum of the decomposition products of the organic layer shown in Figure 3. [Figure 5] This figure shows the 1H NMR spectra of the decomposition products of the aqueous and organic layers recovered in Test Example 2. [Figure 6] This figure shows the results of the reference example (the plant growth promoting effect of samples 1-3). [Modes for carrying out the invention]

[0012] [Method for producing urea] The present invention provides a method for producing urea, comprising: a first step of depolymerizing a carbonate resin by ammonia by contacting the carbonate resin with ammonia, thereby causing ammonia-induced depolymerization (also known as ammonia-induced decomposition or ammonium decomposition); and a second step of recovering urea from the decomposition products generated in the first step.

[0013] (Carbonate resin) The carbonate resin used in the first step is a copolymer (copolycarbonate) in which structures based on two or more polyvalent hydroxy monomers are linked via carbonate bonds. Furthermore, the two or more polyvalent hydroxy monomers include one or more petroleum-derived polyvalent hydroxy monomers. The two or more polyvalent hydroxy monomers may further include other polyvalent hydroxy monomers other than petroleum-derived polyvalent hydroxy monomers.

[0014] A "polyvalent hydroxy monomer" is a polymerizable compound having two or more hydroxyl groups, and it constitutes the repeating unit of a polyester compound produced by the condensation polymerization of this compound with carbonic acid. A "structure based on a polyvalent hydroxy monomer" is a structure obtained by removing two hydroxyl groups from a polyvalent hydroxy monomer. The number of hydroxyl groups in a polyvalent hydroxy monomer is preferably 2 to 6, and particularly preferably 2.

[0015] When a carbonate resin is depolymerized by ammonialysis, polyvalent hydroxy monomers of the carbonate resin and urea are produced as decomposition products. Therefore, the decomposition products produced in the first step include two or more polyvalent hydroxy monomers and urea. Furthermore, the two or more polyvalent hydroxy monomers in the decomposition products include one or more petroleum-derived polyvalent hydroxy monomers. The two or more polyvalent hydroxy monomers in the decomposition products may further include other polyvalent hydroxy monomers other than petroleum-derived polyvalent hydroxy monomers.

[0016] The carbonate resin specifically includes a structure represented by the following formula (A).

[0017] [ka] (In the formula, R is a structure based on a polyvalent hydroxy monomer, n is an integer greater than or equal to 2, at least some of the n Rs are distinct from one another, and at least some of the n Rs are structures based on petroleum-derived polyvalent hydroxy monomers.)

[0018] Typical compounds that are petroleum-derived polyvalent hydroxy monomers are polymerizable compounds that constitute the repeating units of plastics produced from petrochemicals using naphtha, which is produced by the thermal decomposition of crude oil, as a raw material. Specifically, examples include monomers in which two or more hydrogen atoms in aromatic hydrocarbons (i.e., hydrocarbons containing at least one aromatic ring in one molecule) are replaced by hydroxyl groups. More specifically, examples of petroleum-derived polyhydric hydroxy monomers include the compound represented by the following formula (1) (hereinafter also referred to as compound (1)).

[0019] [ka] (In the formula, A 1 and A 2 Each of these independently represents a linear or branched alkylene group having 1 to 8 carbon atoms, or a single bond, A 3 This may be a linear or branched alkylene group having 1 to 8 carbon atoms, which may be substituted with a phenyl group and may have a phenylene group interposed between carbon atoms, a divalent cyclic hydrocarbon group, -O-, -S-, -CO-, -SO-, -SO2-, or a single bond, X 1 and X 2 Each of these independently represents a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, where a represents 0 or 1, and b and c independently represent integers from 0 to 4.

[0020] The structure based on compound (1) is represented by the following formula (i).

[0021] [ka]

[0022] A 1 , A 2 and A 3 Examples of "linear or branched alkylene groups having 1 to 8 carbon atoms" in this context include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptalene, and octalene groups. A 3 Examples of "divalent cyclic hydrocarbon groups" in this context include cycloalkylene groups such as 1,4-cyclohexylene and 2-isopropyl-1,4-cyclohexylene. X 1 and X 2Examples of "halogen atoms" in this context include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and so on. X 1 and X 2 Examples of "carbon hydrocarbon groups having 1 to 6 carbon atoms" in this context include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.

[0023] Specific examples of compound (1) include dihydroxybiphenyls such as 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)methane, 1,1-bis(4'-hydroxyphenyl)ethane, 1,2-bis(4'-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4'-hydroxyphenyl)-1-phenylethane, 2-(4'-hydroxyphenyl)-2-(3'-hydroxyphenyl)propane, 2,2-bis( 4'-Hydroxyphenyl)butane, 1,1-bis(4'-Hydroxyphenyl)isobutane, 1,1-bis(4-Hydroxyphenyl)-2-methylpropane, 2,2-bis(4-Hydroxyphenyl)pentane, 2,2-bis(4-Hydroxyphenyl)-4-methylpentane, 2,2-bis(4-Hydroxyphenyl)octane, 1,1-bis(4-Hydroxyphenyl)-1,1-diphenylmethane, 1,1-bis(4-Hydroxyphenyl)-1-phenylethane, 1,1-bis(4-Hydroxyphenyl)-2-phenylethane, 2,2-bis Bis(hydroxyaryl)alkanes such as (3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(4-hydroxy-3-s-butylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane; 1,1'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,1'-bis Bis(hydroxyaryl)dialkylbenzenes such as (4-hydroxyphenyl)-m-diisopropylbenzene; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane; bis(hydroxyaryl) ethers such as bis(4-hydroxyphenyl) ether; bis(hydroxyaryl) sulfides such as bis(4-hydroxyphenyl) sulfide; bis(hydroxyaryl) ketones such as bis(4-hydroxyphenyl) ketone;Examples include bis(hydroxyaryl) sulfoxides such as bis(4-hydroxyphenyl) sulfoxide, and bis(hydroxyaryl) sulfones such as bis(4-hydroxyphenyl) sulfone.

[0024] Among compound (1), one or more compounds selected from the group consisting of bisphenol A and 1,4-benzenedimethanol are preferred, and bisphenol A is particularly preferred. Bisphenol A and 1,4-benzenedimethanol may be used in combination. Carbonate resin copolymerized with bisphenol A and 1,4-benzenedimethanol is expected to improve upon the physical properties and characteristics of carbonate resin polymerized with bisphenol A alone, such as fatigue properties and wear resistance.

[0025] Other examples of polyhydric hydroxy monomers besides petroleum-derived polyhydric monomers include plant-derived polyhydric monomers. Depending on the purpose, plant-derived polyhydric monomers may be used as appropriate. Typical plant-derived polyvalent hydroxy monomers are compounds derived from renewable raw materials such as biomass like sugarcane and corn, and in many cases, they are monomers in which two or more hydrogen atoms in biochemically or biologically synthesized compounds are replaced by hydroxyl groups. More specifically, examples of plant-derived polyhydric hydroxy monomers include heterocondensed aliphatic cyclic polyhydric alcohol compounds and aliphatic polyhydric alcohol compounds. Heterocondensed aliphatic cyclic polyhydric alcohol compounds are polyhydric alcohol compounds that have a condensed aliphatic ring containing a heteroatom (e.g., an oxygen atom) in their ring skeleton. Examples of heterocondensed aliphatic cyclic polyhydric alcohol compounds include isosorbide. Examples of aliphatic polyhydric alcohol compounds include sugar alcohols. Examples of sugar alcohols include sorbitol.

[0026] Among the aforementioned plant-derived polyvalent hydroxy monomers, compounds having plant growth-promoting activity are preferred because they can be used in the production of fertilizers (hereinafter also referred to as "plant growth-promoting activity-containing monomers"). Isosorbide is preferred as the monomer containing plant growth-promoting activity. Isosorbide is a compound represented by the following formula (2).

[0027] [ka]

[0028] The structure based on isosorbide is represented by the following formula (ii).

[0029] [ka]

[0030] The two or more polyhydric hydroxy monomers may consist of two or more petroleum-derived polyhydric hydroxy monomers, or they may consist of one or more petroleum-derived polyhydric hydroxy monomers and one or more other polyhydric hydroxy monomers. The ratio of petroleum-derived polyhydric hydroxy monomers to the total of 100 mol% of two or more polyhydric hydroxy monomers (the ratio of R in formula (A) that is a structure based on petroleum-derived polyhydric hydroxy monomers among the n Rs) can be appropriately set according to the physical properties and characteristics required for the intended use of the carbonate resin. For example, values ​​within the range of 1 mol% to 100 mol% can be cited. Preferably, for example, values ​​within the range of 10 mol% to 100 mol% can be cited. More preferably, for example, values ​​within the range of 50 mol% to 100 mol% can be cited. Furthermore, if the carbonate resin is close to the physical properties and characteristics of poly(bisphenol A carbonate) (hereinafter sometimes referred to as PBPAC), for example, values ​​within the range of 80 mol% to 100 mol% can be preferably cited. More preferably, values ​​within the range of 90 mol% to 100 mol% can be cited. Particularly preferably, 100 mol% can be cited. When two or more polyvalent hydroxy monomers include one or more other polyvalent hydroxy monomers, the ratio of petroleum-derived polyvalent hydroxy monomers to the total of 100 mol% of the two or more polyvalent hydroxy monomers can be appropriately set according to the physical properties and characteristics required for the carbonate resin's intended use. For example, a value within the range of 1 mol% to 100 mol% can be given. Furthermore, when the carbonate resin is expected to have physical properties and characteristics derived from the one or more other polyvalent hydroxy monomers, for example, the ratio of the one or more other polyvalent hydroxy monomers to the total of 100 mol% of the two or more polyvalent hydroxy monomers (the ratio of R in formula (A) that is a structure based on the one or more other polyvalent hydroxy monomers) can be a value within the range of 50 mol% to 99 mol%. Preferably, for example, a value within the range of 70 mol% to 99 mol% can be given. More preferably, for example, a value within the range of 80 mol% to 90 mol% can be given.

[0031] When two or more polyvalent hydroxy monomers include one or more polyvalent hydroxy monomers containing plant growth promoting activity, the ratio of petroleum-derived polyvalent hydroxy monomers to 100 mol% of the total of the two or more polyvalent hydroxy monomers can be appropriately set according to the physical properties and characteristics required for the carbonate resin's intended use. For example, a value within the range of 1 mol% to 100 mol% can be cited. Furthermore, when the carbonate resin is expected to have physical properties and characteristics derived from the one or more polyvalent hydroxy monomers containing plant growth promoting activity, for example, the ratio of the one or more polyvalent hydroxy monomers containing plant growth promoting activity to 100 mol% of the total of the two or more polyvalent hydroxy monomers (the ratio of R in formula (A) that is a structure based on the one or more polyvalent hydroxy monomers containing plant growth promoting activity) can be a value within the range of 50 mol% to 99 mol%. Preferably, for example, a value within the range of 70 mol% to 99 mol% can be cited. More preferably, for example, a value within the range of 80 mol% to 90 mol% can be cited. In such cases, depending on the proportion of petroleum-derived polyhydric monomers, it is desirable that the molar ratio of plant growth-promoting activity-containing polyhydric monomer to urea in the decomposition product generated in the first step (plant growth-promoting activity-containing polyhydric monomer: urea) be within the range of 1:1 to 1:0.4, preferably 1:0.9 to 1:0.5, and more preferably 1:0.8 to 0.6. If this molar ratio is within the above range, the fertilizer composition obtained by mixing the separated urea and plant growth-promoting activity-containing polyhydric monomer exhibits a particularly excellent plant growth-promoting effect. Of course, the molar ratio of plant growth-promoting activity-containing polyhydric monomer to urea in the obtained fertilizer composition may be adjusted by separately adding urea or plant growth-promoting activity-containing polyhydric monomer to the obtained fertilizer composition.

[0032] In this invention, two or more polyhydric hydroxy monomers include one or more petroleum-derived polyhydric hydroxy monomers, and each compound of the two or more polyhydric hydroxy monomers and urea has an n-octanol / water partition coefficient (Log Pow ) and acid dissociation constant (pK a There is a difference in either one or both of the following. Here, the Log P of each compound ow and pK a This value is the temperature at which liquid-liquid extraction is performed. Log P ow This is an indicator of resistance to water (hydrophobicity), and Log P ow A larger value indicates higher hydrophobicity (pK). a pK is an indicator of acid strength. a A smaller value indicates a stronger acid. The Log P of each compound ow and pK a The presence of differences in either one or both of these factors allows for the separation of each compound in the second step.

[0033] Log P ow This may be determined by known methods commonly used in the relevant technical field. Furthermore, for simple evaluation, literature values, publicly known values ​​provided by reagent companies, etc., may be referred to. In addition, various Log P values ​​known in the field of cheminformatics may also be used. ow The calculation can also be performed using an estimation approach; specifically, for example, it can be calculated from the structural formula of the target compound using the "CLog P" program in Chem Draw Professional 16.0. Log P ow Methods for determining this include, for example, the flask shaking method and the HPLC method. 1. Flask shaking method: This method involves placing the target substance and two solvents into a flask and shaking them thoroughly. The standard method for measuring the octanol / water partition coefficient using the flask shaking method is detailed in "OECD Test Guideline 107" and "JIS Z7260-107". In particular, Log P ow It is preferable to apply this to samples ranging from -2 to 4 (and possibly 5). Determine the concentration of octanol in water (Co) and the concentration of Cw in water, respectively, and then take the common logarithm of the concentration ratio Co / Cw = Pow (partition coefficient) Log P ow You can calculate it as follows. Incidentally, while the flask shaking method for measuring partition coefficients has a wide range of applications because it can be used even for substances with unknown chemical structures, it is important to note that it takes a long time to reach equilibrium (for example, 15 minutes to 1 hour) and is only applicable to substances that are completely soluble in both solvents (for example, the amount of solute should be 0.01 mol / L or less). Furthermore, especially if an emulsion has formed, centrifugation can be used to separate the two phases. 2.HPLC method: Log P using high-performance liquid chromatography (HPLC) ow The method for calculating this is specified in "OECD Test Guideline 117," and Log P ow It is preferable to apply this to samples ranging from 0 to 6. Incidentally, while HPLC can determine the partition coefficient more quickly than the flask shaking method if data for known substances is available, and is less affected by impurities, it is important to note that it cannot be applied to substances with low solubility in water, those that react with the column support, or complexes that may decompose during measurement. Furthermore, since the partition coefficient is calculated by regression analysis from known sample data, it is necessary to have multiple substances for which the partition coefficient is known, and it is important to note that the correlation coefficient will differ for compounds with significantly different structures, making comparison difficult.

[0034] pK a This may be determined by known methods commonly used in the relevant technical field. Alternatively, for a simpler evaluation, literature values, publicly known values ​​provided by reagent companies, etc., may be referenced. pK a Methods for determining the pK of a substance include, for example, neutralization titration, spectrophotometric analysis, and capillary electrophoresis. Among these, the neutralization titration method is highly accurate and can be used to determine the pK of a target substance. a The method for measuring this is described below. 1. Neutralization titration method: A neutralization titration curve is created for the target substance, which is a weak acid. In the created titration curve, the substance is weakly acidic before the addition of alkaline solutions such as LiOH, NaOH, and KOH, and immediately after the start of addition, a pH increase of about 1 to 2 units is observed due to the weak acid. Thereafter, as the alkaline solution is added, the pH gradually increases up to the equivalence point, at which point a rapid increase in pH is observed. After the equivalence point, a change is observed where the pH approaches that of the alkaline solution. Differences in the weak acidity of the target sample are observed as differences in pH around the half-equivalence point. Incidentally, this is explained by the Henderson equation, and at the half-equivalence point, log (C) A / CH A )(Here C A The value indicates the analytical concentration of the target substance that reacted with the alkaline solution, CH A The value indicates the analytical concentration of the target substance that did not react with the alkaline solution. ) becomes 0 and pH = pK a This is the relationship. Therefore, from the titration curve created, the amount at which neutralization is completed is identified, and the pH at the point when half of that amount is added (i.e., the center point of the buffer region, the ionization equilibrium state) is defined as pK. a The pH of the solution of the target substance when a predetermined amount of the alkaline solution is added dropwise can be determined as log (C). A / CH A By plotting the data against the given parameters and determining the linear regression line, the value of pKa can also be calculated as the intercept of that linear regression line.

[0035] For example, the Log P of urea at room temperature (20-25°C) ow The values ​​range from -1.54 to 2.96, and the pK at 21°C is [value missing]. a It is 0.10. Incidentally, the distribution coefficient (P ow The effect of temperature on ) is generally not very large; for example, per 1°C, Log P ow It is said to be a small value of about 0.001 to 0.01. On the other hand, pK a The effect of temperature on pH is based on the temperature change with respect to pH, and the value decreases slightly as the temperature rises, resulting in a pK value per unit temperature. aThe actual rate of change (ΔpKa / ℃) is known to generally show linearity. Therefore, the Log P of each of two or more monomer polyhydric hydroxy monomers ow and pK a The influence of temperature on the difference in either one or both of these factors is unlikely to be significant from the standpoint of the purpose, implementation, and effectiveness of the present invention. Each of the two or more polyhydric hydroxy monomers is a Log P ow and pK a It is sufficient if there is a difference in either one or both of the following: For example, two or more polyhydric hydroxymonomers are weakly acidic substances, and urea has pK a Larger pK a It is preferable that it has Furthermore, for example, it is preferable that each of the two or more polyvalent hydroxy monomers satisfies either or both of the following conditions 1 and 2. Condition 1: Log P between the polyhydric hydroxymonomer and other polyhydric hydroxymonomers ow The difference is 2 or more (preferably 5 or more). Condition 2: The pK between the polyhydric hydroxymonomer and other polyhydric hydroxymonomers a The difference is 2 or more (preferably 3 or more).

[0036] Log P of specific polyhydric hydroxy monomers ow and pK a The following is shown. Bisphenol A: Log P ow =3.84, pK a =10.29±0.10 1,4-Benzenedimethanol:Log P ow = -0.15, pK a = 14.2. Isosorbide: Log P ow = 1.31, pK a =13.17±0.40 Sorbitol: Log P ow = -2.20, pK a = 13.6.

[0037] Preferred embodiments of the carbonate resin (preferred combinations of two or more polyvalent hydroxy monomers) are shown below. However, the carbonate resin is not limited to these embodiments. Embodiment 1: Copolymer of bisphenol A and 1,4-benzenedimethanol. Embodiment 2: Copolymer of bisphenol A and isosorbide. Embodiment 3: Copolymer of bisphenol A and sorbitol. Embodiment 4: Copolymer of bisphenol A, 1,4-benzenedimethanol, and isosorbide. Embodiment 5: A copolymer of bisphenol A, 1,4-benzenedimethanol, and sorbitol. Embodiment 6: Copolymer of bisphenol A, isosorbide, and sorbitol. Embodiment 7: A copolymer of bisphenol A, 1,4-benzenedimethanol, isosorbide, and sorbitol.

[0038] The number-average molecular weight (Mn) of the carbonate resin is not particularly limited, but for example, it is between 2000 and 100000. The molecular weight dispersion (PDI) of the carbonate resin, which is the value obtained by dividing the weight-average molecular weight (Mw) by Mn, has no particular restrictions, but for example, it is between 1.5 and 5.0. The manganese (Mn) and manganese (Mw) values ​​of carbonate resins are measured by gel permeation chromatography (GPC) and are based on standard polystyrene equivalents.

[0039] (First step) In the first step, the carbonate resin is brought into contact with ammonia, causing the carbonate resin to depolymerize by ammonia monolysis. The method for contacting the carbonate resin with ammonia may be the same as known methods. For example, a method of contacting the carbonate resin with an aqueous ammonia solution may be used. The reaction temperature when contacting the carbonate resin with ammonia can be, for example, 10 to 100°C. Preferably, it can be, for example, 20 to 100°C, more preferably, for example, 40 to 100°C, and particularly preferably, for example, 60 to 95°C. If the reaction temperature is above the lower limit, the ammonia lysis reaction proceeds more easily, and the higher the temperature, the more the decarboxylation reaction is suppressed, improving the yield of urea. More specifically, for example, at 90°C, the yield of urea was 95%. The contact time (reaction time) between the carbonate resin and ammonia varies depending on the reaction temperature, but can range from 1 to 24 hours. Preferably, it can range from 4 to 12 hours. More specifically, for example, at 90°C, it can range from 4 to 8 hours. In this way, a reaction product containing decomposition products of the carbonate resin by ammonia monolysis is obtained. After the reaction, the reaction product may be dried if necessary to remove any remaining ammonia, water, etc.

[0040] The decomposition products include two or more polyhydric hydroxy monomers and urea. The molar ratio of two or more polyvalent hydroxy monomers in the decomposition product is basically the same as the molar ratio of the structures based on each of the two or more polyvalent hydroxy monomers in the carbonate resin when the carbonate resin is completely depolymerized by ammonialysis.

[0041] When two or more polyvalent hydroxymonomers include one or more polyvalent hydroxymonomers containing plant growth promoting activity, the molar ratio of one or more polyvalent hydroxymonomers containing plant growth promoting activity to urea in the decomposition product (polyvalent hydroxymonomers containing plant growth promoting activity: urea) can be, for example, 1:1 to 1:0.4. Preferably, it can be 1:0.9 to 1:0.5. More preferably, it can be 1:0.8 to 0.6. If the molar ratio is within the above range, a fertilizer composition containing these as active ingredients will exhibit excellent plant growth promotion.

[0042] (Second step) In the second step, the decomposition products generated in the first step can be separated from each of the two or more polyhydric hydroxy monomers and urea compounds by performing multiple liquid-liquid extractions using, for example, water and an organic solvent, and the urea can be recovered.

[0043] Liquid-liquid extraction separates the target compounds (two or more polyhydric hydroxymonomers and urea) using Log P ow or pK a It is done based on the differences. The following explanation will use the case where the decomposition products include urea, bisphenol A, 1,4-benzenedimethanol, isosorbide, and sorbitol as an example. First, Log P at room temperature (e.g., 20-25°C) ow Urea, isosorbide, and sorbitol, which have a ratio of less than 2 and are water-soluble, are extracted into the aqueous layer in the liquid-liquid extraction at room temperature. On the other hand, Log P at room temperature ow Bisphenol A, which has a Log Pow of 2 or more and is poorly soluble in water, is extracted into the organic layer during liquid-liquid extraction at room temperature. Therefore, the former and the latter can be separated by liquid-liquid extraction using water and an organic solvent. Under these temperature conditions, 1,4-benzenedimethanol, which has a Log Pow of less than 2 at room temperature and exhibits neutral solubility between water and organic solvents, can be extracted into either the aqueous or organic layer. Next, the pK of urea, isosorbide, sorbitol, and 1,4-benzenedimethanol in the aqueous layer is a There are differences between them. Therefore, they can be separated using the following procedure. When performing liquid-liquid extraction of an aqueous layer containing urea, isosorbide, sorbitol, and 1,4-benzenedimethanol using an organic solvent such as ethyl acetate or chloroform, the substances can be effectively and efficiently separated by changing the partition concentration ratio between water and the organic solvent during liquid-liquid extraction by adding an alkaline solution dropwise to the extraction system to change the pH value of the system to, for example, less than 13, 13.4, or 13.9. To recover substances of higher purity, this separation operation can be repeated multiple times. Next, the solubility and pK of bisphenol A and 1,4-benzenedimethanol in the organic layer in water at high temperatures (e.g., water above 50°C) a There are differences between them. Therefore, they can be separated using the following procedure. The organic layer containing bisphenol A and 1,4-benzenedimethanol can be effectively and efficiently separated by washing and extracting with, for example, an aqueous sodium bicarbonate solution (preferably the aqueous sodium bicarbonate solution at a high temperature) to which an alkaline solution has been added beforehand as needed. For other polyvalent hydroxy monomers as well, Log P ow or pK a Based on the differences, they can be separated in the same manner as described above.

[0044] In the second step, the two or more separated polyhydric hydroxy monomers may be recovered individually. The recovered polyvalent hydroxymonomers can be reused as raw materials for polymer materials that use polyvalent hydroxymonomers, such as carbonate resins and polyester resins. Furthermore, if two or more types of polyvalent hydroxymonomers include one or more polyvalent hydroxymonomers containing plant growth promoting activity, the polyvalent hydroxymonomers containing plant growth promoting activity can be reused not only as raw materials for polymer materials but also as fertilizer components.

[0045] [Recycling Method] In the recycling method of the present invention, all or part of the urea recovered in the second step of the above-described manufacturing method can be reused as a fertilizer component. In the recycling method of the present invention, in addition to urea, two or more polyhydric hydroxy monomers may be recovered from the decomposition products generated in the first step of the urea production method described above. When recovering the two or more polyvalent hydroxy monomers, all or part of the recovered polyvalent hydroxy monomers can be reused as fertilizer components and / or monomers for carbonate resin. If the two or more polyvalent hydroxy monomers include the one or more polyvalent hydroxy monomers containing plant growth promoting activity, all or part of the recovered urea and / or the one or more polyvalent hydroxy monomers containing plant growth promoting activity can be reused as fertilizer components. Furthermore, all or part of the two or more polyhydric hydroxy monomers other than those reused as fertilizer components can be reused as monomers for carbonate resin.

[0046] The method for producing a fertilizer composition in which recovered polyvalent hydroxy monomers containing plant growth-promoting activity are reused as fertilizer components, and the method for producing recycled carbonate resin in which recovered polyvalent hydroxy monomers are reused as monomers for carbonate resin, will be explained in detail later.

[0047] [Method for producing fertilizer composition] The fertilizer composition produced by the method for producing the fertilizer composition of the present invention contains urea as an active ingredient. The fertilizer composition may consist solely of urea. The fertilizer composition may further contain one or more polyvalent hydroxy monomers containing plant growth-promoting activity as active ingredients. The fertilizer composition may further contain other active ingredients (such as minerals), additives, water, etc., in addition to urea and polyvalent hydroxy monomers containing plant growth-promoting activity.

[0048] In a fertilizer composition, the molar ratio of one or more polyvalent hydroxy monomers containing plant growth-promoting activity to urea (polyvalent hydroxy monomers containing plant growth-promoting activity: urea) can be, for example, 1:1 to 1:0.4. Preferably, it can be 1:0.9 to 1:0.5. More preferably, it can be 1:0.8 to 0.6. If the molar ratio is within the above range, the fertilizer composition exhibits excellent plant growth promotion.

[0049] The method for producing the fertilizer composition of the present invention comprises the step of granulating or blending a powdered or liquid raw material containing a urea component with water, either alone or together with other components, wherein the urea component is urea produced by the above-described method for producing urea. Other components include, for example, all or part of the one or more polyhydric hydroxy monomers containing plant growth promoting activity obtained by recovering one or more of the two or more polyhydric hydroxy monomers containing plant growth promoting activity from the decomposition product generated in the first step of the above-described method for producing urea, or other active ingredients or auxiliary agents.

[0050] [Method for producing recycled carbonate resin] In the method for producing recycled carbonate resin of the present invention, two or more polyvalent hydroxy monomers are recovered from the decomposition products generated in the first step of the urea production method described above, and a recycled carbonate resin can be obtained by polymerizing one or more polyvalent hydroxy monomers containing all or part of the recovered two or more polyvalent hydroxy monomers as all or part of the raw material monomers.

[0051] The polyvalent hydroxy monomers polymerized may be one type or two or more types. From the standpoint of the excellent physical properties of recycled carbonate resin, it is preferable that at least a portion of the one or more polyvalent hydroxy monomers are petroleum-derived polyvalent hydroxy monomers. There are no particular restrictions on the polymerization method, and known methods such as transesterification and phosgene polymerization can be used.

[0052] The number-average molecular weight (Mn) of recycled carbonate resin is not particularly limited, but for example, it is between 2,000 and 100,000. There are no particular restrictions on the molecular weight dispersion (PDI) of recycled carbonate resin, but for example, it should be between 1.5 and 5.0.

[0053] The resulting recycled carbonate resin can be used in the same applications as known carbonate resins. Examples of applications for recycled carbonate resin are shown below, but are not limited to these. Home appliance parts (television parts, VTR parts, hair dryer housings, iron parts, microwave oven parts, various optical discs), electronic communications equipment (relay cases, LED lamps, computer structural parts), lighting fixtures (lighting covers, flashlights), headlamp lenses, door handles, meter covers, motorcycle windshields, louvers, camera bodies and their parts, copier or printer structural parts, FDD parts, personal computer parts, pump parts, power tool housings, toys, stroller parts, plumbing fixture parts, water bottles, combs, pencil sharpeners, ski goggles, kendo protective gear, windsurfing fins, pachinko parts, helmets, artificial kidney cases, eye drop containers, construction helmets, safety glasses, fire extinguisher parts, highway sound barriers, window glass, packaging film, capacitor film, optical film for FPD (flat panel display), etc. [Examples]

[0054] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0055] GPC and in this embodiment 1 The method for measuring 1H NMR is shown below. <gpc> The measurements were taken using a JASCO HSS-1500 system equipped with a refractive index (RI) detector under the following conditions. Column: GPC column Tetrahydrofuran (THF) containing lithium bromide (5 mM) was used as the eluent at a flow rate of 0.6 mL / min. For GPC system calibration, polystyrene standards (number-average molecular weight (Mn): 4,430~3,242,000 gmol) were used. -1 A polyvariance index (PDI): 1.03-1.08 was used. < 1 H NMR> (Equipment) A Bruker Topspin AVANCE III HD500 spectrometer was used for the measurements under the following conditions. Solvent: DMSO-d6 Internal standard: 1,3,5-trimethoxybenzene

[0056] (Synthesis Example 1) A copolycarbonate (poly(BPA carbonate-co-BDM carbonate)) (hereinafter also referred to as P(BPAC-co-BDMC)) was synthesized using bisphenol A (hereinafter also referred to as BPA) and 1,4-benzenedimethanol (hereinafter also referred to as BDM) as polyvalent hydroxy monomers according to the following scheme.

[0057] [ka]

[0058] The details of the synthesis method for P(BPAC-co-BDMC) are shown below. BPA (2.50 g, 11.0 mmol), BDM (1.51 g, 11.0 mmol), diphenyl carbonate (4.69 g, 21.9 mmol), and zinc acetate (1.00 mg, 5.45 μmol) were added to a 100 mL two-necked flask, and the gas phase inside the flask was replaced with nitrogen. The reaction system consisting of the mixture contained in the flask was then heated at 140 °C for 1 hour, and then at 200 °C for 30 minutes. Subsequently, the reaction temperature of the reaction system was raised to 220 °C, and the inside of the flask was reduced to a vacuum (ca. 13.5 mmHg). The reaction system was then heated for 30 minutes while removing the generated phenol. Furthermore, the reaction system was heated at 240 °C under high vacuum (<0.2 mmHg) for 1.5 hours. After the reaction was complete, the reaction product contained in the flask was cooled to room temperature. Then, chloroform was added to the flask to dissolve the reaction product. The resulting chloroform solution containing the reaction product was added to an excess of methanol, and the resulting solid was filtered off and dried to obtain P(BPAC-co-BDMC) as a white solid (4.27 g, yield 93.2%, Mn=11,600, PDI=3.39).

[0059] The obtained P(BPAC-co-BDMC) 1 The 1H NMR spectrum and GPC elution curve are shown in Figures 1 and 2, respectively. In Figure 1, all signals were consistently assigned. Furthermore, the copolymerization ratio calculated from the integral ratio of the NMR spectra was BPA skeleton:BDM skeleton = 52.5:47.5, which closely matched the theoretical value. Based on these results, the synthesis of the target P(BPAC-co-BDMC) was confirmed.

[0060] (Test Example 1) In this study, we performed ammonia-based decomposition (ammonolithesis) of P(BPAC-co-BDMC) obtained in Synthesis Example 1, liquid-liquid extraction of the decomposition products, and analysis of the extracted decomposition products. The scheme for the ammonolithesis reaction of P(BPAC-co-BDMC) is shown below.

[0061] [Chemical]

[0062] <Ammonolysis of P(BPAC-co-BDMC) and Liquid-Liquid Extraction of Degradation Products> After adding P(BPAC-co-BDMC) (250 mg) to a 50 mL eggplant flask, the gas phase inside the flask was replaced with nitrogen. Then, water (7.40 mL) and aqueous ammonia (2.50 mL, 14.8 M) were added to the flask, and the reaction system consisting of the mixture contained in the flask was heated at 90 °C for 1 week. After completion of the reaction, water and ammonia were removed from the mixture contained in the flask by freeze-drying to obtain a white powder. The obtained white powder was mixed with 20 mL of ethyl acetate, 5 mL of hexane, and 20 mL of water. After allowing the obtained mixture to stand, the resulting organic layer was recovered. On the other hand, to the remaining aqueous layer, a mixed solution of 20 mL of ethyl acetate and 5 mL of hexane was added, and then, by the same operation as described above, the resulting organic layer was recovered. Further, the operation was repeated again. For each of the organic layers obtained by these three liquid-liquid extractions, the degradation products were recovered by distilling off the solvent under reduced pressure. On the other hand, for the aqueous layer after three liquid-liquid extractions, the degradation products were recovered by removing water by freeze-drying.

[0063] <Analysis of Degradation Products> 1. Analysis of Degradation Products in the Organic Layer DMSO-d6 (2.00 mL) was added to the degradation products recovered from the organic layer to completely dissolve the degradation products. Here, 1, \alpha, 5-trimethoxybenzene (15.0 mg) was added as an internal standard, and 1 mL of the solution was used for 1 analysis by 1H NMR.

[0064] 2. Analysis of Degradation Products in the Aqueous Layer DMSO-d6 (4.00 mL) was added to the decomposition products recovered from the aqueous layer to completely dissolve the decomposition products. Here, 1,3,5-trimethoxybenzene (30.0 mg) was added as an internal standard, and 1 mL of the solution was used for 1 analysis by 1H NMR.

[0065] <Results and Discussion> The 1H NMR spectra of the decomposition products in each of the aqueous and organic layers are shown in Figure 3, and a partially enlarged 1H NMR spectrum of the decomposition products in the organic layer is shown in Figure 4. The yields of each decomposition product calculated from the integral ratio of the spectra are shown in Table 1.

[0066]

Table 1

[0067] Focusing on the NMR spectrum of the decomposition products in the aqueous layer, it was confirmed that a large amount of urea was recovered without containing BPA. However, in addition to urea, a small amount of BDM residue was confirmed, and the isolation of urea with a purity of 100% was not achieved. This is presumably because the hydrophilicity of BDM is relatively high and not all of the BDM was efficiently extracted into the organic layer. In addition, since the pK of urea and BDM is different, they can be separated by changing the pH of water in liquid-liquid extraction. For example, by adding hydrochloric acid, acetic acid, sodium hydroxide, etc. to water to adjust the pH to a value within the range of the difference in pK, having a difference of 2 or more (preferably, a value corresponding to around the median of the pK difference range), urea and BDM can be effectively separated. Also, by performing liquid-liquid extraction at a lower temperature, the hydrophilicity of BDM can be reduced, and urea and BDM can be efficiently separated.

[0068] ​​​​​​​​​​​​Focusing on the NMR spectrum of the organic layer, only BPA and BDM, which are polyhydroxy monomers, remained in the organic layer, and urea was not contained. From this result, it was confirmed that urea could be completely removed from the mixture of polyhydroxy monomers by liquid-liquid extraction. Furthermore, the total yield of BPA in three liquid-liquid extractions calculated from the integration ratio of the NMR spectrum was 91.5%, which was a high yield. On the other hand, the total yield of BDM including that contained in the aqueous layer was 68.0%. Therefore, focusing on the NMR spectrum again, as shown in Fig. 4, many signals of unknown attribution were observed near the signal of BDM. Considering that BPA was obtained in a high yield, it is highly likely that these signals of unknown attribution are derived from BDM, and it is considered that the yield of BDM decreased apparently due to their appearance.

[0069] Incidentally, as a factor for the decrease in the yield of urea in the above test, it is considered that the decarboxylation reaction proceeded due to the coexistence of BDM having an alcoholic hydroxyl group (see the following scheme).

[0070]

Chemical formula

[0071] (Test Example 2) This test example was carried out for the purpose of evaluating the influence of the organic solvent used in liquid-liquid extraction on the yield.

[0072] <Liquid-liquid extraction of ammonolysis and decomposition products of P(BPAC-co-BDMC)> After adding P(BPAC-co-BDMC) (250 mg) to a 50 mL eggplant flask, the gas phase inside the flask was replaced with nitrogen. Then, after adding water (7.40 mL) and aqueous ammonia (2.50 mL, 14.8 M) into the flask, the reaction system consisting of the mixture contained in the flask was heated at 90 °C for 1 week. After the reaction was completed, water and ammonia were removed from the mixture contained in the flask by freeze-drying to obtain a white powder. The obtained white powder was mixed with 20 mL of chloroform, 5 mL of acetone, and 20 mL of water. After allowing the resulting mixture to stand, the formed organic layer was recovered. On the other hand, 20 mL of chloroform was added to the remaining aqueous layer, and then, by the same operation as described above, the formed organic layer was recovered. Further, this operation was repeated again. For each of the organic layers obtained by these three liquid-liquid extractions, the decomposition products were recovered by distilling off the solvent under reduced pressure. On the other hand, for the aqueous layer after the three liquid-liquid extractions, the decomposition products were recovered by removing water by freeze drying.

[0073] <Analysis of decomposition products> 1. Analysis of decomposition products in the organic layer DMSO-d6 (2.00 mL) was added to the decomposition products recovered from the organic layer to completely dissolve the decomposition products. Here, 1,3,5-trimethoxybenzene (15.0 mg) was added as an internal standard, and 1 mL of the solution was used for 1 analysis by 1H NMR.

[0074] 2. Analysis of decomposition products in the aqueous layer DMSO-d6 (4.00 mL) was added to the decomposition products recovered from the aqueous layer to completely dissolve the decomposition products. Here, 1,3,5-trimethoxybenzene (30.0 mg) was added as an internal standard, and 1 mL of the solution was used for 1 analysis by 1H NMR.

[0075] <Results and discussion> The 1H NMR spectra of the decomposition products in each of the aqueous layer and the organic layer 1 are shown in Fig. 5, and the yields of each decomposition product calculated from the integral ratio of the spectra are shown in Table 2. When compared with the results of Test Example 1, the yields of BPA and urea were higher in Test Example 2. As the reason for this, the existence of differences in the solubility of the formed decomposition products in the organic solvents was considered, and it was confirmed that liquid-liquid extraction using chloroform rather than ethyl acetate could more efficiently recover each of the formed decomposition products.

[0076] [Table 2]

[0077] (Reference example) The following four types of samples were prepared. Sample 1: A 250 mL mixture of 2.5 mL of an aqueous solution of urea dissolved in water to a concentration of 300 mM and 247.5 mL of an aqueous solution of other nutrients (minerals). The aqueous solution of urea was prepared by dissolving a reaction product containing decomposition products from the ammonialysis of carbonate resin in water. Sample 2: A 250 mL mixture of 2.5 mL of an aqueous solution prepared by dissolving urea and isosorbide in a 1:1 molar ratio in water to a total concentration of 300 mM, and 247.5 mL of an aqueous solution of other nutrients (minerals). The aqueous solutions of urea and isosorbide were prepared by dissolving commercially available urea and isosorbide in water. Sample 3: A 250 mL mixture of 2.5 mL of an aqueous solution prepared by dissolving urea and isosorbide in water in a molar ratio of 0.7:1 to a total of 300 mM, and 247.5 mL of an aqueous solution of other nutrients (minerals). The aqueous solution of urea and isosorbide was prepared by dissolving a reaction product containing decomposition products from the ammoniaxation of carbonate resin in water. • Control sample: 250 mL of aqueous solution of other nutrients (minerals). Furthermore, the concentrations of each nutrient, excluding the nitrogen source, were the same as those described in the literature by Fujiwara et al. (T. Fujiwara, MY Hirai, M. Chino, Y. Komeda and S. Naito, Plant Physiol., 1992, 99, 263-268.). Using these samples, Arabidopsis thaliana was cultivated according to the following procedure. Seeds of the Arabidopsis thaliana ecotype Col-0 were disinfected with bleach and then sown in a culture medium solidified with 1% gellan gum and 1% by mass of sucrose. Next, the seeds were incubated at 4°C for 2 days after sowing. Then, the plates on which the seeds were fixed were placed vertically, and the plants were grown using each of the above-mentioned samples under light conditions of 16 hours of light / 8 hours of darkness at 22°C for 2 weeks. As a control, Arabidopsis thaliana was cultivated in the same manner as above, except that 250 mL of aqueous solutions of other nutrients (minerals) were used instead of samples 1-3.

[0078] As a result, the growth of Arabidopsis thaliana was significantly more pronounced when using samples 1-3, which contain urea, compared to when using a control sample that does not contain either urea or isosorbide, confirming that samples 1-3 have a growth-promoting effect. In particular, as is clear from Figure 6, samples 2 and 3, which contain isosorbide along with urea, showed good root development, and sample 3 also showed good root elongation, indicating that samples 2 and 3 have an excellent growth-promoting effect.< / gpc>

Claims

1. A first step involves contacting the carbonate resin with ammonia to depolymerize the carbonate resin by ammonia monolysis, A second step involves performing liquid-liquid extraction using water and an organic solvent on the decomposition products generated in the first step, Includes, The carbonate resin is a copolymer in which a structure based on two or more polyvalent hydroxy monomers, including one or more petroleum-derived polyvalent hydroxy monomers, is linked via carbonate bonds. The aforementioned one or more petroleum-derived polyhydric hydroxy monomers are monomers selected from the group consisting of compounds represented by the following formula (1): The n-octanol / water partition coefficient (Log P) of each of the two or more polyhydric hydroxymonomers and urea compounds that become the decomposition products. ｏｗ ) and acid dissociation constant (pK ａ If there is a difference in either one or both of the following, In the first step described above, the carbonate resin is brought into contact with ammonia in a solid state, and the temperature at which the carbonate resin and ammonia are brought into contact is 40 to 100°C. A method for producing a petroleum-derived polyhydric monomer-containing phase, characterized in that, in the second step, the liquid-liquid extraction is performed multiple times based on the difference to separate at least one of the one or more petroleum-derived polyhydric monomers from urea, thereby obtaining a petroleum-derived polyhydric monomer-containing phase that contains at least one of the one or more petroleum-derived polyhydric monomers and does not contain urea. 【Chemistry 1】 (In the formula, A1 and A2 each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, or a single bond; A3 represents a linear or branched alkylene group having 1 to 8 carbon atoms, which may be substituted with a phenyl group and may have phenylene groups interposed between carbon atoms; a divalent cyclic hydrocarbon group; -O-, -S-, -CO-, -SO-, -SO2-, or a single bond; X1 and X2 each independently represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms; a represents 0 or 1; and b and c each independently represent an integer from 0 to 4.)

2. A first step involves contacting the carbonate resin with ammonia to depolymerize the carbonate resin by ammonia monolysis, A second step involves performing liquid-liquid extraction using water and an organic solvent on the decomposition products generated in the first step, Includes, The carbonate resin is a copolymer in which a structure based on two or more polyvalent hydroxy monomers, including one or more petroleum-derived polyvalent hydroxy monomers, is linked via carbonate bonds. The aforementioned one or more petroleum-derived polyhydric hydroxy monomers are monomers selected from the group consisting of compounds represented by the following formula (1): The n-octanol / water partition coefficient (Log P) of each of the two or more polyhydric hydroxymonomers and urea compounds that become the decomposition products. ｏｗ ) and acid dissociation constant (pK ａ If there is a difference in either one or both of the following, In the first step described above, the carbonate resin is brought into contact with ammonia in a solid state, and the temperature at which the carbonate resin and ammonia are brought into contact is 40 to 100°C. A method for producing a urea-containing phase, characterized in that, in the second step, the liquid-liquid extraction is performed multiple times based on the difference to separate at least one of the one or more petroleum-derived polyhydric hydroxy monomers from urea, thereby obtaining a urea-containing phase that contains urea and does not contain at least one of the one or more petroleum-derived polyhydric hydroxy monomers. 【Chemistry 2】 (In the formula, A1 and A2 each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, or a single bond; A3 represents a linear or branched alkylene group having 1 to 8 carbon atoms, which may be substituted with a phenyl group and may have phenylene groups interposed between carbon atoms; a divalent cyclic hydrocarbon group; -O-, -S-, -CO-, -SO-, -SO2-, or a single bond; X1 and X2 each independently represent a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms; a represents 0 or 1; and b and c each independently represent an integer from 0 to 4.)

3. The two or more polyvalent hydroxy monomers are weakly acidic substances, The acid dissociation constant (pK) of the two or more polyvalent hydroxy monomers ａ ) is the acid dissociation constant (pK) of urea. ａ The manufacturing method according to claim 1 or 2, wherein the value is greater than )

4. The production method according to claim 1 or 2, wherein the one or more petroleum-derived polyhydric hydroxy monomers are monomers selected from the group consisting of bisphenol A and 1,4-benzenedimethanol.

5. The manufacturing method according to claim 1 or 2, wherein in the first step, the gas phase is replaced with nitrogen and then the carbonate resin is depolymerized.

6. The manufacturing method according to claim 1 or 2, wherein the second step includes a step of performing liquid-liquid extraction based on the difference in the n-octanol / water partition coefficient (Log P ow) and a step of performing liquid-liquid extraction based on the difference in the acid dissociation constant (pKa).

7. The method for producing liquid according to claim 1 or 2, wherein the organic solvent used for liquid-liquid extraction comprises ethyl acetate.

8. The manufacturing method according to claim 1 or 2, wherein the organic solvent used in the liquid-liquid extraction comprises chloroform.

9. The manufacturing method according to claim 1 or 2, wherein the temperature at which the carbonate resin and ammonia are brought into contact is 60 to 95°C.

10. The manufacturing method according to claim 1 or 2, wherein the number of times the liquid-liquid extraction is performed is three.

11. A method for producing a recycled carbonate resin, characterized by recovering two or more polyvalent hydroxy monomers from the decomposition products generated in the first step of the production method according to claim 1 or 2, and polymerizing one or more polyvalent hydroxy monomers containing all or part of the recovered two or more polyvalent hydroxy monomers as all or part of the raw material monomers to obtain a recycled carbonate resin.

12. A recycling method characterized by comprising the steps of recovering two or more polyvalent hydroxy monomers from the decomposition products generated in the first step of the manufacturing method according to claim 1 or 2, and reusing all or part of the recovered two or more polyvalent hydroxy monomers as monomers for a carbonate resin.

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