Novel isosorbide derivative useful as plasticizer for resin

Abstract

To provide a bio-based plasticizer that exhibits good compatibility with various resins and is useful in improving moldability and other properties of the resins, as well as a resin composition containing the plasticizer.SOLUTION: An isosorbide derivative, which is a compound in which a substructure represented by -C(=O)-O-(CH2CH2O)nH (n is an integer of 1 to 10) is bonded to each of two oxygen atoms derived from hydroxyl groups on the isosorbide condensed ring, or an oligomer or polymer having the following repeating unit (where m is an integer of 1 to 10 and x is an integer of 2 to 100).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound that is a sugar-derived hetero-condensed aliphatic cyclic polyhydric alcohol derivative and is useful as a resin plasticizer, which is made from the sugar-derived hetero-condensed aliphatic cyclic polyhydric alcohol as a raw material, and to a resin composition obtained by blending the compound with various resins. [Background technology]

[0002] Polymer materials (plastics) have become indispensable in everyday life, but most of them are discarded, with the recycling rate of materials remaining at less than 15%. While measures to address environmental issues are urgently needed in relation to the Sustainable Development Goals (SDGs), the demand for plastics remains high, and there is a need to develop a new recycling system that balances the use of plastics with the conservation of the global environment.

[0003] Plastic recycling processes are mainly divided into material recycling and chemical recycling, with the former accounting for the majority of modern recycling. Material recycling is a method of collecting, processing, and reusing used plastics, but the issue is that quality can deteriorate due to the introduction of foreign matter during the processing process and a decrease in molecular weight. In contrast, chemical recycling is a method of returning plastics to their original raw materials through depolymerization and reusing them, which has the advantage of avoiding quality deterioration.

[0004] Polycarbonate is a general-purpose polymeric material with excellent physical properties such as heat resistance, mechanical properties, and melting characteristics, but in the context of the trend toward addressing environmental issues such as those mentioned above, polycarbonate produced using isosorbide, a sugar-derived dihydroxy compound, has attracted attention (Patent Documents 1 to 5). The present inventors have proposed a recycling system in which polycarbonate (polyisosorbide carbonate), synthesized from sugar-derived raw materials, is decomposed with ammonia to directly convert the polycarbonate into fertilizer (Non-Patent Documents 1 and 2).

[0005] Polyisosorbide carbonate is a suitable polymer for demonstrating the concept of directly converting plastics into fertilizer, but the polymer obtained using conventional manufacturing methods is brittle. Although attempts have been made to tune the physical properties by making it into a copolymer with different monomers, there have been few reports of using plasticizers to improve the processability of polymers, and there have been challenges in widely using it as a functional material in its original form.

[0006] In general, there are various methods for improving the physical properties of polymeric materials, such as flexibility, processability, and ductility, including copolymerization with flexible polymer monomers of different types and cross-linking with cross-linking agents. Among these, plasticization using plasticizers is known to be the most economical and simple technique. For example, in the case of polyvinyl chloride, a typical example of a general-purpose resin, phthalate-based plasticizers such as diethyl phthalate (DEP), dioctyl phthalate (DOP), and bis(2-ethylhexyl) phthalate (DEHP) are often used.

[0007] By adjusting the proportion of plasticizer added to the polyvinyl chloride matrix, the properties of the resin composition can be changed from a hard material when a small proportion of plasticizer is added to a soft material when resin and plasticizer are added in approximately equal amounts. Thus, even if the matrix polymer is the same, the material properties of the resulting resin composition can be significantly changed depending on the amount of plasticizer added, which is a major feature of the modification method using plasticizer addition.

[0008] There are many types of plasticizers available on the market, but the most widely used plasticizers are the phthalate-based plasticizers mentioned above. The use of these plasticizers can achieve a good balance of various physical properties, such as compatibility, durability, cost efficiency, and processability (Patent Document 6). On the other hand, in recent years, due to environmental and health concerns, the use of some phthalate esters has been restricted, and attention has been focused on the development of low-toxicity alternative plasticizers that can replace phthalate compounds (Patent Document 7).

[0009] As such alternative plasticizers, it has been proposed to use those synthesized from green bio-based renewable resources, such as vegetable oils, glycerol esters, fatty acids, citrate esters, cardanol, lactic acid, isosorbide (ISB), waste cooking oil, low-molecular-weight polyesters derived from diols and dicarboxylic acids, all of which are bio-based, and tung oil. In particular, ISB is a bis-heterocyclic diol with a chiral and rigid molecular structure, and is characterized by its excellent thermal stability, biodegradability, and biocompatibility, making it a promising raw material for bio-based plasticizers (Patent Document 8).

[0010] Against this background, the present inventors proposed a new ISB-based plasticizer (ISB-TEG) ​​that exhibits a significant plasticizing effect on polyisosorbide (PIC), a polycarbonate synthesized using ISB as a monomer (Non-Patent Document 3). This plasticizer is expected to exhibit good compatibility with polyisosorbide carbonate resins due to the similarity in their chemical structures, and further expanding the range of matrix polymers for which the plasticizer's effects are effective will pave the way for further promotion of the use of bio-based plasticizers. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-146019 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-046519 [Patent Document 3] Patent No. 4351675 [Patent Document 4] Patent No. 5708087 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-292603 [Patent Document 6] Patent No. 7235112 [Patent Document 7] Special Publication No. 2017-537185 [Patent Document 8] Special Publication No. 2002-513816 [Non-patent literature]

[0012] [Non-Patent Document 1] "Development of a recycling system that converts plastic into fertilizer", [online], published October 28, 2021, Tokyo Institute of Technology and Japan Science and Technology Agency, Internet<URL:https: / / www.jst.go.jp / pr / announce / 20211028 / pdf / 20211028.pdf> [Non-patent document 2] Aoki et al., Green Chem., 2021, 23, 9030-9037 [Non-patent document 3] "Modification of the physical properties of sugar-derived polycarbonate by additives and construction of its recycling system," 104th Annual Meeting of the Chemical Society of Japan, D342-2am-11, March 19, 2024, published online<URL:https: / / pub-files.atlas.jp / fs / public / csj104th / ver_43 / abstract / ja / D342-2am-11.pdf> Summary of the Invention [Problem to be solved by the invention]

[0013] Under these circumstances, the inventors have focused on polyisosorbide carbonate, which can be produced from biomass resources, among polycarbonates, which are considered to be representative recyclable polymer materials, and have investigated the improvement of its physical properties and functions by blending a plasticizer. As a result, it was found that by blending a compound having a structure similar to isosorbide as a plasticizer with a polyisosorbide carbonate resin, the compatibility between the polyisosorbide carbonate and the plasticizer is improved, thereby improving functionality. Next, the present inventors discovered that even when a compound having a structure similar to that of isosorbide is blended with cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP), which are naturally occurring cellulose derivatives, or with polyvinyl chloride (PVC), a typical example of a general-purpose resin, compatibility is improved and a plasticizing effect is exerted by adjusting the blending ratio, leading to the present invention. That is, the present invention provides a plasticizer for resins, which is a sugar-derived hetero-condensed aliphatic cyclic polyhydric alcohol derivative and contains an isosorbide derivative made from the sugar-derived hetero-condensed aliphatic cyclic polyhydric alcohol as a raw material; and a resin composition obtained by blending the plasticizer with polyisosorbide carbonate, a resin made from a naturally-occurring compound, a general-purpose resin, or the like. [Means for solving the problem]

[0014] The present invention has the following aspects. [1] An isosorbide derivative, wherein the oxygen atoms derived from the two hydroxyl groups on the isosorbide condensed ring are: -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) A compound formed by bonding together [2] The compound according to [1] above, having the following structure, in which n in the partial structure is 3: [ka] [3] An oligomer or polymer having the following repeating unit: [ka] (where m is an integer from 1 to 10, and x is an integer from 2 to 100) [4] A plasticizer for resins, comprising the compound according to [1] or [2] above, or the oligomer or polymer according to [3] above. [5] The plasticizer for resins according to [4], wherein the resin is a polyisosorbide carbonate containing polyisosorbide carbonate as a main component. [6] The plasticizer for resin according to [4] above, wherein the resin is a cellulose ester. [7] The plasticizer for resin according to [4], wherein the resin is polyvinyl chloride. [8] A resin composition, comprising: -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) or an oligomer or polymer having the following repeating units: [ka] (where m is an integer from 1 to 10, and x is an integer from 2 to 100) The resin composition contains 0.2 to 40 mass % of the above. [9] The resin composition according to [8], which contains a compound having the following structure, in which n in the partial structure is 3: [ka]

[10] The resin composition according to [8] or [9], wherein the resin is a polyisosorbide carbonate having polyisosorbide carbonate as a main component.

[11] The resin composition according to [8] or [9], wherein the resin is a cellulose ester.

[12] The resin composition according to [8] or [9], wherein the resin is polyvinyl chloride.

[13] A resin composition, comprising: -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) or an oligomer or polymer having the following repeating units: [ka] (where m is an integer from 1 to 10, and x is an integer from 2 to 100) The resin composition contains 0.2 to 40 mass % of the above-mentioned compound, and the resin composition is decomposed with ammonia to produce a fertilizer composition.

[14] A method for producing the fertilizer composition according to

[13] above, which uses a resin composition containing a compound having the following structure, in which n in the partial structure is 3: [ka]

[15] The method for producing a fertilizer composition according to

[13] or

[14] above, wherein the resin is a polyisosorbide carbonate containing polyisosorbide carbonate as a main component.

[16] The method for producing a fertilizer composition according to

[13] or

[14] above, wherein the resin is a cellulose ester.

[17] A method for producing a fertilizer composition according to

[13] or

[14] , wherein the resin is polyvinyl chloride. [Effects of the Invention]

[0015] According to the present invention, by blending a bio-based plasticizer derived from isosorbide with various matrix resins and adjusting the blending ratio, it is possible to tune the physical properties of the matrix resin according to its intended use, as well as improve its functionality, such as heat resistance. When the plasticizer of the present invention is blended with polyisosorbide carbonate, particularly good compatibility is exhibited due to the similarity in chemical structure between the matrix resin and the plasticizer. Furthermore, the resin composition containing the plasticizer of the present invention produces urea when treated with ammonia, and is therefore expected to be useful as a fertilizer. In particular, when the matrix resin is polyisosorbide carbonate, it can be used as a fertilizer in its original form by treating it with ammonia, just like a polyisosorbide carbonate resin containing no plasticizer, which can lead to the development of biomass utilization and chemical recycling. [Brief explanation of the drawings]

[0016] [Figure 1]FIG. 1 is a diagram showing the 1H NMR spectrum of ISB-CDI obtained as an intermediate in Example 1. [Figure 2] FIG. 1 shows the 1H NMR spectrum of ISB-TEG obtained as the final product in Example 1. [Figure 3] FIG. 1 is a diagram showing the film-forming properties of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2 when the composition was made into a film by varying the mixing ratio. [Figure 4] FIG. 1 is a graph showing the predicted compatibility of a polyisosorbide carbonate composition (PIC / ISB-TEG) ​​using Hansen solubility parameters. [Figure 5] FIG. 2 is a graph showing the relationship between the mixing ratio and the glass transition temperature of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2. [Figure 6] FIG. 1 is a graph showing the relationship between the mixing ratio of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2 and the results of a tensile test (stress, strain). [Figure 7] FIG. 10 shows the 1H NMR spectrum of the product obtained by decomposing a blend of PIC alone with 30% ISB-TEG as a plasticizer using ammonia in Example 5. [Figure 8] FIG. 10 is a graph showing the effect on the growth of Arabidopsis thaliana when the decomposition products obtained in Example 5 are used to cultivate the plants. [Figure 9] FIG. 1 is a graph showing the relationship between the mixing ratio and the glass transition temperature of the polyisosorbide carbonate resin compositions (PIC / ISB-DEG 1400, 1800, 2700) obtained in Example 7. [Figure 10] FIG. 1 is a graph showing the relationship between the mixing ratio of the polyisosorbide carbonate resin composition (PIC / ISB-DEG1400, 1800, 2700) obtained in Example 7 and the results of a tensile test (stress, strain). [Figure 11]FIG. 1 shows the film-forming properties of the cellulose acetate butyrate resin (CAB) and the resin composition (CAB / ISB-TEG) ​​obtained in Example 9, the latter of which was observed when the mixture ratio was changed to form a film. [Figure 12] FIG. 1 shows the film-forming properties of the cellulose acetate propionate resin (CAP) and the resin composition (CAP / ISB-TEG) ​​obtained in Example 9, the latter of which was observed when the mixture ratio was changed to form a film. [Figure 13] FIG. 1 is a diagram showing the state of bleed-out over time observed for the cellulose acetate butyrate ester resin composition (CAB / ISB-TEG) ​​obtained in Example 9. [Figure 14] FIG. 1 is a view showing the state of bleed-out over time observed for the cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9. [Figure 15] FIG. 1 is a schematic diagram showing the association relationship between polyisosorbide carbonate (PIC) or cellulose ester resin (CAB or CAP) and plasticizer (ISB-TEG) ​​in a resin composition. [Figure 16] FIG. 1 is a graph showing the glass transition temperature of the cellulose acetate butyrate resin composition (CAB / ISB-TEG; mixing ratio 9:1) obtained in Example 9. [Figure 17] FIG. 1 is a graph showing the relationship between the mixing ratio of the cellulose acetate butyrate resin composition (CAB / ISB-TEG) ​​obtained in Example 9 and the results of a tensile test (stress, strain). [Figure 18] FIG. 1 is a graph showing the glass transition temperature and melting point of the cellulose acetate propionate resin composition (CAP / ISB-TEG; mixing ratio 9:1) obtained in Example 9. [Figure 19] FIG. 1 is a graph showing the relationship between the mixing ratio of the cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 and the results of a tensile test (stress, strain). [Figure 20]FIG. 1 is a diagram showing the film-forming properties of the polyvinyl chloride resin (PVC) obtained in Example 11 and the resin composition (PVC / ISB-TEG; mixing ratio 9:1). [Figure 21] The polyvinyl chloride resin (PVC) and the resin composition (PVC / ISB-TEG) ​​obtained in Example 11 <1> , DEP <2> or PEHP <3> 1: a mixture ratio of 9:1). DETAILED DESCRIPTION OF THE INVENTION

[0017] [An isosorbide derivative, wherein the oxygen atoms derived from two hydroxyl groups on the isosorbide condensed ring are -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) a compound in which each of the following is bonded to each other] The compound useful as a plasticizer for resin of the present invention is an isosorbide derivative, and has the following structure attached to the oxygen atoms derived from two hydroxyl groups on the isosorbide condensed ring: -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) have a structure in which each of these is bonded.

[0018] "An isosorbide derivative, in which the oxygen atoms derived from the two hydroxyl groups on the isosorbide condensed ring are -C(=O)-O-(CH2CH2O) n A partial structure represented by H (n is an integer from 1 to 10) As the "compound in which each of the following is bonded," those in which n in the partial structure is 2 to 4 are preferred, and among these, the following compound (ISB-TEG) ​​in which n is 3 is particularly preferred. [ka]

[0019] The compound was prepared based on the method by D. Hult et al. (D. Hult, S. Garcia-Gallego, T. Ingverud, OCJ Andren, M. Malkoch, Degradable high Tg sugar-derived polycarbonates from isosorbide and dihydroxyacetone. Polymer Chemistry 9, 2238-2246 (2018)). It can be obtained by following the two-step process below. [ka]

[0020] The first step of the above process involves reacting isosorbide (ISB) with carbonyldiimidazole (CDI) in the presence of a solvent. Examples of the solvent include acetone, chloroform, THF, and ethyl acetate, with acetone being particularly preferred. ISB-CDI is obtained by reacting at a temperature of 0 to 40°C, preferably 10 to 30°C, for 1 to 12 hours, preferably 2 to 6 hours.

[0021] The second step of the above process involves reacting ISB-CDI with triethylene glycol (TEG) in the presence of a solvent. Examples of the solvent include acetone, chloroform, THF, and ethyl acetate, with chloroform being particularly preferred. ISB-TEG can be obtained by reacting at a temperature of 10 to 60°C, preferably 40 to 50°C, for 4 to 24 hours, preferably 10 to 18 hours.

[0022] ISB-TEG can also be derived into oligomers or polymers in which m=3 among the following repeating units, and these oligomers or polymers are also expected to exhibit high compatibility with polyisosorbide carbonate, and therefore can be used as plasticizers for polyisosorbide carbonate resins. [ka] (where m is an integer from 1 to 10, and x is an integer from 2 to 100) In the above formula, m is preferably an integer of 2 to 4. In addition, x in the above formula is preferably an integer of 2-10.

[0023] An oligomer or polymer having the above structure can be synthesized by reacting ISB-CDI with, for example, diethylene glycol (DEG) or triethylene glycol (TEG) in the presence of a solvent. Examples of the solvent include acetone, chloroform, THF, and ethyl acetate, with chloroform being particularly preferred. The reaction can be carried out at a temperature of 10 to 60°C, preferably 40 to 50°C, for 4 to 48 hours, preferably 24 hours, to form an oligomer or polymer. After the reaction is complete, the product is reprecipitated using hexane / ethanol (v / v=9 / 1) as a poor solvent, and purified by decantation. The solvent is then distilled off under reduced pressure to obtain an oligomer or polymer-type compound as a colorless oily liquid. The molecular weight (Mn) range that can be used as a plasticizer is 100 to 5,000, and the preferred molecular weight (Mn) range is 500 to 3,000.

[0024] [Plasticizer for resin and resin composition] The resin composition of the present invention can be obtained by incorporating the compound useful as the plasticizer of the present invention described above into various matrix resins.

[0025] Examples of the matrix resin include polyisosorbide carbonate having a structure similar to that of the plasticizer of the present invention in its molecule, or other polycarbonates containing units derived from isosorbide, as well as cellulose esters and polyvinyl chloride (PVC).

[0026] Polyisosorbide carbonate can be obtained by polycondensing isosorbide and a carbonic acid diester as monomers using a known transesterification reaction. Examples of the other polycarbonates include those obtained by polycondensation reaction of the above-mentioned monomers for polyisosorbide carbonate with any diol compound as a comonomer.

[0027] Cellulose ester is a reaction product of cellulose and organic carboxylic acid, and examples of the organic carboxylic acid include acetic acid, butyric acid, and propionic acid. Preferably, it is a mixture of acetic acid and butyric acid (product CAB) or a mixture of acetic acid and propionic acid (product CAP). Various commercially available products can be used.

[0028] Polyvinyl chloride (PVC), a general-purpose resin, is readily available as a commercially available product.

[0029] The compounding ratio of the compound useful as a plasticizer of the present invention varies depending on the similarity of the structure to the matrix polymer, etc., but can be in the range of 0.2 to 40 mass% relative to the entire resin composition. When the resin is polyisosorbide carbonate, the content is preferably 10 to 40 mass%, more preferably 20 to 30 mass%. When the resin is a cellulose ester or polyvinyl chloride, it is preferable to contain a compound useful as a plasticizer in an amount of 10 to 20% by mass based on the entire resin composition.

[0030] The resin composition of the present invention may contain other additives such as a heat stabilizer, an antioxidant, a lubricant, a light stabilizer, etc., to the extent that the effects of the present invention are not impaired.

[0031] The use of the resin composition of the present invention is not particularly limited, and it can be used in a wide variety of fields including optical materials, packaging materials, various machine parts, and building materials. Further, the resin composition of the present invention generates urea as a decomposition product by being treated with ammonia. In particular, when the matrix resin is polyisosorbide carbonate, it can be sprayed directly onto the soil without separating the decomposition products and used as a fertilizer.

[0032] The method of treating the resin composition with ammonia may be the same as known methods. For example, a method of contacting the resin composition with an aqueous ammonia solution can be mentioned. There is no particular limitation on the concentration of ammonia, but 5 to 15% is preferable, and particularly, 10 to 15% is preferable. The treatment temperature can be, for example, 10 to 100°C. Preferably, it is 60 to 100°C, and particularly preferably, 80 to 100°C. The treatment time varies depending on the treatment temperature, but can be, for example, 1 to 24 hours. Preferably, it is 12 to 24 hours.

[0033] Hereinafter, the present invention will be described more specifically based on examples. However, the following examples are provided only for illustrative purposes and not for the purpose of limiting the present invention. The scope of the present invention is limited only by the claims.

Examples

[0034] Example 1: Synthesis of a novel plasticizer for resins <Synthesis of ISB-CDI> Into a 50 ml round-bottom flask, 1.00 g (6.84 mmol) of isosorbide (ISB), 20 ml of acetone, and 2.78 g (17.1 mmol) of carbonyldiimidazole (CDI) were added, and the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. After the reaction was completed, the precipitated solid was removed by washing with diethyl ether and filtering, and the solvent was distilled off under reduced pressure to obtain a white powder (2.06 g, 90.0%).

[0035] of the product 11H NMR spectrum measurement was performed (Figure 1). In the spectrum of the product, both the peak derived from CDI and the peak derived from ISB were confirmed. Although the change in the peak derived from CDI was slight, it was confirmed that the peak derived from ISB was shifted to the low magnetic field side. From the above, it is suggested that ISB-CDI was successfully synthesized.

[0036] <Synthesis of ISB-TEG> In a 50 ml round-bottom flask, 1.41 g (4.18 mmol) of ISB-CDI, TE G 1.89 g (12.56 mmol), 13.7 mg (83.6 μmol) of DBU, and 17 ml of chloroform were added, and the mixture was stirred at 50 °C for 16 hours under a nitrogen atmosphere.

[0037] After completion of the reaction, the mixture was washed once with 1N HCl and three times with distilled water, and then anhydrous sodium sulfate was added to remove the water present in the system. Then, chloroform was distilled off under reduced pressure to obtain a colorless oily liquid. This was subjected to column chromatography (chloroform / methanol = 18 / 1) to produce the target product. Further, the developing solvent was distilled off under reduced pressure to obtain a colorless oily liquid (0.51 g, 24.5%).

[0038] For the product 1 1H NMR spectrum measurement was performed (Figure 2). Since the peaks h~j confirmed in ISB-CDI and the peak a at the TEG terminal disappeared in ISB-TEG, it is suggested that the reaction is proceeding. Also, in this reaction, it is considered that imidazole is produced as a by-product, but 1 the peak derived from imidazole was not confirmed in 1H NMR. This is thought to be because imidazole, which has a high water solubility of 159100 mg / l and shows basicity, was completely removed into the aqueous layer by the liquid separation operation. layer.

[0039] Example 2: Evaluation of film-forming property and compatibility of PIC / ISB-TEG PIC (1.4 g, Mn 17600, Mw / Mn 2.17) and chloroform (35 ml) were added to a 50 ml screw tube and dissolved by stirring at room temperature for 10 minutes. <1> ). In another 50 ml screw cap bottle, add ISB-TEG (0.3 g), chloroform (7. 5 ml) was added and stirred at room temperature for 10 minutes to dissolve ( <2> ). <1> and <2> The PIC and ISB-TEG were mixed in arbitrary proportions to a total of 6 ml, stirred at room temperature for 5 minutes, and then subjected to ultrasonic waves for 5 minutes to mix the PIC and ISB-TEG. Five ml of the mixed solution was cast into a film on a petri dish at 50°C using the solution casting method, and the film-forming properties and compatibility were evaluated. The compatibility was judged visually based on the transparency of the resulting film.

[0040] Figure 3 shows the PIC / ISB-TEG film. The mixture ratio of PIC to ISB-TEG was varied to 9.8:0.2, 9.5:0.5, 9:1, 8:2, 7:3, and 6:4, and in all cases, the solution transformed into a film, demonstrating high film-forming properties. Furthermore, all of the films obtained were colorless and transparent, confirming the good compatibility of PIC and ISB-TEG.

[0041] Compatibility was also predicted using Hansen solubility parameters (HSP) (Figure 4). The HSP value of ISB-TEG was within the PIC solubility sphere, which led to the prediction that they would be compatible with each other, which was consistent with the compatibility determined by film formation.

[0042] Example 3: Evaluation of thermophysical properties of PIC / ISB-TEG In Example 2, the compatibility of PIC and ISB-TEG was evaluated by forming films. Compatibility is also measured by a decrease in the glass transition temperature (Tg) of the polymer, as determined by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA). Blends of immiscible polymers and plasticizers can lead to phase separation within the material, as observed by a wide range of glass transition temperatures or the presence of multiple glass transition temperatures.

[0043] Effective plasticization also lowers the glass transition temperature of the polymer below the product's use temperature, enabling flexible, rubber-like behavior. In this study, the glass transition temperatures of the PIC / ISB-TEG blends prepared in Example 2 were measured by DSC to confirm the compatibility of PIC and ISB-TEG and the effect of ISB-TEG as a plasticizer for PIC.

[0044] The DSC results are shown in Figure 5. The peak representing the glass transition temperature of PIC alone was not observed in the PIC / ISB-TEG blend, suggesting good compatibility between PIC and ISB-TEG. Furthermore, the glass transition temperature, which was 161°C for PIC alone, decreased as the amount of ISB-TEG added increased, reaching 40°C for the 6:4 blend.

[0045] These results demonstrate that ISB-TEG functions as a plasticizer with a significant plasticizing effect on PICs. Furthermore, by further varying the ratio of ISB-TEG, it is expected that a library of polymers with a wide range of glass transition temperatures can be created.

[0046] Example 4: Mechanical property evaluation of PIC / ISB-TEG Dumbbell specimens were prepared using each sample (a blend of PIC and a plasticizer) obtained in Example 2, and a tensile test was carried out. The tensile test was carried out at 30°C and a tensile speed of 10 mm / min. carried out. As shown in Fig. 6, in the blend of the polymer and the plasticizer, the tensile stress decreased and the elongation at break increased compared with the case of PIC alone. That is, it was confirmed that the addition of the plasticizer affected the mechanical properties of the resin composition.

[0047] Example 5: Method for producing a fertilizer composition by decomposing PIC / ISB-TEG with ammonia A blend obtained by adding 30% of ISB-TEG as a plasticizer to PIC alone was reacted in aqueous ammonia at 90 °C for 24 hours to decompose it into isosorbide, urea, and triethylene glycol. The analysis of the decomposition products 1 was quantitatively confirmed to proceed using 1H NMR (Fig. 7). and (Fig. 7).

[0048] When the obtained decomposition products were given to Arabidopsis thaliana as fertilizers, it was found that the same fertilizer effect as urea was obtained (Fig. 8).

[0049] Example 6: Synthesis of a novel plasticizer (oligomer or polymer type) for polyisosorbide carbonate (PIC) One with m = 2 was synthesized. It can be produced in the same manner for the case of m = 3 and so on. <Synthesis of ISB-CDI> Synthesized in the same manner as in Example 1.

[0050] <ISB-DEG 1400 Synthesis of> In a 20 ml eggplant flask, 1.51 g (4.52 mmol) of ISB-CDI, 1.44 g (12.5 mmol) of diethylene glycol (DEG), 11.8 mg (77 .5 μmol) of DBU, and 15 ml of chloroform were added, and the mixture was stirred at 50 °C for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. Purification was performed by decantation, and the solvent was distilled off under reduced pressure to obtain a colorless oily liquid (molecular weight (Mn) was 1400) (1.79 g).

[0051] <ISB-DEG 1800 Synthesis of> In a 20 ml recovery flask, 1.40 g (4.19 mmol) of ISB-CDI and diethyl Diethyl ether (DEG) 0.667 g (6.28 mmol), DBU 10.0 mg ( 65.6 μmol) and 15 ml of chloroform were added, and the mixture was incubated at 50°C for 24 hours under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. The product was purified by decantation, and the solvent was distilled off under reduced pressure to obtain 1.34 g of a colorless oily liquid (molecular weight (Mn) 1800).

[0052] <ISB-DEG 2700 Synthesis of> In a 20 ml recovery flask, 1.50 g (4.49 mmol) of ISB-CDI and diethyl Diethyl ether (DEG) 0.484 g (4.49 mmol), DBU 10.0 mg ( The reaction mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the product was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. The product was purified by decantation, and the solvent was removed under reduced pressure to obtain 1.27 g of a colorless oily liquid (molecular weight (Mn) 2700).

[0053] Example 7: PIC / ISB-DEG 1400 , 1800 , 2700 Evaluation of thermophysical properties As in Example 3, PIC / ISB-DEG 1400 , 1800 , 2700 Blend of glass The transition temperatures of PIC and ISB-DEG were measured by DSC. 1400 , 1800 , 2700 Compatibility of ISB-DEG with PIC 1400 , 1800 , 2700 The effect of this compound as a plasticizer was confirmed. Oligomers or polymers with molecular weights (Mn) of 1400, 1800, and 2700, respectively Blend of mer-type plasticizer and PIC (PIC / ISB-DEG 1400 , 1800 , 2700 ) was obtained by the same method as in Example 2.

[0054] The DSC results are shown in Figure 9. The peak representing the glass transition temperature of PIC alone is 1400 , 1800 , 2700 It was not observed in the blend of PIC and ISB-DEG. 1400 , 1800 , 2700 DSC also suggested that the compatibility of the two materials was good. In addition, the glass transition temperature of PIC alone was 161°C, but the glass transition temperature of ISB-DEG was 161°C. 1400 , 1800 , 2700 It was confirmed that the temperature decreased as the amount of added increased, and in the 6:4 blend, those with molecular weights (Mn) of 1400, 1800, and 2700 showed 35°C, 45°C, and 55°C, respectively.

[0055] From these results, ISB-DEG 1400 , 1800 , 2700 It was revealed that ISB-DEG acts as a plasticizer with a large plasticizing effect on PIC. 1400 , 1800 , 2700 By further varying the ratio, it is expected that a library of polymers with a wide range of glass transition temperatures can be created.

[0056] Example 8: PIC / ISB-DEG 1400 , 1800 , 2700 Mechanical property evaluation of Dumbbell specimens were prepared using blends of PIC and oligomeric or polymeric plasticizers with molecular weights (Mn) of 1400, 1800, and 2700, respectively, obtained by the same method as in Example 2, and tensile tests were conducted at 30°C and a tensile speed of 10 mm / min. As shown in Figure 10, blends of PIC and plasticizer tended to have a lower tensile stress and an increased elongation at break compared to PIC alone. This confirms that the addition of a plasticizer affects the mechanical properties of the resin composition.

[0057] Example 9: Evaluation of film-forming properties and compatibility of CAB / ISB-TEG and CAP / ISB-TEG A polymer (CAB or CAP: 1.0 g) and chloroform (40 ml) were added to a 50 ml screw tube bottle and stirred overnight at room temperature to dissolve. <1> ). In another 50 ml screw tube, ISB-TEG (0.4 g) and chloroform (16 ml) were added and stirred at room temperature overnight to dissolve ( <2> ). <1> and <2> The polymer and ISB-TEG were mixed in arbitrary proportions to a total volume of 8 ml, stirred at room temperature for 1 hour, and then sonicated for 10 minutes to mix the polymer and ISB-TEG. The mixed solution was solution-cast into a film at 50°C in a petri dish, and the resulting polymer film was molded into a disk using a thermoforming machine (150-200°C, 15 min).

[0058] Figures 11 and 12 show films of CAB alone, CAB / ISB-TEG, and CAP alone and CAP / ISB-TEG. The blends with ISB-TEG were prepared by varying the polymer / ISB-TEG ratios at 9:1, 8:2, 7:3, and 6:4. Figures 11 and 12 show photographs taken immediately after thermoforming. For both CAB and CAP, highly transparent freestanding films were obtained for all systems in which the ISB-TEG ratio was varied between 0 and 40% by mass. It is known that blends with good compatibility result in a uniform mixture of polymer and additive, eliminating the presence of domain regions that scatter light, resulting in transparent films. Therefore, it can be concluded that the CAB and CAP obtained in this example are well compatible with ISB-TEG.

[0059] In addition, when using plasticizers, it is important to prevent "bleed-out," a phenomenon in which the plasticizer seeps out onto the surface of the material over time. For example, if the plasticizer migrates to the surface of the material, it can cause deterioration in the appearance of the product, so preventing this can affect the quality of the product. This directly affects the quality of the film. Furthermore, since bleeding out can lead to a decrease in the flexibility and durability of the material, it is important to evaluate bleeding not only immediately after molding, but also after a certain period of time has passed since molding. Therefore, we compared the state of the film immediately after heat molding and after a certain number of days had passed.

[0060] The changes in the appearance of the film over time were observed when CAB or CAP was mixed with ISB-TEG in a ratio of 8:2 or 6:4, respectively, and the results are shown in Figures 13 and 14. These show the case where the cellulose ester / plasticizer ratio was 6:4, as an example of a system with a high blending ratio of plasticizer, and in samples with 30% or more by mass of ISB-TEG added, obvious bleeding out was visually confirmed after one week.

[0061] On the other hand, in samples containing 20% ​​or less ISB-TEG, no visible bleeding was observed even after 30 days. In blends of PIC and ISB-TEG, such as in Example 2, the association of the polar carbonate bonds present in both components is thought to result in particularly good compatibility. On the other hand, when CAB or CAP was used as the polymer, the polar ester bond was used, and the association force with ISB-TEG was relatively weak, which is thought to result in poorer compatibility compared to when the polymer was PIC (Figure 15).

[0062] Example 10: Evaluation of physical properties of CAB / ISB-TEG and CAP / ISB-TEG (thermal properties, mechanical properties) Differential scanning calorimetry (DSC) and tensile testing were carried out in the same manner as in Examples 3 and 4, and the results are shown in FIGS. 16 to 19, respectively. DSC measurements showed that the glass transition temperature (Tg) of both CAB and CAP shifted to lower temperatures with the addition of ISB-TEG, confirming the plasticizing effect and good compatibility (Figures 16 and 18). This is thought to be because the plasticizer ISB-TEG penetrates between polymer chains, increasing the free volume and reducing the intermolecular forces and entanglement between polymer chains, thereby increasing the flexibility of the polymer. The addition of ISB-TEG also eliminated the melting point due to crystallization in CAB (Figure 16), while it shifted to lower temperatures in CAP (Figure 18).

[0063] Furthermore, in the tensile test of CAB / ISB-TEG, the addition of ISB-TEG decreased the breaking stress, which corresponds to hardness, but no corresponding increase in breaking strain was observed (Figure 17). In other words, the breaking energy decreased with increasing ISB-TEG addition. In contrast, in the tensile test of CAP / ISB-TEG, not only did the breaking stress decrease but also the breaking strain increased (Figure 19). As described in Example 9, no bleeding was observed with the addition of approximately 20% ISB-TEG by mass. This suggests that ISB-TEG can be effectively used as a plasticizer to improve flexibility and processability, and to tune the physical properties of CAB or CAP by adjusting the addition amount.

[0064] Example 11: Evaluation of film-forming properties, compatibility, and thermal properties of PVC / ISB-TEG PVC (1.0 g) and tetrahydrofuran (40 ml) were added to a 50 ml screw tube bottle and stirred overnight at room temperature to dissolve ( <1> ). Into another 50 ml screw cap bottle, ISB-TEG (0.4 g) and tetrahydrofuran (16 ml) were added and stirred at room temperature overnight to dissolve ( <2> ). <1> and <2> The PVC and ISB-TEG were mixed in arbitrary proportions to a total volume of 8 ml, stirred at room temperature for 1 hour, and then subjected to ultrasonic irradiation for 10 minutes to mix the PVC and ISB-TEG. The mixed solution was formed into a film at 50°C in a petri dish using the solution casting method, and the resulting polymer film was molded into a disk using a thermoforming machine (160°C, 15 min).

[0065] Figure 20 shows films made from PVC alone and a 9:1 blend of PVC and ISB-TEG. Both were thermoformed at 160°C, which is below the decomposition temperature of PVC. However, with PVC, 160°C is almost the same as its melting point, so a transparent film was not obtained. In contrast, a colorless, transparent film was obtained with PVC / ISB-TEG. This suggests that the melting point is also lowered by the addition of ISB-TEG, and indeed, the second DSC thermogram from the top in Figure 21 <1> However, a shift in the melting point to a lower temperature (from 158°C to 135°C) was confirmed. Furthermore, the Tg also decreased by approximately 30°C by adding 10% by mass of ISB-TEG, confirming that ISB-TEG functions satisfactorily as a plasticizer.

[0066] Figure 21 also shows the DSC results for blends in which diethyl phthalate and bis(2-ethylhexyl) phthalate, both of which are phthalate compounds commonly used as plasticizers, were added to PVC at 10% by mass (the third from the top is diethyl phthalate). <2> The fourth is bis(2-ethylhexyl) phthalate <3> Although no clear decrease in melting point was observed for any of the phthalate diesters, Tg did decrease, with diethyl phthalate at the same level as ISB-TEG (53°C), and bis(2-ethylhexyl) phthalate shifting to an even lower temperature than ISB-TEG (38°C).

[0067] Although ISB-TEG is less efficient than bis(2-ethylhexyl) phthalate in terms of lowering the Tg, it has a comparable plasticizing effect to diethyl phthalate, and its plasticizing effect is significant. It is also noteworthy that ISB-TEG is suggested to have a greater effect on the melting point than both phthalate diesters.

[0068] To confirm the bleed-out of PVC / ISB-TEG, the film surface of blends of PVC and ISB-TEG in ratios of 9:1 to 6:4 was observed over time in the same manner as in Example 9. Clear bleed-out was observed visually after one week in samples containing 30% or more ISB-TEG. In contrast, no bleed-out was observed visually even after 30 days in samples containing 20% ​​or less ISB-TEG. Although PVC is a polar polymer, its interaction with ISB-TEG is weaker than that of PIC, which is thought to be why bleed-out occurs more easily than with PIC.

Claims

1. An isosorbide derivative, wherein the oxygen atoms derived from two hydroxyl groups on the isosorbide condensed ring are -C(=O)-O-(CH 2 CH 2 O) n A partial structure represented by H (n is an integer of 1 to 10) A compound formed by bonding together.

2. 2. The compound of claim 1 having the following structure, wherein n in said substructure is 3: 【Chemical 1】

3. An oligomer or polymer having the following repeating units: 【Chemistry 2】 (where m is an integer of 1 to 10, and x is an integer of 2 to 100)

4. A plasticizer for resins, comprising the compound according to claim 1 or 2, or the oligomer or polymer according to claim 3.

5. The plasticizer for resin according to claim 4, wherein the resin is a polyisosorbide carbonate containing polyisosorbide carbonate as a main component.

6. 5. The plasticizer for resin according to claim 4, wherein the resin is a cellulose ester.

7. 5. The plasticizer for resin according to claim 4, wherein the resin is polyvinyl chloride.

8. A resin composition, comprising: -C(=O)-O-(CH 2 CH 2 O) n A partial structure represented by H (n is an integer of 1 to 10) or an oligomer or polymer having the following repeating units: 【Chemistry 3】 (where m is an integer of 1 to 10, and x is an integer of 2 to 100) The resin composition contains 0.2 to 40 mass% of the above.

9. The resin composition according to claim 8, comprising a compound having the following structure, in which n in the partial structure is 3: 【Chemistry 4】

10. The resin composition according to claim 8 or 9, wherein the resin is a polyisosorbide carbonate containing polyisosorbide carbonate as a main component.

11. The resin composition according to claim 8 or 9, wherein the resin is a cellulose ester.

12. The resin composition according to claim 8 or 9, wherein the resin is polyvinyl chloride.

13. A resin composition, comprising: -C(=O)-O-(CH 2 CH 2 O) n A partial structure represented by H (n is an integer of 1 to 10) or an oligomer or polymer having the following repeating units: 【Chemistry 5】 (where m is an integer of 1 to 10, and x is an integer of 2 to 100) A method for producing a fertilizer composition by decomposing the resin composition with ammonia, wherein the resin composition contains 0.2 to 40 mass % of the above.

14. 14. The method for producing a fertilizer composition according to claim 13, wherein a resin composition containing a compound having the following structure, in which n in the partial structure is 3, is used. 【Chemistry 6】

15. 15. The method for producing a fertilizer composition according to claim 13 or 14, wherein the resin is a polyisosorbide carbonate containing polyisosorbide carbonate as a main component.

16. 15. The method for producing a fertilizer composition according to claim 13 or 14, wherein the resin is a cellulose ester.

17. 15. The method for producing a fertilizer composition according to claim 13 or 14, wherein the resin is polyvinyl chloride.

Images