New isosorbide derivative useful as plasticizer for resin

Abstract

To provide a bio-based plasticizer having good compatibility with various resins and useful for improving moldability, etc., of the resin, and a resin composition containing the plasticizer.　Provided is an isosorbide derivative that is a compound obtained by bonding partial structures represented by -C(=O)-O-(CH2CH2O)nH (n is an integer of 1-10) to oxygen atoms derived from each of two hydroxyl groups on an isosorbide condensed ring, or an oligomer or a polymer having the following repeating unit. (In the formula, m is an integer of 1-10, and x is an integer of 2-100.)

Description

Novel isosorbide derivatives useful as plasticizers for resins

[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.

[0002] Polymer materials (plastics) have become indispensable in our daily lives, but most of them are discarded, with the recycling rate for materials remaining at less than 15%. While there is an urgent need to take measures to address environmental issues 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 can balance the conservation of the global environment with the use of plastics.

[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. In response to the environmental issues described 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 synthesized from sugar-derived raw materials (polyisosorbide carbonate) 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 different flexible polymer monomers and crosslinking with a crosslinking agent. Among these methods, plasticization using a plasticizer 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 commercially available plasticizers, but the most widely used plasticizers are the phthalate-based plasticizers described 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). Meanwhile, 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 using 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-veils, tung oil, etc. 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, and has therefore attracted attention as a 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. Furthermore, 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.

[0011] Japanese Patent Application Laid-Open No. 2007-146019 Japanese Patent Application Laid-Open No. 2009-046519 Japanese Patent No. 4351675 Japanese Patent No. 5708087 Japanese Patent Application Laid-Open No. 2003-292603 Japanese Patent No. 7235112 Special Publication No. 2017-537185 Special Publication No. 2002-513816

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

[0013] Under these circumstances, the present 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 conducted extensive research into improving its physical properties and functions by incorporating a plasticizer. As a result, they have found that incorporating a compound having a structure similar to isosorbide as a plasticizer into a polyisosorbide carbonate resin improves the compatibility between the polyisosorbide carbonate and the plasticizer, thereby improving functionality. They then discovered that even when the compound having a structure similar to isosorbide is incorporated into cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP), which are naturally occurring cellulose derivatives, or polyvinyl chloride (PVC), a representative example of a general-purpose resin, compatibility is improved and a plasticizing effect is exerted by adjusting the compounding 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.

[0014] The present invention has the following aspects: [1] An isosorbide derivative, wherein the oxygen atoms derived from two hydroxyl groups on an isosorbide condensed ring are each substituted with -C(=O)-O-(CH2CH2O). n [2] A compound having the following structure, in which n in the partial structure is 3: [3] An oligomer or polymer having the following repeating unit: (wherein m is an integer of 1 to 10, and x is an integer of 2 to 100) [4] A plasticizer for resin, comprising the compound according to [1] or [2] above, or the oligomer or polymer according to [3] above. [5] The plasticizer for resin according to [4] above, wherein the resin is polyisosorbide carbonate containing polyisosorbide carbonate as a main component. [6] The plasticizer for resin according to [4] above, wherein the resin is cellulose ester. [7] The plasticizer for resin according to [4] above, wherein the resin is polyvinyl chloride. [8] A resin composition, wherein oxygen atoms derived from two hydroxyl groups on an isosorbide condensed ring are joined by -C(=O)-O-(CH2CHO) n A compound formed by bonding partial structures represented by H (n is an integer of 1 to 10), or an oligomer or polymer having the following repeating units: (wherein m is an integer of 1 to 10, and x is an integer of 2 to 100) in an amount of 0.2 to 40 mass %. [9] The resin composition according to [8] above, which contains a compound having the following structure, in which n in the partial structure is 3:

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

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

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

[13] A resin composition, wherein oxygen atoms derived from two hydroxyl groups on an isosorbide condensed ring are joined with -C(=O)-O-(CH2CHO) nA compound formed by bonding partial structures represented by H (n is an integer of 1 to 10), or an oligomer or polymer having the following repeating units: (wherein m is an integer of 1 to 10, and x is an integer of 2 to 100) in an amount of 0.2 to 40 mass %.

[14] A method for producing a 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:

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

[13] or

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

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

[13] or

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

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

[13] or

[14] above, wherein the resin is polyvinyl chloride.

[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. Furthermore, 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, resin compositions blended with the plasticizer of the present invention produce urea upon treatment with ammonia, and are therefore expected to be useful as fertilizer. In particular, when the matrix resin is polyisosorbide carbonate, it is expected that the resulting fertilizer can be used as is as a fertilizer by treating it with ammonia, just like polyisosorbide carbonate resins without the plasticizer, which can lead to the development of biomass utilization and chemical recycling.

[0016] In Example 1, ISB-CDI obtained as an intermediate 1 1 is a diagram showing the 1 H NMR spectrum of ISB-TEG obtained as the final product in Example 1. 11 is a diagram showing the H NMR spectrum. 2 is a diagram showing the film-forming properties of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2 when the mixing ratio was changed to form a film. 3 is a diagram showing the compatibility of the polyisosorbide carbonate composition (PIC / ISB-TEG) ​​predicted using Hansen solubility parameters. 4 is a diagram showing the relationship between the mixing ratio and glass transition temperature of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2. 5 is a diagram showing the relationship between the mixing ratio and tensile test results (stress, strain) of the polyisosorbide carbonate resin composition (PIC / ISB-TEG) ​​obtained in Example 2. 6 is a diagram showing the relationship between the mixing ratio and tensile test results (stress, strain) of the product obtained in Example 5 by decomposing a blend of PIC alone with 30% ISB-TEG as a plasticizer with ammonia. 1 1 is a diagram showing the H NMR spectrum. 2 is a diagram showing the effect on the growth of Arabidopsis thaliana when the decomposition product obtained in Example 5 is used to cultivate the plant. 3 is a diagram showing the effect on the growth of Arabidopsis thaliana when the decomposition product obtained in Example 7 is used to cultivate the plant. 1400 , 1800 , 2700 1 is a graph showing the relationship between the mixing ratio of the polyisosorbide carbonate resin composition (PIC / ISB-DEG) obtained in Example 7 and the glass transition temperature. 1400 , 1800 , 2700) and tensile test results (stress, strain). The cellulose acetate butyrate resin (CAB) and the resin composition (CAB / ISB-TEG) ​​obtained in Example 9 were formed into films with varying mixing ratios, and the film-forming properties of the latter were observed. The cellulose acetate propionate resin (CAP) and the resin composition (CAP / ISB-TEG) ​​obtained in Example 9 were formed into films with varying mixing ratios, and the film-forming properties of the latter were observed. The cellulose acetate butyrate resin composition (CAB / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios, and the film-forming properties of the latter were observed. The cellulose acetate butyrate resin composition (CAB / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP ...CAP / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 was formed into films with varying mixing ratios. The cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 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. It is a diagram showing the glass transition temperature of the cellulose acetate butyrate resin composition (CAB / ISB-TEG; mixing ratio 9:1) obtained in Example 9. It is a diagram showing the relationship between the mixing ratio of the cellulose acetate butyrate resin composition (CAB / ISB-TEG) ​​obtained in Example 9 and tensile test results (stress, strain). It is a diagram 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. It is a diagram showing the relationship between the mixing ratio of the cellulose acetate propionate resin composition (CAP / ISB-TEG) ​​obtained in Example 9 and tensile test results (stress, strain). 1 is a diagram showing the film-forming properties of the polyvinyl chloride resin (PVC) and the resin composition (PVC / ISB-TEG; mixing ratio 9:1) obtained in Example 11. It is a diagram showing the glass transition temperatures of the polyvinyl chloride resin (PVC) and the resin composition (PVC / ISB-TEG<1>, DEP<2>, or PEHP<3>; mixing ratio 9:1) obtained in Example 11.

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

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

[0019] This compound can be obtained by following the following two-step flow with reference to 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)).

[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 the mixture 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 the mixture at a temperature of 10 to 60°C, preferably 40 to 50°C, for 4 to 24 hours, preferably 10 to 18 hours.

[0022] Furthermore, ISB-TEG can be derived into an oligomer or polymer having the following repeating unit, m=3, and such oligomer or polymer is also a compound that is expected to exhibit high compatibility with polyisosorbide carbonate. Therefore, it can be used as a plasticizer for polyisosorbide carbonate resins. (In the formula, m is an integer of 1 to 10, and x is an integer of 2 to 100) In the above formula, m is preferably an integer of 2 to 4. Furthermore, x in the above formula is preferably an integer of 2 to 10.

[0023] Oligomers or polymers 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 oligomer or polymer can be formed by reacting at a temperature of 10 to 60°C, preferably 40 to 50°C, for 4 to 48 hours, preferably 24 hours. After the reaction is complete, the product is reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent, purified by decantation, and 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 for use as a plasticizer is 100 to 5,000, with a preferred molecular weight (Mn) range being 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 polycondensation of isosorbide and a carbonic acid diester as monomers by a known transesterification reaction. Examples of the other polycarbonates include those obtained by polycondensation of the above-mentioned monomers for polyisosorbide carbonate and 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 is CAB) or a mixture of acetic acid and propionic acid (product is 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 blending 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 blending ratio is preferably 10 to 40 mass%, more preferably 20 to 30 mass%. When the resin is cellulose ester or polyvinyl chloride, the compound useful as a plasticizer is preferably in the range of 10 to 20 mass% relative to 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 resin composition of the present invention is not particularly limited in its applications and can be widely used in various fields, including optical materials, packaging materials, various machine parts, and building materials. Furthermore, the resin composition of the present invention produces urea as a decomposition product when treated with ammonia. In particular, when the matrix resin is polyisosorbide carbonate, the decomposition product can be directly applied to soil without separation and used as fertilizer.

[0032] The method for treating the resin composition with ammonia may be the same as known methods, but examples thereof include a method in which the resin composition is brought into contact with an aqueous ammonia solution. There are no particular restrictions on the concentration of ammonia, but 5 to 15% is preferred, and 10 to 15% is particularly preferred. The treatment temperature may 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 may be, for example, 1 to 24 hours. Preferably, it is 12 to 24 hours.

[0033] The present invention will be described in more detail below with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention, which is limited only by the claims.

[0034] Example 1: Synthesis of a new plasticizer for resins <Synthesis of ISB-CDI> 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 to a 50 ml round-bottom flask and stirred at room temperature for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was washed with diethyl ether and the precipitated solid was removed by filtration. The solvent was then distilled off under reduced pressure to obtain a white powder (2.06 g, 90.0%).

[0035] Product 1H NMR spectrum measurement was performed (Figure 1). In the spectrum of the product, both peaks derived from CDI and peaks derived from ISB were confirmed. While the change in the peak derived from CDI was slight, it was confirmed that the peak derived from ISB was shifted to the downfield side. These results suggest that ISB-CDI was successfully synthesized.

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

[0037] After the reaction was complete, 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. The chloroform was then evaporated under reduced pressure to obtain a colorless oily liquid. This was then purified by column chromatography (chloroform / methanol = 18 / 1) to produce the target product. The developing solvent was then evaporated under reduced pressure to obtain a colorless oily liquid (0.51 g, 24.5%).

[0038] Product 1 H NMR spectrum measurement was performed (Figure 2). The peaks h to j observed in ISB-CDI and the peak a at the TEG terminal disappeared in ISB-TEG, suggesting that the reaction was proceeding. In addition, imidazole is thought to be produced as a by-product in this reaction, but 1 No peaks derived from imidazole were observed in H NMR, which is thought to be because imidazole, which has a high water solubility of 159,100 mg / L and is basic, was completely removed into the aqueous layer by the separation operation.

[0039] Example 2: Evaluation of film-forming properties 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-top vial and stirred at room temperature for 10 minutes to dissolve (<1>). ISB-TEG (0.3 g) and chloroform (7.5 ml) were added to another 50 ml screw-top vial and stirred at room temperature for 10 minutes to dissolve (<2>). <1> and <2> were mixed in arbitrary ratios to make 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. 5 ml of the mixed solution was formed into a film on a petri dish at 50°C by solution casting, and film-forming properties and compatibility were evaluated. The compatibility was visually determined based on the transparency of the obtained 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. 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 between 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 solubility sphere of PIC, 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 Thermal Properties of PIC / ISB-TEG In Example 2, the compatibility of PIC and ISB-TEG was evaluated by forming them into films. Compatibility was also measured by a decrease in the glass transition temperature (Tg) of the polymer obtained by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA). Blends of immiscible polymers and plasticizers can cause phase separation within the material, which is observed as 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 temperature of the PIC / ISB-TEG blend prepared in Example 2 was 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. No peak representing the glass transition temperature of PIC alone was observed in the PIC / ISB-TEG blend, suggesting good compatibility between PIC and ISB-TEG. Furthermore, the glass transition temperature of PIC alone, which was 161°C, decreased as the amount of ISB-TEG added increased, reaching 40°C in the 6:4 blend.

[0045] These results demonstrate that ISB-TEG functions as a plasticizer with a significant plasticizing effect on PIC. 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: Evaluation of mechanical properties of PIC / ISB-TEG Dumbbell specimens were prepared using each sample (a blend of PIC and plasticizer) obtained in Example 2, and a tensile test was performed. The tensile test was performed at 30°C and a tensile speed of 10 mm / min. As shown in Figure 6, the blend of polymer and plasticizer tended to have a reduced 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.

[0047] Example 5: Method for producing a fertilizer composition by decomposing PIC / ISB-TEG with ammonia A blend of PIC and 30% ISB-TEG as a plasticizer was reacted in ammonia water at 90°C for 24 hours to decompose it into isosorbide, urea, and triethylene glycol. Analysis of the decomposition products was carried out. 1 Using H NMR, it was confirmed that the decomposition reaction proceeded quantitatively (FIG. 7).

[0048] When the resulting decomposition product was applied to Arabidopsis thaliana as fertilizer, it was found to have the same fertilizing effect as urea (Figure 8).

[0049] Example 6: Synthesis of a new plasticizer (oligomer or polymer type) for polyisosorbide carbonate (PIC) A plasticizer with m = 2 was synthesized. It can also be produced in the same manner when m = 3, etc. <Synthesis of ISB-CDI> The synthesis was carried out in the same manner as in Example 1.

[0050] <ISB-DEG 1400 Synthesis of > 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 to a 20 ml recovery flask and stirred at 50°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the product was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. Purification was carried out by decantation, and the solvent was distilled off under reduced pressure to obtain 1.79 g of a colorless oily liquid (molecular weight (Mn) 1400).

[0051] <ISB-DEG 1800 Synthesis of > 1.40 g (4.19 mmol) of ISB-CDI, 0.667 g (6.28 mmol) of diethylene glycol (DEG), 10.0 mg (65.6 μmol) of DBU, and 15 ml of chloroform were added to a 20 ml recovery flask and stirred at 50°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the product was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. Purification was carried out 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 2700Synthesis of > 1.50 g (4.49 mmol) of ISB-CDI, 0.484 g (4.49 mmol) of diethylene glycol (DEG), 10.0 mg (65.6 μmol) of DBU, and 15 ml of chloroform were added to a 20 ml recovery flask and stirred at 50°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the product was reprecipitated using hexane / ethanol (v / v = 9 / 1) as a poor solvent. Purification was carried out by decantation, and the solvent was distilled off 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 As in Example 3, PIC / ISB-DEG 1400 , 1800 , 2700 The glass transition temperature of the blend of PIC and ISB-DEG was measured by DSC. 1400 , 1800 , 2700 Compatibility of ISB-DEG with PIC 1400 , 1800 , 2700 The effect of the blends of PIC and oligomeric or polymeric plasticizers with molecular weights (Mn) of 1400, 1800, and 2700 (PIC / ISB-DEG) was confirmed. 1400 , 1800 , 2700 ) was obtained by the same method as in Example 2.

[0054] The DSC results obtained by the measurement are shown in Figure 9. The peak representing the glass transition temperature of PIC alone is 1400 , 1800 , 2700 It was not confirmed 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 it was 161°C when ISB-DEG was used. 1400 , 1800 , 2700It 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 functions 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 Dumbbell specimens were prepared using blends of PIC and oligomer or polymer plasticizers with molecular weights (Mn) of 1400, 1800, and 2700, respectively, obtained by the same method as in Example 2, and tensile tests were performed. The tensile tests were performed at 30°C and a tensile speed of 10 mm / min. As shown in Figure 10, the blends of PIC and plasticizer tended to have a reduced 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 (1.0 g of CAB or CAP) and chloroform (40 ml) were added to a 50 ml screw cap vial and stirred overnight at room temperature to dissolve (<1>). ISB-TEG (0.4 g) and chloroform (16 ml) were added to a separate 50 ml screw cap vial and stirred overnight at room temperature to dissolve (<2>). <1> and <2> were mixed in arbitrary proportions to a total volume of 8 ml, stirred at room temperature for 1 hour, and then subjected to ultrasonic waves for 10 minutes to mix the polymer and ISB-TEG. The mixed solution was formed into a film at 50°C on a petri dish by solution casting, and the resulting polymer film was molded into a disk using a thermoforming machine (150-200°C, 15 min).

[0058] Films of CAB alone, CAB / ISB-TEG, and CAP alone and CAP / ISB-TEG are shown in Figures 11 and 12. For blends with ISB-TEG, the polymer / ISB-TEG mixing ratio was varied to 9:1, 8:2, 7:3, and 6:4. Figures 11 and 12 show photographs of the state immediately after thermoforming. For both CAB and CAP, freestanding films with high transparency were obtained for all systems in which the ISB-TEG mixing 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 cause light scattering, resulting in transparent films when formed into films. Therefore, it can be concluded that the CAB and CAP obtained in this example are well compatible with ISB-TEG.

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

[0060] The results of examining the change in the appearance of the film over time when CAB or CAP was mixed with ISB-TEG at a ratio of 8:2 or 6:4, respectively, 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 the sample to which 30% by mass or more of ISB-TEG was added, obvious bleeding out was visually confirmed after one week.

[0061] On the other hand, in samples containing 20% ​​or less ISB-TEG by mass, no visible bleed-out was observed even after 30 days. It is believed that a blend of PIC and ISB-TEG, such as that in Example 2, exhibits particularly good compatibility due to the association of the polar carbonate bonds present in both components. On the other hand, when CAB or CAP is used as the polymer, the polar ester bond is used, and the association force with ISB-TEG is relatively weaker, resulting in poorer compatibility compared to when the polymer is PIC (Figure 15).

[0062] Example 10: Evaluation of Physical Properties (Thermal Properties, Mechanical Properties) of CAB / ISB-TEG and CAP / ISB-TEG Differential scanning calorimetry (DSC) and tensile testing were performed using the same methods as in Examples 3 and 4. The results are shown in Figures 16 to 19, respectively. In the DSC measurements, 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 favorable compatibility (Figures 16 and 18). This is thought to be because the plasticizer ISB-TEG penetrates between polymer chains, increasing the free volume and thereby reducing intermolecular forces and entanglement between polymer chains, thereby enhancing 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). That is, 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% by mass of ISB-TEG. This suggests that ISB-TEG can be effectively used as a plasticizer to improve flexibility and processability, thereby tuning the physical properties of CAB or CAP, depending on the amount added.

[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 cap bottle and stirred overnight at room temperature to dissolve (<1>). ISB-TEG (0.4 g) and tetrahydrofuran (16 ml) were added to a separate 50 ml screw cap bottle and stirred overnight at room temperature to dissolve (<2>). <1> and <2> were mixed in arbitrary ratios to a total of 8 ml, stirred at room temperature for 1 hour, and then subjected to ultrasonic waves 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 by solution casting, 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, below the decomposition temperature of PVC. However, with PVC, 160°C is approximately the 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 addition of ISB-TEG also lowers the melting point. In fact, the second DSC thermogram from the top in Figure 21 (<1>) confirms a shift in the melting point (from 158°C to 135°C). The Tg also lowered by approximately 30°C with the addition of 10% ISB-TEG, confirming that ISB-TEG functions adequately as a plasticizer.

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

[0067] Although ISB-TEG is inferior to bis(2-ethylhexyl) phthalate in terms of the plasticization efficiency in terms of lowering the Tg, it can be said to have the same plasticization efficiency as diethyl phthalate, and its plasticization 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 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 is more likely to occur in PVC than in PIC.

Claims

1. An isosorbide derivative, in which the oxygen atoms derived from the two hydroxyl groups on the isosorbide condensed ring are bonded to -C(=O)-O-(CH2CH2O). n A compound formed by bonding together partial structures represented by H (n is an integer of 1 to 10).

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

3. An oligomer or polymer having the following repeating units: (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. The plasticizer for resins according to claim 4, wherein the resin is a cellulose ester.

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

8. A resin composition, comprising: -C(=O)-O-(CH2CH2O) at oxygen atoms derived from two hydroxyl groups on an isosorbide condensed ring. n A compound formed by bonding partial structures represented by H (n is an integer of 1 to 10), or an oligomer or polymer having the following repeating units: (wherein m is an integer of 1 to 10, and x is an integer of 2 to 100) in an amount of 0.2 to 40 mass %.

9. The resin composition according to claim 8, which contains a compound having the following structure, in which n in the partial structure is 3:

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

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-(CH2CH2O) at oxygen atoms derived from two hydroxyl groups on an isosorbide condensed ring. n A compound formed by bonding partial structures represented by H (n is an integer of 1 to 10), or an oligomer or polymer having the following repeating units: (wherein m is an integer of 1 to 10, and x is an integer of 2 to 100) in an amount of 0.2 to 40 mass %.

14. A method for producing the fertilizer composition according to claim 13, which uses a resin composition containing a compound having the following structure, in which n in the partial structure is 3:

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

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

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