Eco-friendly biodegradable plasticizer based on polycaprolactone and polylactone, and eco-friendly biodegradable composition comprising same

Abstract

The present invention relates to: a biodegradable plasticizer based on a polycaprolactone and polylactone-based block copolymer, the plasticizer comprising a hydrophilic part including an alcoholic functional group, and a hydrophobic part including a caprolactone unit and a lactone-based unit; and a biodegradable composition comprising same.

Description

Eco-friendly biodegradable plasticizer based on polycaprolactone and polylactone and eco-friendly biodegradable composition containing the same

[0001] The present invention relates to an eco-friendly biodegradable plasticizer based on polycaprolactone and polylactone, and an eco-friendly biodegradable composition comprising the same.

[0002] Plasticizers are low-volatile additives that reduce the viscosity and increase the plasticity of polymers. They are added to modify the physical properties of polymers, reducing the interchain forces and enhancing flexibility. Petrochemical-based, non-degradable plasticizers are primarily used to overcome the rigidity and brittleness of polymers. These non-degradable plasticizers can be classified into aromatic plasticizers (Di-2-ethylhexyl phthalate, Di-n-octyl phthalate, Di-i-octyl phthalate, Di-i-decyl phthalate, Di-n-undecyl phthalate, Di-n-tridecyl phthalate, Tri-2-ethylhexyl trimellitate, etc.), aliphatic plasticizers (Di-2-ethylhexyl adipate, Di-2-ethylhexyl sebacate, Di-2-ethylhexyl azelate, etc.), epoxy plasticizers (Epoxidized linseed oil, Epoxidized soya oil, etc.), polymeric plasticizers (Polyalkylene adipates, Polyalkylene sebacates, Polyalkylene azelates, etc.), and flame retardant plasticizers (Chlorinated paraffins, Phosphate esters).

[0003] Meanwhile, the US FDA notice and Europe (France) explained that repeated exposure to phthalate plasticizers affects patients with reduced immunity, metabolism, decomposition, and excretion capabilities, such as pregnant women, infants, hemodialysis patients, and cancer patients.

[0004] Therefore, although research on biodegradable plasticizers that do not cause environmental hormone problems has recently begun, previous studies have been limited in that there is no disclosure at all on polycaprolactone and lactone-based biodegradable plasticizers, and in particular, there is no consideration at all for inflammation suppression.

[0005] The present invention provides a biodegradable plasticizer based on polycaprolactone and polylactone block copolymers, which includes a hydrophilic portion including an alcoholic functional group and a hydrophobic portion including a caprolactone unit and a lactone unit.

[0006] However, the technical problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0007] The present invention provides a biodegradable plasticizer based on polycaprolactone and polylactone block copolymers, which comprises a hydrophilic portion including an alcoholic functional group and a hydrophobic portion including a caprolactone unit and a lactone unit.

[0008] The alcohol functional group may include at least one selected from the group consisting of methoxypolyethylene glycol, polyethylene glycol, polypropylene glycol, carbitol, glycerol, isosorbide, and dipentaerythritol.

[0009] The above lactone unit may be at least one selected from the group consisting of a lactide (LA) unit; a trimethylene carbonate (TMC) unit; a 1,4-dioxan-2-one (DO) unit; and a glycolide (GA) unit.

[0010] The molar ratio of the caprolactone unit and the lactone unit may be 5:95 to 95:5.

[0011] The average molecular weight (M) of the above block copolymer W ) is 300 g / mol to 30,000 g / mol, and the polydispersity index (PDI=Mw / Mn) can be 1.0 to 2.5.

[0012] The biodegradable plasticizer may have a controllable biodegradation period.

[0013] The above biodegradable plasticizer has an anti-inflammatory function and may not exhibit genotoxicity or acute toxicity.

[0014] In one embodiment of the present invention, a biodegradable composition comprising a polymer material and the biodegradable plasticizer is provided.

[0015] The polymer material may include at least one selected from the group consisting of polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, and polylactic acid.

[0016] The content of the biodegradable plasticizer relative to the polymer material may be 5 wt% to 70 wt%.

[0017] Due to the biodegradable plasticizer, the glass transition temperature of the polymer material can be lowered by 3°C to 100°C.

[0018] The biodegradable plasticizer based on polycaprolactone and polylactone block copolymer according to the present invention is characterized by including a hydrophilic portion including an alcoholic functional group; and a hydrophobic portion including a caprolactone unit and a lactone unit, so that not only is it biodegradable in the natural state after use, but in particular, it has an anti-inflammatory function and no genotoxicity or acute toxicity is detected, so that it has the advantage of causing no problems to the human body even after the plasticizer is exposed to the natural world.

[0019] The biodegradable plasticizer based on polycaprolactone and polylactone block copolymer according to the present invention can be utilized as a biodegradable plasticizer by effectively lowering the glass transition temperature of a polymer material when blended with the polymer material.

[0020] Figure 1 is a schematic diagram showing the action and post-use biodegradation of a biodegradable plasticizer based on polycaprolactone and polylactone-based block copolymer according to one embodiment of the present invention.

[0021] Figures 2(a) to (n) show polycaprolactone and polylactone-based block copolymers synthesized according to Examples 1 to 14. 1 This shows the results of the H-NMR spectrum.

[0022] Figure 3 shows the results of thermal property measurements according to the content and type of biodegradable plasticizer for biodegradable compositions manufactured according to Examples 13 to 24.

[0023] Figures 4(a) to (d) show the results of a biodegradability test in deionized water (DI) for polycaprolactone and polylactone-based block copolymers synthesized according to Examples 1 to 4, and Figure 4(e) shows the results of a biodegradability test in seawater (East Sea) for polycaprolactone and polylactone-based block copolymers synthesized according to Example 2.

[0024] As shown in Fig. 1, the inventors of the present invention synthesized polycaprolactone and polylactone-based block copolymers using alcoholic functional groups as initiators, and confirmed that these, when blended with polymeric substances, can effectively lower the glass transition temperature of the polymeric substances. Furthermore, they confirmed that not only are they biodegradable in natural conditions after use, but they also have anti-inflammatory properties and no genotoxicity or acute toxicity is detected, thereby completing the present invention.

[0025]

[0026] Hereinafter, the present invention will be described in detail.

[0027]

[0028] Biodegradable plasticizers based on polycaprolactone and polylactone-based block copolymers

[0029]

[0030] The present invention provides a biodegradable plasticizer based on polycaprolactone and polylactone block copolymers, which comprises a hydrophilic portion including an alcoholic functional group and a hydrophobic portion including a caprolactone unit and a lactone unit.

[0031]

[0032] First, the biodegradable plasticizer based on polycaprolactone and polylactone-based block copolymer according to the present invention includes a hydrophilic portion including an alcoholic functional group.

[0033] The hydrophilic portion can be manufactured using an alcohol functional group as an initiator, and the alcohol functional group can include at least one selected from the group consisting of methoxypolyethylene glycol, polyethylene glycol, polypropylene glycol, carbitol, glycerol, isosorbide, and dipentaerythritol. In order to properly change the thermal properties of the polymer material, it is preferably methoxypolyethylene glycol, and at this time, the optimal molecular weight (Mw) is preferably 350 g / mol to 2,000 g / mol, but is not limited thereto.

[0034]

[0035] Next, the biodegradable plasticizer based on polycaprolactone and polylactone-based block copolymer according to the present invention includes a hydrophobic portion including a caprolactone unit and a lactone-based unit.

[0036] In the hydrophobic portion, the caprolactone unit can be manufactured using a 7-membered cyclic carboxyl ester as a starting material, and at this time, the 7-membered cyclic carboxyl ester can be ε-caprolactone. For example, the caprolactone unit It could be.

[0037] In addition, the lactone-based unit may be at least one selected from the group consisting of a lactide (LA) unit; a trimethylene carbonate (TMC) unit; a 1,4-dioxan-2-one (DO) unit; and a glycolide (GA) unit, and is preferably a lactide (LA) unit, but is not limited thereto. Such a lactone-based unit may be prepared using a six-membered cyclic carboxyl ester as a starting material, and at this time, the six-membered cyclic carboxyl ester may be lactide (LA); trimethylene carbonate (TMC); 1,4-dioxan-2-one (DO); and glycolide (GA). For example, the lactide (LA) unit It can be, and the trimethylene carbonate (TMC) unit is It can be, and the above 1,4-Dioxan-2-one (DO) unit is It may be, and the glycolide (GA) unit is It could be.

[0038]

[0039] The molar ratio of the caprolactone unit and the lactone unit may be 5:95 to 95:5, preferably 40:60 to 60:40, and more preferably 45:55 to 55:45, but is not limited thereto. In this case, if the molar ratio of the caprolactone unit or the molar ratio of the lactone unit becomes too high, there is a problem that the biodegradation period becomes excessively long and the plasticizer effect becomes reduced.

[0040]

[0041] Accordingly, in the biodegradable plasticizer based on polycaprolactone and polylactone block copolymer according to the present invention, the molecular weight (M) of the block copolymer W ) is 300 g / mol to 30,000 g / mol, the polydispersity index (PDI=Mw / Mn) may be 1.0 to 2.5, and the molecular weight (M) of the block copolymer W ) is preferably 300 g / mol to 5,000 g / mol, and more preferably 300 g / mol to 2,500 g / mol, but is not limited thereto. At this time, if the molecular weight of the block copolymer becomes too large, there is a limitation that it cannot properly change the thermal properties of the polymer material, and thus cannot properly function as a plasticizer.

[0042]

[0043] The above biodegradable plasticizer is not only biodegradable in the natural environment after use, but also has an anti-inflammatory function and, as no genotoxicity or acute toxicity is detected, it has the advantage of causing no problems to the human body even after the plasticizer is exposed to the natural environment.

[0044] In particular, the biodegradable plasticizer has a degradation half-life of 3.0×10 under a decomposition solution of deionized water (DI) or seawater (East Sea) at a temperature of 28°C. -2 / day can be more than 3.5×10 -2 / day to 7.0×10 -2 / day is preferable, and 5.5×10 -2 / day to 7.0×10 -2 / day is preferable, but is not limited to this.

[0045]

[0046] biodegradable composition

[0047]

[0048] The present invention provides a biodegradable composition comprising a polymer material and a biodegradable plasticizer based on polycaprolactone and a polylactone-based block copolymer.

[0049]

[0050] First, the biodegradable composition according to the present invention includes a polymer material.

[0051] The above polymer material is a polymer material that requires a decrease in viscosity or an increase in plasticity, and various known polymer materials can be used, and may include at least one selected from the group including polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, and polylactic acid. At this time, the glass transition temperature of polystyrene is about 101°C, the glass transition temperature of polymethyl methacrylate is about 118.6°C, the glass transition temperature of polyvinyl chloride is about 85.8°C, and the glass transition temperature of polylactic acid is about 49.6°C.

[0052] Next, the biodegradable composition according to the present invention comprises a biodegradable plasticizer based on the polycaprolactone and polylactone-based block copolymer.

[0053] Since the biodegradable plasticizer based on the above polycaprolactone and polylactone block copolymer has been described above, a duplicate description will be omitted.

[0054] The content of the biodegradable plasticizer relative to the polymer material may be 5 wt% to 70 wt%, preferably 10 wt% to 70 wt%, more preferably 30 wt% to 70 wt%, and most preferably 40 wt% to 60 wt%, but is not limited thereto. If the content of the biodegradable plasticizer is too small, there is a limitation in that the thermal properties of the polymer material cannot be properly changed, and if the content of the biodegradable plasticizer is too large, there is a limitation in that the properties of the polymer material cannot be properly exhibited due to excessive additives.

[0055] Due to the biodegradable plasticizer, the glass transition temperature of the polymer material can be lowered by 3°C to 100°C, preferably by 5°C to 100°C, more preferably by 10°C to 100°C, and most preferably by 25°C to 100°C, but is not limited thereto.

[0056]

[0057] As reviewed above, the biodegradable plasticizer based on polycaprolactone and polylactone-based block copolymer according to the present invention is characterized by including a hydrophilic portion including an alcoholic functional group; and a hydrophobic portion including a caprolactone unit and a lactone-based unit, so that not only is it biodegradable in a natural state after use, but in particular, it has an anti-inflammatory function, and since no genotoxicity or acute toxicity is detected, it has the advantage of causing no problems to the human body even after the plasticizer is exposed to the natural world.

[0058] The biodegradable plasticizer based on polycaprolactone and polylactone block copolymer according to the present invention can be utilized as a biodegradable plasticizer by effectively lowering the glass transition temperature of a polymer material when blended with the polymer material.

[0059]

[0060] Hereinafter, preferred examples are presented to aid in understanding the present invention. However, the following examples are provided solely to facilitate a better understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[0061]

[0062] [Example]

[0063] Example 1-14: Synthesis of polycaprolactone and polylactone-based block copolymers

[0064] Referring to Table 1 below, polycaprolactone and polylactone block copolymers were synthesized by reacting them at 110°C for 12 hours using ε-caprolactone (CL) as a starting material for producing a caprolactone unit and lactide (LA), trimethylene carbonate (TMC), 1,4-dioxan-2-one (DO) unit or glycolide (GA) as a starting material for producing a lactone unit, using an alcoholic functional group as an initiator for producing a hydrophilic portion.

[0065] Synthetic block copolymers 1 Molecular weight (M) based on H-NMR spectrum results W )(NMR) and Mw / Mn(GPC) were calculated, and the yield (%) was measured (see Table 1, Figs. 2(a) to (n)).

[0066] Example Hydrophilic and hydrophobic partial charge (M W)(NMR)Mw / Mn(GPC)YieldMol Ratio(Theoretical)Mol Ratio(NMR)Example 1(M7-CL55-0.75k)Methoxypolyethylene glycolCL:LA50:50CL:LA56:44720g / mol1.1495.9%Example 2(M7-CL55-1.7k)Methoxypolyethylene glycolCL:LA50:50CL:LA46:541,714g / mol1.2584.2%Example 3(M7-CL55-3k)Methoxypolyethylene glycolCL:LA50:50CL:LA49:513,162g / mol1.7598.9%Example 4(M7-CL55-4k)Methoxypolyethylene Glycol CL:LA50:50 CL:LA48:524,145 g / mol 1.6299.3% Example 5 (PE2-CL55-0.5k) Polyethylene glycol CL:LA50:50 CL:LA58:42503 g / mol 1.16~100% Example 6 (PE4-CL55-1.7k) Polyethylene glycol CL:LA50:50 CL:LA51:491,850 g / mol 1.2498.8% Example 7 (PP4-CL55-1.7k) Polypropylene glycol CL:LA50:50 CL:LA56:441,640 g / mol 1.3188.5% Example 8(GR-CL55-1.7k) Glycerol CL:LA50:50 CL:LA53:471,910g / mol 1.3588.1% Example 9(C-CL55-1.7k) Carbitol CL:LA50:50 CL:LA51:492,079g / mol 1.4699.7% Example 10(M7-CT55-1.7k) Methoxypolyethylene glycol CL:TMC50:50 CL:TMC52:481,705g / mol 1.1895.1% Example 11(M7-CD55-1.7k) Methoxypolyethylene glycol CL:DO50:50 CL:TMC51:49 Modified 1,690g / mol 1.2194.2% Example 12(M7-CG91-1.7k) Methoxypolyethylene glycol CL:GA90:10 CL:GA91:91,680g / mol 1.4892.3% Example 13(Isosorbide-CL55-1.7k) Isosorbide CL:LA50:50 CL:LA48:52 1,990g / mol 1.46~100% Example 14(Dipentaerythritol- CL55-1.7k) Dipentaerythritol CL:LA50:50 CL:LA46:542,190 g / mol 1.26~100%.

[0067] As shown in Table 1, it was confirmed that all polycaprolactone and polylactone-based block copolymers synthesized according to Examples 1 to 14 were synthesized in high yields.

[0068]

[0069] Example 15-24: Preparation of a biodegradable composition comprising a biodegradable plasticizer

[0070] Referring to Table 2 below, biodegradable compositions were prepared by blending synthesized polycaprolactone and polylactone-based block copolymers and polymer materials such as polystyrene (PS), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), or polylactic acid (PLA), and the thermal properties according to the content and type of biodegradable plasticizer were measured (see Fig. 3). At this time, the glass transition temperature (Tg) was measured in the range of -80 to 200°C at a heating rate of 5°C / min using a differential scanning calorimeter (DSC) (Q10, TA Instrument, New Castle, DE, USA) (Table 2).

[0071] Example Block copolymerPolymer materialPolymer material Block copolymer content TgComparative Example 1-1-PS0 (w / w)% 101℃Comparative Example 1-2-PMMA0 (w / w)% 118.6℃Comparative Example 1-3-PVC0 (w / w)% 85.8℃Comparative Example 1-4-PLA0 (w / w)% 49.6℃Example 15Example 2(M7-CL55-1.7k)PS10 (w / w)% 97.2℃Example 16Example 2(M7-CL55-1.7k)PS30 (w / w)% 91.4℃Example 17-1Example 2(M7-CL55-1.7k)PS50 (w / w)% 73.5℃Example 17-2Example 2(M7-CL55-1.7k)PMMA50 (w / w)%59.9℃Example 18-1Example 1(M7-CL55-0.75k)PS50 (w / w)%68.2℃Example 18-2Example 1(M7-CL55-0.75k)PMMA50 (w / w)%43.9℃Example 18-3Example 1(M7-CL55-0.75k)PVC50 (w / w)%40.3℃Example 18-4Example 1(M7-CL55-0.75k)PLA50 (w / w)%-13.2℃Example 19-1Example 3(M7-CL55-3k)PS50 (w / w)%81.9℃Example 19-2 Example 3 (M7-CL55-3k) PMMA 50 (w / w) % 62.7℃ Example 19-3 Example 3 (M7-CL55-3k) PVC 50 (w / w) % 51.4℃ Example 19-4 Example 3 (M7-CL55-3k) PLA 50 (w / w) % 5.8℃ Example 20-1 Example 4 (M7-CL55-4k) PS 50 (w / w) % 89.5℃ Example 20-2 Example 4 (M7-CL55-4k) PMMA 50 (w / w) % 63.4℃ Example 20-3 Example 4 (M7-CL55-4k) PVC 50 (w / w) % 52.1℃ Example 20-4 Example 4(M7-CL55-4k)PLA50 (w / w)%10.4℃Example 21Example 8(GR-CL55-1.7k)PS50 (w / w)%89.9℃Example 22Example 9(C-CL55-1.7k)PS50 (w / w)%89.2℃Example 23-1Example 13(Isosorbide-CL55-1.7k)PS50 (w / w)%89.9℃Example 23-2Example 13(Isosorbide-CL55-1.7k)PMMA50 (w / w)%55.7℃Example 24-1Example 14(Dipentaerythritol- CL55-1.7k)PS50 (w / w)%90.9℃Example 24-2Example 14(Dipentaerythritol- CL55-1.7k)PMMA50 (w / w)%56.9℃.

[0072] As shown in Table 2, the biodegradable compositions manufactured according to Examples 15 to 24 were all biodegradable plasticizers, and since they contained polycaprolactone and a polylactone-based block copolymer, it was confirmed that the glass transition temperature of the polymer material could be lowered. In particular, in the case of Examples 17-1, 17-2, 18-1, 18-2, 18-3, and 18-4, since the molar ratio and molecular weight between monomers in polycaprolactone and a polylactone-based block copolymer were optimized, the glass transition temperature of the polymer material could be significantly lowered, and thus the compositions were confirmed to have excellent performance as plasticizers. In particular, according to a previously reported literature [European Polymer Journal 39 (2003) 1947-1953], 50% of commercial dioctyl phthalate (DOP) was confirmed to reduce the Tg of PMMA by about 70°C. In the case of Example 18-2, it can be seen that the performance as a plasticizer is superior to that of commercial DOP by reducing the Tg of PMMA by approximately 75°C, while also having the advantage of being environmentally friendly and biodegradable.

[0073]

[0074] Experimental Example 1: Biodegradation Experiment with Biodegradable Plasticizers / Compositions

[0075] The polycaprolactone and polylactone block copolymers synthesized according to Examples 1 to 4 were dissolved in deionized water (DI) or seawater (East Sea) at 28°C at a concentration of 3 (w / v)% for a certain period of time, and then the DI or East Sea was removed by lyophilization. Thereafter, the Mw / Mn of the decomposed block copolymers was measured through gel permeation chromatography (GPC) (YL 9170 RI detector) (see Figs. 3(a) to (e)). At this time, GPC was set to a flow rate of 1.0 mL / min using chloroform (JT Baker, USA) as a mobile phase (Table 3).

[0076] Example Decomposition solution Decomposition half-life Example 1 (M7-CL55-0.75k) DI5.8×10 -2 / dayExample 2 (M7-CL55-1.7k)DI5.63×10 -2 / dayExample 3 (M7-CL55-3k)DI3.56×10 -2 / dayExample 4 (M7-CL55-4k)DI3.52×10 -2 / dayExample 2 (M7-CL55-1.7k)East Sea6.54×10 -2 / day

[0077] As shown in Table 3, it was confirmed that all polycaprolactone and polylactone block copolymers synthesized according to Examples 1 to 4 had controllable biodegradation periods, and under a decomposition solution of deionized water (DI) or seawater (East Sea) at a temperature of 28°C, the decomposition half-life was 3.0×10 -2 / day or more (preferably 3.5×10 -2 / day to 7.0×10 -2 / day). In particular, in the case of Examples 1 and 2, as the molar ratio and molecular weight between monomers in polycaprolactone and polylactone-based block copolymers were optimized, the decomposition half-life was 5.0×10 under a decomposition solution of deionized water (DI) or seawater (East Sea) at a temperature of 28°C. -2 / day or more (preferably 5.5×10 -2 / day to 7.0×10 -2 / day). In addition, the biodegradability of the biodegradable composition manufactured according to Example 2 was measured by KOTITI Testing & Research Institute, a nationally accredited testing and inspection research institute, under aquatic conditions (KS I ISO 7827: Water quality - Evaluation method for "final" aerobic biodegradability of organic matter in liquid medium - Dissolved organic carbon analysis method), and the biodegradability was confirmed to be 99%.

[0078]

[0079] Experimental Example 2: Anti-inflammatory Experiment Using Biodegradable Plasticizers

[0080] The biodegradable plasticizer manufactured according to Example 2 was sent to the Stability Evaluation Laboratory for anti-inflammatory efficacy evaluation in LPS-induced RAW264.7 cells. As a result, it was confirmed that the biodegradable plasticizer manufactured according to Example 2 concentration-dependently decreased NO and PGE2 production in LPS-induced RAW264.7 cells, and also concentration-dependently suppressed the expression of inflammation-related proteins.

[0081]

[0082] Experimental Example 3: Genotoxicity / acute toxicity test using biodegradable plasticizers.

[0083] The biodegradable plasticizer manufactured according to Example 3 was submitted to the Stability Evaluation Laboratory for genotoxicity evaluation in bacteria. As a result, negative revertant mutations were confirmed in the histidine-requiring TA-98 and TA-100 strains of Salmonella typhimurium. Therefore, it was confirmed that no genotoxicity was observed in bacteria.

[0084] In addition, the biodegradable plasticizer manufactured according to Example 3 was tested for acute toxicity (ISO 10993-11: 2017) on ICR mice by the Korea Testing & Research Institute for Chemical Industry, and it was confirmed that no systemic toxicity changes were observed within 72 hours after intraperitoneal administration.

[0085]

[0086] The foregoing description of the present invention is for illustrative purposes only. Those skilled in the art will readily appreciate that modifications to other specific embodiments can be made without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A hydrophilic portion containing an alcoholic functional group; and A biodegradable plasticizer based on a polycaprolactone and polylactone block copolymer comprising a hydrophobic portion comprising a caprolactone unit and a lactone unit.

2. In paragraph 1, A biodegradable plasticizer based on a polycaprolactone and polylactone block copolymer, characterized in that the alcohol functional group comprises at least one selected from the group consisting of methoxypolyethylene glycol, polyethylene glycol, polypropylene glycol, carbitol, glycerol, isosorbide, and dipentaerythritol.

3. In paragraph 1, A biodegradable plasticizer based on polycaprolactone and polylactone block copolymer, characterized in that the lactone unit is at least one selected from the group consisting of a lactide (LA) unit, a trimethylene carbonate (TMC) unit, a 1,4-dioxan-2-one (DO) unit, and a glycolide (GA) unit.

4. In paragraph 1, A biodegradable plasticizer based on a polycaprolactone and polylactone block copolymer, characterized in that the molar ratio of the caprolactone unit and the lactone unit is 5:95 to 95:

5.

5. In paragraph 1, The average molecular weight (M) of the above block copolymer W ) is 300 g / mol to 30,000 g / mol and polydispersity index (PDI=Mw / Mm) is 1.0 to 2.5, a biodegradable plasticizer based on polycaprolactone and polylactone block copolymers.

6. In paragraph 1, The above biodegradable plasticizer is a biodegradable plasticizer based on polycaprolactone and polylactone block copolymer, characterized in that the biodegradable plasticizer has a controllable biodegradation period.

7. In paragraph 1, A biodegradable plasticizer based on polycaprolactone and polylactone block copolymer, characterized in that the biodegradable plasticizer has an anti-inflammatory function and no genotoxicity or acute toxicity is detected.

8. Polymer materials; and A biodegradable composition comprising a biodegradable plasticizer based on polycaprolactone and a polylactone-based block copolymer according to any one of claims 1 to 7.

9. In paragraph 8, A biodegradable composition, characterized in that the polymer material comprises at least one selected from the group consisting of polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, and polylactic acid.

10. In paragraph 8, A biodegradable composition, characterized in that the content of the biodegradable plasticizer relative to the polymer material is 5 wt% to 70 wt%.

11. In paragraph 8, A biodegradable composition characterized in that the glass transition temperature of the polymer material is lowered by 3°C to 100°C due to the biodegradable plasticizer.

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