Glycol gel comprising glass phase and entangled phase, and preparation method therefor

Abstract

The objective of the present invention is to provide a gel having excellent strength and toughness while being biocompatible, and a preparation method therefor. In order to accomplish the objective, the glycol gel according to the present invention comprises: a solvent containing a glycol-based solution; and a three-dimensional-network-structured cross-linked polymer support.

Description

Glycol gel containing a glass phase and an entangled phase and a method for manufacturing the same

[0001] This invention was supported by the following national research and development project.

[0002] [Project ID] 2710006314

[0003] [Assignment No.] 00408989

[0004] [Ministry Name] Ministry of Science and ICT

[0005] [Name of Project Management (Specialized) Agency] National Research Foundation of Korea

[0006] [Research Project Name] Nanomaterial Technology Development

[0007] [Research Project Title] Development of Shape-Variable Display Technology Using Tg-Dispersed Dual-Phase Glycol Gel

[0008] The present invention relates to a glycol gel using glycol as a solvent, and in particular to a glycol gel and a method for manufacturing the same, characterized in that the polymer support inside the gel simultaneously includes a glass phase and an entangled phase while using glycol as a solvent.

[0009]

[0010] Recently, polymer gels have been actively utilized in flexible devices, batteries, actuators, drug delivery systems, and separators. However, these polymer gels still have limitations, such as low mechanical strength and, in particular, poor resilience under repeated deformation. To address this, it is necessary to strategically develop high-strength gels based on the interactions between polymer chains and solvents, by considering the fundamental mechanical limitations arising from the internal structure of the polymer gels in a hierarchical manner from the micro to the macro scale.

[0011] Hydrogels consist of a structure in which a large amount of water, acting as a solvent, is filled within a cross-linked hydrophilic polymer network. Consequently, their composition is very similar to that of biological tissues, and their mechanical properties, such as viscoelasticity, are also similar, making them highly useful as biomaterials. However, hydrogels face persistent problems: expansion due to osmotic pressure occurs when used in water for extended periods, and water evaporation occurs when used in air for long periods. To address these issues, ionic gels have been developed using ionic liquids as solvents, which possess very low vapor pressure and excellent thermal stability. While most ionic liquids offer advantages such as thermal stability over a wide temperature range, non-volatility, and ionic conductivity, their biocompatibility has not yet been verified. Furthermore, they have the disadvantage of being expensive to use as solvents, which constitute the majority of polymer gels.

[0012]

[0013] The present invention aims to provide a gel that is biocompatible, has excellent mechanical properties, and can be used even at high temperatures, as well as a method for manufacturing the same.

[0014]

[0015] To achieve the above objectives, the glycol gel according to the present invention comprises a solvent containing a glycol-based solution and a cross-linked polymer support having a three-dimensional network structure, wherein the polymer support comprises a glass phase and an entangled phase.

[0016] In addition, the polymer support of the glycol gel according to one embodiment of the present invention may have a glass transition temperature and a melting point.

[0017] In addition, the glycol gel according to one embodiment of the present invention may have a melting point of 160°C or higher when measured under conditions of heating at a rate of 10°C / min using a Differential Scanning Calorimetry (DSC).

[0018] In addition, the glass transition temperature of the polymer support according to one embodiment of the present invention may be 110°C or higher when heated at a heating rate of 3°C / min while applying a deformation of 0.05% in tensile mode using a Dynamic Mechanical Analyzer (DMA) at a rate of 1 Hz.

[0019] In addition, the glycol gel according to one embodiment of the present invention may have temperature-dependent shape memory characteristics around the glass transition temperature.

[0020] In addition, the glycol gel according to one embodiment of the present invention may have a maximum tensile strength of 15 MPa or more.

[0021] In addition, the glycol gel according to one embodiment of the present invention comprises, wherein the polymer support is a glassy polymer selected from the group consisting of polyacrylamide (PAAm), polyacrylic acid (PAAc), polymethacrylic acid (PMAA), poly 2-hydroxyethyl methacrylate (PHEMA), poly N-isopropyl acrylamide (PNIPAAm), polyacrylonitrile (PAN), nylon (Polyamide), polyethylene terephthalate (PET), polyurethane (PU), polyvinyl alcohol (PVA), polycaprolactone (PCL), and combinations thereof, and poly N,N-dimethylacrylamide (PDMAA), polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polyisobutyl methacrylate (PIBMA), polyisopropyl acrylate (PIPA), polymethoxyethyl methacrylate (PMEMA), polyethylene oxide (PEO), polypropylene oxide (PPO), poly It may include an entangled polymer selected from the group consisting of styrene (PS), polyisoprene, polytetrafluoroethylene (PTFE), and combinations thereof.

[0022] Meanwhile, the method for manufacturing a glycol gel according to the present invention may include the steps of preparing a mixture by adding and dissolving a first monomer for forming a glassy polymer, a second monomer for forming an entangled polymer, a crosslinking agent, and an initiator into a glycol solvent, and irradiating the mixture with ultraviolet light.

[0023] In addition, in a method for preparing a glycol gel according to one embodiment of the present invention, the first monomer may be selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, N-isopropylacryamide, acrylonitrile, amide, ethylene terephthalate, urethane, vinyl alcohol, caprolactone, and combinations thereof.

[0024] In addition, in a method for preparing a glycol gel according to one embodiment of the present invention, the second monomer may be selected from the group consisting of N,N-dimethylacrylamide, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, isopropyl acrylate, methoxyethyl methacrylate, ethylene oxide, propylene oxide, styrene, isoprene, tetrafluoroethylene, and combinations thereof.

[0025] In addition, in the method for preparing a glycol gel according to one embodiment of the present invention, the polymer concentration of the first monomer, the second monomer, and the crosslinking agent in the mixture may be 6M or higher.

[0026] Meanwhile, a flexible electronic device comprising a glycol gel according to the present invention can be provided.

[0027]

[0028] The glycol gel that can be provided according to the present invention has excellent strength and toughness, excellent biocompatibility, and has shape memory properties depending on temperature, so it can be applied not only to cosmetics and medical uses but also to various electronic products such as stretchable displays.

[0029]

[0030] Figure 1 is a graph comparing the characteristics of hydrogel, ionic gel, and glycol gel.

[0031] FIG. 2 is a schematic diagram illustrating the concept of a glycol gel according to the present invention.

[0032] Figure 3 is a graph showing the results of characteristic evaluation of a glycol gel according to an embodiment of the present invention using Differential Scanning Calorimetry (DSC).

[0033] Figure 4 is a graph showing the results of a characteristic evaluation of a glycol gel according to one embodiment of the present invention using a Dynamic Mechanical Analyzer (DMA).

[0034] Figure 5 is an image and graph showing the results of shape memory characteristic evaluation for a glycol gel according to one embodiment of the present invention.

[0035] Figure 6 is a graph showing the results of the tensile property evaluation for a glycol gel according to one embodiment of the present invention.

[0036] Figure 7 is an image illustrating the structure and glass transition temperature of glass-forming polymers and entangled-forming polymers.

[0037] FIG. 8 is a graph showing the results of the tensile property evaluation for a glycol gel according to one embodiment of the present invention.

[0038] FIG. 9 is a graph showing the results of the tensile property evaluation for a glycol gel according to one embodiment of the present invention.

[0039] FIG. 10 is a graph showing the results of the tensile property evaluation for a glycol gel according to one embodiment of the present invention.

[0040]

[0041] Embodiments of the present invention are described below with reference to the attached drawings so that those skilled in the art can easily implement them. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0042] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0043] As used herein, terms of degree such as “about,” “substantially,” etc., are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the stated meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute values ​​are mentioned to aid in understanding the invention. Furthermore, throughout this specification, “a step of” or “a step of” does not mean “a step for”.

[0044] Throughout this specification, the term “combination thereof” included in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including one or more selected from the group consisting of said components.

[0045] Throughout the entire specification, the description "A and / or B" means "A or B, or, A and B".

[0046] The glycol gel according to the present invention comprises a solvent containing a glycol-based solution and a cross-linked polymer support having a three-dimensional network structure, wherein the polymer support comprises a glass phase and an entangled phase.

[0047] Glycol is a general term for dihydric alcohols, and various types exist, including ethylene glycol, propylene glycol, and butylene glycol. Inexpensive ethylene glycol is widely used in industry as an antifreeze, while propylene glycol has been reported to pose very low human health risks in safety assessments by the DA, USEPA, NTP, and ATSDR. Butylene glycol is a food additive approved by the U.S. FDA and has been rated as a Grade 1 safe substance by the Environmental Working Group (EWG), indicating a very low risk of cancer, allergies, and skin immune reactions. Furthermore, glycols have lower freezing points and higher boiling points compared to other liquids; propylene glycol has a freezing point of -59°C and a boiling point of 187°C, while butylene glycol has a freezing point of -77°C and a boiling point of 207°C. Therefore, glycols can exist in a stable liquid state over a wide temperature range, from sub-zero temperatures to over 100°C. Therefore, utilizing this as a new solvent for polymer gels can solve all the aforementioned problems, such as volatility, low biocompatibility, and high cost, at once.

[0048] Figure 1 is a graph comparing the properties of polymer gels according to the solvent. It can be seen that glycol is superior to water and expensive ionic liquids in terms of biocompatibility, usable temperature, mechanical properties, and price, and is equivalent to or superior to them except for the maximum usable temperature.

[0049] Meanwhile, conventionally known highly entangled gels have the advantage of improving ductility and toughness by forming a structure in which polymer chains are entangled. This dense entanglement does not easily break because it transmits force to many other chains along the elongated polymer chains when deformation is applied to the gel, and as a result, these gels exhibit high ductility, toughness, and fatigue resistance. However, there are still limits to the improvement of stiffness.

[0050] In order to solve this problem, the present invention ensures that the polymer support in the gel contains both a glass phase and an entangled phase. Vitrification refers to the glass transition temperature (T g It refers to the process in which a polymer having ) forms a glassy solid at a temperature below its glass transition temperature. By applying this vitrification phenomenon to a gel, the stiffness can be significantly improved.

[0051] This concept is illustrated in FIG. 2. By using glycol as a solvent and mixing and reacting a polymer favorable for glass phase formation with a polymer favorable for entanglement phase formation to form a polymer support having a mixture of glass phase and entanglement phase, a glycol gel according to the present invention can be provided.

[0052] Accordingly, the glycol gel according to the present invention is characterized by having not only a melting point but also a glass transition temperature. The melting point and glass transition temperature depend on the melting point and glass transition temperature of the polymer support formed inside the gel.

[0053] These glass transition temperatures and melting points can be measured using Differential Scanning Calorimetry (DSC) or a Dynamic Mechanical Analyzer (DMA).

[0054] First, the melting point can be easily measured using a differential scanning calorimeter, and the glycol gel according to the present invention may be characterized by having a melting point of 160°C or higher when measured under conditions of increasing the temperature at a rate of 10°C / min using a differential scanning calorimeter.

[0055] In a polymer support in which a glass phase and an entangled phase coexist, as the temperature rises, the solid phase of the polymer support melts and an endothermic reaction occurs, allowing the melting point to be measured. The temperature is 160°C or higher, which is a higher level compared to conventional gels.

[0056] Meanwhile, since the gel contains about 60% to 90% of the solvent, the polymer concentration is low, and the mobility of the polymer chains is limited due to the cross-linked structure. As a result, the glass transition temperature may become very low or lower than the freezing point of the solvent, so the glass transition temperature may not be observed by differential scanning calorimetry. Accordingly, the glass transition temperature can be observed through dynamic mechanical analyzers, and in the glycol gel according to the present invention, the polymer support can have a glass transition temperature of 110°C or higher when heated at a heating rate of 3°C / min while applying a 0.05% strain in tensile mode and measured under a frequency condition of 1 Hz.

[0057] Furthermore, the glycol gel according to the present invention can possess temperature-dependent shape memory properties. Above the glass transition temperature of the polymer support, plastic deformation occurs upon application of force, thereby maintaining the deformed state; however, when the temperature is lowered below the glass transition temperature, the polymer support undergoes a phase change to a glassy state and can return to its original state prior to the application of force. Accordingly, the glycol gel according to the present invention can possess temperature-dependent shape memory properties around the glass transition temperature.

[0058] The glycol gel according to the present invention is characterized by the coexistence of a glass phase and an entangled phase as described above. Accordingly, it can have excellent toughness, and in particular, can have a tensile strength of 15 MPa or more.

[0059] Meanwhile, the glycol gel according to the present invention can enhance its effectiveness by being applied particularly to flexible electronic devices. In particular, it can be applied to flexible electronic devices used in displays that require expansion and bending functions.

[0060] Flexible electronic devices are electronic devices that secure flexibility by utilizing elastomer or gel materials, and the glycol gel according to the present invention is stable even at high process temperatures, so when included in a flexible electronic device, process stability can be improved.

[0061] In addition, it possesses shape memory characteristics around the glass transition temperature, allowing for easy processing at high process temperatures and enabling it to return to its original dimensions when the temperature is lowered, thereby enhancing process convenience.

[0062] The polymer support containing a glass phase in the glycol gel according to the present invention includes both a glass phase and an entangled phase simultaneously as described above. To this end, in the glycol gel according to the present invention, the polymer support comprises a glassy polymer selected from the group consisting of polyacrylamide (PAAm), polyacrylic acid (PAAc), polymethacrylic acid (PMAA), poly 2-hydroxyethyl methacrylate (PHEMA), poly N-isopropyl acrylamide (PNIPAAm), polyacrylonitrile (PAN), nylon (Polyamide), polyethylene terephthalate (PET), polyurethane (PU), polyvinyl alcohol (PVA), polycaprolactone (PCL), and combinations thereof, and poly N,N-dimethylacrylamide (PDMAA), polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polyisobutyl methacrylate (PIBMA), polyisopropyl acrylate (PIPA), polymethoxyethyl methacrylate (PMEMA), polyethylene oxide (PEO), polypropylene oxide (PPO), poly It may be characterized by including an entangled polymer selected from the group consisting of styrene (PS), polyisoprene, polytetrafluoroethylene (PTFE), and combinations thereof.

[0063] For the formation of a glassy phase of a polymer, hydrogen bonds, ionic bonds, or alignment of polymer chains must basically be present, and for this, the aforementioned polymers can be a possible combination. In addition, for the formation of an entangled phase, the monomer must be dissolved in the solvent at a sufficient concentration or higher before polymerization so that long polymer chains can be formed during the polymerization process to form an entangled phase, and the polymer suitable for this can be the aforementioned entangled polymer.

[0064] Meanwhile, a method for manufacturing a glycol gel according to the present invention described above may include ultraviolet irradiation, and may include the steps of preparing a mixture by adding and dissolving a first monomer for forming a glassy polymer, a second monomer for forming an entangled polymer, a crosslinking agent, and an initiator into a glycol solvent, and irradiating the mixture with ultraviolet light.

[0065] Glassy polymers must have hydrogen bonds, ionic bonds, or alignment of polymer chains between polymer chains. Accordingly, the first monomer for forming the glassy polymer may be selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, N-isopropylacryamide, acrylonitrile, amide, ethylene terephthalate, urethane, vinyl alcohol, caprolactone, and combinations thereof. In particular, acrylamide, which is a monomer capable of hydrogen bonding, may be advantageous.

[0066] In addition, for entangled polymers, long polymer chains must be formed during the polymerization process, so it is necessary for the monomer to have a solubility of at least a certain level in a glycol solvent. To this end, the second monomer may be selected from the group consisting of N,N-dimethylacrylamide, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, isopropyl acrylate, methoxyethyl methacrylate, ethylene oxide, propylene oxide, styrene, isoprene, tetrafluoroethylene, and combinations thereof.

[0067] In addition, the crosslinking agent and the initiator can be poly(ethylene glycol) diacrylate and 2-hydroxy-2-methylpropiophenone, respectively.

[0068] The glycol solvent may be a solution composed of ethylene glycol, propylene glycol, butylene glycol, or a combination thereof.

[0069] Meanwhile, the concentration in the mixture of the polymer containing the first monomer, the second monomer, and the crosslinking agent needs to be 6M or higher. This is a condition for the formation of long polymer chains for the entanglement phase.

[0070]

[0071] [Example]

[0072] Preparation of ingredients

[0073] Acrylamide (monomer), N,N-dimethylacrylamide (monomer), poly(ethylene glycol) diacrylate (crosslinking agent), 2-hydroxy-2-methylpropiophenone (initiator), and 1,3-butylene glycol (solvent) were prepared.

[0074]

[0075] Synthesis of glycol gel through photopolymerization

[0076] Acrylamide, N,N-dimethylacrylamide, a crosslinking agent, and an initiator were dissolved in 1,3-butylene glycol at 100 °C. The mixture was transferred to a UV-transmitting mold of the desired shape and polymerization was carried out by exposure to UV light. Glycol gels were prepared by varying the monomer ratios and UV irradiation conditions. The conditions of the prepared examples are shown in Table 1 below.

[0077]

[0078] UV Intensity (mW / cm²) UV Irradiation Time Acrylamide (AAm) Dimethylacrylamide (DMA) Poly(ethylene glycol) diacrylate (crosslinking agent) Polymer Concentration Example 1 5 30 mins 160 (mol%) 40 (mol%) 0.1 (mol%) 8M Example 2 2 0 40 sec 160 (mol%) 40 (mol%) 0.1 (mol%) 8M Example 3 2 0 40 sec 180 (mol%) 20 (mol%) 0.1 (mol%) 8M Example 4 2 0 40 sec 160 (mol%) 40 (mol%) 0.1 (mol%) 6M Example 5 2 0 40 sec 140 (mol%) 60 (mol%) 0.1 (mol%) 6M Example 6 2 0 40 sec 120 (mol%) 80 (mol%) 0.1 (mol%) 6M Example 7 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 6M Example 8 200 40 sec 40 (mol%) 160 (mol%) 0.1 (mol%) 6M Example 9 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 6M Example 10 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 6.5M Example 11 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 7M Example 12 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 7.5M Example 13 200 40 sec 100 (mol%) 100 (mol%) 0.1 (mol%) 8M

[0079] Figure 3 shows measurement data obtained through differential scanning calorimetry. Figure 3(a) shows the result of measuring only the solvent, butylene glycol, which exhibits a strong endothermic peak around 240°C, which corresponds to the boiling point of the solvent, butylene glycol.

[0080] Figures 3(b), (c), and (d) show the measurement results for Example 1, Example 2, and Example 3, respectively. The endothermic peaks appearing at 184.24°C, 193.53°C, and 201.96°C, respectively, were determined to correspond to the melting point of the polymer support. This confirmed that a glass phase was formed within the glycol. Meanwhile, a fine endothermic peak appeared at temperatures lower than the melting point, which was confirmed to correspond to the glass transition temperature. Through this, it was confirmed that the glycol gel according to the present invention contains a glass phase.

[0081] Comparing Examples 2 and 3, it was confirmed that the melting point was higher when the content of the glassy acrylamide was higher. In addition, the melting point was higher as a result of reducing the UV irradiation time and increasing the intensity.

[0082] Meanwhile, as can be seen in Figure 3, the endothermic peak corresponding to the melting point is clearly visible, but the endothermic peak corresponding to the glass transition temperature appears very low due to the high solvent content and the low mobility of the polymer chains.

[0083] To more clearly understand this glass transition temperature, it becomes possible to measure the glass transition temperature by evaluating the rate of change of the elastic modulus through dynamic mechanical analysis.

[0084] To this end, the glass transition temperature was observed through the change in E' (Storage modulus, dynamic elastic modulus) and Tan Delta of the glycol gel according to Example 2 under a frequency condition of 1 Hz while applying a deformation of 0.05% in tensile mode and heating at a rate of 3℃ / min using a dynamic mechanical analyzer. Figure 4 shows the resulting graph, which indicates that the temperature at which Tan Delta has a maximum value is 125℃, which represents the glass transition temperature.

[0085] Meanwhile, it was confirmed that the rate of change of E' changes by approximately 250 times, from 110.6 to 0.43, around the glass transition temperature. This indicates that shape memory properties can be possessed around the glass transition temperature.

[0086] Figure 5 shows the results of evaluating the shape memory properties of the glycol gel according to Example 2. It was observed that the glycol gel returned to its original shape when deformed above its glass transition temperature and then lowered below its glass transition temperature. By utilizing these properties, it can be applied to flexible electronic devices, allowing for easy processing at high process temperatures and subsequent shrinkage to return to its original dimensions at low temperatures, thereby achieving high processability.

[0087] Figure 6 shows the results of evaluating the tensile properties of the glycol gel according to Example 2 at room temperature by repeating the evaluation several times. It was confirmed that it exhibits high strength and elongation.

[0088] In addition, to demonstrate that phase separation between polymers in a glycol solvent can be applied to other polymers in the same manner, two additional candidate polymers were selected and polymerized in addition to polyacrylamide and polydimethylacrylamide. During this process, it was confirmed that polymers exhibiting strong interactions with the glycol solvent due to weak interactions with the glycol solvent (e.g., PAAm, PNIPAAm, PAN, etc.) formed a glass phase with a glass transition temperature higher than room temperature, while conversely, polymers interacting strongly with the glycol solvent (e.g., PDMA, PAAc, PHEA, etc.) formed an entangled phase with a glass transition temperature lower than room temperature (see Fig. 7). These results demonstrate that the concept of a glycol gel containing both a glass phase and an entangled phase is not limited to a specific polymer system but can be extended to various polymer systems.

[0089] Figure 8 shows the results of the tensile property evaluation for Examples 4 to 8. It was observed that as the concentration of AAm increased, the strength increased but the elongation decreased. Therefore, it was found that strength and elongation could be controlled by adjusting the concentration.

[0090] Figure 9 shows the results of tensile property evaluation when the total polymer concentration is varied while the molar ratio of AAm and DMA is kept the same in Examples 9 to 13. It was observed that as the concentration increased, the strength increased and the elongation decreased, thereby enabling control of strength-elongation characteristics.

[0091] Meanwhile, Figure 10 shows the results of the tensile property evaluation for a glycol gel prepared by applying HEMA (Hydroxyethylmethacrylate) instead of AAm as the monomer, with a HEMA : DMA = 5 : 5 ratio and a polymer concentration of 7 M. It exhibited a combination of high strength and excellent elongation.

Claims

1. A solvent containing a glycol-based solution and It includes a cross-linked polymer support having a three-dimensional network structure, and The above polymer support is a glycol gel comprising a glass phase and an entangled phase.

2. In Paragraph 1, The glycol gel above, wherein the polymer support has a glass transition temperature and a melting point.

3. In Paragraph 2, A glycol gel in which the melting point of the polymer support, measured under conditions of heating the glycol gel at a rate of 10°C / min using Differential Scanning Calorimetry (DSC), is 160°C or higher.

4. In Paragraph 2, A glycol gel in which the glass transition temperature of the polymer support measured at 1 Hz while applying a 0.05% strain in tensile mode using a Dynamic Mechanical Analyzer (DMA) is 110°C or higher.

5. In Paragraph 2, Glycol gel having temperature-dependent shape memory properties around the above glass transition temperature.

6. In Paragraph 1, Glycol gel with a maximum tensile strength of 15 MPa or more.

7. In Paragraph 1, The above polymer support is a glassy polymer selected from the group consisting of polyacrylamide (PAAm), polyacrylic acid (PAAc), polymethacrylic acid (PMAA), poly 2-hydroxyethyl methacrylate (PHEMA), poly N-isopropylacrylamide (PNIPAAm), polyacrylonitrile (PAN), nylon (Polyamide), polyethylene terephthalate (PET), polyurethane (PU), polyvinyl alcohol (PVA), polycaprolactone (PCL), and combinations thereof, and Glycol gel comprising an entangled polymer selected from the group consisting of poly N,N-dimethylacrylamide (PDMAA), polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polyisobutyl methacrylate (PIBMA), polyisopropyl acrylate (PIPA), polymethoxyethyl methacrylate (PMEMA), polyethylene oxide (PEO), polypropylene oxide (PPO), polystyrene (PS), polyisoprene, polytetrafluoroethylene (PTFE), and combinations thereof.

8. A method for manufacturing a glycol gel according to any one of claims 1 to 7, A step of preparing a mixture by adding and dissolving a first monomer for forming a glassy polymer, a second monomer for forming an entangled polymer, a crosslinking agent, and an initiator in a glycol solvent; and A method for preparing a glycol gel, comprising the step of irradiating the above mixture with ultraviolet light.

9. In Paragraph 8, A method for preparing a glycol gel, wherein the first monomer is selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, N-isopropylacryamide, acrylonitrile, amide, ethylene terephthalate, urethane, vinyl alcohol, caprolactone, and combinations thereof.

10. In Paragraph 8, A method for preparing a glycol gel, wherein the second monomer is selected from the group consisting of N,N-dimethylacrylamide, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, isopropyl acrylate, methoxyethyl methacrylate, ethylene oxide, propylene oxide, styrene, isoprene, tetrafluoroethylene, and combinations thereof.

11. In Paragraph 8, A method for preparing a glycol gel, wherein the polymer concentration of the first monomer, the second monomer, and the crosslinking agent in the above mixture is 6M or higher.

12. A flexible electronic device comprising a glycol gel according to any one of claims 1 to 7.

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