Preparation method of high-temperature-resistant and high-toughness respiratory membrane

Abstract

The present disclosure relates to the technical field of high polymer materials, and particularly relates to a preparation method of a high-temperature-resistant and high-toughness respiratory membrane. The preparation method comprises the following steps: preparing first microparticles; the first microparticles are modified halloysite composite microparticles; then, polylactic acid, polybutylene succinate and polybutylene adipate terephthalate are dried and mixed to obtain a polymer premix; then, the first microparticles, the polymer premix, and a titanate compound, a reinforcing filler and an auxiliary agent are subjected to melt extrusion to obtain a master batch; finally, a blowing film process is performed to obtain the high-temperature-resistant and high-toughness respiratory membrane. The present disclosure provides a preparation method of a respiratory membrane with high air permeability, high-temperature resistance and high toughness.

Description

Technical Field

[0001] This disclosure relates to the field of polymer materials technology, and in particular to a method for preparing a high-temperature resistant and high-toughness breathing membrane. Background Technology

[0002] Breathable membranes, also known as "breathable films," are functional films with breathable properties. Currently, microporous breathable membranes are mainly made from polyolefins through casting and stretching methods, and are widely used in daily life fields such as agricultural films, mulch films, disposable medical protective clothing, pharmaceutical packaging, and food packaging, for scenarios requiring good breathability. An ideal medical breathable membrane needs to meet the following conditions simultaneously: (1) high gas flux; (2) high toughness; (3) high temperature resistance, preferably maintaining structural and performance stability under steam sterilization or dry heat sterilization conditions; (4) biocompatibility; (5) processing reliability, preferably being able to be continuously formed to achieve uniform thickness and few defects.

[0003] Existing technologies generally use polyolefin (PP / PE) hollow fiber membranes, polysulfone (PSF) or polytetrafluoroethylene (PTFE) microporous membranes as gas exchange layers, supplemented by silicone rubber or polyurethane coatings to seal the micropores. However, these solutions have obvious shortcomings: (1) Polyolefin membranes have poor heat resistance, and will shrink and creep significantly when the sterilization temperature is high, resulting in the collapse of the pore structure and a decrease in gas flux; (2) Polysulfone microporous membranes have low elongation at break, and are prone to cracking during bending or encapsulation; (3) Silicone rubber coatings have high air permeability, but low modulus and poor tear strength. After high-temperature sterilization, they crosslink and age, and the surface is prone to stickiness and embrittlement. In order to balance air permeability and barrier properties, existing technologies use a "polyolefin + hydrophilic / hydrophobic double-layer coating" process, which is complex, costly, and has a large difference in the coefficient of thermal expansion between the coating and the substrate, which is prone to interfacial peeling.

[0004] Therefore, there is an urgent need for a method to prepare a breathable membrane that is simple to process, allows for continuous film formation, and also has high air permeability, high temperature resistance, and high toughness. Summary of the Invention

[0005] This disclosure provides a method for preparing a high-temperature resistant and high-toughness breathing membrane to address the shortcomings of related technologies.

[0006] According to a first aspect of the present disclosure, a method for preparing a high-temperature resistant and high-toughness breathable membrane is provided, the method comprising the following steps: Step 1: Prepare the first microparticle; the first microparticle is a modified halloysite composite microparticle; Step 2: Provide polylactic acid, polybutylene succinate, and polybutylene adipate; dry and mix the polylactic acid, polybutylene succinate, and polybutylene adipate to obtain a polymer premix; Step 3: Provide titanate compounds, reinforcing fillers, and additives; the first microparticles obtained in Step 1, the polymer premix obtained in Step 2, and the titanate compounds, reinforcing fillers, and additives are melt-extruded to obtain masterbatch; Step 4: The masterbatch obtained in Step 3 is subjected to a blown film process to obtain the high-temperature resistant and high-toughness breathable membrane.

[0007] In one aspect of this disclosure, in the preparation method, the raw materials in steps 1 to 3 have the following parts by weight: 2-5 parts by weight of the first microparticle, 45-60 parts by weight of polylactic acid, 15-25 parts by weight of polybutylene adipate terephthalate, 10-20 parts by weight of polybutylene succinate, 0.5-2 parts by weight of titanate compound, 1-3 parts by weight of reinforcing filler and 5 parts by weight of additives.

[0008] In one aspect of the embodiments of this disclosure, specifically, in the preparation method, the raw materials in steps 1 to 3 have the following parts by weight: 2.5 parts by weight of the first microparticle, 55 parts by weight of polylactic acid, 20 parts by weight of polybutylene adipate terephthalate, 15 parts by weight of polybutylene succinate, 1 part by weight of titanate compound, 1.5 parts by weight of reinforcing filler and 5 parts by weight of additives.

[0009] In one aspect of the embodiments of this disclosure, the titanate compound is selected from one or more of tetrabutyl titanate, isopropyl dioleoyloxy titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, and isopropyl trioleoyloxy titanate.

[0010] In one aspect of the embodiments of this disclosure, the reinforcing filler is selected from one or more of carbon nanotubes, graphene, nano-hydrotalcite, nano-silica, nano-alumina, nano-zinc oxide, nano-titanium dioxide, and nano-magnesium oxide.

[0011] In one aspect of this disclosure, the modified halloysite composite microparticles are obtained by reacting epoxy-based polysilsesquioxane with modified halloysite microtubes.

[0012] In one aspect of this disclosure, the modified halloysite microtube is an halloysite microtube modified by alkali etching and amination; the halloysite microtube modified by alkali etching and amination is prepared by the following steps: Step 1-a: Provide halloysite microtubes; mix the halloysite microtubes with sodium hydroxide solution by stirring, and sonicate at 50℃-60℃ for 1-2 hours; Step 2-a: After ultrasonic treatment, the tubes are cooled to room temperature, then centrifuged, washed, and dried to obtain alkaline-etched halloysite microtubes; Step 3-a: Add the alkaline-etched halloysite microtubes to anhydrous ethanol, then add 3-aminopropyltriethoxysilane, water and glacial acetic acid in sequence; then heat to 75℃-85℃ and reflux for 10-16 hours; Step 4-a: After the reaction is complete, cool to room temperature, then centrifuge, wash and dry to obtain the halloysite microtubes modified by alkali etching and amination.

[0013] In one aspect of this disclosure, the epoxy-based polysilsesquioxane is prepared by the following steps: Step 1-b: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, add anhydrous ethanol and anhydrous methanol, stir and heat to 30℃-40℃, then add water and hydrochloric acid, and stir for 30-60 min; add phenyltriethoxysilane and β-3,4-epoxycyclohexylethyltrimethoxysilane dropwise; hydrolyze for 36-72 h to obtain a colorless and transparent liquid; Step 2-b: Add an alkaline solution to adjust the pH to neutral; remove the solvent by vacuum distillation, and obtain the epoxy-based polysilsesquioxane after washing, filtration, and drying.

[0014] In one aspect of this disclosure, the modified halloysite composite microparticles are prepared by the following steps: Step 1-c: The epoxy-based polysilsesquioxane prepared in step 2-b and the halloysite microtubes modified by alkali etching and amination prepared in step 4-a are ultrasonically dispersed in tetrahydrofuran, respectively. Step 2-c: Mix the dispersion and react it in a water bath at 70℃-80℃ for 10-16 hours under nitrogen protection; Step 3-c: Remove tetrahydrofuran by vacuum distillation; then wash and dry to obtain the modified halloysite composite microparticles.

[0015] In one aspect of the present disclosure, in step 3, extrusion is performed using a twin-screw extruder; the temperature range of the twin-screw extruder is sequentially set to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃.

[0016] In one aspect of the present disclosure, in step 4, a blown film machine is used to blow film; the temperature range of the blown film machine is sequentially set to 145℃-150℃, 155℃-160℃, 165℃-170℃ and 140℃-145℃; and the traction speed of the blown film machine is 5-7m / min, and the blow-up ratio is selected from 3-4.

[0017] In one aspect of this disclosure, the additives include one or more of the following: opening agents, lubricants, antioxidants, accelerators, chain extenders, and plasticizers.

[0018] In one aspect of this disclosure, the opening agent is selected from barium sulfate, diatomaceous earth, talc, clay, and calcium carbonate.

[0019] In one aspect of this disclosure, the lubricant is selected from pentaerythritol stearate, polyethylene wax, ethylene bis-stearamide, stearate, and dimethylsilane.

[0020] In one aspect of the embodiments of this disclosure, the antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 626, antioxidant 264, and antioxidant 2112.

[0021] In one aspect of the embodiments of this disclosure, the accelerator is selected from one of erucamide, stearamide, ethylene bis-stearamide, ethylene bis-oleamide, and phthalamide.

[0022] In one aspect of this disclosure, the chain extender is selected from isocyanate compounds or styrene-glycidyl acrylate.

[0023] In one aspect of this disclosure, the plasticizer is selected from tributyl citrate, glycerol, or epoxidized soybean oil.

[0024] According to a second aspect of the present disclosure, a breathing membrane is provided, which is prepared by the aforementioned preparation method.

[0025] According to a third aspect of the present disclosure, the application of the aforementioned breathing membrane in the field of medical devices is provided.

[0026] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects: As can be seen from the above embodiments, this disclosure provides a method for preparing a breathable membrane that combines high air permeability, high temperature resistance, and high toughness.

[0027] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Detailed Implementation

[0028] Exemplary embodiments will now be described in detail. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0029] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0030] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0031] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0032] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0033] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0034] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0035] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0036] The present disclosure will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present disclosure are obtained through conventional commercial means. Unless otherwise specified, all contents mentioned below are mass contents. Unless otherwise specified, it is understood that the process is carried out at room temperature. Example Example 1

[0037] Example 1 includes the following steps: 1. Preparation of halloysite microtubes modified by alkali etching and amination: Provide 25 parts by weight of halloysite microtubes; prepare 120 parts by weight of 1 mol / L sodium hydroxide aqueous solution; mix the halloysite microtubes and sodium hydroxide aqueous solution by stirring and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain alkaline-etched halloysite microtubes; distribute the alkaline-etched halloysite microtubes (approximately 2... 0 parts by weight) were added to 67 parts by weight of anhydrous ethanol, and then 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water and 4 parts by weight of glacial acetic acid were added in sequence; then the mixture was heated to 80°C and refluxed for 12 h; after the reaction was completed, the mixture was cooled to room temperature, and then centrifuged (centrifuged at 2000 rpm for 4 min), washed (washed with water once, washed with alcohol once, and then washed with water once), and dried (at 60°C) to obtain the halloysite microtubes modified by alkali etching and amination of Example 1 (about 20 parts by weight).

[0038] 2. Preparation of epoxy-based polysilsesquioxanes: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 142 parts by weight of anhydrous ethanol and 57 parts by weight of anhydrous methanol were added. The mixture was stirred and heated to 35°C. Water (twice the molar amount of water added) and 2 parts by weight of hydrochloric acid (2 mol / L) were then added, and the mixture was stirred for 45 min. 49 parts by weight of phenyltriethoxysilane and 7 parts by weight of β-3,4-epoxycyclohexylethyltrimethoxysilane were added dropwise. The hydrolysis reaction was carried out for 48 h to obtain a colorless and transparent liquid. Then, sodium hydroxide aqueous solution (0.25 mol / L) was added dropwise to adjust the pH to neutral. The solvent was removed by vacuum distillation. After washing, filtration, and drying, the epoxy-based polysilsesquioxane of Example 1 (approximately 41 parts by weight) was obtained. The chemical reaction process is shown below:

[0039] 3. Preparation of modified halloysite composite microparticles: 15 parts by weight of epoxy-based polysilsesquioxane and 20 parts by weight of halloysite microtubes modified by alkali etching and amination were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The mixture was then washed and dried to obtain the modified halloysite composite microparticles of Example 1.

[0040] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified halloysite composite microparticles, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Example 1.

[0041] Example 2: Example 2 includes the following steps: 1. Preparation of alkaline-etched halloysite microtubes: Provide 25 parts by weight of halloysite microtubes; prepare 120 parts by weight of 1 mol / L sodium hydroxide aqueous solution; stir and mix the halloysite microtubes and sodium hydroxide aqueous solution, and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, and then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain the alkaline-etched halloysite microtubes of Example 2 (approximately 20 parts by weight).

[0042] 2. Preparation of epoxy-based polysilsesquioxanes: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 142 parts by weight of anhydrous ethanol and 57 parts by weight of anhydrous methanol were added. The mixture was stirred and heated to 35°C. Water (the molar amount of water added was twice the molar amount of silane added later) and 2 parts by weight of hydrochloric acid (concentration 2 mol / L) were then added, and the mixture was stirred for 45 min. 49 parts by weight of phenyltriethoxysilane and 7 parts by weight of β-3,4-epoxycyclohexylethyltrimethoxysilane were added dropwise. The hydrolysis reaction was carried out for 48 h to obtain a colorless and transparent liquid. Then, an aqueous solution of sodium hydroxide (0.25 mol / L) was added dropwise to adjust the pH to neutral. The solvent was removed by vacuum distillation. After washing, filtration, and drying, the epoxy polysilsesquioxane of Example 2 (approximately 41 parts by weight) was obtained.

[0043] 3. Preparation of modified halloysite composite microparticles: 15 parts by weight of epoxy-based polysilsesquioxane and 20 parts by weight of alkaline-etched halloysite microtubes were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The particles were then washed and dried to obtain the modified halloysite composite microparticles of Example 2.

[0044] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified halloysite composite microparticles, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Example 2.

[0045] The main difference between Example 2 and Example 1 is that the halloysite microtubes in Example 2 were not modified by amination.

[0046] Example 3: Example 3 includes the following steps: 1. Preparation of halloysite microtubes modified by alkali etching and amination: 25 parts by weight of halloysite microtubes were provided; about 20 parts by weight of halloysite microtubes were added to 67 parts by weight of anhydrous ethanol, and then 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water and 4 parts by weight of glacial acetic acid were added in sequence; the mixture was then heated to 80°C and refluxed for 12 h; after the reaction was completed, the mixture was cooled to room temperature, and then centrifuged (centrifuged at 2000 rpm for 4 min), washed (washed with water once, washed with alcohol once, and then washed with water once), and dried (at 60°C) to obtain the aminated modified halloysite microtubes of Example 3 (about 25 parts by weight).

[0047] 2. Preparation of epoxy-based polysilsesquioxanes: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 142 parts by weight of anhydrous ethanol and 57 parts by weight of anhydrous methanol were added. The mixture was stirred and heated to 35°C. Water (twice the molar amount of water added) and 2 parts by weight of hydrochloric acid (2 mol / L) were then added, and the mixture was stirred for 45 min. 49 parts by weight of phenyltriethoxysilane and 7 parts by weight of β-3,4-epoxycyclohexylethyltrimethoxysilane were added dropwise. The hydrolysis reaction was carried out for 48 h to obtain a colorless and transparent liquid. Then, an aqueous solution of sodium hydroxide (0.25 mol / L) was added dropwise to adjust the pH to neutral. The solvent was removed by vacuum distillation. After washing, filtration, and drying, the epoxy-based polysilsesquioxane of Example 3 (approximately 41 parts by weight) was obtained. 3. Preparation of modified halloysite composite microparticles: 15 parts by weight of epoxy-based polysilsesquioxane and 20 parts by weight of aminated halloysite microtubes were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The mixture was then washed and dried to obtain the modified halloysite composite microparticles of Example 3.

[0048] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified halloysite composite microparticles, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Example 3.

[0049] The main difference between Example 3 and Example 1 is that the halloysite microtubes in Example 3 were not subjected to alkaline etching treatment.

[0050] Example 4: Example 4 includes the following steps: 1. Preparation of halloysite microtubes modified by alkali etching and amination: Provide 25 parts by weight of halloysite microtubes; prepare 120 parts by weight of 1 mol / L sodium hydroxide aqueous solution; mix the halloysite microtubes and sodium hydroxide aqueous solution by stirring and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain alkaline-etched halloysite microtubes; distribute the alkaline-etched halloysite microtubes (approximately 2... 0 parts by weight) were added to 67 parts by weight of anhydrous ethanol, and then 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water and 4 parts by weight of glacial acetic acid were added in sequence; then the mixture was heated to 80°C and refluxed for 12 h; after the reaction was completed, the mixture was cooled to room temperature, and then centrifuged (centrifuged at 2000 rpm for 4 min), washed (washed with water once, washed with alcohol once, and then washed with water once), and dried (at 60°C) to obtain the halloysite microtubes modified by alkali etching and amination of Example 4 (about 20 parts by weight).

[0051] 2. Provide polysilsesquioxane compounds: Commercially available octaaminopropylsilsesquioxane (POSS) is provided as a raw material.

[0052] 3. Preparation of modified halloysite composite microparticles: 15 parts by weight of octaaminopropylsilsesquioxane and 20 parts by weight of halloysite microtubes modified by alkali etching and amination were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The mixture was then washed and dried to obtain the modified halloysite composite microparticles of Example 4.

[0053] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified halloysite composite microparticles, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Example 4.

[0054] The main difference between Example 4 and Example 1 is that Example 4 uses commercially available octaaminopropyl silsesquioxane (POSS) as a raw material instead of the epoxy-based polysilsesquioxane prepared in Example 1.

[0055] Example 5: Example 5 includes the following steps: 1. Preparation of halloysite microtubes modified by alkali etching and amination: Provide 25 parts by weight of halloysite microtubes; prepare 120 parts by weight of 1 mol / L sodium hydroxide aqueous solution; mix the halloysite microtubes and sodium hydroxide aqueous solution by stirring and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain alkaline-etched halloysite microtubes; distribute the alkaline-etched halloysite microtubes (approximately 2... 0 parts by weight) were added to 67 parts by weight of anhydrous ethanol, and then 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water and 4 parts by weight of glacial acetic acid were added in sequence; then the mixture was heated to 80°C and refluxed for 12 h; after the reaction was completed, the mixture was cooled to room temperature, and then centrifuged (centrifuged at 2000 rpm for 4 min), washed (washed with water once, washed with alcohol once, and then washed with water once), and dried (at 60°C) to obtain the halloysite microtubes modified by alkali etching and amination of Example 4 (about 20 parts by weight).

[0056] 2. Provide polysilsesquioxane compounds: Commercially available octaisobutyl-cage polysilsesquioxane is provided as a raw material.

[0057] 3. Preparation of modified halloysite composite microparticles: 15 parts by weight of octaisobutyl-cage polysilsesquioxane and 20 parts by weight of halloysite microtubes modified by alkali etching and amination were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The mixture was then washed and dried to obtain the modified halloysite composite microparticles of Example 5.

[0058] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified halloysite composite microparticles, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Example 5.

[0059] The main difference between Example 5 and Example 1 is that Example 5 uses commercially available octaisobutyl-cage polysilsesquioxane as a raw material, instead of the epoxy-based polysilsesquioxane prepared in Example 1.

[0060] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of halloysite microtubes modified by alkali etching and amination: Provide 25 parts by weight of halloysite microtubes; prepare 120 parts by weight of 1 mol / L sodium hydroxide aqueous solution; mix the halloysite microtubes and sodium hydroxide aqueous solution by stirring and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain alkaline-etched halloysite microtubes; distribute the alkaline-etched halloysite microtubes (approximately 2... 0 parts by weight) were added to 67 parts by weight of anhydrous ethanol, followed by 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water and 4 parts by weight of glacial acetic acid; then the mixture was heated to 80°C and refluxed for 12 h; after the reaction was completed, the mixture was cooled to room temperature, and then centrifuged (centrifuged at 2000 rpm for 4 min), washed (washed with water once, washed with alcohol once, and then washed with water once again), and dried (at 60°C) to obtain the halloysite microtubes modified by alkali etching and amination of Comparative Example 1 (approximately 20 parts by weight).

[0061] 2. Preparation of respiratory membrane: Provide 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate; the polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer, mixed at 25 rpm for 10 min) to obtain a polymer premix; provide 1 part by weight of the titanate compound isopropyltris(dioctylpyrophosphoryloxy) titanate, 1.5 parts by weight of the reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of the lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of the accelerator erucamide); 2. Five parts by weight of alkali-etched and amination-modified halloysite microtubes, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. The extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Comparative Example 1.

[0062] The main difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not use polysilsesquioxane as a raw material.

[0063] Comparative Example 2: Comparative Example 2 includes the following steps: 1. Preparation of epoxy-based polysilsesquioxanes: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 142 parts by weight of anhydrous ethanol and 57 parts by weight of anhydrous methanol were added. The mixture was stirred and heated to 35°C. Water (the molar amount of water added was twice the molar amount of silane added later) and 2 parts by weight of hydrochloric acid (concentration 2 mol / L) were then added, and the mixture was stirred for 45 min. 49 parts by weight of phenyltriethoxysilane and 7 parts by weight of β-3,4-epoxycyclohexylethyltrimethoxysilane were added dropwise. The hydrolysis reaction was carried out for 48 h to obtain a colorless and transparent liquid. Then, an aqueous solution of sodium hydroxide (0.25 mol / L) was added dropwise to adjust the pH to neutral. The solvent was removed by vacuum distillation. After washing, filtration, and drying, the epoxy polysilsesquioxane of Example 2 (approximately 41 parts by weight) was obtained.

[0064] 2. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of epoxy-based polysilsesquioxane, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Comparative Example 2.

[0065] The main difference between Comparative Example 2 and Example 1 is that Comparative Example 2 does not use halloysite microtubes as raw materials.

[0066] Comparative Example 3: Comparative Example 3 includes the following steps: 1. Preparation of silica microspheres modified by alkaline etching and amination: Provide 25 parts by weight of silica microspheres (D50 value 10 μm, commercially available); prepare 120 parts by weight of a 1 mol / L sodium hydroxide aqueous solution; mix the silica microspheres and sodium hydroxide aqueous solution by stirring and disperse by ultrasonication (20 kHz) at 50 °C for 1.5 h; after ultrasonication, cool to room temperature, then centrifuge (centrifuge at 2000 rpm for 4 min), wash (wash once with water, wash once with alcohol, and then wash once with water), and dry (at 60 °C) to obtain alkaline-etched silica microspheres; [The text abruptly ends here, likely due to an incomplete sentence or missing information.] 20 parts by weight of silica microspheres were added to 67 parts by weight of anhydrous ethanol, followed by 6 parts by weight of 3-aminopropyltriethoxysilane, 15 parts by weight of water, and 4 parts by weight of glacial acetic acid. The mixture was then heated to 80°C and refluxed for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and then centrifuged (4 min at 2000 rpm), washed (once with water, once with alcohol, and then once with water), and dried (at 60°C) to obtain approximately 20 parts by weight of silica microspheres modified by alkali etching and amination as in Comparative Example 3.

[0067] 2. Preparation of epoxy-based polysilsesquioxanes: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 142 parts by weight of anhydrous ethanol and 57 parts by weight of anhydrous methanol were added. The mixture was stirred and heated to 35°C. Water (the molar amount of water added was twice the molar amount of silane added later) and 2 parts by weight of hydrochloric acid (concentration 2 mol / L) were then added, and the mixture was stirred for 45 min. 49 parts by weight of phenyltriethoxysilane and 7 parts by weight of β-3,4-epoxycyclohexylethyltrimethoxysilane were added dropwise. The hydrolysis reaction was carried out for 48 h to obtain a colorless and transparent liquid. Then, an aqueous solution of sodium hydroxide (0.25 mol / L) was added dropwise to adjust the pH to neutral. The solvent was removed by vacuum distillation. After washing, filtration, and drying, approximately 41 parts by weight of epoxy-based polysilsesquioxane (Comparative Example 3) was obtained.

[0068] 3. Preparation of modified silica microspheres: 15 parts by weight of epoxy-based polysilsesquioxane and 20 parts by weight of silica microspheres modified by alkali etching and amination were ultrasonically dispersed in 40 parts by weight of tetrahydrofuran. The dispersions were mixed and reacted in a water bath at 75°C for 12 hours under nitrogen protection. After the reaction was completed, the tetrahydrofuran was removed by vacuum distillation. The microspheres were then washed and dried to obtain the modified silica microspheres of Comparative Example 3.

[0069] 4. Preparation of respiratory membrane: The product comprises 55 parts by weight of polylactic acid (PLA D070), 15 parts by weight of polybutylene succinate, and 20 parts by weight of polybutylene adipate-terephthalate. The polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate are dried and mixed (using a V-type mixer at 25 rpm for 10 min) to obtain a polymer premix. It also comprises 1 part by weight of a titanate compound isopropyltris(dioctylpyrophosphate) titanate, 1.5 parts by weight of a reinforcing filler nano-silica (D50 value of 100 nm), and 5 parts by weight of additives (2.5 parts by weight of a lubricant pentaerythritol stearate, 1 part by weight of antioxidant 1010, and 1.5 parts by weight of an accelerator erucamide). 2.5 parts by weight of modified silica microspheres, polymer premix, titanate compound, reinforcing filler, and additives were melt-extruded to obtain masterbatch. Extrusion was performed using a twin-screw extruder with temperature ranges set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. Then, a blown film extrusion was performed using a blown film extruder with temperature ranges set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃, and 140℃-145℃. The blown film extruder had a traction speed of 5 m / min and a blow-up ratio of 4, resulting in the breathable membrane of Comparative Example 3.

[0070] Performance testing: Mechanical property testing: The tensile strength and elongation at break of the samples of Examples 1-5 and Comparative Examples 1-3 were tested according to the testing standard ISO527; the results are shown in Table 1.

[0071] Heat resistance test: The samples of Examples 1-5 and Comparative Examples 1-3 were cut into 100mm*100mm sizes and placed at 120℃ under no-load conditions for 30 minutes. The side length was measured again to obtain the heat shrinkage rate. The results are shown in Table 1.

[0072] Air permeability test: The oxygen permeability of the samples in Examples 1-5 and Comparative Examples 1-3 was tested according to GB / T 1038-2000. The oxygen permeability of the film samples was characterized by testing with an OX2 / 2231 oxygen permeability tester at room temperature and relative humidity of (50±5)%. The results are shown in Table 1.

[0073] Table 1

[0074] This disclosure discloses a halloysite microparticle obtained by using epoxy-based polysilsesquioxane and halloysite microtubes modified by alkali etching and amination. When added to polylactic acid, polybutylene succinate, and polybutylene adipate-terephthalate masterbatches, the resulting blown film produces a breathable membrane that combines high permeability, high temperature resistance, and high toughness. Comparative examples 1, 3, and 2-3 show that the breathable membrane obtained in this application has excellent permeability. This is because the inner diameter of the halloysite microtubes is further enlarged after alkali etching, forming good gas diffusion channels. Comparing Examples 1-2 and Examples 4-5, it can be seen that the breathable membrane prepared by the epoxy polysilsesquioxane prepared in this application has better overall performance. This is because the epoxy polysilsesquioxane can (1) react with the carboxyl / hydroxyl end groups of PLA to generate a branched-crosslinked structure of PLA, thereby increasing the mechanical properties and heat resistance of the membrane; (2) also react with the terminal carboxyl groups or ester bond side groups of PBAT to reduce the size of the PBAT dispersed phase, improve interfacial adhesion, and increase the mechanical properties and heat resistance of the membrane; (3) combine with the amino groups of the aminated halloysite microtubes to improve the degree of dispersion, improve interfacial adhesion, and increase the mechanical properties and heat resistance of the membrane.

[0075] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method for preparing a high-temperature resistant and high-toughness breathable membrane, characterized in that, The preparation method includes the following steps: Step 1: Prepare the first microparticle; the first microparticle is a modified halloysite composite microparticle; Step 2: Provide polylactic acid, polybutylene succinate, and polybutylene adipate; dry and mix the polylactic acid, polybutylene succinate, and polybutylene adipate to obtain a polymer premix; Step 3: Provide titanate compounds, reinforcing fillers, and additives; the first microparticles obtained in Step 1, the polymer premix obtained in Step 2, and the titanate compounds, reinforcing fillers, and additives are melt-extruded to obtain masterbatch; Step 4: The masterbatch obtained in Step 3 is subjected to a blown film process to obtain the high-temperature resistant and high-toughness breathable membrane.

2. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 1, characterized in that, In the preparation method, the raw materials in steps 1 to 3 have the following parts by weight: 2-5 parts by weight of the first microparticle, 45-60 parts by weight of polylactic acid, 15-25 parts by weight of polybutylene adipate terephthalate, 10-20 parts by weight of polybutylene succinate, 0.5-2 parts by weight of titanate compound, 1-3 parts by weight of reinforcing filler and 5 parts by weight of additives.

3. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 1 or 2, characterized in that, The titanate compounds are selected from one or more of tetrabutyl titanate, isopropyl dioleoyloxy titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, and isopropyl trioleoyloxy titanate.

4. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 1 or 2, characterized in that, The reinforcing filler is selected from one or more of the following: carbon nanotubes, graphene, nano-hydrotalcite, nano-silica, nano-alumina, nano-zinc oxide, nano-titanium dioxide, and nano-magnesium oxide.

5. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 1, characterized in that, The modified halloysite composite microparticles are obtained by reacting epoxy-based polysilsesquioxane with modified halloysite microtubes.

6. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 5, characterized in that, The modified halloysite microtubes are halloysite microtubes modified by alkali etching and amination; the halloysite microtubes modified by alkali etching and amination are prepared by the following steps: Step 1-a: Provide halloysite microtubes; mix the halloysite microtubes with sodium hydroxide solution by stirring, and sonicate at 50℃-60℃ for 1-2 hours; Step 2-a: After ultrasonic treatment, the tubes are cooled to room temperature, then centrifuged, washed, and dried to obtain alkaline-etched halloysite microtubes; Step 3-a: Add the alkaline-etched halloysite microtubes to anhydrous ethanol, then add 3-aminopropyltriethoxysilane, water and glacial acetic acid in sequence; then heat to 75℃-85℃ and reflux for 10-16 hours; Step 4-a: After the reaction is complete, cool to room temperature, then centrifuge, wash and dry to obtain the halloysite microtubes modified by alkali etching and amination.

7. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 5, characterized in that, The epoxy-based polysilsesquioxane is prepared by the following steps: Step 1-b: In a three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, add anhydrous ethanol and anhydrous methanol, stir and heat to 30℃-40℃, then add water and hydrochloric acid, and stir for 30-60 min; add phenyltriethoxysilane and β-3,4-epoxycyclohexylethyltrimethoxysilane dropwise; hydrolyze for 36-72 h to obtain a colorless and transparent liquid; Step 2-b: Add an alkaline solution to adjust the pH to neutral; remove the solvent by vacuum distillation, and obtain the epoxy-based polysilsesquioxane after washing, filtration, and drying.

8. The method for preparing a high-temperature resistant and high-toughness breathable membrane according to any one of claims 5-7, characterized in that, The modified halloysite composite microparticles were prepared through the following steps: Step 1-c: The epoxy-based polysilsesquioxane prepared in step 2-b and the halloysite microtubes modified by alkali etching and amination prepared in step 4-a are ultrasonically dispersed in tetrahydrofuran, respectively. Step 2-c: Mix the dispersion and react it in a water bath at 70℃-80℃ for 10-16 hours under nitrogen protection; Step 3-c: Remove tetrahydrofuran by vacuum distillation; then wash and dry to obtain the modified halloysite composite microparticles.

9. The method for preparing a high-temperature resistant and high-toughness breathable membrane according to claim 1, characterized in that, In step 3, extrusion is performed using a twin-screw extruder; the temperature range of the twin-screw extruder is set sequentially to 150℃-155℃, 160℃-165℃, 170℃-175℃, and 180℃-185℃. In step 4, a blown film machine is used for blown film production; the temperature range of the blown film machine is set sequentially to 145℃-150℃, 155℃-160℃, 165℃-170℃ and 140℃-145℃; and the traction speed of the blown film machine is 5-7m / min, and the blow-up ratio is selected from 3-4.

10. The method for preparing the high-temperature resistant and high-toughness breathable membrane according to claim 1, characterized in that, The additives include one or more of the following: opening agents, lubricants, antioxidants, accelerators, chain extenders, and plasticizers; wherein: The opening agent is selected from one of barium sulfate, diatomaceous earth, talc, clay, and calcium carbonate; The lubricant is selected from one of pentaerythritol stearate, polyethylene wax, ethylene bis-stearamide, stearate, and dimethylsilane; The antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 626, antioxidant 264, and antioxidant 2112; The accelerator is selected from one of erucamide, stearamide, ethylene bis-stearamide, ethylene bis-oleamide, and phthalamide; The chain extender is selected from isocyanate compounds or styrene-glycidyl acrylate; The plasticizer is selected from tributyl citrate, glycerin, or epoxidized soybean oil.

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