High-strength degradable packaging material and application thereof in cosmetic packaging material

Abstract

The invention relates to the technical field of environment-friendly materials, and discloses a high-strength degradable packaging material and application of the high-strength degradable packaging material in cosmetic packaging materials.The preparation method of the high-strength degradable packaging material comprises the steps that polylactic acid, vanillic aldehyde modified polyester, polyadipic acid, triethyl citrate, calcium stearate and an antioxidant are added into a high-speed mixing machine, and the mixture is stirred to be uniform; mixing at 60 to 80 DEG C for 10 to 20 minutes to obtain a mixed material; the mixed material is subjected to melt blending through a double-screw extruder, the blending temperature is 160-180 DEG C, the screw rotating speed is 250-300 rpm, extrusion granulation and drying are conducted, and the high-strength degradable packaging material is obtained. The high-strength degradable packaging material can be applied to cosmetic packaging materials such as bottle bodies, bottle caps, hoses and packaging boxes. The prepared packaging material is high in mechanical strength and has good degradability and flame retardance.

Description

Technical Field

[0001] The present invention relates to the technical field of environmentally friendly materials, and in particular to a high-strength degradable packaging material and its application in cosmetic packaging. Background Art

[0002] Traditional cosmetic packaging mostly uses materials such as petroleum-based polyethylene and polypropylene. Due to their non-degradability, their production and use have brought serious environmental problems. Early degradable materials have problems such as low mechanical strength, making it difficult to replace components such as cosmetic bottles and pump heads that require high sealing and drop resistance. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN120059275A discloses a PET material surface treatment agent and a method for using the same. The PET material surface treatment agent, measured by weight, includes 12-20 parts of an alcoholysis agent, 5-8 parts of a small molecule hydrophilic substance, and 8-10 parts of an anti-hydrolysis agent. The PET material surface treatment agent treats the interior of the PET material with a hydrophilic property. When used as a cosmetic packaging material, it can absorb and retain moisture in cosmetics, prevent the loss of moisture in cosmetics, and maintain the stability and effectiveness of cosmetics. However, the strength is low and the degradability needs to be improved. Summary of the Invention

[0003] Technical problems solved

[0004] In response to the shortcomings of the existing technology, the present invention provides a high-strength degradable packaging material and its application in cosmetic packaging. The packaging material prepared by the present invention has high mechanical strength, good degradability and flame retardant properties, and can be used in cosmetic packaging materials such as bottles, bottle caps, hoses, and packaging boxes.

[0005] Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a high-strength degradable packaging material, comprising the following components by weight: 50-70 parts by weight of polylactic acid, 3-5 parts by weight of vanillin-modified polyester, 12-15 parts by weight of polyadipic acid, 2-5 parts by weight of triethyl citrate, 1-3 parts by weight of calcium stearate, and 0.5-1 part by weight of an antioxidant.

[0007] Furthermore, the preparation method of the vanillin-modified polyester is:

[0008] S1: Add water, propanol, acetonitrile, and tetraethylammonium hydroxide to a reactor, stir and mix, then slowly add γ-aminopropyltriethoxysilane dropwise, and stir at 45-55°C for 22-26 hours. After the reaction is complete, remove the solvent by rotary evaporation, wash, and dry to obtain intermediate 1;

[0009] S2: Add graphene oxide to dimethyl sulfoxide solvent, ultrasonicate for 8-10 minutes, then add intermediate 1 and paraformaldehyde, stir and heat at 170-190°C for 20-24 hours under nitrogen atmosphere. After the reaction is completed, centrifuge, wash and dry to obtain modified silane;

[0010] S3: Add vanillin and hydrazine hydrate to the ethanol solution, stir evenly, and react at 45-50°C for 1-2 hours. After the reaction is complete, filter to obtain Schiff base vanillin;

[0011] S4: Under nitrogen protection, Schiff base vanillin and pyridine are added to an ethanol solvent, stirred to dissolve, and then sodium 3-chloro-2-hydroxypropanesulfonate is added dropwise. The mixture is reacted at 40-45°C for 4-6 hours, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin.

[0012] S5: Add modified silane to tetrahydrofuran solvent, sonicate for 20-25 min, add p-toluenesulfonic acid, introduce nitrogen protection, stir at 75-85°C for 4-6 h, then slowly add sodium sulfonate-modified vanillin dropwise, react at 80-85°C for 45-50 h. After the reaction, cool to room temperature, wash, and dry to obtain intermediate 2;

[0013] S6: Add intermediate 2 to deionized water, ultrasonically treat for 12-15 minutes, then add polyhydroxyalkanoate, stir and mix, and spray dry to obtain vanillin-modified polyester.

[0014] In the above reaction process, tetraethylammonium hydroxide and γ-aminopropyltriethoxysilane react to introduce amino groups, which then react with some carboxyl groups in graphene oxide to obtain modified silane.

[0015] Vanillin and hydrazine hydrate were subjected to a Schiff base reaction to introduce a hydroxyl group, thereby obtaining Schiff base vanillin, which was then further reacted with the chlorine in sodium 3-chloro-2-hydroxypropanesulfonate to introduce a hydroxyl group, thereby obtaining sodium sulfonate-modified vanillin; the carboxyl group in the modified silane was reacted with the hydroxyl group in the sodium sulfonate-modified vanillin to obtain intermediate 2.

[0016] Furthermore, the usage ratio of water, propanol, acetonitrile, tetraethylammonium hydroxide, and γ-aminopropyltriethoxysilane in S1 is 42-45 g: 18-20 mL: 4-5 mL: 1-1.2 mL: 110.2-110.6 g.

[0017] Furthermore, the usage ratio of dimethyl sulfoxide, graphene oxide, intermediate 1, and paraformaldehyde in S2 is 48-50 mL: 0.025-0.026 g: 0.262-0.263 g: 0.082-0.084 g.

[0018] Furthermore, the usage ratio of ethanol, vanillin and hydrazine hydrate in S3 is 20-22 mL: 6.02-6.04 g: 1.05-1.08 g.

[0019] Furthermore, the usage ratio of ethanol, Schiff base vanillin, pyridine, and sodium 3-chloro-2-hydroxypropanesulfonate in S4 is 30-35 mL: 1.82-1.86 g: 0.03-0.04 g: 2.38-2.42 g.

[0020] Furthermore, the usage ratio of tetrahydrofuran, modified silane, p-toluenesulfonic acid, and sodium sulfonate-modified vanillin in S5 is 28-30 mL: 1.53-1.57 g: 0.04-0.05 g: 1.72-1.76 g.

[0021] Furthermore, the usage ratio of the intermediate 2, deionized water, and polyhydroxyalkanoate in S6 is 1.14-1.18 g: 20-25 mL: 3.02-3.06 g.

[0022] Furthermore, the preparation method of the high-strength degradable packaging material is: adding polylactic acid, vanillin-modified polyester, polyadipic acid, triethyl citrate, calcium stearate, and antioxidant 1010 to a high-speed mixer, mixing at 60-80°C for 10-20 minutes to obtain a mixture; melt-blending the mixture through a twin-screw extruder at a blending temperature of 160-180°C and a screw speed of 250-300rpm, extruding and granulating, and drying to obtain the high-strength degradable packaging material.

[0023] Furthermore, the high-strength degradable packaging material is used in cosmetic packaging materials; the cosmetic packaging materials include a bottle body, a bottle cap, a hose, and a packaging box.

[0024] Beneficial technical effects

[0025] The present invention uses polylactic acid as the main raw material. Polylactic acid is a biodegradable polyester synthesized from bio-based raw materials such as corn starch or sugarcane, and has good degradation controllability. Graphene oxide itself has extremely high mechanical strength, and its layered structure can be used as a nanofiller. By dispersing in the polymer matrix to form physical crosslinking points, it effectively transmits stress and improves the tensile strength and toughness of the material. The layered structure of graphene oxide can form a dense carbon layer during combustion, isolating oxygen and heat, delaying combustion, and improving the flame retardant effect of the material. γ-aminopropyltriethoxysilane is bridged with graphene oxide and the polymer matrix through silicon-oxygen covalent bonds to reduce Fewer interface defects, avoid filler agglomeration, and further optimize mechanical properties; a Schiff base structure is introduced through the reaction of vanillin and hydrazine hydrate. The Schiff base structure can interact with the polymer matrix through hydrogen bonds or intermolecular forces to improve the tensile strength or rigidity of the material. The nitrogen element in the Schiff base may decompose at high temperatures to produce non-flammable gases such as ammonia and nitrogen, which dilute oxygen and combustible gases, inhibit the combustion chain reaction, and have a flame retardant effect; the carboxyl-terminated biodegradable polyester elastomer particles themselves are flexible, which can improve the impact resistance and elongation at break of brittle degradable materials, and avoid brittle cracking of packaging materials during transportation or use. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0027] The reagents used in the following specific embodiments are analytically pure;

[0028] Polylactic acid: relative molecular weight is 50,000.

[0029] Polyhydroxyalkanoate: relative molecular weight is 100,000.

[0030] Polyadipic acid, relative molecular weight is 600.

[0031] Example 1

[0032] This application provides a method for preparing a high-strength degradable packaging material, which adopts the following technical solution:

[0033] A method for preparing a high-strength degradable packaging material, comprising the following steps:

[0034] (1) 42 g of water, 18 mL of propanol, 4 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide were added to a reactor and stirred to mix. Then, 110.2 g of γ-aminopropyltriethoxysilane was slowly added dropwise and stirred at 45 ° C for 22 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was washed and dried to obtain intermediate 1;

[0035] (2) 0.025 g of graphene oxide was added to 48 mL of dimethyl sulfoxide solvent, and ultrasonic treatment was performed for 8 min. Then, 0.262 g of intermediate 1 and 0.082 g of paraformaldehyde were added. The mixture was stirred and heated at 170 ° C for 20 h under a nitrogen atmosphere. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified silane;

[0036] (3) Add 6.02 g of vanillin and 1.05 g of hydrazine hydrate to 20 mL of ethanol solution, stir evenly, and react at 45°C for 1 h. After the reaction is complete, filter to obtain Schiff base vanillin;

[0037] (4) Under nitrogen protection, 1.82 g of Schiff base vanillin and 0.03 g of pyridine were added to 30 mL of ethanol solvent and stirred to dissolve. Then, 2.38 g of sodium 3-chloro-2-hydroxypropanesulfonate was added dropwise. The mixture was reacted at 40°C for 4 h, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin.

[0038] (5) 1.53 g of modified silane was added to 28 mL of tetrahydrofuran solvent, and ultrasonic treatment was performed for 20 min at a frequency of 25 kHz and a power of 100 W. 0.04 g of p-toluenesulfonic acid was added, and nitrogen protection was introduced. The mixture was stirred at 75°C for 4 h, and then 1.72 g of sodium sulfonate-modified vanillin was slowly added dropwise. The mixture was reacted at 80°C for 45 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and dried to obtain intermediate 2.

[0039] (6) 1.14 g of intermediate 2 was added to 20 mL of deionized water and ultrasonicated for 12 min at a frequency of 30 kHz and a power of 100 W. Then, 3.02 g of polyhydroxyalkanoate was added, the mixture was stirred and mixed, and spray-dried to obtain vanillin-modified polyester.

[0040] (7) 50 parts by weight of polylactic acid, 3 parts by weight of vanillin-modified polyester, 12 parts by weight of polyadipic acid, 2 parts by weight of triethyl citrate, 1 part by weight of calcium stearate, and 0.5 parts by weight of antioxidant 1010 were added to a high-speed mixer and mixed at 60°C for 10 minutes to obtain a mixture; the mixture was melt-blended through a twin-screw extruder at a blending temperature of 160°C and a screw speed of 250 rpm, extruded into granules, and dried to obtain a high-strength biodegradable packaging material.

[0041] Example 2

[0042] This application provides a method for preparing a high-strength degradable packaging material, which adopts the following technical solution:

[0043] A method for preparing a high-strength degradable packaging material, comprising the following steps:

[0044] (1) 45 g of water, 20 mL of propanol, 5 mL of acetonitrile, and 1.2 mL of tetraethylammonium hydroxide were added to a reactor and stirred to mix. Then, 110.6 g of γ-aminopropyltriethoxysilane was slowly added dropwise and stirred at 55 ° C for 26 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was washed and dried to obtain intermediate 1;

[0045] (2) 0.026 g of graphene oxide was added to 50 mL of dimethyl sulfoxide solvent, and ultrasonic treatment was performed for 10 min. Then, 0.263 g of intermediate 1 and 0.084 g of paraformaldehyde were added. The mixture was stirred and heated at 190 ° C for 24 h under a nitrogen atmosphere. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified silane;

[0046] (3) Add 6.04 g of vanillin and 1.08 g of hydrazine hydrate to 22 mL of ethanol solution, stir evenly, and react at 50°C for 2 h. After the reaction is complete, filter to obtain Schiff base vanillin;

[0047] (4) Under nitrogen protection, 1.86 g of Schiff base vanillin and 0.04 g of pyridine were added to 35 mL of ethanol solvent and stirred to dissolve. Then, 2.42 g of sodium 3-chloro-2-hydroxypropanesulfonate was added dropwise. The mixture was reacted at 45 °C for 6 h, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin.

[0048] (5) 1.57 g of modified silane was added to 30 mL of tetrahydrofuran solvent, and ultrasonic treatment was performed for 25 min at a frequency of 25 kHz and a power of 100 W. 0.05 g of p-toluenesulfonic acid was added, and nitrogen protection was introduced. The mixture was stirred at 85°C for 6 h, and then 1.76 g of sodium sulfonate-modified vanillin was slowly added dropwise. The reaction was carried out at 85°C for 50 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and dried to obtain intermediate 2;

[0049] (6) 1.18 g of intermediate 2 was added to 25 mL of deionized water and ultrasonicated for 15 min at a frequency of 30 kHz and a power of 100 W. Then, 3.06 g of polyhydroxyalkanoate was added, the mixture was stirred and mixed, and spray-dried to obtain vanillin-modified polyester.

[0050] (7) 70 parts by weight of polylactic acid, 5 parts by weight of vanillin-modified polyester, 15 parts by weight of polyadipic acid, 5 parts by weight of triethyl citrate, 3 parts by weight of calcium stearate, and 1 part by weight of antioxidant 1010 were added to a high-speed mixer and mixed at 80°C for 20 minutes to obtain a mixture; the mixture was melt-blended through a twin-screw extruder at a blending temperature of 180°C and a screw speed of 300 rpm, extruded into granules, and dried to obtain a high-strength biodegradable packaging material.

[0051] Example 3

[0052] This application provides a method for preparing a high-strength degradable packaging material, which adopts the following technical solution:

[0053] A method for preparing a high-strength degradable packaging material, comprising the following steps:

[0054] (1) 43 g of water, 19 mL of propanol, 4.5 mL of acetonitrile, and 1.1 mL of tetraethylammonium hydroxide were added to a reactor and stirred to mix. Then, 110.4 g of γ-aminopropyltriethoxysilane was slowly added dropwise and stirred at 50 ° C for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was washed and dried to obtain intermediate 1;

[0055] (2) 0.025 g of graphene oxide was added to 49 mL of dimethyl sulfoxide solvent, and ultrasonic treatment was performed for 9 min. Then, 0.262 g of intermediate 1 and 0.083 g of paraformaldehyde were added. The mixture was stirred and heated at 180° C. for 22 h under a nitrogen atmosphere. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified silane;

[0056] (3) Add 6.03 g of vanillin and 1.06 g of hydrazine hydrate to 21 mL of ethanol solution, stir evenly, and react at 48°C for 1.5 h. After the reaction is complete, filter to obtain Schiff base vanillin;

[0057] (4) Under nitrogen protection, 1.84 g of Schiff base vanillin and 0.03 g of pyridine were added to 33 mL of ethanol solvent and stirred to dissolve. Then, 2.4 g of sodium 3-chloro-2-hydroxypropanesulfonate was added dropwise. The mixture was reacted at 42°C for 5 h, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin.

[0058] (5) 1.55 g of modified silane was added to 29 mL of tetrahydrofuran solvent, and ultrasonic treatment was performed for 22 min at a frequency of 25 kHz and a power of 100 W. 0.04 g of p-toluenesulfonic acid was added, and nitrogen protection was introduced. The mixture was stirred at 80°C for 5 h, and then 1.74 g of sodium sulfonate-modified vanillin was slowly added dropwise. The reaction was carried out at 82°C for 48 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and dried to obtain intermediate 2;

[0059] (6) 1.16 g of intermediate 2 was added to 22 mL of deionized water and ultrasonicated for 13 min at a frequency of 30 kHz and a power of 100 W. Then, 3.04 g of polyhydroxyalkanoate was added, the mixture was stirred and mixed, and spray-dried to obtain vanillin-modified polyester.

[0060] (7) 60 parts by weight of polylactic acid, 4 parts by weight of vanillin-modified polyester, 13 parts by weight of polyadipic acid, 3 parts by weight of triethyl citrate, 2 parts by weight of calcium stearate, and 0.8 parts by weight of antioxidant 1010 were added to a high-speed mixer and mixed at 70°C for 15 minutes to obtain a mixture; the mixture was melt-blended through a twin-screw extruder at a blending temperature of 170°C and a screw speed of 275 rpm, extruded into granules, and dried to obtain a high-strength biodegradable packaging material.

[0061] Example 4

[0062] This application provides a method for preparing a high-strength degradable packaging material, which adopts the following technical solution:

[0063] A method for preparing a high-strength degradable packaging material, comprising the following steps:

[0064] (1) 43 g of water, 18 mL of propanol, 4 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide were added to a reactor and stirred to mix. Then, 110.3 g of γ-aminopropyltriethoxysilane was slowly added dropwise and stirred at 48 ° C for 23 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was washed and dried to obtain intermediate 1;

[0065] (2) 0.025 g of graphene oxide was added to 48 mL of dimethyl sulfoxide solvent, and ultrasonic treatment was performed for 9 min. Then, 0.262 g of intermediate 1 and 0.083 g of paraformaldehyde were added. The mixture was stirred and heated at 175 ° C for 21 h under a nitrogen atmosphere. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified silane;

[0066] (3) Add 6.02 g of vanillin and 1.06 g of hydrazine hydrate to 21 mL of ethanol solution, stir evenly, and react at 46°C for 1 h. After the reaction is complete, filter to obtain Schiff base vanillin;

[0067] (4) Under nitrogen protection, 1.83 g of Schiff base vanillin and 0.03 g of pyridine were added to 31 mL of ethanol solvent and stirred to dissolve. Then, 2.39 g of sodium 3-chloro-2-hydroxypropanesulfonate was added dropwise. The mixture was reacted at 41°C for 4 h, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin.

[0068] (5) 1.54 g of modified silane was added to 28 mL of tetrahydrofuran solvent, and ultrasonic treatment was performed for 21 min at a frequency of 25 kHz and a power of 100 W. 0.04 g of p-toluenesulfonic acid was added, and nitrogen protection was introduced. The mixture was stirred at 78 ° C for 5 h, and then 1.73 g of sodium sulfonate-modified vanillin was slowly added dropwise. The reaction was carried out at 81 ° C for 46 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and dried to obtain intermediate 2;

[0069] (6) 1.15 g of intermediate 2 was added to 21 mL of deionized water and ultrasonicated for 13 min at a frequency of 30 kHz and a power of 100 W. Then, 3.04 g of polyhydroxyalkanoate was added, the mixture was stirred and mixed, and spray-dried to obtain vanillin-modified polyester.

[0070] (7) 55 parts by weight of polylactic acid, 3 parts by weight of vanillin-modified polyester, 13 parts by weight of polyadipic acid, 3 parts by weight of triethyl citrate, 1 part by weight of calcium stearate, and 0.6 parts by weight of antioxidant 1010 were added to a high-speed mixer and mixed at 65°C for 12 minutes to obtain a mixture; the mixture was melt-blended through a twin-screw extruder at a blending temperature of 165°C and a screw speed of 260 rpm, extruded into granules, and dried to obtain a high-strength biodegradable packaging material.

[0071] Example 5

[0072] This application provides a method for preparing a high-strength degradable packaging material, which adopts the following technical solution:

[0073] A method for preparing a high-strength degradable packaging material, comprising the following steps:

[0074] (1) 44 g of water, 19 mL of propanol, 5 mL of acetonitrile, and 1.2 mL of tetraethylammonium hydroxide were added to a reactor and stirred to mix. Then, 110.5 g of γ-aminopropyltriethoxysilane was slowly added dropwise and stirred at 52 ° C for 25 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was washed and dried to obtain intermediate 1;

[0075] (2) 0.026 g of graphene oxide was added to 50 mL of dimethyl sulfoxide solvent, and ultrasonic treatment was performed for 9 min. Then, 0.263 g of intermediate 1 and 0.083 g of paraformaldehyde were added. The mixture was stirred and heated at 185 ° C for 23 h under a nitrogen atmosphere. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain modified silane;

[0076] (3) Add 6.03 g of vanillin and 1.07 g of hydrazine hydrate to 22 mL of ethanol solution, stir evenly, and react at 48°C for 2 h. After the reaction is complete, filter to obtain Schiff base vanillin;

[0077] (4) Under the protection of nitrogen gas, 1.85 g of vanillin Schiff base, 0.04 g of pyridine was added into 34 mL of ethanol solvent, stirred and dissolved, then 2.41 g of 3-chloro-2-hydroxypropanesulfonic acid sodium was added dropwise, reacted at 44°C for 6 h, filtered, washed and dried to obtain sulfonic acid sodium modified vanillin;

[0078] (5) 1.56 g of modified silane was added into 30 mL of tetrahydrofuran solvent, ultrasonically treated for 24 min at a frequency of 25 kHz and a power of 100 W, 0.05 g of p-toluenesulfonic acid was added, protected by nitrogen gas, stirred at 82°C for 6 h, then 1.75 g of sulfonic acid sodium modified vanillin was slowly added dropwise, reacted at 84°C for 49 h, after the reaction was completed, cooled to room temperature, washed and dried to obtain intermediate 2;

[0079] (6) 1.17 g of intermediate 2 was added into 24 mL of deionized water, ultrasonically treated for 14 min at a frequency of 30 kHz and a power of 100 W, then 3.05 g of polyhydroxyaliphatic acid ester was added, stirred and mixed, and spray dried to obtain vanillin modified polyester;

[0080] (7) 65 parts by weight of polylactic acid, 5 parts by weight of vanillin modified polyester, 14 parts by weight of polyadipic acid, 5 parts by weight of triethyl citrate, 3 parts by weight of calcium stearate and 0.8 parts by weight of antioxidant 1010 were added into a high-speed mixer, mixed at 75°C for 18 min to obtain a mixture; the mixture was melt blended by a twin-screw extruder, the blending temperature was 175°C, the screw rotation speed was 280 rpm, extruded and granulated, and dried to obtain a high-strength degradable packaging material.

[0081] Comparative Example 1

[0082] The difference between this comparative example and Example 5 is that modified silane is used instead of vanillin modified polyester.

[0083] Comparative Example 2

[0084] The difference between this comparative example and Example 5 is that sulfonic acid sodium modified vanillin is used instead of vanillin modified polyester.

[0085] Performance test:

[0086] The packaging materials prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance test.

[0087] (1) Mechanical strength test:

[0088] The tensile strength test method is as follows: a tensile testing machine was used to test the tensile strength of the packaging material, the tensile speed was 5 mm / min, and the national standard GB / T 1040.1-2006 was referred to.

[0089] The notched impact strength test method of the cantilever beam is as follows: an impact testing machine is used to measure the notched impact strength of the sample, with a pendulum energy of 1J, referring to the national standard: GB / T 1843-2008.

[0090] The test results are shown in Table 1.

[0091] Table 1: Mechanical strength tests.

[0092]

[0093]

[0094] It can be seen from Table 1 that the packaging materials of Examples 1-5 have higher tensile strength and Izod notched impact strength than the packaging materials prepared in Comparative Examples 1-2, and have better mechanical strength.

[0095] (2) Degradability test method: Refer to the national standard GB / T 19277.2-2013, use a 60°C composting environment, and test for 60 days to test biodegradability. The test results are shown in Table 2.

[0096] Table 2: Degradability test.

[0097] project 60-day biodegradation rate (%) Example 1 64.2 Example 2 66.3 Example 3 65.7 Example 4 64.6 Example 5 66.1 Comparative Example 1 65.4 Comparative Example 2 65.1

[0098] It can be seen from Table 2 that the high-strength degradable packaging material prepared by the present invention has good degradability.

[0099] (3) Flame retardancy testing methods are as follows: an oxygen index meter is used to test the oxygen index of the packaging material, and a horizontal and vertical combustion tester is used to test the combustion grade of the packaging material. The test results are shown in Table 3.

[0100] Table 3: Flame retardant performance test.

[0101] project Oxygen index (%) UL-94 Example 1 30.8 V-0 Example 2 33.2 V-0 Example 3 32.4 V-0 Example 4 31.6 V-0 Example 5 32.3 V-0 Comparative Example 1 26.1 V-1 Comparative Example 2 24.5 V-1

[0102] It can be seen from Table 3 that the packaging materials of Examples 1-5 have a higher oxygen index than the packaging materials prepared in Comparative Examples 1-2, so that the materials can only burn at a higher oxygen concentration and have good flame retardancy.

[0103] It should be noted that, in the present document, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element preceded by "comprises a" does not, without more constraints, foreclose the existence of additional identical elements in the process, method, article, or apparatus that comprises the recited element.

[0104] The above embodiments are only used to illustrate the technical solutions of the present application, rather than limiting them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements for some technical features therein; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

[0105] Those skilled in the art should understand that the above only describes some specific embodiments of the present application, rather than all embodiments. It should be noted that many modifications and improvements can be made by those of ordinary skill in the art, and all modifications or improvements that do not exceed the scope of the claims should be considered as the protection scope of the present application.

Claims

1. A high-strength degradable packaging material, characterized in that: The invention comprises the following components by weight: 50-70 parts by weight of polylactic acid, 3-5 parts by weight of vanillin modified polyester, 12-15 parts by weight of polyadipic acid, 2-5 parts by weight of triethyl citrate, 1-3 parts by weight of calcium stearate and 0.5-1 part by weight of antioxidant.

2. The high-strength degradable packaging material according to claim 1, characterized in that: The preparation method of the vanillin modified polyester is as follows: S1: Add water, propanol, acetonitrile, and tetraethylammonium hydroxide to a reactor, stir and mix, then slowly add γ-aminopropyltriethoxysilane dropwise, and stir at 45-55°C for 22-26 hours. After the reaction is complete, remove the solvent by rotary evaporation, wash, and dry to obtain intermediate 1; S2: Add graphene oxide to dimethyl sulfoxide solvent, ultrasonicate for 8-10 minutes, then add intermediate 1 and paraformaldehyde, stir and heat at 170-190°C for 20-24 hours under nitrogen atmosphere. After the reaction is completed, centrifuge, wash and dry to obtain modified silane; S3: Add vanillin and hydrazine hydrate to the ethanol solution, stir evenly, and react at 45-50°C for 1-2 hours. After the reaction is complete, filter to obtain Schiff base vanillin; S4: Under nitrogen protection, Schiff base vanillin and pyridine are added to an ethanol solvent, stirred to dissolve, and then sodium 3-chloro-2-hydroxypropanesulfonate is added dropwise. The mixture is reacted at 40-45°C for 4-6 hours, filtered, washed, and dried to obtain sodium sulfonate-modified vanillin. S5: Add modified silane to tetrahydrofuran solvent, sonicate for 20-25 min, add p-toluenesulfonic acid, introduce nitrogen protection, stir at 75-85°C for 4-6 h, then slowly add sodium sulfonate-modified vanillin dropwise, react at 80-85°C for 45-50 h. After the reaction, cool to room temperature, wash, and dry to obtain intermediate 2; S6: Add intermediate 2 to deionized water, ultrasonically treat for 12-15 minutes, then add polyhydroxyalkanoate, stir and mix, and spray dry to obtain vanillin-modified polyester.

3. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of water, propanol, acetonitrile, tetraethylammonium hydroxide, and γ-aminopropyltriethoxysilane in S1 is 42-45 g: 18-20 mL: 4-5 mL: 1-1.2 mL: 110.2-110.6 g.

4. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of dimethyl sulfoxide, graphene oxide, intermediate 1 and paraformaldehyde in S2 is 48-50 mL: 0.025-0.026 g: 0.262-0.263 g: 0.082-0.084 g.

5. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of ethanol, vanillin and hydrazine hydrate in S3 is 20-22 mL: 6.02-6.04 g: 1.05-1.08 g.

6. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of ethanol, Schiff base vanillin, pyridine, and sodium 3-chloro-2-hydroxypropanesulfonate in S4 is 30-35 mL: 1.82-1.86 g: 0.03-0.04 g: 2.38-2.42 g.

7. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of tetrahydrofuran, modified silane, p-toluenesulfonic acid, and sodium sulfonate-modified vanillin in S5 is 28-30 mL: 1.53-1.57 g: 0.04-0.05 g: 1.72-1.76 g.

8. The high-strength degradable packaging material according to claim 2, characterized in that: The usage ratio of the intermediate 2, deionized water, and polyhydroxyalkanoate in S6 is 1.14-1.18 g: 20-25 mL: 3.02-3.06 g.

9. A method for preparing the high-strength degradable packaging material according to any one of claims 1 to 8, characterized in that: The preparation method of the high-strength degradable packaging material comprises the following steps: adding polylactic acid, vanillin-modified polyester, polyadipic acid, triethyl citrate, calcium stearate, and antioxidant 1010 into a high-speed mixer, and mixing at 60-80° C. for 10-20 minutes to obtain a mixture; and subjecting the mixture to melt blending through a twin-screw extruder at a blending temperature of 160-180° C. and a screw speed of 250-300 rpm, extruding and granulating the mixture, and drying the mixture to obtain the high-strength degradable packaging material.

10. A high-strength degradable packaging material according to any one of claims 1 to 9, characterized in that: The application of the high-strength degradable packaging material in cosmetic packaging; the cosmetic packaging material includes a bottle body, a bottle cap, a hose, and a packaging box.

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