Anti-collision degradable packaging box and manufacturing process thereof

Abstract

The present application relates to the field of packaging box, specifically to a kind of anti-collision degradable packaging box and manufacturing process thereof.The raw materials of packaging box include the following weight components: 40-50 parts of polylactic acid, 12-14 parts of polycaprolactone, 20-30 parts of reactant A, 30-40 parts of microcrystalline cellulose, 4-6 parts of compatibilizer, 1-5 parts of epoxy soybean oil, 20-30 parts of filler, 0.5-2 parts of antioxidant;wherein the reactant A is the inner core of esterified starch, and the shell is a copolymer containing lactone unit.These raw materials jointly act in the manufacturing process, and through extrusion granulation and injection molding, an anti-collision degradable packaging box is prepared, which not only has high hardness, high toughness and anti-impact performance, but also can be naturally degraded after use, reducing the pollution to the environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of packaging boxes, in particular to a kind of anti-collision degradable packaging box and manufacturing process thereof. BACKGROUND

[0002] With the continuous improvement of people's environmental protection consciousness, the demand for degradable packaging materials is also increasing. Traditional plastic packaging materials cause great pollution and harm to the environment, while degradable packaging materials can decompose into harmless substances after use, reducing the impact on the environment. Packaging boxes made of degradable materials have become a trend, and in the field of degradable packaging, anti-collision packaging boxes are a very important application.

[0003] With the rapid development of e-commerce, express industry and other industries, anti-collision packaging boxes are particularly important for the safety of goods. Traditional anti-collision packaging mostly uses foam plastic, PE foam and other materials, but these materials are difficult to decompose due to their petrochemical properties, which is not conducive to environmental protection. Degradable materials can naturally degrade and release plant nutrients, without causing pollution to the environment, meeting people's demand for environmental protection. In the future development, anti-collision degradable packaging boxes will have wider application and larger market space.

[0004] Therefore, we propose a kind of anti-collision degradable packaging box and manufacturing process thereof. SUMMARY

[0005] The purpose of the present application is to provide an anti-collision degradable packaging box and manufacturing process thereof to solve the problems raised in the background.

[0006] In order to solve the above technical problems, the present application provides the following technical scheme:

[0007] A manufacturing process of an anti-collision degradable packaging box, comprising the following steps:

[0008] S1: Mix dry corn starch and ethyl acetate uniformly, add acrylic acid chloride and stearoyl chloride and mix uniformly, heat to 50-60℃, react for 1-3h, vacuum filter, wash and dry to obtain esterified starch;

[0009] S2: Under nitrogen protection, mix esterified starch and deionized water uniformly, heat to 80-90℃, drop in potassium persulfate aqueous solution, drop in methyl acrylate, glycidyl methacrylate, double bond containing monomer and 2-methylene-1, 3-dioxane for 1-2h, drop in 1-2h, react for 2-4h; After the reaction, the white emulsion is broken, filtered, washed and vacuum dried at 70-80℃ for 12-24h to obtain reaction A;

[0010] S3: the polylactic acid, polycaprolactone, reactant A, microcrystalline cellulose and the compatilizer are uniformly mixed, and the temperature is raised to 80-100℃, and the epoxy soybean oil, filler and antioxidant are uniformly mixed to prepare the raw material of the packaging box;

[0011] S4: the raw material of the packaging box is extruded and granulated to prepare the degradable granules;

[0012] S5: the degradable granules are injection molded to prepare the packaging box.

[0013] Further, the drying process conditions of the corn starch in step S1 are as follows: vacuum drying at 90-110℃ for 1-3h.

[0014] Further, the mass ratio of the corn starch to ethyl acetate in step S1 is 1:(3-4).

[0015] Further, the mass ratio of the acrylic acid chloride to the stearoyl chloride in step S1 is 1:(1-2), and the mass of the acrylic acid chloride is 4-6% of the mass of the corn starch.

[0016] Further, the mass ratio of the esterified starch to deionized water in step S2 is 1:(5-7).

[0017] Further, the concentration of the potassium persulfate aqueous solution in step S2 is 2-5wt%, and the amount is 30-40% of the mass of the esterified starch.

[0018] Further, the amount of the mixed monomers in step S2 is 2.5-3.0 times of the mass of the esterified starch.

[0019] Further, the mass ratio of the methyl acrylate, glycidyl methacrylate, double bond-containing monomer and 2-methylene-1,3-dioxolane in step S2 is 1:(1-1.2):(1:1.5):(2-3).

[0020] Further, the preparation steps of the double bond-containing monomer in step S2 are as follows:

[0021] (1) under the protection of nitrogen, the tung oil is heated to 100-110℃, stirred for 1-2h, cooled to 60-70℃, 3-dimethylamino-1,2-propanediol and sodium methoxide are added, and reacted for 4-6h, and then washed, suction filtered, and rotary evaporated to prepare the product B;

[0022] (2) under the protection of nitrogen, the product B, phthalic anhydride and N,N-dimethylformamide are uniformly mixed, heated to 55-65℃, reacted for 8-10h, and then uniformly mixed with tetrahydrofuran and deionized water, stirred for 3-5h, and then rotary evaporated, washed and dried to prepare the double bond-containing monomer.

[0023] In the above technical solution, 3-dimethylamino-1,2-propanediol and triglyceride in tung oil are subjected to ester exchange reaction to obtain product B containing an alcohol group, and then subjected to esterification reaction with phthalic anhydride to obtain a monomer containing a double bond.

[0024] Further, the mass ratio of tung oil to 3-dimethylamino-1,2-propanediol in step (1) is 1:(0.2-0.4).

[0025] Further, the mass of sodium methoxide in step (1) is 1-3% of the total mass of tung oil and 3-dimethylamino-1,2-propanediol.

[0026] Further, the mass ratio of product B to phthalic anhydride in step (2) is 1:(0.5-1.0).

[0027] Further, the mass of N,N-dimethylformamide in step (2) is 2-4% of the total mass of product B and phthalic anhydride.

[0028] Further, the mass ratio of tetrahydrofuran to deionized water in step (2) is (3-4):1.

[0029] Further, the raw materials for the packaging box in step S3 include the following components by weight: 40-50 parts of polylactic acid, 12-14 parts of polycaprolactone, 20-30 parts of reactant A, 25-35 parts of microcrystalline cellulose, 4-6 parts of a compatibilizer, 1-5 parts of epoxy soybean oil, 20-30 parts of a filler, and 0.5-2 parts of an antioxidant.

[0030] Further, the compatibilizer is maleic anhydride grafted polypropylene.

[0031] Further, the filler is composed of 10-14 parts by mass of talc and 10-16 parts by mass of straw powder.

[0032] Further, the antioxidant is BASF antioxidant 1010 from Shanghai Jingyan Chemical Co., Ltd.

[0033] Further, in step S4, the extrusion process conditions are as follows: the temperature of each section of the extruder is 160-200℃, and the screw rotation speed is 250-290ppm.

[0034] Further, in step S5, the injection molding temperature is 190-210℃.

[0035] Compared with the prior art, the present application has the following advantages:

[0036] 1. The anti-collision degradable packaging box and its manufacturing process of the present application, the raw materials of the packaging box include microcrystalline cellulose, polycaprolactone, reactant A, maleic anhydride grafted polypropylene, epoxy soybean oil, talcum powder, straw powder and antioxidant. These raw materials jointly act in the manufacturing process, so that the packaging box has high strength, high hardness, high toughness, high ductility and anti-impact performance. Among them, microcrystalline cellulose as a reinforcing body can improve the strength and hardness of the packaging box; polycaprolactone and reactant A as a toughening body can improve the toughness and ductility of polylactic acid and enhance its anti-impact performance; maleic anhydride grafted polypropylene as a compatibilizer can make the compatibility between various raw materials better; epoxy soybean oil as a plasticizer can increase the flexibility and toughness of the packaging box and improve its impact resistance; talcum powder and straw powder as fillers can increase the weight and hardness of the packaging box; antioxidant can prolong the service life of the packaging box. These raw materials are prepared into an anti-collision degradable packaging box through processes such as extrusion granulation and injection molding.

[0037] 2. The anti-collision degradable packaging box and its manufacturing process of the present application, the esterified starch prepared by reacting corn starch and ethyl acetate is used as the inner core; the mixed monomers of methyl acrylate, glycidyl methacrylate, double bond-containing monomer and 2-methylene-1,3-dioxane are added dropwise in the presence of potassium persulfate aqueous solution as an initiator, and react with the double bonds in the esterified starch under the action of the initiator to form a firm chemical bond; the methyl acrylate, glycidyl methacrylate and double bond-containing monomer can also undergo free radical ring-opening hybridization copolymerization with 2-methylene-1,3-dioxane to prepare a copolymer containing lactone units as a shell layer, and finally a biodegradable reactant A is prepared. This reactant A has good biodegradability and is friendly to the environment. The packaging box produced by this manufacturing process not only has good anti-collision performance, but also can be naturally degraded after use, reducing pollution to the environment and achieving the purpose of environmental protection.

[0038] 3. The anti-collision degradable packaging box and its manufacturing process of the present application, using tung oil and 3-dimethylamino-1,2-propanediol as raw materials, sodium methoxide as catalyst, ester exchange reaction of 3-dimethylamino-1,2-propanediol and the main component of tung oil triglyceride is carried out to obtain product B containing alcohol group, then esterification reaction with phthalic anhydride to obtain double bond-containing monomer. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0040] Corn starch: food grade, from Jinan Shengteng Chemical Co., Ltd.; tung oil: triglyceride content ≥80%, from Shandong Longhui Chemical Co., Ltd.; polylactic acid: American NatureWorks 4032D, injection grade, from Shanghai Jiyong Import & Export Co., Ltd.; polycaprolactone: Sweden Capa 6500, from Dongguan Suyun Plastic Co., Ltd.; microcrystalline cellulose: PH112, food grade, from Huzhou Linghu Xinyang Chemical Co., Ltd.; maleic anhydride grafted polypropylene: American DuPont PP 50E806, extrusion grade, grafting rate 0.2-0.5%, from Dongguan Suijia Polymer Raw Material Co., Ltd.; epoxy soybean oil: epoxy value ≥6.2 mol / 100g, from Guangdong Suxin Chemical Technology Co., Ltd.; talc: silicon dioxide content ≥60.1%, magnesium oxide content ≥30.2%, particle size 5000 mesh, from Jiangyin Guangyuan Superfine Powder Co., Ltd.; straw powder: particle size 100-200 mesh, from Shaanxi Jinhuo Agricultural Technology Co., Ltd.; antioxidant is German BASF antioxidant 1010, from Shanghai Jingyan Chemical Co., Ltd.

[0041] In the following examples and comparative examples, 1 part is equal to 10 g.

[0042] Example 1: A manufacturing process of a crash-proof degradable packaging box, comprising the following processes:

[0043] S1: corn starch was vacuum dried at 90°C for 3h to obtain dried corn starch; 20 parts of dried corn starch and 60 parts of ethyl acetate were mixed uniformly, 0.8 parts of acrylic acid chloride and 0.8 parts of stearoyl chloride were added and mixed uniformly, the temperature was raised to 50°C, and the reaction was carried out for 3h; after vacuum filtration, washing and drying, esterified starch was obtained;

[0044] S2: 20 parts of esterified starch and 100 parts of deionized water were mixed uniformly under nitrogen protection, the temperature was raised to 80°C, 6 parts of 2wt% potassium persulfate aqueous solution was added dropwise, 1h was added dropwise, 10 parts of methyl acrylate, 10 parts of glycidyl methacrylate, 10 parts of double bond containing monomer and 20 parts of 2-methylene-1, 3-dioxane were added dropwise, 1h was added dropwise, and the reaction was carried out for 2h; after the reaction was completed, the white emulsion was demulsified, filtered, washed and vacuum dried at 70°C for 24h to obtain a reaction product A;

[0045] S3: 40 parts of polylactic acid, 12 parts of polycaprolactone, 20 parts of reaction product A, 25 parts of microcrystalline cellulose, 4 parts of maleic anhydride grafted polypropylene were mixed uniformly, the temperature was raised to 80°C, 1 part of epoxy soybean oil, 10 parts of talc, 10 parts of straw powder and 0.5 parts of antioxidant 1010 were mixed uniformly to obtain a packaging box raw material;

[0046] S4: The packaging box raw material is extruded and granulated (the temperature of each section of the extruder is 160°C, and the screw rotation speed is 250 rpm) to obtain degradable granules;

[0047] S5: The degradable granules are injection molded at 190°C to obtain a packaging box;

[0048] The preparation step of the double bond-containing monomer in step S2 is as follows:

[0049] (1) Under nitrogen protection, 10 parts of tung oil is heated to 100°C, stirred for 1 hour, cooled to 60°C, 2 parts of 3-dimethylamino-1,2-propanediol, 0.12 parts of sodium methoxide are added, and reacted for 4 hours. After washing, suction filtration, and rotary evaporation, product B is obtained;

[0050] (2) Under nitrogen protection, 10 parts of product B, 5 parts of phthalic anhydride, and 0.3 parts of N,N-dimethylformamide are uniformly mixed, heated to 55°C, and reacted for 8 hours. 30 parts of tetrahydrofuran and 10 parts of deionized water are uniformly mixed, stirred for 3 hours, and then rotary evaporated, washed, and dried to obtain a double bond-containing monomer.

[0051] Example 2: A manufacturing process of an anti-collision degradable packaging box, comprising the following processes:

[0052] S1: Corn starch is vacuum dried at 100°C for 2 hours to obtain dried corn starch; 25 parts of dried corn starch and 87.5 parts of ethyl acetate are uniformly mixed, 1.25 parts of acrylic acid chloride and 1.8 parts of stearoyl chloride are uniformly mixed, heated to 55°C, and reacted for 2 hours. After vacuum suction filtration, washing, and drying, esterified starch is obtained;

[0053] S2: Under nitrogen protection, 25 parts of esterified starch and 150 parts of deionized water are uniformly mixed, heated to 85°C, 9 parts of 3wt% potassium persulfate aqueous solution is added dropwise, and 1.5 hours are required for dropwise addition. Meanwhile, 11 parts of methyl acrylate, 12 parts of glycidyl methacrylate, 14 parts of double bond-containing monomer, and 28 parts of 2-methylene-1,3-dioxane are added dropwise, and 1.5 hours are required for dropwise addition. After 3 hours of reaction, the white emulsion obtained is demulsified, filtered, washed, and vacuum dried at 75°C for 18 hours to obtain a reaction product A;

[0054] S3: 45 parts of polylactic acid, 13 parts of polycaprolactone, 25 parts of reaction product A, 30 parts of microcrystalline cellulose, 5 parts of maleic anhydride grafted polypropylene are uniformly mixed, heated to 90°C, and 3 parts of epoxy soybean oil, 12 parts of talc, 13 parts of straw powder, and 1 part of antioxidant 1010 are uniformly mixed to obtain a packaging box raw material;

[0055] S4: The packaging box raw material is extruded and granulated (the temperature of each section of the extruder is 180°C, and the screw rotation speed is 270 rpm) to obtain degradable granules;

[0056] S5: The degradable granules are injection molded at 190°C to obtain a packaging box.

[0057] The preparation step of the double bond-containing monomer in step S2 is as follows:

[0058] (1) Under nitrogen protection, 14 parts of tung oil is heated to 105°C, stirred for 1.5 h, cooled to 65°C, 4.2 parts of 3-dimethylamino-1,2-propanediol, 0.36 parts of sodium methoxide are added, and reacted for 5 h. After washing, suction filtration, and rotary evaporation, product B is obtained.

[0059] (2) Under nitrogen protection, 14 parts of product B, 9.8 parts of phthalic anhydride, and 0.7 parts of N,N-dimethylformamide are uniformly mixed, heated to 60°C, and reacted for 9 h. 50 parts of tetrahydrofuran and 14 parts of deionized water are uniformly mixed, stirred for 4 h, and then rotary evaporated, washed, and dried to obtain a double bond-containing monomer.

[0060] Example 3: A manufacturing process of an anti-collision degradable packaging box, comprising the following processes:

[0061] S1: Corn starch is vacuum dried at 110°C for 1 h to obtain dried corn starch. 30 parts of the dried corn starch and 120 parts of ethyl acetate are uniformly mixed, 1.8 parts of acrylic acid chloride and 3.6 parts of stearoyl chloride are uniformly mixed, heated to 60°C, and reacted for 3 h. After vacuum suction filtration, washing, and drying, esterified starch is obtained.

[0062] S2: Under nitrogen protection, 30 parts of esterified starch and 210 parts of deionized water are uniformly mixed, heated to 90°C, 12 parts of 5wt% potassium persulfate aqueous solution is added dropwise, 2 h for dropwise addition, and 13 parts of methyl acrylate, 15.6 parts of glycidyl methacrylate, 20 parts of double bond-containing monomer, and 39 parts of 2-methylene-1,3-dioxane are added dropwise, 2 h for dropwise addition, and reacted for 4 h. After the reaction, the white emulsion is demulsified, filtered, washed, and vacuum dried at 80°C for 12 h to obtain a reaction product A.

[0063] S3: 50 parts of polylactic acid, 14 parts of polycaprolactone, 30 parts of reaction product A, 35 parts of microcrystalline cellulose, 6 parts of maleic anhydride grafted polypropylene are uniformly mixed, heated to 80°C, 5 parts of epoxy soybean oil, 14 parts of talc, 16 parts of straw powder, and 2 parts of antioxidant 1010 are uniformly mixed to obtain a packaging box raw material.

[0064] S4: The packaging box raw material is extruded and granulated (the temperature of each section of the extruder is 200°C, and the screw rotation speed is 290 rpm) to obtain a degradable granule.

[0065] S5: The degradable pellets are injection molded at 210℃ to obtain the packaging box;

[0066] The preparation step of the double bond-containing monomer in step S2 is as follows:

[0067] (1) Under nitrogen protection, 20 parts of tung oil is heated to 110℃ and stirred for 2h, then cooled to 70℃, 8 parts of 3-dimethylamino-1,2-propanediol, 0.84 parts of sodium methoxide are added, and reacted for 4h. After washing, suction filtration, and rotary evaporation, the product B is obtained;

[0068] (2) Under nitrogen protection, 20 parts of product B, 5 parts of phthalic anhydride, and 1 part of N,N-dimethylformamide are uniformly mixed, heated to 65℃, and reacted for 10h. Then 60 parts of tetrahydrofuran and 15 parts of deionized water are uniformly mixed, stirred for 5h, and then rotary evaporated, washed, and dried to obtain the double bond-containing monomer.

[0069] Comparative Example 1: Compared with Example 1, Comparative Example 1 omits step S1, and replaces the esterified starch in step S2 with the same amount of corn starch; other steps and processes are the same as those in Example 1.

[0070] Comparative Example 2: The raw materials of the packaging box include the following components by weight: 40 parts of polylactic acid, 12 parts of polycaprolactone, 20 parts of ethylene-acrylate copolymer, 25 parts of microcrystalline cellulose, 4 parts of maleic anhydride grafted polypropylene, 1 part of epoxy soybean oil, 10 parts of talc, 10 parts of straw powder, and 0.5 parts of antioxidant 1010. In Comparative Example 2, the reactant A is replaced with ethylene-vinyl acetate copolymer (model: U.S. DuPont EVA 260, from Shanghai Xingyun International Trade Co., Ltd.), and other steps and processes are the same as those in Example 1.

[0071] Comparative Example 3: The raw materials of the packaging box include the following components by weight: 40 parts of polylactic acid, 12 parts of polycaprolactone, 20 parts of reactant A, 25 parts of microcrystalline cellulose, 4 parts of maleic anhydride grafted polypropylene, 1 part of epoxy soybean oil, 10 parts of straw powder, and 0.5 parts of antioxidant 1010. In Comparative Example 3, no talc is added, and other steps and processes are the same as those in Example 1.

[0072] Comparative Example 4: A manufacturing process of a degradable anti-collision packaging box, comprising the following processes:

[0073] S1: The corn starch is vacuum dried at 100℃ for 2h to obtain dried corn starch; 25 parts of the dried corn starch and 87.5 parts of ethyl acetate are uniformly mixed, 1.25 parts of acrylic acid chloride and 1.8 parts of stearoyl chloride are uniformly mixed, heated to 55℃, and reacted for 2h. After vacuum suction filtration, washing, and drying, the esterified starch is obtained;

[0074] S2: 25 parts of esterified starch and 150 parts of deionized water were mixed uniformly under nitrogen protection, and the temperature was raised to 85°C. 9 parts of 3wt% potassium persulfate aqueous solution was added dropwise, and 6.25 parts of methyl acrylate, 6.25 parts of glycidyl methacrylate, 6.25 parts of double bond containing monomer and 6.25 parts of 2-methylene-1,3-dioxolane were added dropwise at the same time. The reaction was carried out for 1.5h, and then the reaction was carried out for 3h. After the reaction was completed, the white emulsion was broken, and after filtration, washing and drying at 75°C for 18h, the reaction product A was prepared;

[0075] S3: 45 parts of polylactic acid, 13 parts of polycaprolactone, 25 parts of reaction product A, 30 parts of microcrystalline cellulose, 5 parts of maleic anhydride grafted polypropylene were mixed uniformly, and the temperature was raised to 90°C. 3 parts of epoxy soybean oil, 12 parts of talc, 13 parts of straw powder and 1 part of antioxidant 1010 were mixed uniformly to prepare the packaging box raw material;

[0076] S4: The packaging box raw material was extruded and granulated (the temperature of each section of the extruder was 180°C, and the screw rotation speed was 270rpm) to prepare the degradable granules;

[0077] S5: The degradable granules were injection molded at 190°C to prepare the packaging box;

[0078] Compared with Example 2, the amount of the mixed monomer in Comparative Example 4 was 1 times the mass of the esterified starch, and the mass ratio of methyl acrylate, glycidyl methacrylate, double bond containing monomer and 2-methylene-1,3-dioxolane was 1:1:1:1. The remaining steps were the same as those of Example 2.

[0079] Comparative Example 5: A manufacturing process of a degradable packaging box, comprising the following steps:

[0080] The double bond containing monomer preparation step in step S2 is as follows:

[0081] (1) Under nitrogen protection, 14 parts of tung oil was heated to 105°C, stirred for 1.5h, cooled to 65°C, and then 4.2 parts of 3-dimethylamino-1,2-propanediol, 0.36 parts of sodium methoxide were added, and the reaction was carried out for 5h. After washing, suction filtration and rotary evaporation, product B was prepared;

[0082] (2) Under nitrogen protection, 14 parts of product B, 42 parts of phthalic anhydride and 0.7 parts of N,N-dimethylformamide were mixed uniformly, and the temperature was raised to 60°C. The reaction was carried out for 9h, and then 50 parts of tetrahydrofuran and 14 parts of deionized water were mixed uniformly, and stirred for 4h. After rotary evaporation, washing and drying, the double bond containing monomer was prepared;

[0083] Compared with Example 2, the mass ratio of product A and phthalic anhydride in Comparative Example 5 was 1:3, and the remaining steps were the same as those of Example 2.

[0084] Experiment

[0085] The packaging boxes obtained in Examples 1-3 and Comparative Examples 1-5 were taken to prepare samples, and the performances of the samples were detected respectively and the detection results were recorded.

[0086] The tensile properties were determined according to GB / T 1040.1-2006 "Determination of tensile properties of plastics - Part 1: General principles", and the experimental steps were as follows: the measured packaging box was cut into a dumbbell-shaped sample with a size of 100 mm x 10 mm, a tensile testing machine was used, the test was started under the condition of 23℃ and a tensile speed of 50 mm / min, and the data was recorded.

[0087] The elongation at break was determined according to GB / T 1040.1-2006 "Determination of tensile properties of plastics - Part 1: General principles", and the experimental steps were as follows: the measured packaging box was cut into a sample with a size of 50 mm in length, 10 mm in width and 4 mm in thickness, the sample was fixed on the clamps of a tensile testing machine to ensure that the sample was perpendicular to the tensile direction. The two ends of the sample should be parallel to the clamps, and the tension of the clamps should be evenly distributed on the two ends of the sample. The tensile testing machine was started and the tensile force was started to be applied under room temperature conditions. During the tensile process, the elongation and load data of the sample were recorded until the sample was broken. The elongation at break was calculated according to the test data. The calculation formula of the elongation at break was: elongation at break = (L2-L1) / L1 x 100%, wherein L1 was the length of the sample before the test, and L2 was the breaking length of the sample during the test.

[0088] The degradation rate was determined as follows: the measured packaging box was cut into a sample with a size of 100 mm x 50 mm x 10 mm, which was immersed in a phosphate buffer solution with a pH of 6 for 50 days. The sample was taken out, the liquid on the surface was absorbed with a paper towel, and then the weight of the sample was measured to calculate the degradation rate. The degradation rate = (weight before test-weight after test) / weight before test x 100%.

[0089] Tensile strength / MPa Elongation at break / % Degradation rate / % Example 1 16 336 88 Example 2 18 348 92 Example 3 17 342 90 Comparative Example 1 12 335 75 Comparative Example 2 10 305 65 Comparative Example 3 13 318 80 Comparative Example 4 15 330 84 Comparative Example 5 14 328 83

[0090] According to the data in the above table, the following conclusions can be clearly obtained:

[0091] 1. Compared with Comparative Example 1, the degradation rate of the samples of Examples 1-3 is larger, which indicates that the degradation effect of the esterified starch prepared in the application is obviously better than that of corn starch, and the degradation rate of the packaging box can be improved.

[0092] 2. Compared with Examples 1-3, the tensile strength of the sample of Comparative Example 2 is reduced, which indicates that compared with ethylene-vinyl acetate copolymer, the product made of the reactant A prepared in the application has better toughness and better degradable performance; the tensile strength and wear resistance of the sample of Comparative Example 3 are both decreased, which indicates that the addition of talc in the application can improve the tensile properties and wear resistance of the material.

[0093] 3、Compared with examples 1-3, the tensile strength, elongation at break and degradation rate of comparative example 4 and comparative example 5 all decrease, which indicates that the reactant A and the double bond-containing monomer prepared by the present application are affected by the ratio of each reagent in the preparation process, and the selection of the reagent ratio in the range can improve the toughness and degradable performance of the packaging box, so as to realize the anti-collision and degradable performance of the packaging box.

[0094] It should be noted that in this paper, the relationship terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between the entities or operations. Moreover, the term "include" "contain" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process method article or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process method article or equipment.

[0095] Finally, it should be noted that: the above only for the preferred embodiments of the present application, and not for limiting the present application, although the present application is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still can modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part of the technical features. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A manufacturing process for a shockproof and biodegradable packaging box, characterized in that: Includes the following steps: S1: Mix dry corn starch and ethyl acetate evenly, add chlorinated acrylic acid and stearoyl chloride and mix evenly, heat to 50-60℃, react for 1-3 hours, and then obtain esterified starch after vacuum filtration, washing and drying. S2: Under nitrogen protection, esterified starch and deionized water are mixed evenly, heated to 80-90℃, and potassium persulfate aqueous solution is added dropwise over 1-2 hours. Simultaneously, methyl acrylate, glycidyl methacrylate, a mixed monomer containing double bonds and 2-methylene-1,3-dioxane are added dropwise over 1-2 hours. The reaction is carried out for 2-4 hours. After the reaction is completed, the resulting white emulsion is broken, filtered, washed, and then vacuum dried at 70-80℃ for 12-24 hours to obtain reactant A. S3: Mix polylactic acid, polycaprolactone, reactant A, microcrystalline cellulose and compatibilizer evenly, heat to 80-100℃, add epoxidized soybean oil, filler and antioxidant and mix evenly to obtain packaging box raw material; S4: Extrude and granulate the packaging box raw materials to obtain biodegradable granules; S5: Injection mold the biodegradable granules to make packaging boxes; The preparation steps of the double-bonded monomer in step S2 are as follows: (1) Under nitrogen protection, tung oil is heated to 100-110℃ and stirred for 1-2 hours. Then, it is cooled to 60-70℃ and 3-dimethylamino-1,2-propanediol and sodium methoxide are added. The reaction is carried out for 4-6 hours. After washing, filtration and spin evaporation, product B is obtained. (2) Under nitrogen protection, product B, phthalic anhydride and N,N-dimethylformamide are mixed evenly, heated to 55-65℃ and reacted for 8-10h. Tetrahydrofuran and deionized water are added and mixed evenly. After rotary evaporation, washing and drying, a monomer containing double bonds is obtained.

2. The manufacturing process of an anti-collision biodegradable packaging box according to claim 1, characterized in that: In step S1, the mass ratio of corn starch to ethyl acetate is 1:(3-4).

3. The manufacturing process of an anti-collision biodegradable packaging box according to claim 1, characterized in that: In step (1), the mass ratio of tung oil to 3-dimethylamino-1,2-propanediol is 1:(0.3-0.5).

4. The manufacturing process of an anti-collision biodegradable packaging box according to claim 1, characterized in that: In step (2), the mass ratio of product B to phthalic dianhydride is 1:(0.5-1.0).

5. The manufacturing process of an anti-collision biodegradable packaging box according to claim 1, characterized in that: The raw materials for the packaging box in step S3 include the following weight components: 40-50 parts polylactic acid, 12-14 parts polycaprolactone, 20-30 parts reactant A, 30-40 parts microcrystalline cellulose, 4-6 parts compatibilizer, 1-5 parts epoxidized soybean oil, 20-30 parts filler, and 0.5-2 parts antioxidant.

6. The manufacturing process of an anti-collision biodegradable packaging box according to claim 5, characterized in that: The compatibilizer is maleic anhydride-grafted polypropylene.

7. The manufacturing process of an anti-collision biodegradable packaging box according to claim 1, characterized in that: The extrusion process conditions in step S4 are: the temperature of each section of the extruder is 160-200℃.

8. The manufacturing process of a shockproof and biodegradable packaging box according to claim 1, characterized in that: The injection temperature in step S5 is 190-210℃.

9. A shockproof and biodegradable packaging box manufactured according to any one of claims 1-8.