High-temperature-resistant biodegradable plastic and production process thereof

Abstract

The application discloses a kind of high-temperature-resistant biodegradable plastics and its production process, belongs to the technical field of degradable plastics, including following weight parts raw materials: polybutylene succinate 60-80 parts, glass fiber 15-21 parts, compatible agent 7-11 parts, modified graphene oxide 12-18 parts, dispersing agent 2-4 parts, antioxidant 2-5 parts;Its production process is: after each raw material is mixed, extrusion granulation and injection molding, obtain high-temperature-resistant biodegradable plastics, wherein, modified graphene oxide is made by following steps: KH-570, ethanol solution, graphene oxide is mixed after adjusting pH, after heating, centrifugal drying is cooled, obtain modified graphene oxide, add toluene, initiator and eugenol are reacted at 75-85 DEG C for 24-36h, filter washing and drying, obtain modified graphene oxide;The application is by adding glass fiber, modified graphene oxide, enhance the high-temperature-resistant, antibacterial and other properties of biodegradable plastics.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of degradable plastics, and particularly relates to a high-temperature-resistant biodegradable plastic and a production process thereof. BACKGROUND

[0002] Plastics have the advantages of light weight, high strength, corrosion resistance and easy molding processing, and are widely used in many fields, but most plastics are made of low-density polyethylene, high-density polyethylene, polypropylene and other raw materials, which are difficult to be degraded in nature, and cause serious pollution to the environment due to overuse and improper recycling. Biodegradable plastics are a kind of environment-friendly plastics that have developed rapidly in recent years, have excellent performance and can be degraded by microorganisms in the natural environment after being discarded. For example, a preparation method of a biodegradable plastic is disclosed in Chinese Patent CN103319828B: plant fiber starch is added to acrylic resin, and a high molecular integrator and a degradation promoter are added, so that the plastic can be biodegraded. However, the biodegradable plastic has poor high-temperature resistance and antibacterial property, and is prone to distortion when contacting high temperature. Therefore, it is a technical problem to be solved to provide a biodegradable plastic with high-temperature resistance and antibacterial effect. SUMMARY

[0003] The application aims to provide a high-temperature-resistant biodegradable plastic and a production process thereof, so as to solve the problems of poor high-temperature resistance and antibacterial property of biodegradable plastics.

[0004] The object of the application can be achieved by the following technical solutions.

[0005] A high-temperature-resistant biodegradable plastic comprises the following raw materials by weight: 60-80 parts of polybutylene succinate, 15-21 parts of glass fiber, 7-11 parts of a compatibilizer, 12-18 parts of modified graphene oxide, 2-4 parts of a dispersant, and 2-5 parts of an antioxidant.

[0006] The high-temperature-resistant biodegradable plastic is made by the following steps:

[0007] The polybutylene succinate, glass fiber, compatibilizer, modified graphene oxide, dispersant and antioxidant are uniformly mixed in a high-speed mixer, and then sent to a double-screw extrusion granulator for extrusion granulation. The granulation is placed in a micro injection molding machine for injection molding to obtain the high-temperature-resistant biodegradable plastic.

[0008] Further, the modified graphene oxide is made by the following steps:

[0009] Step 1, the silane coupling agent KH-570 is dissolved in an ethanol solution with a volume fraction of 45%, and the graphene oxide is mixed in a high-speed disperser at a speed of 500 r / min for 10 min, the pH value is adjusted to 4-5 with a hydrochloric acid solution, and the reaction is stirred in a 50℃ water bath for 1-1.5 h, then the temperature is increased to 70℃ and the reaction is continued for 0.5-1 h, after cooling to room temperature, centrifugal treatment is carried out at 4000 r / min, and the obtained precipitate is dried at 65℃ to constant weight to obtain modified graphene oxide;

[0010] The amount ratio of KH-570, ethanol solution and graphene oxide is 6g:225mL:1g, and the mass fraction of the used hydrochloric acid solution is 15%; graphene oxide has a large number of oxygen-containing functional groups, strong hydrophilicity, and is prone to aggregation due to strong van der Waals forces between layers; after modification by the silane coupling agent, the unsaturated double bond alkyl group is grafted onto the graphene oxide, reducing its hydrophilicity and increasing the interlayer spacing of the graphene oxide, making it disperse uniformly and significantly enhancing its heat resistance;

[0011] Step 2, the modified graphene oxide is placed in a reaction container, toluene, initiator benzoyl peroxide and eugenol are added, and the reaction is stirred at 75-85℃ for 24-36 h, after the reaction is completed, filtration is carried out and washing is carried out with anhydrous ether, and drying treatment is carried out at 50℃ to obtain modified graphene oxide;

[0012] The amount ratio of modified graphene oxide, eugenol and toluene is 1-1.2g:5-7mL:10mL, and the amount of benzoyl peroxide is 1% of the total mass of modified graphene oxide and eugenol; under the action of the initiator benzoyl peroxide, the unsaturated double bond on the surface of the modified graphene oxide reacts with eugenol to obtain modified graphene oxide; eugenol is a natural aromatic compound with antibacterial properties, and after polymerization with modified graphene oxide, the modified graphene oxide has strong antibacterial properties.

[0013] Further, the double-screw extrusion granulator is model SY-6217, and six temperature controls are set from feeding to discharging: the first temperature control is 80-85℃, the second temperature control is 88-92℃, the third temperature control is 95-100℃, the fourth temperature control is 105-110℃, the fifth temperature control is 110-115℃, and the sixth temperature control is 118-125℃, and the screw rotation speed is 50 r / min.

[0014] Further, the micro injection molding machine is model WZS10, the injection molding temperature is 120-130℃, the mold temperature is 75-85℃, and the pressure holding time is 15 s.

[0015] Further, the length of the glass fiber is 5-13 mm, and the diameter is 6-12 μm.

[0016] Further, the compatibilizer is maleic anhydride.

[0017] Further, the dispersing agent is hydroxymethyl cellulose.

[0018] Further, the antioxidant is pentaerythritol ester.

[0019] Advantages of the present application:

[0020] 1. In order to make the biodegradable plastics obtain the properties of high temperature resistance and antibacterial, the present application adds the high temperature resistant material glass fiber and the strong antibacterial material modified graphene oxide in the polybutylene succinate plastics, the glass fiber has the property of high temperature resistance, can make the high temperature resistance of the polybutylene succinate plastics from 80-90℃ to 250-300℃, significantly improve the high temperature resistance and thermal stability of the biodegradable plastics, the glass fiber can enhance the rigidity of the degradable plastics, reduce the deformation of the degradable plastics due to shrinkage, and improve the durability of the plastics.

[0021] 2. The graphene oxide in the modified graphene oxide has special specific surface area and monolayer two-dimensional network structure, can improve the strength and toughness of the composite material, the van der Waals force in the graphene oxide produces strong force with the phospholipid molecules on the cell membrane, destroys the integrity of the bacterial cell membrane, so as to make the bacteria die, when the graphene oxide and other antibacterial substances are compounded, the antibacterial effect can be significantly improved; the eugenol in the modified graphene oxide contains phenolic hydroxyl in the molecular structure, can remove the free radicals in the reaction system, and the eugenol has strong hydrophobicity, can change the permeability of the bacterial cell membrane, so the eugenol has the properties of antiseptic and antibacterial, so the modified graphene oxide obtained after the polymerization of eugenol and modified graphene oxide has strong antibacterial property, antiseptic property and good heat resistance, can improve the mechanical properties and friction properties of the biodegradable plastics.

[0022] 3. The present application adds glass fiber, modified graphene oxide and other additives in the polybutylene succinate, not only improves the high temperature resistance and antibacterial property of the biodegradable plastics, but also enhances the thermal stability, wear resistance, antiseptic property and other comprehensive properties of the biodegradable plastics. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below combined with the embodiments of the present application. Obviously, the described embodiments are only 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 belong to the scope of protection of the present application.

[0024] Embodiment 1

[0025] The present embodiment provides a kind of modified graphene oxide, which is made by the following steps:

[0026] Step 1, 6g silane coupling agent KH-570 is dissolved in 225mL ethanol solution with a volume fraction of 45%, 1g graphene oxide is added, mixed in a high-speed disperser at a speed of 500r / min for 10min, the pH value is adjusted to 4 with a hydrochloric acid solution with a mass fraction of 15%, stirred in a 50℃ water bath for 1h, then heated to 70℃ and continue to stir for 1h, cooled to room temperature and centrifuged at 4000r / min, the obtained precipitate is dried at 65℃ to constant weight to obtain modified graphene oxide;

[0027] Step 2, 1g modified graphene oxide is placed in a reaction container, 5mL eugenol, 10mL toluene and benzoyl peroxide with a dosage of 1% of the total mass of modified graphene oxide and eugenol are added, stirred at 75℃ for 36h, after the reaction is completed, filtration and washing with anhydrous ether are carried out, and drying treatment is carried out at 50℃ to obtain modified graphene oxide.

[0028] Example 2

[0029] The example provides a modified graphene oxide, which is made by the following steps:

[0030] Step 1, 6g silane coupling agent KH-570 is dissolved in 225mL ethanol solution with a volume fraction of 45%, 1g graphene oxide is added, mixed in a high-speed disperser at a speed of 500r / min for 10min, the pH value is adjusted to 5 with a hydrochloric acid solution with a mass fraction of 15%, stirred in a 50℃ water bath for 1.5h, then heated to 70℃ and continue to stir for 0.5h, cooled to room temperature and centrifuged at 4000r / min, the obtained precipitate is dried at 65℃ to constant weight to obtain modified graphene oxide;

[0031] Step 2, 1.2g modified graphene oxide is placed in a reaction container, 7mL eugenol, 10mL toluene and benzoyl peroxide with a dosage of 1% of the total mass of modified graphene oxide and eugenol are added, stirred at 85℃ for 24h, after the reaction is completed, filtration and washing with anhydrous ether are carried out, and drying treatment is carried out at 50℃ to obtain modified graphene oxide.

[0032] Example 3

[0033] The example provides a modified graphene oxide, which is made by the following steps:

[0034] Step 1, 6g silane coupling agent KH-570 was dissolved in 225mL ethanol solution with a volume fraction of 45%, 1g graphene oxide was added and mixed in a high-speed disperser at a speed of 500r / min for 10min, the pH value was adjusted to 4.5 with a 15% mass fraction hydrochloric acid solution, and stirred and reacted in a 50℃ water bath for 1.2h, then the temperature was increased to 70℃ and the stirring reaction was continued for 0.8h, then cooled to room temperature and centrifuged at 4000r / min, and the obtained precipitate was dried at 65℃ to constant weight to obtain modified graphene oxide;

[0035] Step 2, 1g of the modified graphene oxide was placed in a reaction container, 6mL of eugenol, 10mL of toluene and 1% of the total mass of the modified graphene oxide and eugenol of benzoyl peroxide were added, and stirred and reacted at 80℃ for 28h, then filtered and washed with anhydrous ether, and dried at 50℃ to obtain modified graphene oxide.

[0036] Comparative Example 1

[0037] This example provides a modified graphene oxide, and the forming step is the same as step 1 in example 1.

[0038] Example 4

[0039] A high-temperature-resistant biodegradable plastic includes the following raw materials by weight: 60 parts of polybutylene succinate, 15 parts of glass fiber, 7 parts of maleic anhydride, 12 parts of modified graphene oxide of example 1, 2 parts of hydroxymethyl cellulose, and 2 parts of pentaerythritol ester.

[0040] The high-temperature-resistant biodegradable plastic is made by the following steps:

[0041] The polybutylene succinate, glass fiber, maleic anhydride, modified graphene oxide, hydroxymethyl cellulose, and pentaerythritol ester were uniformly mixed in a high-speed mixer, and then fed into a double-screw extruder granulator, with six temperature controls set as follows: the first segment temperature control was 80℃, the second segment temperature control was 88℃, the third segment temperature control was 95℃, the fourth segment temperature control was 105℃, the fifth segment temperature control was 110℃, and the sixth segment temperature control was 118℃, and the screw rotation speed was 50r / min. After extrusion granulation in the double-screw extruder granulator, the product was placed into a micro injection molding machine for injection molding, with the injection molding temperature of the micro injection molding machine set to 120℃ and the mold temperature set to 75℃, and the holding pressure time set to 15s, thereby obtaining the high-temperature-resistant biodegradable plastic.

[0042] The length of the glass fiber is 5mm and the diameter is 6μm, the model of the double-screw extruder granulator is SY-6217, and the model of the micro injection molding machine is WZS10.

[0043] Example 5

[0044] A high-temperature-resistant biodegradable plastic, comprising the following raw materials by weight: 70 parts of polybutylene succinate, 18 parts of glass fiber, 9 parts of maleic anhydride, 16 parts of modified graphene oxide of Example 3, 3 parts of hydroxymethyl cellulose, and 3 parts of pentaerythritol ester.

[0045] The high-temperature-resistant biodegradable plastic is made by the following steps:

[0046] The polybutylene succinate, glass fiber, maleic anhydride, modified graphene oxide, hydroxymethyl cellulose, and pentaerythritol ester are uniformly mixed in a high-speed mixer, and then fed into a double-screw extrusion granulator. Six temperature controls are set, with the first segment temperature control being 82℃, the second segment temperature control being 90℃, the third segment temperature control being 97℃, the fourth segment temperature control being 108℃, the fifth segment temperature control being 112℃, and the sixth segment temperature control being 120℃. The screw speed is set to 50r / min. After extrusion granulation in the double-screw extrusion granulator, the product is placed into a micro injection molding machine for injection molding. The injection molding temperature of the micro injection molding machine is set to 125℃, the mold temperature is set to 80℃, and the holding pressure time is set to 15s. Thus, the high-temperature-resistant biodegradable plastic is obtained.

[0047] The length of the glass fiber is 10mm, the diameter is 8μm, the model of the double-screw extrusion granulator is SY-6217, and the model of the micro injection molding machine is WZS10.

[0048] Example 6

[0049] A high-temperature-resistant biodegradable plastic, comprising the following raw materials by weight: 80 parts of polybutylene succinate, 21 parts of glass fiber, 11 parts of maleic anhydride, 18 parts of modified graphene oxide of Example 2, 4 parts of hydroxymethyl cellulose, and 5 parts of pentaerythritol ester.

[0050] The high-temperature-resistant biodegradable plastic is made by the following steps:

[0051] The polybutylene succinate, glass fiber, maleic anhydride, modified graphene oxide, hydroxymethyl cellulose, and pentaerythritol ester are uniformly mixed in a high-speed mixer, and then fed into a double-screw extrusion granulator. Six temperature controls are set, with the first segment temperature control being 85℃, the second segment temperature control being 92℃, the third segment temperature control being 100℃, the fourth segment temperature control being 110℃, the fifth segment temperature control being 115℃, and the sixth segment temperature control being 125℃. The screw speed is set to 50r / min. After extrusion granulation in the double-screw extrusion granulator, the product is placed into a micro injection molding machine for injection molding. The injection molding temperature of the micro injection molding machine is set to 130℃, the mold temperature is set to 85℃, and the holding pressure time is set to 15s. Thus, the high-temperature-resistant biodegradable plastic is obtained.

[0052] The length of the glass fiber is 13mm, the diameter is 12μm, the model of the double-screw extrusion granulator is SY-6217, and the model of the micro injection molding machine is WZS10.

[0053] Comparative Example 2

[0054] The modified graphene oxide in Example 4 was replaced by the modified graphene oxide in Comparative Example 1, and the remaining raw materials and preparation process were the same as in Example 4.

[0055] Comparative Example 3

[0056] The glass fiber in Example 5 was removed, and the remaining raw materials and preparation process were the same as in Example 5.

[0057] Examples 4-6 and Comparative Examples 2-3 were tested for antibacterial and high-temperature resistance properties. The antibacterial property test was performed according to QB / T 2591 "Antibacterial Performance Test Method and Antibacterial Effect of Antibacterial Plastics", and the antibacterial rate against Staphylococcus aureus and Escherichia coli was calculated by using the blank sample control and the film sticking method. The high-temperature resistance property test was performed by the Vicat heat resistance experiment, and the results are shown in Table 1:

[0058] Table 1

[0059]

[0060]

[0061] As can be seen from Table 1, the Staphylococcus aureus and Escherichia coli antibacterial rates of Examples 4-6 are all above 99%, which have strong antibacterial properties and are superior to Comparative Examples 2-3. The deformation temperature and heat resistance time of Examples 4-6 are superior to Comparative Examples 2-3, which shows that the addition of the high-temperature resistant material glass fiber and the strong antibacterial material modified graphene oxide in polybutylene succinate effectively improves the antibacterial and high-temperature resistance properties of the polybutylene succinate degradable plastic.

[0062] It should be noted that, in this document, the terms such as first and second are used only 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 terms "include", "contain" or any other variants thereof are 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.

[0063] Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high temperature resistant biodegradable plastic, characterized in that, The following raw materials by weight are included: polybutylene succinate 60-80 parts, glass fiber 15-21 parts, compatibilizer 7-11 parts, modified graphene oxide 12-18 parts, dispersant 2-4 parts, antioxidant 2-5 parts; The modified graphene oxide is made by the following steps: Step 1, dissolve KH-570 in ethanol solution, add graphene oxide, mix for 10 min, adjust pH value to 4-5 with hydrochloric acid solution, react at 50℃ water bath for 1-1.5 h, increase temperature to 70℃ and react for 0.5-1 h, cool, centrifuge and dry to obtain modified graphene oxide; Step 2, add toluene, benzoyl peroxide and eugenol to the modified graphene oxide, stir and react at 75-85℃ for 24-36 h, filter, wash and dry to obtain modified graphene oxide; The amount ratio of KH-570, ethanol solution and graphene oxide in step 1 is 6g:225mL:1g; The amount ratio of modified graphene oxide, eugenol and toluene in step 2 is 1-1.2g:5-7mL:10mL, and the amount of benzoyl peroxide is 1% of the total mass of modified graphene oxide and eugenol.

2. A high temperature resistant biodegradable plastic according to claim 1, characterized in that, The length of the glass fiber is 5-13mm and the diameter is 6-12μm.

3. The high temperature resistant biodegradable plastic according to claim 1, characterized in that, The mass fraction of the hydrochloric acid solution is 15%.

4. The process for producing a high-temperature-resistant biodegradable plastic according to claim 1, characterized by, The following steps are included: Put polybutylene succinate, glass fiber, compatibilizer, modified graphene oxide, dispersant and antioxidant into a high-speed mixer and mix uniformly, then send into a double-screw extrusion granulator to extrude and granulate, put the granules into a micro injection molding machine to injection mold to obtain high-temperature resistant biodegradable plastic.

5. A process for the production of a high temperature resistant biodegradable plastic according to claim 4, characterized in that, The double-screw extrusion granulator is provided with six temperature controls from feeding to discharging: the first section temperature control is 80-85℃, the second section temperature control is 88-92℃, the third section temperature control is 95-100℃, the fourth section temperature control is 105-110℃, the fifth section temperature control is 110-115℃, and the sixth section temperature control is 118-125℃, and the screw rotation speed is 50r / min.

6. A process for the production of a high temperature resistant biodegradable plastic according to claim 4, characterized in that, The injection molding temperature of the micro injection molding machine is 120-130℃, the mold temperature is 75-85℃, and the pressure maintaining time is 15s.

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