CN115558252B - Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof - Google Patents
Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention relates to the technical field of biodegradable materials, and provides a biodegradable injection molding cutter, fork and spoon master batch and a preparation method thereof, wherein the porous nano silicon dioxide reacts with functional groups in lignin and vinyl trimethoxy silane to generate stable chemical bonds, so that an antibacterial agent and a flame retardant can be firmly adsorbed in a reticular structure molecular gap formed among the porous nano silicon dioxide, the lignin and the vinyl trimethoxy silane; and secondly, the lignin is modified in a vinyl trimethoxy silane grafting mode, so that the dispersion effect of the lignin in the biodegradable copolyester can be improved, the compatibility between the modified lignin and the biodegradable copolyester is improved, the modified lignin and the biodegradable copolyester are compatible to form a compound with antibacterial and flame-retardant properties, the mechanical properties of the biodegradable copolyester are improved, the biodegradability can be maintained, and the quality of injection molding finished products is improved to a certain extent.
Description
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a biodegradable injection molding cutter, fork and spoon master batch and a preparation method thereof.
Background
With the continuous promotion of the national plastic restriction, the research and application of the degradable polymer material are widely concerned. Under the natural environment condition, the molecular chain segments of the degradable high polymer material are broken through the actions of microorganisms, enzymes, light or temperature and the like, the binding capacity of the functional groups is reduced, and small molecular compounds such as carbon dioxide, water and the like are generated by decomposition, so that the recycling of organisms is realized.
At present, the degradable high polymer materials mainly comprise petroleum-based polymers such as polylactic acid, polybutylene terephthalate, polyethylene lactone, polyhydroxyalkanoate and the like, and natural high polymer materials such as starch, lignin, protein, chitosan and the like. However, the degradable high polymer materials are single in performance, can not simultaneously have various performances suitable for market demands, are poor in antibacterial performance and flame retardant performance, can not maintain the biodegradability and simultaneously improve the antibacterial performance and flame retardant performance, and are not suitable for large-scale popularization, so that how to produce a novel high polymer material can be biodegraded and can be used for processing injection molding knives, forks and spoons, and the technical problem to be solved by the technicians in the field is urgent.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a biodegradable injection molding knife, fork and spoon master batch and a preparation method thereof, aiming at ensuring that the prepared high polymer master batch has better antibacterial property and flame retardant property and is suitable for injection molding processing of knives, forks and spoons.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a biodegradable injection molding cutter, fork and spoon master batch is prepared from the following raw materials in parts by weight: 60-65 parts of biodegradable copolyester, 30-40 parts of modified lignin, 3-4 parts of tributyl citrate, 2-3 parts of zinc stearate, 3-5 parts of antibacterial modified components and 2-3 parts of flame retardant modified components.
Further, the preparation method of the biodegradable copolyester comprises the following steps:
step1, pumping air for 3 times in a four-neck flask with mechanical stirring, and then adding a certain amount of dimethyl succinate, dimethyl terephthalate, 1, 4-butanediol and titanium tetraisopropoxide at one time under the protection of nitrogen; wherein, the molar ratio of the dimethyl succinate to the dimethyl terephthalate is 7:3, the dosage of the tetraisopropoxy titanium is 1/3000mol of total dimethyl ester, and the feeding ratio of 1, 4-butanediol to the total dimethyl ester is 1.05:1, the total dimethyl ester is the sum of dimethyl succinate and dimethyl terephthalate;
step2, placing the four-neck flask into a silicone oil bath under the protection of nitrogen, increasing the temperature to 180 ℃ under the condition of continuous stirring, and keeping the constant temperature for reaction for 2 hours;
step 3, gradually decompressing the system in the step2 and raising the temperature of the oil bath to 230 ℃ until the product is cohesive on a stirring rod to form balls, and ending the reaction;
and 4, dissolving the product in chloroform, precipitating and filtering with methanol, and drying in a vacuum drying box at 40-45 ℃ for 24 hours after filtering, thus obtaining the biodegradable copolyester.
Further, the stirring speed in the step2 is 500-600r/min.
Further, the vacuum degree of the system in the step 3 is controlled within 0.5mmHg during the decompression.
Further, the preparation method of the modified lignin comprises the following steps:
step one, adding 60 parts by weight of 60% ethanol aqueous solution into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and regulating the pH value to 3.5-5.5;
slowly dripping 0.5-1 part by weight of vinyltrimethoxysilane into the system in the first step by using a constant pressure dropping funnel, hydrolyzing for 1.5 hours at 60 ℃, adding 3-5 parts by weight of lignin, hydrolyzing for 2 hours again at 60 ℃, and continuously stirring at a speed of 300-500r/min in the hydrolysis process;
and thirdly, after the reaction in the second step is finished, pumping and washing the product in the second step by using N, N-dimethylformamide/dichloromethane mixed solution, distilled water, absolute ethyl alcohol and acetone in sequence to enable the product to reach neutrality, drying the product in a drying oven at 75 ℃ for 6 hours, and cooling the product to room temperature in a dryer to obtain the modified lignin.
Further, the method for adjusting the pH value in the first step comprises the following steps: glacial acetic acid is slowly added dropwise until the pH value of the system reaches the specified range.
Further, the preparation method of the antibacterial modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.1g/mL, adding 15-18% antibacterial agent and 3-5% sorbitan oleate polyoxyethylene ether into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain the antibacterial modified component; wherein the antibacterial agent is one of dodecyl trimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride.
Further, the preparation method of the flame retardant modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.2g/mL, adding 22-25% flame retardant and 4-5% sodium dodecyl benzene sulfonate into the container, performing ultrasonic dispersion uniformly, and performing filtration and drying treatment to obtain a flame retardant modified component; wherein the flame retardant is one of aluminum hydroxide or magnesium hydroxide.
A preparation method of biodegradable injection molding knife, fork and spoon master batch, which comprises the following steps:
step1, pouring the modified lignin, the antibacterial modified component and the flame retardant modified component with the formula amounts into a flask with a stirrer according to the following formula amounts of 1:5 (g/mL) of ethanol water solution with the concentration of 60 percent is added, the mixture is stirred for 3 to 4 hours at the temperature of 45 to 55 ℃, and the obtained product is filtered and then is dried;
step2, pouring the biodegradable copolyester, tributyl citrate and zinc stearate with the formula amounts into a mixing mill, adding the products in Step1, then carrying out melt blending, and extruding and granulating in a double-screw extruder after uniform mixing, thus obtaining the biodegradable injection molding knife, fork and spoon master batch.
Further, the stirring speed in Step1 is 400-500r/min, and the drying treatment temperature in Step1 is 50-55 ℃.
Advantageous effects
The invention provides a biodegradable injection molding cutter, fork and spoon master batch and a preparation method thereof, and compared with the prior art, the biodegradable injection molding cutter, fork and spoon master batch has the following beneficial effects:
1. the biodegradable copolyester is prepared from dimethyl succinate, dimethyl terephthalate and 1, 4-butanediol through copolymerization reaction, has the biodegradability of aliphatic polyesters and the physical processability of aromatic polyesters, is suitable for various processing technologies in injection molding processing, and can be biodegraded in the recovery processing process.
2. In the process of preparing the antibacterial modified component and the flame-retardant modified component, uniformly dispersing an antibacterial agent and a flame retardant on the inner wall of a porous nano silicon dioxide pore by ultrasonic dispersion, and then enabling the porous nano silicon dioxide to react with lignin grafted by vinyl trimethoxy silane to enable the porous nano silicon dioxide to react with lignin and functional groups in the vinyl trimethoxy silane to generate stable chemical bonds, so that the antibacterial agent and the flame retardant can be firmly adsorbed in a reticular structure molecular gap formed among the porous nano silicon dioxide, the lignin and the vinyl trimethoxy silane; and secondly, the lignin is modified in a vinyl trimethoxy silane grafting mode, so that the dispersion effect of the lignin in the biodegradable copolyester can be improved, the compatibility between the modified lignin and the biodegradable copolyester is improved, the modified lignin and the biodegradable copolyester are compatible to form a compound with antibacterial and flame-retardant properties, the mechanical properties of the biodegradable copolyester are improved, the biodegradability can be maintained, and the quality of injection molding finished products is improved to a certain extent.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the biodegradable injection molding cutter, fork and spoon master batch is prepared from the following raw materials in parts by weight: 60 biodegradable copolyester, 30 parts of modified lignin, 3 parts of tributyl citrate, 2 parts of zinc stearate, 3 parts of antibacterial modified component and 2 parts of flame retardant modified component.
The preparation method of the biodegradable copolyester comprises the following steps:
step1, pumping air for 3 times in a four-neck flask with mechanical stirring, and then adding a certain amount of dimethyl succinate, dimethyl terephthalate, 1, 4-butanediol and titanium tetraisopropoxide at one time under the protection of nitrogen; wherein, the molar ratio of the dimethyl succinate to the dimethyl terephthalate is 7:3, the dosage of the tetraisopropoxy titanium is 1/3000mol of total dimethyl ester, and the feeding ratio of 1, 4-butanediol to the total dimethyl ester is 1.05:1, the total dimethyl ester is the sum of dimethyl succinate and dimethyl terephthalate;
step2, placing the four-neck flask into a silicone oil bath under the protection of nitrogen, increasing the temperature to 180 ℃ under the condition of continuous stirring, and keeping the constant temperature for reaction for 2 hours;
step 3, gradually decompressing the system in the step2 and raising the temperature of the oil bath to 230 ℃ until the product is cohesive on a stirring rod to form balls, and ending the reaction;
and 4, dissolving the product in chloroform, precipitating and filtering with methanol, and drying the filtered product in a vacuum drying box at 40 ℃ for 24 hours to obtain the biodegradable copolyester.
The stirring speed in the step2 was 500r/min.
The vacuum degree of the system in the step 3 is controlled within 0.5mmHg during the decompression process.
The preparation method of the modified lignin comprises the following steps:
step one, adding 60 parts by weight of 60% ethanol aqueous solution into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and regulating the pH value to 3.5;
slowly dripping 0.5 part by weight of vinyltrimethoxysilane into the system in the first step by using a constant pressure dropping funnel, hydrolyzing for 1.5 hours at 60 ℃, adding 3 parts by weight of lignin, hydrolyzing for 2 hours again at 60 ℃, and continuously stirring at a speed of 300r/min in the hydrolysis process;
and thirdly, after the reaction in the second step is finished, pumping and washing the product in the second step by using N, N-dimethylformamide/dichloromethane mixed solution, distilled water, absolute ethyl alcohol and acetone in sequence to enable the product to reach neutrality, drying the product in a drying oven at 75 ℃ for 6 hours, and cooling the product to room temperature in a dryer to obtain the modified lignin.
The method for adjusting the pH value in the first step comprises the following steps: glacial acetic acid is slowly added dropwise until the pH value of the system reaches the specified range.
The preparation method of the antibacterial modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.1g/mL, adding 15% antibacterial agent and 3% sorbitan oleate polyoxyethylene ether into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain the antibacterial modified component; wherein the antibacterial agent is one of dodecyl trimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride.
The preparation method of the flame retardant modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.2g/mL, adding 22% flame retardant and 4% sodium dodecyl benzene sulfonate into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain a flame retardant modified component; wherein the flame retardant is one of aluminum hydroxide or magnesium hydroxide.
A preparation method of biodegradable injection molding knife, fork and spoon master batch comprises the following steps:
step1, pouring the modified lignin, the antibacterial modified component and the flame retardant modified component with the formula amounts into a flask with a stirrer according to the following formula amounts of 1:5 (g/mL) of ethanol aqueous solution with the concentration of 60 percent is added, the mixture is stirred for 3 hours at the temperature of 45 ℃, and the obtained product is filtered and then is dried;
step2, pouring the biodegradable copolyester, tributyl citrate and zinc stearate with the formula amounts into a mixing mill, adding the products in Step1, then carrying out melt blending, and extruding and granulating in a double-screw extruder after uniform mixing, thus obtaining the biodegradable injection molding knife, fork and spoon master batch.
The stirring speed in Step1 was 400r/min, and the drying treatment temperature in Step1 was 50 ℃.
Example 2:
the biodegradable injection molding cutter, fork and spoon master batch is prepared from the following raw materials in parts by weight: 65 parts of biodegradable copolyester, 40 parts of modified lignin, 4 parts of tributyl citrate, 3 parts of zinc stearate, 5 parts of antibacterial modified components and 3 parts of flame retardant modified components.
The preparation method of the biodegradable copolyester comprises the following steps:
step1, pumping air for 3 times in a four-neck flask with mechanical stirring, and then adding a certain amount of dimethyl succinate, dimethyl terephthalate, 1, 4-butanediol and titanium tetraisopropoxide at one time under the protection of nitrogen; wherein, the molar ratio of the dimethyl succinate to the dimethyl terephthalate is 7:3, the dosage of the tetraisopropoxy titanium is 1/3000mol of total dimethyl ester, and the feeding ratio of 1, 4-butanediol to the total dimethyl ester is 1.05:1, the total dimethyl ester is the sum of dimethyl succinate and dimethyl terephthalate;
step2, placing the four-neck flask into a silicone oil bath under the protection of nitrogen, increasing the temperature to 180 ℃ under the condition of continuous stirring, and keeping the constant temperature for reaction for 2 hours;
step 3, gradually decompressing the system in the step2 and raising the temperature of the oil bath to 230 ℃ until the product is cohesive on a stirring rod to form balls, and ending the reaction;
and 4, dissolving the product in chloroform, precipitating and filtering with methanol, and drying the filtered product in a vacuum drying box at 45 ℃ for 24 hours to obtain the biodegradable copolyester.
The stirring speed in the step2 was 600r/min.
The vacuum degree of the system in the step 3 is controlled within 0.5mmHg during the decompression process.
The preparation method of the modified lignin comprises the following steps:
step one, adding 60 parts by weight of 60% ethanol aqueous solution into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and regulating the pH value to 5.5;
slowly dripping 1 part by weight of vinyltrimethoxysilane into the system in the first step by using a constant pressure dropping funnel, hydrolyzing for 1.5 hours at 60 ℃, adding 5 parts by weight of lignin, hydrolyzing for 2 hours again at 60 ℃, and continuously stirring at a speed of 500r/min in the hydrolysis process;
and thirdly, after the reaction in the second step is finished, pumping and washing the product in the second step by using N, N-dimethylformamide/dichloromethane mixed solution, distilled water, absolute ethyl alcohol and acetone in sequence to enable the product to reach neutrality, drying the product in a drying oven at 75 ℃ for 6 hours, and cooling the product to room temperature in a dryer to obtain the modified lignin.
The method for adjusting the pH value in the first step comprises the following steps: glacial acetic acid is slowly added dropwise until the pH value of the system reaches the specified range.
The preparation method of the antibacterial modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.1g/mL, adding an antibacterial agent with the dosage of 18% of the ethanol water solution and sorbitan oleate polyoxyethylene ether with the dosage of 5% of the ethanol water solution into the container, performing ultrasonic dispersion uniformly, and performing filtration and drying treatment to obtain an antibacterial modified component; wherein the antibacterial agent is one of dodecyl trimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride.
The preparation method of the flame retardant modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.2g/mL, adding 25% flame retardant and 5% sodium dodecyl benzene sulfonate into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain a flame retardant modified component; wherein the flame retardant is one of aluminum hydroxide or magnesium hydroxide.
A preparation method of biodegradable injection molding knife, fork and spoon master batch comprises the following steps:
step1, pouring the modified lignin, the antibacterial modified component and the flame retardant modified component with the formula amounts into a flask with a stirrer according to the following formula amounts of 1:5 (g/mL) of ethanol aqueous solution with the concentration of 60 percent is added, the mixture is stirred for 4 hours at the temperature of 55 ℃, and the obtained product is filtered and then is dried;
step2, pouring the biodegradable copolyester, tributyl citrate and zinc stearate with the formula amounts into a mixing mill, adding the products in Step1, then carrying out melt blending, and extruding and granulating in a double-screw extruder after uniform mixing, thus obtaining the biodegradable injection molding knife, fork and spoon master batch.
The stirring speed in Step1 was 500r/min, and the drying treatment temperature in Step1 was 55 ℃.
Example 3:
the biodegradable injection molding cutter, fork and spoon master batch is prepared from the following raw materials in parts by weight: 63 parts of biodegradable copolyester, 35 parts of modified lignin, 4 parts of tributyl citrate, 2 parts of zinc stearate, 4 parts of antibacterial modified components and 3 parts of flame retardant modified components.
The preparation method of the biodegradable copolyester comprises the following steps:
step1, pumping air for 3 times in a four-neck flask with mechanical stirring, and then adding a certain amount of dimethyl succinate, dimethyl terephthalate, 1, 4-butanediol and titanium tetraisopropoxide at one time under the protection of nitrogen; wherein, the molar ratio of the dimethyl succinate to the dimethyl terephthalate is 7:3, the dosage of the tetraisopropoxy titanium is 1/3000mol of total dimethyl ester, and the feeding ratio of 1, 4-butanediol to the total dimethyl ester is 1.05:1, the total dimethyl ester is the sum of dimethyl succinate and dimethyl terephthalate;
step2, placing the four-neck flask into a silicone oil bath under the protection of nitrogen, increasing the temperature to 180 ℃ under the condition of continuous stirring, and keeping the constant temperature for reaction for 2 hours;
step 3, gradually decompressing the system in the step2 and raising the temperature of the oil bath to 230 ℃ until the product is cohesive on a stirring rod to form balls, and ending the reaction;
and 4, dissolving the product in chloroform, precipitating and filtering with methanol, and drying the filtered product in a vacuum drying box at 43 ℃ for 24 hours to obtain the biodegradable copolyester.
The stirring speed in the step2 was 500r/min.
The vacuum degree of the system in the step 3 is controlled within 0.5mmHg during the decompression process.
The preparation method of the modified lignin comprises the following steps:
step one, adding 60 parts by weight of 60% ethanol aqueous solution into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and regulating the pH value to 4.5;
slowly dripping 0.8 part by weight of vinyltrimethoxysilane into the system in the first step by using a constant pressure dropping funnel, hydrolyzing for 1.5 hours at 60 ℃, adding 4 parts by weight of lignin, hydrolyzing for 2 hours again at 60 ℃, and continuously stirring at a speed of 400r/min in the hydrolysis process;
and thirdly, after the reaction in the second step is finished, pumping and washing the product in the second step by using N, N-dimethylformamide/dichloromethane mixed solution, distilled water, absolute ethyl alcohol and acetone in sequence to enable the product to reach neutrality, drying the product in a drying oven at 75 ℃ for 6 hours, and cooling the product to room temperature in a dryer to obtain the modified lignin.
The method for adjusting the pH value in the first step comprises the following steps: glacial acetic acid is slowly added dropwise until the pH value of the system reaches the specified range.
The preparation method of the antibacterial modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.1g/mL, adding 17% antibacterial agent and 4% sorbitan oleate polyoxyethylene ether into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain the antibacterial modified component; wherein the antibacterial agent is one of dodecyl trimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride.
The preparation method of the flame retardant modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.2g/mL, adding 23% flame retardant and 5% sodium dodecyl benzene sulfonate into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain flame retardant modified component; wherein the flame retardant is one of aluminum hydroxide or magnesium hydroxide.
A preparation method of biodegradable injection molding knife, fork and spoon master batch comprises the following steps:
step1, pouring the modified lignin, the antibacterial modified component and the flame retardant modified component with the formula amounts into a flask with a stirrer according to the following formula amounts of 1:5 (g/mL) of ethanol aqueous solution with the concentration of 60 percent is added, the mixture is stirred for 4 hours at 50 ℃, and the obtained product is filtered and then is dried;
step2, pouring the biodegradable copolyester, tributyl citrate and zinc stearate with the formula amounts into a mixing mill, adding the products in Step1, then carrying out melt blending, and extruding and granulating in a double-screw extruder after uniform mixing, thus obtaining the biodegradable injection molding knife, fork and spoon master batch.
The stirring speed in Step1 was 400r/min, and the drying treatment temperature in Step1 was 52 ℃.
Comparative example: the master batch provided in this example and the production process thereof are substantially the same as those in example 1, and the main differences are that: the lignin obtained in the raw material of the comparative example is unmodified lignin.
Performance testing
The biodegradable injection molding knife, fork and spoon master batches prepared by examples 1 to 3 of the present invention were respectively designated as experimental examples 1 to 3; the master batches prepared by the comparative examples were taken as comparative examples, and then the correlation properties of examples 1 to 3 and comparative examples were examined, and the obtained data are recorded in the following table:
the data in the table show that the biodegradable injection molding knife, fork and spoon master batch prepared in the embodiment 1-3 has higher tensile strength and biodegradation rate and better antibacterial property and flame retardant property, so that the biodegradable injection molding knife, fork and spoon master batch prepared in the invention can be better popularized as injection molding raw materials and has wider market prospect.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation 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 may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A biodegradable injection molding cutter, fork and spoon master batch is characterized by being prepared from the following raw materials in parts by weight: 60-65 parts of biodegradable copolyester, 30-40 parts of modified lignin, 3-4 parts of tributyl citrate, 2-3 parts of zinc stearate, 3-5 parts of antibacterial modified components and 2-3 parts of flame retardant modified components;
the preparation method of the biodegradable copolyester comprises the following steps:
step1, pumping air for 3 times in a four-neck flask with mechanical stirring, and then adding a certain amount of dimethyl succinate, dimethyl terephthalate, 1, 4-butanediol and titanium tetraisopropoxide at one time under the protection of nitrogen; wherein, the molar ratio of the dimethyl succinate to the dimethyl terephthalate is 7:3, the dosage of the tetraisopropoxy titanium is 1/3000mol of total dimethyl ester, and the feeding ratio of 1, 4-butanediol to the total dimethyl ester is 1.05:1, the total dimethyl ester is the sum of dimethyl succinate and dimethyl terephthalate;
step2, placing the four-neck flask into a silicone oil bath under the protection of nitrogen, increasing the temperature to 180 ℃ under the condition of continuous stirring, and keeping the constant temperature for reaction for 2 hours;
step 3, gradually decompressing the system in the step2 and raising the temperature of the oil bath to 230 ℃ until the product is cohesive on a stirring rod to form balls, and ending the reaction;
step 4, dissolving the product in chloroform, precipitating and filtering with methanol, and drying in a vacuum drying box at 40-45 ℃ for 24 hours after filtering, thus obtaining the biodegradable copolyester;
the stirring speed in the step2 is 500-600r/min;
the vacuum degree of the system in the step 3 is controlled within 0.5mmHg in the process of decompression;
the preparation method of the modified lignin comprises the following steps:
step one, adding 60 parts by weight of 60% ethanol aqueous solution into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and regulating the pH value to 3.5-5.5;
slowly dripping 0.5-1 part by weight of vinyltrimethoxysilane into the system in the first step by using a constant pressure dropping funnel, hydrolyzing for 1.5 hours at 60 ℃, adding 3-5 parts by weight of lignin, hydrolyzing for 2 hours again at 60 ℃, and continuously stirring at a speed of 300-500r/min in the hydrolysis process;
after the reaction in the step two is finished, pumping and washing the product in the step two by using N, N-dimethylformamide/dichloromethane mixed solution, distilled water, absolute ethyl alcohol and acetone in sequence to enable the product to reach neutrality, drying the product in a drying oven at 75 ℃ for 6 hours, and cooling the product to room temperature in a dryer to obtain modified lignin;
the method for adjusting the pH value in the first step comprises the following steps: slowly dripping glacial acetic acid until the pH value of the system reaches a specified range;
the preparation method of the antibacterial modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.1g/mL, adding 15-18% antibacterial agent and 3-5% sorbitan oleate polyoxyethylene ether into the container, performing ultrasonic dispersion uniformly, and filtering and drying to obtain the antibacterial modified component; wherein the antibacterial agent is one of dodecyl trimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride;
the preparation method of the flame retardant modified component comprises the following steps: adding porous nano silicon dioxide and 40% ethanol water solution into a container according to the dosage ratio of 0.2g/mL, adding 22-25% flame retardant and 4-5% sodium dodecyl benzene sulfonate into the container, performing ultrasonic dispersion uniformly, and performing filtration and drying treatment to obtain a flame retardant modified component; wherein the flame retardant is one of aluminum hydroxide or magnesium hydroxide.
2. The method for preparing the biodegradable plastic injection molding knife, fork and spoon master batch according to claim 1, which is characterized by comprising the following steps:
step1, pouring the modified lignin, the antibacterial modified component and the flame retardant modified component with the formula amounts into a flask with a stirrer according to the following formula amounts of 1: adding ethanol water solution with the concentration of 60% into the solid-liquid ratio of 5g/mL, stirring for 3-4h at 45-55 ℃, filtering the obtained product, and drying;
step2, pouring the biodegradable copolyester, tributyl citrate and zinc stearate with the formula amounts into a mixing mill, adding the products in Step1, then carrying out melt blending, and extruding and granulating in a double-screw extruder after uniform mixing, thus obtaining the biodegradable injection molding knife, fork and spoon master batch.
3. The method for preparing biodegradable injection molding knife, fork and spoon master batch according to claim 2, wherein the stirring speed in Step1 is 400-500r/min, and the drying treatment temperature in Step1 is 50-55 ℃.
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