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 PDF

Info

Publication number
CN115558252B
CN115558252B CN202211262717.4A CN202211262717A CN115558252B CN 115558252 B CN115558252 B CN 115558252B CN 202211262717 A CN202211262717 A CN 202211262717A CN 115558252 B CN115558252 B CN 115558252B
Authority
CN
China
Prior art keywords
biodegradable
lignin
parts
injection molding
flame retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211262717.4A
Other languages
Chinese (zh)
Other versions
CN115558252A (en
Inventor
王鹏
李成
熊松阳
肖维钢
周海
张兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiang Xi Sheng Ping Xiang Shi Xuan Pin Plastic Cement Products Co ltd
Original Assignee
Jiang Xi Sheng Ping Xiang Shi Xuan Pin Plastic Cement Products Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiang Xi Sheng Ping Xiang Shi Xuan Pin Plastic Cement Products Co ltd filed Critical Jiang Xi Sheng Ping Xiang Shi Xuan Pin Plastic Cement Products Co ltd
Priority to CN202211262717.4A priority Critical patent/CN115558252B/en
Publication of CN115558252A publication Critical patent/CN115558252A/en
Application granted granted Critical
Publication of CN115558252B publication Critical patent/CN115558252B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/223Packed additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/19Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/12Adsorbed ingredients, e.g. ingredients on carriers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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

Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof
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 ℃.
CN202211262717.4A 2022-10-14 2022-10-14 Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof Active CN115558252B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211262717.4A CN115558252B (en) 2022-10-14 2022-10-14 Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211262717.4A CN115558252B (en) 2022-10-14 2022-10-14 Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115558252A CN115558252A (en) 2023-01-03
CN115558252B true CN115558252B (en) 2023-09-19

Family

ID=84746319

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211262717.4A Active CN115558252B (en) 2022-10-14 2022-10-14 Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115558252B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935871A (en) * 2006-09-15 2007-03-28 东华大学 Biodegradable high-molecular-weight aliphatic/aromatic copolymer, and its preparing method and use
WO2012118165A1 (en) * 2011-03-01 2012-09-07 Ricoh Company, Ltd. Flame retardant resin composition and molded product
CN105802168A (en) * 2016-05-23 2016-07-27 江西省萍乡市轩品塑胶制品有限公司 Biodegradable nanometer filling function master batch and preparation method and application thereof
CN106189146A (en) * 2016-08-29 2016-12-07 佛山市高明区尚润盈科技有限公司 A kind of preparation method of polylactic acid antibacterial matrices
CN109181247A (en) * 2018-08-31 2019-01-11 南京工业大学 A kind of Biodegradable film and preparation method thereof that modified lignin resin is compound
CN109608924A (en) * 2018-12-13 2019-04-12 宁艺伟 A kind of flame-proof antibiotic paint preparation method for wooden equipment
CN112048161A (en) * 2020-08-11 2020-12-08 新昌县佳和工艺股份有限公司 High-barrier modified polylactic acid antibacterial material and preparation method thereof
CN113121843A (en) * 2021-03-22 2021-07-16 上海昶法新材料有限公司 Preparation method of silane coupling agent modified lignin
CN114044978A (en) * 2021-12-29 2022-02-15 深圳中塑化工高性能材料有限公司 Quaternary ammonium salt functionalized nano SiO2Antibacterial modified polypropylene material and preparation method thereof
CN114933785A (en) * 2022-04-29 2022-08-23 上海昶法新材料有限公司 Modified lignin/PBAT biodegradable plastic and preparation method thereof
CN115141471A (en) * 2022-07-14 2022-10-04 深圳绿柜产业发展有限公司 Biodegradable material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140051780A1 (en) * 2012-08-16 2014-02-20 Synthezyme Llc COPOLYESTERS HAVING REPEAT UNITS DERIVED FROM w-HYDROXY FATTY ACIDS

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935871A (en) * 2006-09-15 2007-03-28 东华大学 Biodegradable high-molecular-weight aliphatic/aromatic copolymer, and its preparing method and use
WO2012118165A1 (en) * 2011-03-01 2012-09-07 Ricoh Company, Ltd. Flame retardant resin composition and molded product
CN105802168A (en) * 2016-05-23 2016-07-27 江西省萍乡市轩品塑胶制品有限公司 Biodegradable nanometer filling function master batch and preparation method and application thereof
CN106189146A (en) * 2016-08-29 2016-12-07 佛山市高明区尚润盈科技有限公司 A kind of preparation method of polylactic acid antibacterial matrices
CN109181247A (en) * 2018-08-31 2019-01-11 南京工业大学 A kind of Biodegradable film and preparation method thereof that modified lignin resin is compound
CN109608924A (en) * 2018-12-13 2019-04-12 宁艺伟 A kind of flame-proof antibiotic paint preparation method for wooden equipment
CN112048161A (en) * 2020-08-11 2020-12-08 新昌县佳和工艺股份有限公司 High-barrier modified polylactic acid antibacterial material and preparation method thereof
CN113121843A (en) * 2021-03-22 2021-07-16 上海昶法新材料有限公司 Preparation method of silane coupling agent modified lignin
CN114044978A (en) * 2021-12-29 2022-02-15 深圳中塑化工高性能材料有限公司 Quaternary ammonium salt functionalized nano SiO2Antibacterial modified polypropylene material and preparation method thereof
CN114933785A (en) * 2022-04-29 2022-08-23 上海昶法新材料有限公司 Modified lignin/PBAT biodegradable plastic and preparation method thereof
CN115141471A (en) * 2022-07-14 2022-10-04 深圳绿柜产业发展有限公司 Biodegradable material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Fabrication of dimethyl methylphosphonate-loaded mesoporous silica nano fire extinguisher and flame retarding unsaturated polyester;Xiaoqing Qiu,等;《Composites Communications》 *
N-卤胺基纳米抗菌剂的制备及抗菌性能研究;徐家荣;《中国优秀硕士学位论文全文数据库(电子期刊)》;B020-765 *

Also Published As

Publication number Publication date
CN115558252A (en) 2023-01-03

Similar Documents

Publication Publication Date Title
US9163123B2 (en) Chemical modification of lignin and lignin derivatives
KR20140034778A (en) Blends of a polylactic acid and a water soluble polymer
JP2742892B2 (en) Esterified polyester grafted starch
US6958369B2 (en) Component for producing polymer mixtures on the basis of starch and a method for producing the same
CN113736088B (en) Polysilsesquioxane, PLA alloy and straw material
CA2873250A1 (en) Chemical modification of lignin and lignin derivatives
AU707060B2 (en) Esterified and polyester-grafted starch and alloy thereof
CN110655686A (en) High-starch-content film blowing composite material and preparation method thereof
CN115340724A (en) Starch-based antibacterial material and preparation method thereof
CN114516950A (en) Hyperbranched PBAT polyester and preparation method thereof
CN115558252B (en) Biodegradable injection molding cutter, fork and spoon master batch and preparation method thereof
JP2001521947A (en) Reaction of polyhydroxy polymer or its derivative with lactone
CN111378261A (en) Processing method of disposable lunch box
JPH11255801A (en) Biodegradable graft polymer and preparation thereof
CN113603968A (en) Toughening modified PP plastic particle
CN112795149A (en) Biodegradable polyester PBAT composite material and preparation method thereof
CN115304898A (en) Preparation method of high-strength antibacterial high polymer material and application of high-strength antibacterial high polymer material in water emulsion bottle
JPWO2006059606A1 (en) Biodegradable resin composition
WO2010038860A1 (en) Polylactic acid composition and method for producing same
CN113896955A (en) Starch-based sheet composition and preparation method thereof
CN111925592A (en) Glass fiber-added polypropylene plastic and preparation method thereof
JP2003335934A (en) Resin composition and its molded product
CN113265079A (en) Production process of high-extensibility plastic packaging film
CN115725143B (en) Degradable high-strength wear-resistant PVC (polyvinyl chloride) foaming material and preparation method thereof
JPH11240941A (en) Production of hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 337000 No. 1-139, zone B, Xiangdong District Industrial Park, Pingxiang City, Jiangxi Province

Applicant after: JIANG XI SHENG Ping Xiang SHI Xuan PIN Plastic CEMENT Products Co.,Ltd.

Address before: 337016 Area 1-139, Xiangdong Industrial Park B, Pingxiang City, Jiangxi Province

Applicant before: JIANGXI PINGXIANG XUANPIN PLASTIC PRODUCTS Co.,Ltd.

CB02 Change of applicant information
GR01 Patent grant
GR01 Patent grant