CN112552597A - Preparation method of antibacterial plastic for battery case production - Google Patents
Preparation method of antibacterial plastic for battery case production Download PDFInfo
- Publication number
- CN112552597A CN112552597A CN202011459536.1A CN202011459536A CN112552597A CN 112552597 A CN112552597 A CN 112552597A CN 202011459536 A CN202011459536 A CN 202011459536A CN 112552597 A CN112552597 A CN 112552597A
- Authority
- CN
- China
- Prior art keywords
- temperature
- reaction
- parts
- stirring
- washing
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of antibacterial plastic for producing a storage battery shell, which comprises the following steps: firstly, weighing the following raw materials in parts by weight: 30-50 parts of polypropylene, 6-8 parts of allyl chloroacetate, 5-7 parts of 3-methyl-2-butenal, 1-3 parts of magnesium carbonate, 10-12 parts of paraffin, 20-24 parts of filler and 0.6-1 part of antibacterial agent; secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture; and thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case.
Description
Technical Field
The invention belongs to the technical field of plastic preparation, and particularly relates to a preparation method of antibacterial plastic for producing a storage battery shell.
Background
Plastics have become one of the most important materials in modern times and are widely applied to various fields of national economy. Plastic products are one of the most common and most contacted articles in daily life due to the beautiful appearance, bright color and low price, and are highly popular among people. With the continuous improvement of the requirements of people on the service performance of products, the functions of plastics also need to be continuously enhanced. Moreover, some existing plastic antibacterial products have higher cost and are not suitable for large-scale production and use; moreover, the antibacterial agent often has the problems of color change, poor heat resistance, uneven dispersion and the like when being applied, and cannot be normally applied; therefore, the research of novel antibacterial plastic products with high stability and high antibacterial activity is urgent in the prior art, and the preparation process of the plastic with antibacterial performance has the problems that the antibacterial effect is not obvious and the mechanical property of the plastic needs to be improved.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation method of antibacterial plastic for producing a battery case
The technical problems to be solved by the invention are as follows:
the preparation process of the plastic with the antibacterial property has the problems that the antibacterial effect is not obvious and the mechanical property of the plastic needs to be improved; the antibacterial agent often suffers from discoloration, poor heat resistance, and the like in application.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of antibacterial plastic for producing battery cases comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 30-50 parts of polypropylene, 6-8 parts of allyl chloroacetate, 5-7 parts of 3-methyl-2-butenal, 1-3 parts of magnesium carbonate, 10-12 parts of paraffin, 20-24 parts of filler and 0.6-1 part of antibacterial agent;
secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture;
thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case; wherein the rotating speed of the double-screw extruder is 130-150r/min, the length-diameter ratio of the double-screw extruder is 20:1, and the temperature of the extrusion section is as follows: the first section is at 180 ℃ at 170 ℃, the second section is at 200 ℃ at 180 ℃, and the third section is at 220 ℃ at 210 ℃.
Further, the filler is prepared by the following steps:
step S11, adding limestone into distilled water, setting the temperature to be 80-90 ℃ and the rotating speed to be 600-;
step S12, adding the obtained emulsion A into a reaction kettle, setting the temperature to be 40 ℃ and the rotating speed to be 500r/min, simultaneously introducing nitrogen into the reaction liquid, adding absolute ethyl alcohol and phosphoric acid, keeping the temperature and the rotating speed unchanged, continuing stirring for 5min, then introducing carbon dioxide into the reaction liquid, simultaneously tracking and detecting the pH value of the reaction liquid, stopping introducing the carbon dioxide when the pH value of the reaction liquid is less than 7, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing the filter cake with deionized water until the washing liquid is neutral, drying the washed filter cake to constant weight at 100 ℃, and grinding the dried filter cake to obtain a solid B;
and step S13, adding the solid B and an ethanol aqueous solution with the mass fraction of 95% into a three-neck flask, performing ultrasonic dispersion for 2 hours under the condition of 40-50kHz, adding gamma-aminopropyltriethoxysilane, reacting for 8 hours under the condition of 60 ℃, performing reduced pressure suction filtration after the reaction is finished, washing a filter cake for three times by using absolute ethyl alcohol, grinding and mixing the washed filter cake and sodium caseinate, mixing, and performing vacuum drying at 40 ℃ to constant weight to obtain the filler.
Further, the dosage ratio of limestone and distilled water in the step S11 is 2-4 g: 100 mL; in the step S12, the mass fraction of phosphoric acid is 85%, and the volume ratio of the emulsion A, the absolute ethyl alcohol and the phosphoric acid is 1-3: 1: 0.6, in the step S13, the using amount ratio of the solid B, the ethanol water solution with the mass fraction of 95%, the gamma-aminopropyl triethoxysilane and the sodium caseinate is 5 g: 300 mL: 50 mg: 1-3 g.
Further, the antibacterial agent is prepared by the steps of:
step S21, adding 3-bromo-1-propanol and triethylamine into a round-bottom flask, adding dichloromethane, setting the temperature at 0 ℃ and the rotation speed at 300r/min, stirring for 6-10min, then dropwise adding methacryloyl chloride, controlling the dropwise addition of methacryloyl chloride within 2h, after the dropwise addition, slowly increasing the temperature to 20 ℃ at the heating rate of 2-4 ℃/min, keeping the rotation speed unchanged, continuously stirring for 24h, after the reaction is finished, performing rotary evaporation on a rotary evaporator to remove dichloromethane to obtain a concentrated solution, performing dry-method sample mixing on the concentrated solution, purifying by using a column chromatography, eluting a product on a silica gel column, wherein the mobile phase is petroleum ether: ethyl acetate 10: 1, evaporating the eluent by using a rotary evaporator at 45 ℃ to remove the solvent to obtain an intermediate 1;
step S22, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a round-bottom flask, setting the temperature at 80 ℃ and the rotating speed at 400r/min, stirring for reaction for 72 hours, after the reaction is finished, performing rotary evaporation on the obtained reaction liquid on a rotary evaporator to remove the acetonitrile to obtain a concentrated solution, performing dry sample mixing on the concentrated solution, performing column chromatography purification, eluting the product on a silica gel column, wherein the mobile phase is ethyl acetate, and evaporating the solvent of the eluent at 55 ℃ by using the rotary evaporator to obtain an intermediate 2;
and step S23, adding the intermediate 2, the auxiliary agent and benzoin diethyl ether into a tetrafluoroethylene flat plate mold, reacting for 1h under the irradiation of ultraviolet light of 254nm, then ultrasonically washing for 3 times by using tetrahydrofuran, and after washing is finished, drying in vacuum at 40 ℃ to constant weight to obtain the antibacterial agent.
Synthesizing an intermediate 1 from methacryloyl chloride and 3-bromo-1-propanol, preparing an intermediate 2 from the intermediate 1 and triphenylphosphine, wherein the intermediate 2 is an antibacterial monomer containing a quaternary phosphonium salt structure, and the intermediate 2 and an auxiliary agent undergo a copolymerization reaction under the irradiation of 254nm ultraviolet light by taking benzoin diethyl ether as an initiator to prepare the antibacterial agent. The antibacterial agent is a high-molecular non-dissolution type antibacterial agent, and cannot migrate and separate from a matrix along with time, so that the antibacterial property of an antibacterial material is reduced, and meanwhile, potential harm to a human body due to the fact that the antibacterial agent is dissolved out is avoided.
Further, in step S21, the ratio of the amounts of 3-bromo-1-propanol, triethylamine, dichloromethane, and methacryloyl chloride was 5 g: 2.92-3 g: 3.02-3.03 g: 50 mL; in the step S22, the dosage ratio of the intermediate 1, the triphenylphosphine, the benzenediol and the acetonitrile is 5-5.5 g: 8 g: 60 mg: 60 mL; in the step S23, the mass ratio of the intermediate 2, the auxiliary and the benzoin diethyl ether is 10: 0.2-0.8: 0.2.
further, the auxiliary agent is prepared by the following steps:
step S31, adding chlorinated trimellitic anhydride into a three-neck flask under the ice-water bath condition, adding tetrahydrofuran into the three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine to separate out a white precipitate, adding a phenol solution when the amount of the white precipitate is not increased, reacting for 12 hours at 20 ℃, carrying out vacuum filtration on the obtained reaction liquid, carrying out rotary evaporation on the filtrate by using a rotary evaporator to remove an organic solvent to obtain a precipitate, carrying out rotary evaporation to obtain a white solid, recrystallizing by using toluene and acetic anhydride, and drying at 50 ℃ to constant weight after recrystallization to obtain an intermediate 3;
step S32, adding the intermediate 3 into a three-neck flask, adding glacial acetic acid, setting the temperature to be 25 ℃ and the rotating speed to be 400r/min under the protection of nitrogen, stirring to dissolve the intermediate 3, then dropwise adding allylamine by using a constant-pressure dropping funnel, keeping the temperature and the rotating speed unchanged after dropwise adding, continuing stirring for 40-60min, then raising the temperature to be 120 ℃, carrying out reflux reaction for 5-8h, after the reaction is finished, cooling the reaction liquid to room temperature, mixing with isovolumetric deionized water, then carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and after the washing is finished, drying at 50 ℃ to constant weight to obtain the auxiliary agent.
Further, the phenol solution in step S31 was phenol and tetrahydrofuran in an amount of 0.06 mol: 150mL of mixed solution, wherein the dosage ratio of the chlorinated trimellitic anhydride to the tetrahydrofuran to the pyridine to the phenol solution is 0.06 mol: 150-200 mL: 0.06 mol: 150 mL; in the step S32, the dosage ratio of the intermediate 3, the glacial acetic acid and the allylamine is 10 g: 200mL of: 1.6-2 g.
The invention has the beneficial effects that:
the fibrous calcium carbonate can be prepared by taking phosphoric acid as a crystal form control agent, the sodium caseinate is a light yellow powdery solid, is nontoxic and tasteless, contains a large amount of proline residues with a pyrrole ring structure in a molecule, is more intensively distributed on a peptide chain, has unique amphipathy due to the uneven distribution of hydrophobic proline residues and the focusing of 40-50 amino acids at the initial N-terminal, can reduce the tension between interfaces of different substances, forms balance in the interfaces, prevents shrinkage deformation, and improves the compatibility of the filler and a matrix so as to improve the mechanical property.
The antibacterial agent is a high-molecular non-dissolution type antibacterial agent, and cannot migrate and separate from a matrix along with time to cause the antibacterial property of an antibacterial material to be reduced, and meanwhile, potential harm to a human body caused by the fact that the antibacterial agent is dissolved out is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of antibacterial plastic for producing battery cases comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 30 parts of polypropylene, 6 parts of allyl chloroacetate, 5 parts of 3-methyl-2-butenal, 1 part of magnesium carbonate, 10 parts of paraffin, 20 parts of filler and 0.6 part of antibacterial agent;
secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture;
thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case; wherein the rotating speed of the double-screw extruder is 130r/min, the length-diameter ratio of the double-screw extruder is 20:1, and the temperature of the extrusion section is as follows: the first stage is 170 ℃, the second stage is 180 ℃ and the third stage is 210 ℃.
Wherein the filler is prepared by the following steps:
step S11, adding limestone into distilled water, setting the temperature at 80 ℃ and the rotating speed at 600r/min, stirring for 4 hours, after stirring is finished, sieving with a 200-mesh sieve, diluting with distilled water with the same volume, and aging for 20 hours at room temperature to obtain emulsion A;
step S12, adding the obtained emulsion A into a reaction kettle, setting the temperature to be 40 ℃ and the rotating speed to be 500r/min, simultaneously introducing nitrogen into the reaction liquid, adding absolute ethyl alcohol and phosphoric acid, keeping the temperature and the rotating speed unchanged, continuing stirring for 5min, then introducing carbon dioxide into the reaction liquid, simultaneously tracking and detecting the pH value of the reaction liquid, stopping introducing the carbon dioxide when the pH value of the reaction liquid is less than 7, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing the filter cake with deionized water until the washing liquid is neutral, drying the washed filter cake to constant weight at 100 ℃, and grinding the dried filter cake to obtain a solid B;
and step S13, adding the solid B and an ethanol aqueous solution with the mass fraction of 95% into a three-neck flask, performing ultrasonic dispersion for 2 hours under the condition of 40-50kHz, adding gamma-aminopropyltriethoxysilane, reacting for 8 hours under the condition of 60 ℃, performing reduced pressure suction filtration after the reaction is finished, washing a filter cake for three times by using absolute ethyl alcohol, grinding and mixing the washed filter cake and sodium caseinate, mixing, and performing vacuum drying at 40 ℃ to constant weight to obtain the filler.
Wherein the dosage ratio of limestone to distilled water in the step S11 is 2 g: 100 mL; in the step S12, the mass fraction of phosphoric acid is 85%, and the volume ratio of the emulsion A, the absolute ethyl alcohol and the phosphoric acid is 1: 1: 0.6, in the step S13, the using amount ratio of the solid B, the ethanol water solution with the mass fraction of 95%, the gamma-aminopropyl triethoxysilane and the sodium caseinate is 5 g: 300 mL: 50 mg: 1g of the total weight of the composition.
Wherein the antibacterial agent is prepared by the following steps:
step S21, adding 3-bromo-1-propanol and triethylamine into a round-bottom flask, adding dichloromethane, setting the temperature at 0 ℃ and the rotation speed at 300r/min, stirring for 6min, then dropwise adding methacryloyl chloride, controlling the dropwise addition of the methacryloyl chloride within 2h, after the dropwise addition, slowly increasing the temperature to 20 ℃ at the heating rate of 2 ℃/min, keeping the rotation speed unchanged, continuing stirring for reacting for 24h, after the reaction is finished, performing rotary evaporation on a rotary evaporator to remove the dichloromethane to obtain a concentrated solution, performing dry-method sample mixing on the concentrated solution, purifying by using a column chromatography, eluting a product on a silica gel column, wherein the mobile phase is petroleum ether: ethyl acetate 10: 1, evaporating the eluent by using a rotary evaporator at 45 ℃ to remove the solvent to obtain an intermediate 1;
step S22, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a round-bottom flask, setting the temperature at 80 ℃ and the rotating speed at 400r/min, stirring for reaction for 72 hours, after the reaction is finished, performing rotary evaporation on the obtained reaction liquid on a rotary evaporator to remove the acetonitrile to obtain a concentrated solution, performing dry sample mixing on the concentrated solution, performing column chromatography purification, eluting the product on a silica gel column, wherein the mobile phase is ethyl acetate, and evaporating the solvent of the eluent at 55 ℃ by using the rotary evaporator to obtain an intermediate 2;
and step S23, adding the intermediate 2, the auxiliary agent and benzoin diethyl ether into a tetrafluoroethylene flat plate mold, reacting for 1h under the irradiation of ultraviolet light of 254nm, then ultrasonically washing for 3 times by using tetrahydrofuran, and after washing is finished, drying in vacuum at 40 ℃ to constant weight to obtain the antibacterial agent.
Wherein the dosage ratio of the 3-bromo-1-propanol, the triethylamine, the dichloromethane and the methacryloyl chloride in the step S21 is 5 g: 2.92 g: 3.02 g: 50 mL; in the step S22, the dosage ratio of the intermediate 1, triphenylphosphine, benzenediol and acetonitrile is 5 g: 8 g: 60 mg: 60 mL; in the step S23, the mass ratio of the intermediate 2, the auxiliary and the benzoin diethyl ether is 10: 0.2: 0.2.
the auxiliary agent is prepared by the following steps:
step S31, adding chlorinated trimellitic anhydride into a three-neck flask under the ice-water bath condition, adding tetrahydrofuran into the three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine to separate out a white precipitate, adding a phenol solution when the amount of the white precipitate is not increased, reacting for 12 hours at 20 ℃, carrying out vacuum filtration on the obtained reaction liquid, carrying out rotary evaporation on the filtrate by using a rotary evaporator to remove an organic solvent to obtain a precipitate, carrying out rotary evaporation to obtain a white solid, recrystallizing by using toluene and acetic anhydride, and drying at 50 ℃ to constant weight after recrystallization to obtain an intermediate 3;
step S32, adding the intermediate 3 into a three-neck flask, adding glacial acetic acid, setting the temperature to be 25 ℃ and the rotating speed to be 400r/min under the protection of nitrogen, stirring to dissolve the intermediate 3, then dropwise adding allylamine by using a constant-pressure dropping funnel, keeping the temperature and the rotating speed unchanged after dropwise adding, continuing stirring for 40min, then raising the temperature to be 120 ℃, carrying out reflux reaction for 5h, cooling the temperature of the reaction liquid to room temperature after the reaction is completed, mixing with deionized water with the same volume, then carrying out vacuum filtration, washing the obtained filter cake with the deionized water until the washing liquid is neutral, and drying at 50 ℃ until the weight is constant after the washing is completed to obtain the auxiliary agent.
Wherein the phenol solution in the step S31 is phenol and tetrahydrofuran, and the ratio of the phenol solution to the tetrahydrofuran is 0.06 mol: 150mL of mixed solution, wherein the dosage ratio of the chlorinated trimellitic anhydride to the tetrahydrofuran to the pyridine to the phenol solution is 0.06 mol: 150mL of: 0.06 mol: 150 mL; in the step S32, the dosage ratio of the intermediate 3, the glacial acetic acid and the allylamine is 10 g: 200mL of: 1.6 g.
Example 2
A preparation method of antibacterial plastic for producing battery cases comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 40 parts of polypropylene, 7 parts of allyl chloroacetate, 6 parts of 3-methyl-2-butenal, 2 parts of magnesium carbonate, 11 parts of paraffin, 22 parts of filler and 0.8 part of antibacterial agent;
secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture;
thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case; wherein the rotating speed of the double-screw extruder is 140r/min, the length-diameter ratio of the double-screw extruder is 20:1, and the temperature of the extrusion section is as follows: the first stage was 175 deg.C, the second stage 190 deg.C and the third stage 215 deg.C.
Wherein the filler is prepared by the following steps:
step S11, adding limestone into distilled water, setting the temperature to be 85 ℃ and the rotating speed to be 650r/min, stirring for 4 hours, after the stirring is finished, sieving by a 200-mesh sieve, diluting by distilled water with the same volume, and aging for 20 hours at room temperature to obtain emulsion A;
step S12, adding the obtained emulsion A into a reaction kettle, setting the temperature to be 40 ℃ and the rotating speed to be 500r/min, simultaneously introducing nitrogen into the reaction liquid, adding absolute ethyl alcohol and phosphoric acid, keeping the temperature and the rotating speed unchanged, continuing stirring for 5min, then introducing carbon dioxide into the reaction liquid, simultaneously tracking and detecting the pH value of the reaction liquid, stopping introducing the carbon dioxide when the pH value of the reaction liquid is less than 7, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing the filter cake with deionized water until the washing liquid is neutral, drying the washed filter cake to constant weight at 100 ℃, and grinding the dried filter cake to obtain a solid B;
and step S13, adding the solid B and an ethanol aqueous solution with the mass fraction of 95% into a three-neck flask, performing ultrasonic dispersion for 2 hours under the condition of 45kHz, adding gamma-aminopropyltriethoxysilane, reacting for 8 hours under the condition of 60 ℃, performing reduced pressure suction filtration after the reaction is finished, washing a filter cake for three times by using absolute ethyl alcohol, grinding and mixing the washed filter cake and sodium caseinate, and performing vacuum drying at 40 ℃ to constant weight after mixing to obtain the filler.
Wherein the dosage ratio of limestone to distilled water in the step S11 is 3 g: 100 mL; in the step S12, the mass fraction of phosphoric acid is 85%, and the volume ratio of the emulsion A, the absolute ethyl alcohol and the phosphoric acid is 2: 1: 0.6, in the step S13, the using amount ratio of the solid B, the ethanol water solution with the mass fraction of 95%, the gamma-aminopropyl triethoxysilane and the sodium caseinate is 5 g: 300 mL: 50 mg: 2g of the total weight.
Wherein the antibacterial agent is prepared by the following steps:
step S21, adding 3-bromo-1-propanol and triethylamine into a round-bottom flask, adding dichloromethane, setting the temperature to be 0 ℃ and the rotating speed to be 300r/min, stirring for 8min, then dropwise adding methacryloyl chloride, controlling the methacryloyl chloride to be dropwise added within 2h, after dropwise adding, slowly increasing the temperature to 20 ℃ at the heating rate of 3 ℃/min, keeping the rotating speed unchanged, continuing stirring for reacting for 24h, after the reaction is finished, performing rotary evaporation on a rotary evaporator to remove dichloromethane to obtain a concentrated solution, performing dry-method sample mixing on the concentrated solution, purifying by using a column chromatography, eluting a product on a silica gel column, wherein the mobile phase is petroleum ether: ethyl acetate 10: 1, evaporating the eluent by using a rotary evaporator at 45 ℃ to remove the solvent to obtain an intermediate 1;
step S22, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a round-bottom flask, setting the temperature at 80 ℃ and the rotating speed at 400r/min, stirring for reaction for 72 hours, after the reaction is finished, performing rotary evaporation on the obtained reaction liquid on a rotary evaporator to remove the acetonitrile to obtain a concentrated solution, performing dry sample mixing on the concentrated solution, performing column chromatography purification, eluting the product on a silica gel column, wherein the mobile phase is ethyl acetate, and evaporating the solvent of the eluent at 55 ℃ by using the rotary evaporator to obtain an intermediate 2;
and step S23, adding the intermediate 2, the auxiliary agent and benzoin diethyl ether into a tetrafluoroethylene flat plate mold, reacting for 1h under the irradiation of ultraviolet light of 254nm, then ultrasonically washing for 3 times by using tetrahydrofuran, and after washing is finished, drying in vacuum at 40 ℃ to constant weight to obtain the antibacterial agent.
Wherein the dosage ratio of the 3-bromo-1-propanol, the triethylamine, the dichloromethane and the methacryloyl chloride in the step S21 is 5 g: 2.96 g: 3.02 g: 50 mL; in step S22, the amount ratio of intermediate 1, triphenylphosphine, hydroquinone and acetonitrile was 5.2 g: 8 g: 60 mg: 60 mL; in the step S23, the mass ratio of the intermediate 2, the auxiliary and the benzoin diethyl ether is 10: 0.5: 0.2.
the auxiliary agent is prepared by the following steps:
step S31, adding chlorinated trimellitic anhydride into a three-neck flask under the ice-water bath condition, adding tetrahydrofuran into the three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine to separate out a white precipitate, adding a phenol solution when the amount of the white precipitate is not increased, reacting for 12 hours at 20 ℃, carrying out vacuum filtration on the obtained reaction liquid, carrying out rotary evaporation on the filtrate by using a rotary evaporator to remove an organic solvent to obtain a precipitate, carrying out rotary evaporation to obtain a white solid, recrystallizing by using toluene and acetic anhydride, and drying at 50 ℃ to constant weight after recrystallization to obtain an intermediate 3;
step S32, adding the intermediate 3 into a three-neck flask, adding glacial acetic acid, setting the temperature to be 25 ℃ and the rotating speed to be 400r/min under the protection of nitrogen, stirring to dissolve the intermediate 3, then dropwise adding allylamine by using a constant-pressure dropping funnel, keeping the temperature and the rotating speed unchanged after dropwise adding, continuing stirring for 50min, then heating the temperature to be 120 ℃, carrying out reflux reaction for 7h, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, mixing the reaction liquid with deionized water with the same volume, then carrying out vacuum filtration, washing the obtained filter cake with the deionized water until the washing liquid is neutral, and drying at 50 ℃ until the weight is constant after the washing is finished to obtain the auxiliary agent.
Wherein the phenol solution in the step S31 is phenol and tetrahydrofuran, and the ratio of the phenol solution to the tetrahydrofuran is 0.06 mol: 150mL of mixed solution, wherein the dosage ratio of the chlorinated trimellitic anhydride to the tetrahydrofuran to the pyridine to the phenol solution is 0.06 mol: 175mL of: 0.06 mol: 150 mL; in the step S32, the dosage ratio of the intermediate 3, the glacial acetic acid and the allylamine is 10 g: 200mL of: 1.8 g.
Example 3
A preparation method of antibacterial plastic for producing battery cases comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 50 parts of polypropylene, 8 parts of allyl chloroacetate, 7 parts of 3-methyl-2-butenal, 3 parts of magnesium carbonate, 12 parts of paraffin, 24 parts of filler and 1 part of antibacterial agent;
secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture;
thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case; wherein the rotating speed of the double-screw extruder is 150r/min, the length-diameter ratio of the double-screw extruder is 20:1, and the temperature of the extrusion section is as follows: the first section was 180 ℃, the second section was 200 ℃ and the third section was 220 ℃.
Wherein the filler is prepared by the following steps:
step S11, adding limestone into distilled water, setting the temperature at 90 ℃ and the rotation speed at 700r/min, stirring for 4 hours, after stirring is finished, sieving with a 200-mesh sieve, diluting with distilled water with the same volume, and aging for 20 hours at room temperature to obtain emulsion A;
step S12, adding the obtained emulsion A into a reaction kettle, setting the temperature to be 40 ℃ and the rotating speed to be 500r/min, simultaneously introducing nitrogen into the reaction liquid, adding absolute ethyl alcohol and phosphoric acid, keeping the temperature and the rotating speed unchanged, continuing stirring for 5min, then introducing carbon dioxide into the reaction liquid, simultaneously tracking and detecting the pH value of the reaction liquid, stopping introducing the carbon dioxide when the pH value of the reaction liquid is less than 7, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing the filter cake with deionized water until the washing liquid is neutral, drying the washed filter cake to constant weight at 100 ℃, and grinding the dried filter cake to obtain a solid B;
and step S13, adding the solid B and an ethanol aqueous solution with the mass fraction of 95% into a three-neck flask, performing ultrasonic dispersion for 2 hours under the condition of 50kHz, adding gamma-aminopropyltriethoxysilane, reacting for 8 hours under the condition of 60 ℃, performing reduced pressure suction filtration after the reaction is finished, washing a filter cake for three times by using absolute ethyl alcohol, grinding and mixing the washed filter cake and sodium caseinate, and performing vacuum drying at 40 ℃ to constant weight after mixing to obtain the filler.
Wherein the dosage ratio of limestone to distilled water in the step S11 is 4 g: 100 mL; in the step S12, the mass fraction of phosphoric acid is 85%, and the volume ratio of the emulsion A, the absolute ethyl alcohol and the phosphoric acid is 3: 1: 0.6, in the step S13, the using amount ratio of the solid B, the ethanol water solution with the mass fraction of 95%, the gamma-aminopropyl triethoxysilane and the sodium caseinate is 5 g: 300 mL: 50 mg: 3g of the total weight.
Wherein the antibacterial agent is prepared by the following steps:
step S21, adding 3-bromo-1-propanol and triethylamine into a round-bottom flask, adding dichloromethane, setting the temperature to be 0 ℃ and the rotating speed to be 300r/min, stirring for 10min, then dropwise adding methacryloyl chloride, controlling the dropwise addition of the methacryloyl chloride within 2h, after the dropwise addition is finished, slowly increasing the temperature to 20 ℃ at the heating rate of 4 ℃/min, keeping the rotating speed unchanged, continuing stirring for 24h, after the reaction is finished, performing rotary evaporation on a rotary evaporator to remove the dichloromethane to obtain a concentrated solution, performing dry-method sample mixing on the concentrated solution, purifying by using a column chromatography, eluting a product on a silica gel column, wherein the mobile phase is petroleum ether: ethyl acetate 10: 1, evaporating the eluent by using a rotary evaporator at 45 ℃ to remove the solvent to obtain an intermediate 1;
step S22, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a round-bottom flask, setting the temperature at 80 ℃ and the rotating speed at 400r/min, stirring for reaction for 72 hours, after the reaction is finished, performing rotary evaporation on the obtained reaction liquid on a rotary evaporator to remove the acetonitrile to obtain a concentrated solution, performing dry sample mixing on the concentrated solution, performing column chromatography purification, eluting the product on a silica gel column, wherein the mobile phase is ethyl acetate, and evaporating the solvent of the eluent at 55 ℃ by using the rotary evaporator to obtain an intermediate 2;
and step S23, adding the intermediate 2, the auxiliary agent and benzoin diethyl ether into a tetrafluoroethylene flat plate mold, reacting for 1h under the irradiation of ultraviolet light of 254nm, then ultrasonically washing for 3 times by using tetrahydrofuran, and after washing is finished, drying in vacuum at 40 ℃ to constant weight to obtain the antibacterial agent.
Wherein the dosage ratio of the 3-bromo-1-propanol, the triethylamine, the dichloromethane and the methacryloyl chloride in the step S21 is 5 g: 3 g: 3.03 g: 50 mL; in step S22, the amount ratio of intermediate 1, triphenylphosphine, hydroquinone and acetonitrile was 5.5 g: 8 g: 60 mg: 60 mL; in the step S23, the mass ratio of the intermediate 2, the auxiliary and the benzoin diethyl ether is 10: 0.8: 0.2.
the auxiliary agent is prepared by the following steps:
step S31, adding chlorinated trimellitic anhydride into a three-neck flask under the ice-water bath condition, adding tetrahydrofuran into the three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine to separate out a white precipitate, adding a phenol solution when the amount of the white precipitate is not increased, reacting for 12 hours at 20 ℃, carrying out vacuum filtration on the obtained reaction liquid, carrying out rotary evaporation on the filtrate by using a rotary evaporator to remove an organic solvent to obtain a precipitate, carrying out rotary evaporation to obtain a white solid, recrystallizing by using toluene and acetic anhydride, and drying at 50 ℃ to constant weight after recrystallization to obtain an intermediate 3;
step S32, adding the intermediate 3 into a three-neck flask, adding glacial acetic acid, setting the temperature to be 25 ℃ and the rotating speed to be 400r/min under the protection of nitrogen, stirring to dissolve the intermediate 3, then dropwise adding allylamine by using a constant-pressure dropping funnel, keeping the temperature and the rotating speed unchanged after dropwise adding, continuing stirring for 60min, then raising the temperature to be 120 ℃, carrying out reflux reaction for 8h, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, mixing with deionized water with the same volume, then carrying out vacuum filtration, washing the obtained filter cake with the deionized water until the washing liquid is neutral, and drying at 50 ℃ until the weight is constant after the washing is finished to obtain the auxiliary agent.
Wherein the phenol solution in the step S31 is phenol and tetrahydrofuran, and the ratio of the phenol solution to the tetrahydrofuran is 0.06 mol: 150mL of mixed solution, wherein the dosage ratio of the chlorinated trimellitic anhydride to the tetrahydrofuran to the pyridine to the phenol solution is 0.06 mol: 200 mL: 0.06 mol: 150 mL; in the step S32, the dosage ratio of the intermediate 3, the glacial acetic acid and the allylamine is 10 g: 200 mL: 2 g.
Comparative example 1
The comparative example is a common antibacterial plastic on the market.
The samples obtained in each group of examples and comparative examples are tested for antibacterial performance and mechanical performance by taking escherichia coli and staphylococcus aureus as experimental strains,
TABLE 1
As shown in the above table 1, the antibacterial plastic for producing the battery case has a good antibacterial effect, and is strong in resistance strength and tensile strength and excellent in mechanical properties.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The preparation method of the antibacterial plastic for producing the battery case is characterized by comprising the following steps of:
firstly, weighing the following raw materials in parts by weight: 30-50 parts of polypropylene, 6-8 parts of allyl chloroacetate, 5-7 parts of 3-methyl-2-butenal, 1-3 parts of magnesium carbonate, 10-12 parts of paraffin, 20-24 parts of filler and 0.6-1 part of antibacterial agent;
secondly, mixing and stirring polypropylene, allyl chloroacetate, 3-methyl-2-butenal, magnesium carbonate, paraffin, a filler and an antibacterial agent at the temperature of 130 ℃ to obtain a mixture;
thirdly, raising the temperature to 150 ℃, and extruding and granulating the obtained mixture by using a double-screw extruder to obtain the antibacterial plastic for producing the battery case; wherein the rotating speed of the double-screw extruder is 130-150r/min, the length-diameter ratio of the double-screw extruder is 20:1, and the temperature of the extrusion section is as follows: the first section is at 180 ℃ at 170 ℃, the second section is at 200 ℃ at 180 ℃, and the third section is at 220 ℃ at 210 ℃.
2. The preparation method of the antibacterial plastic for battery case production according to claim 1, wherein the filler is prepared by the following steps:
step S11, adding limestone into distilled water, setting the temperature to be 80-90 ℃ and the rotating speed to be 600-;
step S12, adding the obtained emulsion A into a reaction kettle, setting the temperature to be 40 ℃ and the rotating speed to be 500r/min, simultaneously introducing nitrogen into the reaction liquid, adding absolute ethyl alcohol and phosphoric acid, keeping the temperature and the rotating speed unchanged, continuing stirring for 5min, then introducing carbon dioxide into the reaction liquid, simultaneously tracking and detecting the pH value of the reaction liquid, stopping introducing the carbon dioxide when the pH value of the reaction liquid is less than 7, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing the filter cake with deionized water until the washing liquid is neutral, drying the washed filter cake to constant weight at 100 ℃, and grinding the dried filter cake to obtain a solid B;
and step S13, adding the solid B and an ethanol aqueous solution with the mass fraction of 95% into a three-neck flask, performing ultrasonic dispersion for 2 hours under the condition of 40-50kHz, adding gamma-aminopropyltriethoxysilane, reacting for 8 hours under the condition of 60 ℃, performing reduced pressure suction filtration after the reaction is finished, washing a filter cake for three times by using absolute ethyl alcohol, grinding and mixing the washed filter cake and sodium caseinate, mixing, and performing vacuum drying at 40 ℃ to constant weight to obtain the filler.
3. The method for preparing antibacterial plastic for battery case production according to claim 2, wherein the dosage ratio of limestone and distilled water in step S11 is 2-4 g: 100 mL; in the step S12, the mass fraction of phosphoric acid is 85%, and the volume ratio of the emulsion A, the absolute ethyl alcohol and the phosphoric acid is 1-3: 1: 0.6, in the step S13, the using amount ratio of the solid B, the ethanol water solution with the mass fraction of 95%, the gamma-aminopropyl triethoxysilane and the sodium caseinate is 5 g: 300 mL: 50 mg: 1-3 g.
4. The method for preparing the antibacterial plastic for battery case production according to claim 1, wherein the antibacterial agent is prepared by the following steps:
step S21, adding 3-bromo-1-propanol and triethylamine into a round-bottom flask, adding dichloromethane, setting the temperature at 0 ℃ and the rotation speed at 300r/min, stirring for 6-10min, then dropwise adding methacryloyl chloride, controlling the dropwise addition of methacryloyl chloride within 2h, after the dropwise addition, slowly increasing the temperature to 20 ℃ at the heating rate of 2-4 ℃/min, keeping the rotation speed unchanged, continuously stirring for 24h, after the reaction is finished, performing rotary evaporation on a rotary evaporator to remove dichloromethane to obtain a concentrated solution, performing dry-method sample mixing on the concentrated solution, purifying by using a column chromatography, eluting a product on a silica gel column, wherein the mobile phase is petroleum ether: ethyl acetate 10: 1, evaporating the eluent by using a rotary evaporator at 45 ℃ to remove the solvent to obtain an intermediate 1;
step S22, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a round-bottom flask, setting the temperature at 80 ℃ and the rotating speed at 400r/min, stirring for reaction for 72 hours, after the reaction is finished, performing rotary evaporation on the obtained reaction liquid on a rotary evaporator to remove the acetonitrile to obtain a concentrated solution, performing dry sample mixing on the concentrated solution, performing column chromatography purification, eluting the product on a silica gel column, wherein the mobile phase is ethyl acetate, and evaporating the solvent of the eluent at 55 ℃ by using the rotary evaporator to obtain an intermediate 2;
and step S23, adding the intermediate 2, the auxiliary agent and benzoin diethyl ether into a tetrafluoroethylene flat plate mold, reacting for 1h under the irradiation of ultraviolet light of 254nm, then ultrasonically washing for 3 times by using tetrahydrofuran, and after washing is finished, drying in vacuum at 40 ℃ to constant weight to obtain the antibacterial agent.
5. The method for preparing the antibacterial plastic for battery case production according to claim 4, wherein the amount ratio of 3-bromo-1-propanol, triethylamine, dichloromethane and methacryloyl chloride in step S21 is 5 g: 2.92-3 g: 3.02-3.03 g: 50 mL; in the step S22, the dosage ratio of the intermediate 1, the triphenylphosphine, the benzenediol and the acetonitrile is 5-5.5 g: 8 g: 60 mg: 60 mL; in the step S23, the mass ratio of the intermediate 2, the auxiliary and the benzoin diethyl ether is 10: 0.2-0.8: 0.2.
6. the preparation method of the antibacterial plastic for battery case production according to claim 4, wherein the auxiliary is prepared by the following steps:
step S31, adding chlorinated trimellitic anhydride into a three-neck flask under the ice-water bath condition, adding tetrahydrofuran into the three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine to separate out a white precipitate, adding a phenol solution when the amount of the white precipitate is not increased, reacting for 12 hours at 20 ℃, carrying out vacuum filtration on the obtained reaction liquid, carrying out rotary evaporation on the filtrate by using a rotary evaporator to remove an organic solvent to obtain a precipitate, carrying out rotary evaporation to obtain a white solid, recrystallizing by using toluene and acetic anhydride, and drying at 50 ℃ to constant weight after recrystallization to obtain an intermediate 3;
step S32, adding the intermediate 3 into a three-neck flask, adding glacial acetic acid, setting the temperature to be 25 ℃ and the rotating speed to be 400r/min under the protection of nitrogen, stirring to dissolve the intermediate 3, then dropwise adding allylamine by using a constant-pressure dropping funnel, keeping the temperature and the rotating speed unchanged after dropwise adding, continuing stirring for 40-60min, then raising the temperature to be 120 ℃, carrying out reflux reaction for 5-8h, after the reaction is finished, cooling the reaction liquid to room temperature, mixing with isovolumetric deionized water, then carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and after the washing is finished, drying at 50 ℃ to constant weight to obtain the auxiliary agent.
7. The method for preparing antibacterial plastic for battery case production according to claim 1, wherein in step S31, the phenol solution is phenol and tetrahydrofuran in a ratio of 0.06 mol: 150mL of mixed solution, wherein the dosage ratio of the chlorinated trimellitic anhydride to the tetrahydrofuran to the pyridine to the phenol solution is 0.06 mol: 150-200 mL: 0.06 mol: 150 mL; in the step S32, the dosage ratio of the intermediate 3, the glacial acetic acid and the allylamine is 10 g: 200mL of: 1.6-2 g.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011459536.1A CN112552597A (en) | 2020-12-11 | 2020-12-11 | Preparation method of antibacterial plastic for battery case production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011459536.1A CN112552597A (en) | 2020-12-11 | 2020-12-11 | Preparation method of antibacterial plastic for battery case production |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112552597A true CN112552597A (en) | 2021-03-26 |
Family
ID=75062126
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011459536.1A Withdrawn CN112552597A (en) | 2020-12-11 | 2020-12-11 | Preparation method of antibacterial plastic for battery case production |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112552597A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113362985A (en) * | 2021-06-30 | 2021-09-07 | 深圳市正蓝实业有限公司 | Nano rare earth thick film electronic paste and preparation method thereof |
-
2020
- 2020-12-11 CN CN202011459536.1A patent/CN112552597A/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113362985A (en) * | 2021-06-30 | 2021-09-07 | 深圳市正蓝实业有限公司 | Nano rare earth thick film electronic paste and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH01310744A (en) | Separation material | |
CN103265492B (en) | Chlorinated 1-vinyl-3-carboxymethyl imidazole polymerizable acidic ionic liquid and synthetic method thereof | |
CN112552597A (en) | Preparation method of antibacterial plastic for battery case production | |
CN109096507B (en) | Triphenylamine derivative material based on imidazole type ionic liquid modification and preparation method and application thereof | |
CN113480905B (en) | Leather coating with fluorescent response to benzene-series VOCs and preparation method thereof | |
CN113527794A (en) | Processing technology of antibacterial toughened polyethylene plastic | |
CN109988335A (en) | A kind of ferrocenyl Schiff base and the preparation method and application thereof | |
CN1680428A (en) | Preparation of alanyl glutamine dipeptide compound | |
CN108384017A (en) | A kind of chirality Ni(II)Amino Schiff base coordination polymer and preparation method thereof | |
CN110590671B (en) | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone | |
CN109535041B (en) | Method for producing polyester modifier SIPE (styrene-isoprene-styrene) by using composite catalyst | |
CN1634999A (en) | Method for synthesizing delustring polyvinyl chloride special-purpose resin | |
CN102008978A (en) | Chiral catalyst and preparation method and application thereof | |
US4107097A (en) | Process for preparing polycation-polyanion electrolyte complexes having carboxylic acid and alkenyl radical substituents and films thereof | |
CN112778725A (en) | Manufacturing process of high-temperature-resistant film material | |
CN112920439A (en) | Degradable plastic film made of whole corn flour and preparation method of degradable plastic film | |
CN1152108C (en) | Arylheterocycle substituted naphthopyran-type photochromic compound and its preparing process and usage | |
CN118530409B (en) | Hydrophobic film and preparation method thereof | |
CN111574387A (en) | P-aminomethyl benzoic acid and preparation method thereof | |
CN100340558C (en) | N,N-dipyridyl 3,4,9,10-tetraformyl diimine derirative and its synthesis method | |
Wolfrom et al. | Two 3-Epimeric Ketononoses1 | |
CN118125971B (en) | Electrochromic compound, electrochromic gel material and application thereof | |
CN103059203A (en) | Preparation method of acetoacetyl modified ethylene-vinyl alcohol copolymer | |
CN117801378A (en) | Synthesis method of tartaric acid crosslinked starch-based bioplastic | |
CN114805928B (en) | Biological base plasticizer for metaphenylene |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210326 |
|
WW01 | Invention patent application withdrawn after publication |