CN111718568A - Preparation method of environment-friendly plastic toy product - Google Patents
Preparation method of environment-friendly plastic toy product Download PDFInfo
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- CN111718568A CN111718568A CN202010399575.0A CN202010399575A CN111718568A CN 111718568 A CN111718568 A CN 111718568A CN 202010399575 A CN202010399575 A CN 202010399575A CN 111718568 A CN111718568 A CN 111718568A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/52—Sports equipment ; Games; Articles for amusement; Toys
- B29L2031/5209—Toys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/52—Sports equipment ; Games; Articles for amusement; Toys
- B29L2031/5281—Articles for amusement
- B29L2031/529—Toys
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to the field of environment-friendly materials, in particular to a preparation method of an environment-friendly plastic toy product, which comprises the following components in parts by weight: 50-80 parts of modified polylactic acid, 20-50 parts of synthetic resin, 1-10 parts of modified coffee grounds, 1-5 parts of modified bagasse fibers, 0.1-2 parts of plasticizer, 0.2-0.5 part of flame retardant and 0.01-0.1 part of environment-friendly pigment. The raw materials such as polylactic acid, coffee grounds, bagasse, synthetic resin and pigment adopted in the invention are all environment-friendly degradable materials, wherein the coffee grounds and the bagasse belong to waste recycling, and the plastic prepared by the raw materials not only has good biodegradability, but also is beneficial to sustainable development of natural resources.
Description
Technical Field
The invention relates to the field of environment-friendly materials, in particular to a preparation method of an environment-friendly plastic toy product.
Background
The export of the Chinese toy occupies an important proportion, data statistics shows that the export is calculated according to market sales, China is the third largest toy consumer country in the world which is second to America and Japan at present, but the population base of China is huge and is calculated according to per-capita consumption, China is only about one tenth of that of America, and the development space potential of the Chinese toy market is huge. Although 75% of the plastic toys in the world are made by China, China is still not a strong toy country, and from the history of the plastic toys, the plastic toys undergo transition from western countries to Japan, Taiwan China and hong Kong, and are transferred to areas such as Palo Delta in China, and after global economic enthusiasm, plastic toy products in China face huge pressure and become a sacrifice of global financial crisis. Along with the improvement of the living standard year by year, the environmental protection requirement on plastic products is gradually improved, the environment protection and low carbon become industry consensus, export manufacturers need to move ahead actively, toy enterprises owned by China are reduced from more than 8 thousand to more than 6 thousand in recent years, and plastic products which do not meet the requirement are subject to great export restriction.
The plastic toy not only needs to meet the requirement of unique shape, but also needs to be able to withstand the environment. The plastic toys made of traditional materials are not the main requirements of the current market, and the development and application of novel environment-friendly materials can improve the added value and the competitiveness of the plastic toys. In view of the above, there is a need to develop an environmentally friendly plastic which has excellent aging resistance and can exhibit good mechanical properties.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of an environment-friendly plastic toy product, which comprises the following steps:
step 1, weighing modified polylactic acid, modified bagasse fiber, modified coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
and 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain the environment-friendly plastic toy product.
The environment-friendly plastic product comprises the following components in parts by weight:
50-80 parts of modified polylactic acid, 20-50 parts of synthetic resin, 1-10 parts of modified coffee grounds, 1-5 parts of modified bagasse fibers, 0.1-2 parts of plasticizer, 0.2-0.5 part of flame retardant and 0.01-0.1 part of environment-friendly pigment.
Preferably, the charging barrel passes through four temperature intervals, wherein the first temperature interval is 170-190 ℃, the second temperature interval is 190-210 ℃, the third temperature interval is 210-230 ℃, and the fourth temperature interval is 230-260 ℃.
Preferably, the environment-friendly plastic product comprises the following components in parts by weight:
60-80 parts of modified polylactic acid, 20-30 parts of synthetic resin, 3-5 parts of modified coffee grounds, 2-3 parts of modified bagasse fibers, 0.5-1 part of plasticizer, 0.2-0.5 part of flame retardant and 0.01-0.1 part of environment-friendly pigment.
Preferably, the modified polylactic acid is obtained by modifying polylactic acid by a crosslinking modifier; wherein, the crosslinking modifier is prepared by the reaction of dibenzofuran and succinic acid.
More preferably, the preparation method of the modified polylactic acid comprises the following steps:
s1, weighing dibenzofuran and succinic acid, respectively adding the dibenzofuran and succinic acid into toluene, stirring until the dibenzofuran and succinic acid are dissolved, adding ferric chloride particles, stirring until the mixture is uniform, placing the mixture in a water bath at the temperature of 40-60 ℃ for reaction for 2-5 hours, cooling to room temperature, adding deionized water with the same volume as the toluene, stirring for 0.5-1 hour, extracting and separating an organic phase, and removing a solvent by rotary evaporation to obtain a crosslinking modifier;
wherein the mass ratio of dibenzofuran to succinic acid to toluene is 1: 2-3: 15-30; the solid-liquid ratio of the ferric chloride particles to the toluene is 1: 50-80 parts;
s2, respectively weighing the crosslinking modifier and the dried polylactic acid, adding the crosslinking modifier and the dried polylactic acid into a high-speed mixer, and stirring the mixture uniformly to obtain modified polylactic acid;
wherein the mass ratio of the crosslinking modifier to the polylactic acid is 1: 20-50.
Preferably, the modified coffee grounds are obtained by activating the coffee grounds and then modifying the coffee grounds by using ruthenium trichloride trihydrate.
More preferably, the preparation method of the modified coffee grounds comprises the following steps:
s1, weighing coffee grounds, adding the coffee grounds into deionized water, stirring for 1-2 hours, filtering, drying, and then placing in a nano grinder to grind into nano coffee grounds; the method comprises the steps of firstly, placing the nano coffee grounds in an ultraviolet light condition to radiate for 0.5-2 hours, then adding the nano coffee grounds into a 0.1mol/L sodium hydroxide solution, placing the solution in a water bath at the temperature of 60-80 ℃, and stirring for 1-2 hours to obtain a nano coffee grounds suspension;
wherein the solid-to-liquid ratio of the coffee grounds to the deionized water is 1: 10-20; the solid-liquid ratio of the nano coffee grounds to the sodium hydroxide solution is 1: 15-20;
s2, weighing cinnamaldehyde and hydroxyethyl ethylenediamine, sequentially adding the cinnamaldehyde and the hydroxyethyl ethylenediamine into the nano coffee grounds suspension, and placing the nano coffee grounds suspension in a water bath at the temperature of 60-80 ℃ to react for 2-5 hours; then dropwise adding 0.5mol/L hydrochloric acid until the pH value is 5.0-6.0, continuously stirring for 0.5-1 h, filtering while hot to obtain a solid, washing with acetone once, then washing with deionized water to be neutral, and drying in vacuum to obtain a coffee residue activator;
wherein the volume ratio of the cinnamaldehyde to the hydroxyethyl ethylenediamine to the nano coffee grounds suspension is 1: 3-6: 40-60;
s3, weighing ruthenium trichloride trihydrate, adding the ruthenium trichloride trihydrate into deionized water, and stirring until the ruthenium trichloride is dissolved to obtain a ruthenium trichloride solution; adding the coffee grounds activator into the ruthenium trichloride solution, stirring the mixture evenly, placing the mixture in a water bath at the temperature of 40-50 ℃ for reacting for 5-8 hours, cooling the mixture to room temperature, filtering the mixture to obtain a solid, washing the solid for three times by using deionized water, and drying the solid in vacuum to obtain modified coffee grounds;
wherein the mass ratio of the ruthenium trichloride trihydrate to the deionized water is 10-20: 100; the solid-to-liquid ratio of the coffee grounds activator to the ruthenium trichloride solution is 1: 10-20.
Preferably, in step S1, the wavelength of the ultraviolet light is 0.1 to 0.4 μm.
Preferably, the synthetic resin is one or more of polyethylene, polystyrene and ABS.
Preferably, the synthetic resin is polyethylene, polystyrene and ABS in a mass ratio of 1:1: 2.
Preferably, the modified bagasse fibers are obtained by modifying bagasse fibers with Chinese juniper oil.
More preferably, the preparation method of the modified bagasse fiber comprises the following steps:
s1, removing impurities from bagasse, cleaning, drying and crushing to obtain bagasse fibers;
s2, adding bagasse fibers into 0.1mol/L sodium hydroxide solution, soaking for 1-5 hours, adding carboxymethyl cellulose, stirring uniformly, dropwise adding Chinese juniper oil, stirring for 1-3 hours at 40-60 ℃ after uniform ultrasonic dispersion, pouring into a reaction kettle, sealing, reacting for 2-10 hours at 80-100 ℃, filtering to obtain solids, washing with acetone for three times, then washing with deionized water to be neutral, and freeze-drying to obtain modified bagasse fibers;
wherein the solid-to-liquid ratio of the bagasse fibers to the sodium hydroxide solution is 1: 10-20; the mass ratio of the carboxymethyl cellulose to the Chinese juniper oil to the bagasse fibers is 0.02-0.05: 0.1-0.3: 1.
Preferably, the plasticizer is one or more of a synthetic vegetable ester, a citrate ester, and epoxidized soybean oil.
Preferably, the flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
Preferably, the environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
The invention has the beneficial effects that:
1. the raw materials such as polylactic acid, coffee grounds, bagasse, synthetic resin and pigment adopted in the invention are all environment-friendly degradable materials, wherein the coffee grounds and the bagasse belong to waste recycling, and the plastic prepared by the raw materials not only has good biodegradability, but also is beneficial to sustainable development of natural resources.
2. Polylactic acid as a novel biodegradable material has the advantages of no toxicity, no irritation, excellent biocompatibility, biodegradability, strong plasticity and easy processing and forming. However, when the polylactic acid is used in life, the degradation of the polylactic acid accelerates the aging rate, so that the degradation rate is properly reduced to enable the plastic to be better utilized. According to the invention, the cross-linking modifier obtained by reacting and combining dibenzofuran and succinic acid under the catalysis of ferric chloride modifies polylactic acid, and finally the modified polylactic acid is obtained. The modification enables the structure of polylactic acid to be more stable through similar covalent bond connection formed between carboxyl and dibenzofuran group and thermal crosslinking connection between hydroxyl and carboxyl, the degradation rate is weakened, and the aging resistance is correspondingly improved greatly.
3. According to the invention, the waste of the coffee grounds is recycled and modified to obtain the modified coffee grounds, and after the modified coffee grounds are added into the polylactic acid material, the heat resistance and toughness of the polylactic acid can be improved. After the coffee grounds are treated and activated, the prepared coffee grounds activator forms irregular aggregates due to the aggregation effect, the particle size is 200-500 nm, the modified coffee carbon obtained after the chelation with ruthenium ions becomes more regular spherical aggregates, and the particle size range is 300-600 nm. The modified coffee carbon has stronger bonding and adsorption performance to polylactic acid molecular chains, and can greatly increase the toughness of polylactic acid; in addition, the heat resistance of the polylactic acid is improved by adding the modified coffee carbon.
4. Although polylactic acid has good biodegradability, the antibacterial property of polylactic acid is poor, and polylactic acid is not the preferred material for toys. Therefore, the antibacterial property of the polylactic acid is enhanced by adding the modified bagasse fiber into the polylactic acid. The method comprises the steps of removing impurities from the recovered bagasse, cleaning, drying, crushing to obtain bagasse fibers, adding the bagasse fibers into a sodium hydroxide solution for activation treatment, and adding Chinese juniper oil to modify the adsorption of the bagasse fibers, wherein the Chinese juniper oil belongs to a natural antibacterial substance, is grafted and adsorbed by the bagasse and is combined with polylactic acid to be more uniform and stable; in addition, the bagasse fiber also has the capability of enhancing the physical properties of polylactic acid. Therefore, the addition of the modified bagasse fiber not only enhances the antibacterial property of the polylactic acid, but also correspondingly improves the mechanical property of the polylactic acid.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of an environment-friendly plastic toy product comprises the following steps:
step 1, weighing modified polylactic acid, modified bagasse fiber, modified coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
and 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain the environment-friendly plastic toy product.
The environment-friendly plastic product comprises the following components in parts by weight:
65 parts of modified polylactic acid, 35 parts of synthetic resin, 5 parts of modified coffee grounds, 2 parts of modified bagasse fibers, 1 part of plasticizer, 0.3 part of flame retardant and 0.05 part of environment-friendly pigment.
The charging barrel passes through four temperature intervals, wherein the first temperature interval is 170-190 ℃, the second temperature interval is 190-210 ℃, the third temperature interval is 210-230 ℃, and the fourth temperature interval is 230-260 ℃.
The modified polylactic acid is obtained by modifying polylactic acid by a crosslinking modifier; wherein, the crosslinking modifier is prepared by the reaction of dibenzofuran and succinic acid.
The preparation method of the modified polylactic acid comprises the following steps:
s1, weighing dibenzofuran and succinic acid, respectively adding the dibenzofuran and succinic acid into toluene, stirring until the dibenzofuran and succinic acid are dissolved, adding ferric chloride particles, stirring until the mixture is uniform, placing the mixture in a water bath at the temperature of 40-60 ℃ for reaction for 2-5 hours, cooling to room temperature, adding deionized water with the same volume as the toluene, stirring for 0.5-1 hour, extracting and separating an organic phase, and removing a solvent by rotary evaporation to obtain a crosslinking modifier;
wherein the mass ratio of dibenzofuran to succinic acid to toluene is 1: 2-3: 15-30; the solid-liquid ratio of the ferric chloride particles to the toluene is 1: 50-80 parts;
s2, respectively weighing the crosslinking modifier and the dried polylactic acid, adding the crosslinking modifier and the dried polylactic acid into a high-speed mixer, and stirring the mixture uniformly to obtain modified polylactic acid;
wherein the mass ratio of the crosslinking modifier to the polylactic acid is 1: 20-50.
The modified coffee grounds are obtained by activating the coffee grounds and then modifying the coffee grounds by using ruthenium trichloride trihydrate.
The preparation method of the modified coffee grounds comprises the following steps:
s1, weighing coffee grounds, adding the coffee grounds into deionized water, stirring for 1-2 hours, filtering, drying, and then placing in a nano grinder to grind into nano coffee grounds; the method comprises the steps of firstly, placing the nano coffee grounds in an ultraviolet light condition to radiate for 0.5-2 hours, then adding the nano coffee grounds into a 0.1mol/L sodium hydroxide solution, placing the solution in a water bath at the temperature of 60-80 ℃, and stirring for 1-2 hours to obtain a nano coffee grounds suspension;
wherein the solid-to-liquid ratio of the coffee grounds to the deionized water is 1: 10-20; the solid-liquid ratio of the nano coffee grounds to the sodium hydroxide solution is 1: 15-20;
s2, weighing cinnamaldehyde and hydroxyethyl ethylenediamine, sequentially adding the cinnamaldehyde and the hydroxyethyl ethylenediamine into the nano coffee grounds suspension, and placing the nano coffee grounds suspension in a water bath at the temperature of 60-80 ℃ to react for 2-5 hours; then dropwise adding 0.5mol/L hydrochloric acid until the pH value is 5.0-6.0, continuously stirring for 0.5-1 h, filtering while hot to obtain a solid, washing with acetone once, then washing with deionized water to be neutral, and drying in vacuum to obtain a coffee residue activator;
wherein the volume ratio of the cinnamaldehyde to the hydroxyethyl ethylenediamine to the nano coffee grounds suspension is 1: 3-6: 40-60;
s3, weighing ruthenium trichloride trihydrate, adding the ruthenium trichloride trihydrate into deionized water, and stirring until the ruthenium trichloride is dissolved to obtain a ruthenium trichloride solution; adding the coffee grounds activator into the ruthenium trichloride solution, stirring the mixture evenly, placing the mixture in a water bath at the temperature of 40-50 ℃ for reacting for 5-8 hours, cooling the mixture to room temperature, filtering the mixture to obtain a solid, washing the solid for three times by using deionized water, and drying the solid in vacuum to obtain modified coffee grounds;
wherein the mass ratio of the ruthenium trichloride trihydrate to the deionized water is 10-20: 100; the solid-to-liquid ratio of the coffee grounds activator to the ruthenium trichloride solution is 1: 10-20.
In the step S1, the wavelength of the ultraviolet light is 0.1-0.4 μm.
The synthetic resin is one or more of polyethylene, polystyrene and ABS.
The synthetic resin is polyethylene, polystyrene and ABS in a mass ratio of 1:1: 2.
The modified bagasse fiber is obtained by modifying bagasse fiber with Chinese juniper oil.
The preparation method of the modified bagasse fiber comprises the following steps:
s1, removing impurities from bagasse, cleaning, drying and crushing to obtain bagasse fibers;
s2, adding bagasse fibers into 0.1mol/L sodium hydroxide solution, soaking for 1-5 hours, adding carboxymethyl cellulose, stirring uniformly, dropwise adding Chinese juniper oil, stirring for 1-3 hours at 40-60 ℃ after uniform ultrasonic dispersion, pouring into a reaction kettle, sealing, reacting for 2-10 hours at 80-100 ℃, filtering to obtain solids, washing with acetone for three times, then washing with deionized water to be neutral, and freeze-drying to obtain modified bagasse fibers;
wherein the solid-to-liquid ratio of the bagasse fibers to the sodium hydroxide solution is 1: 10-20; the mass ratio of the carboxymethyl cellulose to the Chinese juniper oil to the bagasse fibers is 0.02-0.05: 0.1-0.3: 1.
The plasticizer is one or more of synthetic vegetable ester, citrate and epoxidized soybean oil.
The flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
The environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
Example 2
A preparation method of an environment-friendly plastic toy product comprises the following steps:
step 1, weighing modified polylactic acid, modified bagasse fiber, modified coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
and 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain the environment-friendly plastic toy product.
The environment-friendly plastic product comprises the following components in parts by weight:
50 parts of modified polylactic acid, 20 parts of synthetic resin, 1 part of modified coffee grounds, 1 part of modified bagasse fibers, 0.1 part of plasticizer, 0.2 part of flame retardant and 0.01 part of environment-friendly pigment.
The charging barrel passes through four temperature intervals, wherein the first temperature interval is 170-190 ℃, the second temperature interval is 190-210 ℃, the third temperature interval is 210-230 ℃, and the fourth temperature interval is 230-260 ℃.
The modified polylactic acid is obtained by modifying polylactic acid by a crosslinking modifier; wherein, the crosslinking modifier is prepared by the reaction of dibenzofuran and succinic acid.
The preparation method of the modified polylactic acid comprises the following steps:
s1, weighing dibenzofuran and succinic acid, respectively adding the dibenzofuran and succinic acid into toluene, stirring until the dibenzofuran and succinic acid are dissolved, adding ferric chloride particles, stirring until the mixture is uniform, placing the mixture in a water bath at the temperature of 40-60 ℃ for reaction for 2-5 hours, cooling to room temperature, adding deionized water with the same volume as the toluene, stirring for 0.5-1 hour, extracting and separating an organic phase, and removing a solvent by rotary evaporation to obtain a crosslinking modifier;
wherein the mass ratio of dibenzofuran to succinic acid to toluene is 1: 2-3: 15-30; the solid-liquid ratio of the ferric chloride particles to the toluene is 1: 50-80 parts;
s2, respectively weighing the crosslinking modifier and the dried polylactic acid, adding the crosslinking modifier and the dried polylactic acid into a high-speed mixer, and stirring the mixture uniformly to obtain modified polylactic acid;
wherein the mass ratio of the crosslinking modifier to the polylactic acid is 1: 20-50.
The modified coffee grounds are obtained by activating the coffee grounds and then modifying the coffee grounds by using ruthenium trichloride trihydrate.
The preparation method of the modified coffee grounds comprises the following steps:
s1, weighing coffee grounds, adding the coffee grounds into deionized water, stirring for 1-2 hours, filtering, drying, and then placing in a nano grinder to grind into nano coffee grounds; the method comprises the steps of firstly, placing the nano coffee grounds in an ultraviolet light condition to radiate for 0.5-2 hours, then adding the nano coffee grounds into a 0.1mol/L sodium hydroxide solution, placing the solution in a water bath at the temperature of 60-80 ℃, and stirring for 1-2 hours to obtain a nano coffee grounds suspension;
wherein the solid-to-liquid ratio of the coffee grounds to the deionized water is 1: 10-20; the solid-liquid ratio of the nano coffee grounds to the sodium hydroxide solution is 1: 15-20;
s2, weighing cinnamaldehyde and hydroxyethyl ethylenediamine, sequentially adding the cinnamaldehyde and the hydroxyethyl ethylenediamine into the nano coffee grounds suspension, and placing the nano coffee grounds suspension in a water bath at the temperature of 60-80 ℃ to react for 2-5 hours; then dropwise adding 0.5mol/L hydrochloric acid until the pH value is 5.0-6.0, continuously stirring for 0.5-1 h, filtering while hot to obtain a solid, washing with acetone once, then washing with deionized water to be neutral, and drying in vacuum to obtain a coffee residue activator;
wherein the volume ratio of the cinnamaldehyde to the hydroxyethyl ethylenediamine to the nano coffee grounds suspension is 1: 3-6: 40-60;
s3, weighing ruthenium trichloride trihydrate, adding the ruthenium trichloride trihydrate into deionized water, and stirring until the ruthenium trichloride is dissolved to obtain a ruthenium trichloride solution; adding the coffee grounds activator into the ruthenium trichloride solution, stirring the mixture evenly, placing the mixture in a water bath at the temperature of 40-50 ℃ for reacting for 5-8 hours, cooling the mixture to room temperature, filtering the mixture to obtain a solid, washing the solid for three times by using deionized water, and drying the solid in vacuum to obtain modified coffee grounds;
wherein the mass ratio of the ruthenium trichloride trihydrate to the deionized water is 10-20: 100; the solid-to-liquid ratio of the coffee grounds activator to the ruthenium trichloride solution is 1: 10-20.
In the step S1, the wavelength of the ultraviolet light is 0.1-0.4 μm.
The synthetic resin is one or more of polyethylene, polystyrene and ABS.
The synthetic resin is polyethylene, polystyrene and ABS in a mass ratio of 1:1: 2.
The modified bagasse fiber is obtained by modifying bagasse fiber with Chinese juniper oil.
The preparation method of the modified bagasse fiber comprises the following steps:
s1, removing impurities from bagasse, cleaning, drying and crushing to obtain bagasse fibers;
s2, adding bagasse fibers into 0.1mol/L sodium hydroxide solution, soaking for 1-5 hours, adding carboxymethyl cellulose, stirring uniformly, dropwise adding Chinese juniper oil, stirring for 1-3 hours at 40-60 ℃ after uniform ultrasonic dispersion, pouring into a reaction kettle, sealing, reacting for 2-10 hours at 80-100 ℃, filtering to obtain solids, washing with acetone for three times, then washing with deionized water to be neutral, and freeze-drying to obtain modified bagasse fibers;
wherein the solid-to-liquid ratio of the bagasse fibers to the sodium hydroxide solution is 1: 10-20; the mass ratio of the carboxymethyl cellulose to the Chinese juniper oil to the bagasse fibers is 0.02-0.05: 0.1-0.3: 1.
The plasticizer is one or more of synthetic vegetable ester, citrate and epoxidized soybean oil.
The flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
The environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
Example 3
A preparation method of an environment-friendly plastic toy product comprises the following steps:
step 1, weighing modified polylactic acid, modified bagasse fiber, modified coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
and 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain the environment-friendly plastic toy product.
The environment-friendly plastic product comprises the following components in parts by weight:
80 parts of modified polylactic acid, 50 parts of synthetic resin, 10 parts of modified coffee grounds, 5 parts of modified bagasse fibers, 2 parts of plasticizer, 0.5 part of flame retardant and 0.1 part of environment-friendly pigment.
The charging barrel passes through four temperature intervals, wherein the first temperature interval is 170-190 ℃, the second temperature interval is 190-210 ℃, the third temperature interval is 210-230 ℃, and the fourth temperature interval is 230-260 ℃.
The modified polylactic acid is obtained by modifying polylactic acid by a crosslinking modifier; wherein, the crosslinking modifier is prepared by the reaction of dibenzofuran and succinic acid.
The preparation method of the modified polylactic acid comprises the following steps:
s1, weighing dibenzofuran and succinic acid, respectively adding the dibenzofuran and succinic acid into toluene, stirring until the dibenzofuran and succinic acid are dissolved, adding ferric chloride particles, stirring until the mixture is uniform, placing the mixture in a water bath at the temperature of 40-60 ℃ for reaction for 2-5 hours, cooling to room temperature, adding deionized water with the same volume as the toluene, stirring for 0.5-1 hour, extracting and separating an organic phase, and removing a solvent by rotary evaporation to obtain a crosslinking modifier;
wherein the mass ratio of dibenzofuran to succinic acid to toluene is 1: 2-3: 15-30; the solid-liquid ratio of the ferric chloride particles to the toluene is 1: 50-80 parts;
s2, respectively weighing the crosslinking modifier and the dried polylactic acid, adding the crosslinking modifier and the dried polylactic acid into a high-speed mixer, and stirring the mixture uniformly to obtain modified polylactic acid;
wherein the mass ratio of the crosslinking modifier to the polylactic acid is 1: 20-50.
The modified coffee grounds are obtained by activating the coffee grounds and then modifying the coffee grounds by using ruthenium trichloride trihydrate.
The preparation method of the modified coffee grounds comprises the following steps:
s1, weighing coffee grounds, adding the coffee grounds into deionized water, stirring for 1-2 hours, filtering, drying, and then placing in a nano grinder to grind into nano coffee grounds; the method comprises the steps of firstly, placing the nano coffee grounds in an ultraviolet light condition to radiate for 0.5-2 hours, then adding the nano coffee grounds into a 0.1mol/L sodium hydroxide solution, placing the solution in a water bath at the temperature of 60-80 ℃, and stirring for 1-2 hours to obtain a nano coffee grounds suspension;
wherein the solid-to-liquid ratio of the coffee grounds to the deionized water is 1: 10-20; the solid-liquid ratio of the nano coffee grounds to the sodium hydroxide solution is 1: 15-20;
s2, weighing cinnamaldehyde and hydroxyethyl ethylenediamine, sequentially adding the cinnamaldehyde and the hydroxyethyl ethylenediamine into the nano coffee grounds suspension, and placing the nano coffee grounds suspension in a water bath at the temperature of 60-80 ℃ to react for 2-5 hours; then dropwise adding 0.5mol/L hydrochloric acid until the pH value is 5.0-6.0, continuously stirring for 0.5-1 h, filtering while hot to obtain a solid, washing with acetone once, then washing with deionized water to be neutral, and drying in vacuum to obtain a coffee residue activator;
wherein the volume ratio of the cinnamaldehyde to the hydroxyethyl ethylenediamine to the nano coffee grounds suspension is 1: 3-6: 40-60;
s3, weighing ruthenium trichloride trihydrate, adding the ruthenium trichloride trihydrate into deionized water, and stirring until the ruthenium trichloride is dissolved to obtain a ruthenium trichloride solution; adding the coffee grounds activator into the ruthenium trichloride solution, stirring the mixture evenly, placing the mixture in a water bath at the temperature of 40-50 ℃ for reacting for 5-8 hours, cooling the mixture to room temperature, filtering the mixture to obtain a solid, washing the solid for three times by using deionized water, and drying the solid in vacuum to obtain modified coffee grounds;
wherein the mass ratio of the ruthenium trichloride trihydrate to the deionized water is 10-20: 100; the solid-to-liquid ratio of the coffee grounds activator to the ruthenium trichloride solution is 1: 10-20.
In the step S1, the wavelength of the ultraviolet light is 0.1-0.4 μm.
The synthetic resin is one or more of polyethylene, polystyrene and ABS.
The synthetic resin is polyethylene, polystyrene and ABS in a mass ratio of 1:1: 2.
The modified bagasse fiber is obtained by modifying bagasse fiber with Chinese juniper oil.
The preparation method of the modified bagasse fiber comprises the following steps:
s1, removing impurities from bagasse, cleaning, drying and crushing to obtain bagasse fibers;
s2, adding bagasse fibers into 0.1mol/L sodium hydroxide solution, soaking for 1-5 hours, adding carboxymethyl cellulose, stirring uniformly, dropwise adding Chinese juniper oil, stirring for 1-3 hours at 40-60 ℃ after uniform ultrasonic dispersion, pouring into a reaction kettle, sealing, reacting for 2-10 hours at 80-100 ℃, filtering to obtain solids, washing with acetone for three times, then washing with deionized water to be neutral, and freeze-drying to obtain modified bagasse fibers;
wherein the solid-to-liquid ratio of the bagasse fibers to the sodium hydroxide solution is 1: 10-20; the mass ratio of the carboxymethyl cellulose to the Chinese juniper oil to the bagasse fibers is 0.02-0.05: 0.1-0.3: 1.
The plasticizer is one or more of synthetic vegetable ester, citrate and epoxidized soybean oil.
The flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
The environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
Comparative example
A preparation method of an environment-friendly plastic toy product comprises the following steps:
step 1, weighing polylactic acid, bagasse fiber, coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
and 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain the environment-friendly plastic toy product.
The environment-friendly plastic product comprises the following components in parts by weight:
65 parts of polylactic acid, 35 parts of synthetic resin, 5 parts of coffee grounds, 2 parts of bagasse fibers, 1 part of plasticizer, 0.3 part of flame retardant and 0.05 part of environment-friendly pigment.
The charging barrel passes through four temperature intervals, wherein the first temperature interval is 170-190 ℃, the second temperature interval is 190-210 ℃, the third temperature interval is 210-230 ℃, and the fourth temperature interval is 230-260 ℃.
The plasticizer is one or more of synthetic vegetable ester, citrate and epoxidized soybean oil.
The flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
The environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
To illustrate the present invention more clearly, the materials of the environmentally friendly plastic toy products prepared in examples 1 to 3 and comparative examples of the present invention were prepared into shapes of 150mm long × 100mm × 1mm thick, and mechanical and aging properties were measured, and the results are shown in table 1.
Wherein the tensile strength is detected according to the method of GB/T1043.1-2008;
the impact strength is detected according to the method of GB/T1040.1-2006;
the bending strength is detected according to the method of GB/T9341-2000;
the aging resistance is that the glass is aged for 72 hours at 200 ℃.
TABLE 1 Performance testing of environmentally friendly Plastic toy articles
As can be seen from Table 1, the environment-friendly plastic toy products prepared in the embodiments 1 to 3 of the present invention have excellent tensile strength, impact strength and bending strength, and are not deformed or cracked after being aged at 200 ℃ for 72 hours, wherein the inhibition rate on Escherichia coli is more than 96%, and the inhibition rate on Staphylococcus aureus is more than 97%.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of an environment-friendly plastic toy product is characterized by comprising the following steps:
step 1, weighing modified polylactic acid, modified bagasse fiber, modified coffee grounds and synthetic resin according to the weight, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into a high-speed stirrer for uniform mixing to obtain a first-grade mixture;
step 2, weighing the plasticizer, the flame retardant and the environment-friendly pigment according to the amount, placing the weighed materials in a vacuum drying oven for drying treatment, and then putting the materials into the primary mixture for continuously and uniformly stirring to obtain a secondary mixture;
step 3, putting the secondary mixture into an extruder for extrusion and granulation to obtain mixed material particles;
step 4, putting the mixed material particles into a charging barrel of an injection molding machine, and performing injection molding by using a mold to obtain an environment-friendly plastic toy product;
the environment-friendly plastic product comprises the following components in parts by weight:
50-80 parts of modified polylactic acid, 20-50 parts of synthetic resin, 1-10 parts of modified coffee grounds, 1-5 parts of modified bagasse fibers, 0.1-2 parts of plasticizer, 0.2-0.5 part of flame retardant and 0.01-0.1 part of environment-friendly pigment.
2. The method for preparing an environment-friendly plastic toy product according to claim 1, wherein the environment-friendly plastic product comprises the following components in parts by weight:
60-80 parts of modified polylactic acid, 20-30 parts of synthetic resin, 3-5 parts of modified coffee grounds, 2-3 parts of modified bagasse fibers, 0.5-1 part of plasticizer, 0.2-0.5 part of flame retardant and 0.01-0.1 part of environment-friendly pigment.
3. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the modified polylactic acid is obtained by modifying polylactic acid with a crosslinking modifier; wherein the crosslinking modifier is prepared by the reaction of dibenzofuran and succinic acid;
the preparation method of the modified polylactic acid comprises the following steps:
s1, weighing dibenzofuran and succinic acid, respectively adding the dibenzofuran and succinic acid into toluene, stirring until the dibenzofuran and succinic acid are dissolved, adding ferric chloride particles, stirring until the mixture is uniform, placing the mixture in a water bath at the temperature of 40-60 ℃ for reaction for 2-5 hours, cooling to room temperature, adding deionized water with the same volume as the toluene, stirring for 0.5-1 hour, extracting and separating an organic phase, and removing a solvent by rotary evaporation to obtain a crosslinking modifier;
wherein the mass ratio of dibenzofuran to succinic acid to toluene is 1: 2-3: 15-30; the solid-liquid ratio of the ferric chloride particles to the toluene is 1: 50-80 parts;
s2, respectively weighing the crosslinking modifier and the dried polylactic acid, adding the crosslinking modifier and the dried polylactic acid into a high-speed mixer, and stirring the mixture uniformly to obtain modified polylactic acid;
wherein the mass ratio of the crosslinking modifier to the polylactic acid is 1: 20-50.
4. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the synthetic resin is one or more of polyethylene, polystyrene and ABS.
5. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the modified coffee grounds are obtained by activating coffee grounds and then modifying the coffee grounds with ruthenium trichloride trihydrate;
the preparation method of the modified coffee grounds comprises the following steps:
s1, weighing coffee grounds, adding the coffee grounds into deionized water, stirring for 1-2 hours, filtering, drying, and then placing in a nano grinder to grind into nano coffee grounds; the method comprises the steps of firstly, placing the nano coffee grounds in an ultraviolet light condition to radiate for 0.5-2 hours, then adding the nano coffee grounds into a 0.1mol/L sodium hydroxide solution, placing the solution in a water bath at the temperature of 60-80 ℃, and stirring for 1-2 hours to obtain a nano coffee grounds suspension;
wherein the solid-to-liquid ratio of the coffee grounds to the deionized water is 1: 10-20; the solid-liquid ratio of the nano coffee grounds to the sodium hydroxide solution is 1: 15-20; the wavelength of the ultraviolet light is 0.1-0.4 μm;
s2, weighing cinnamaldehyde and hydroxyethyl ethylenediamine, sequentially adding the cinnamaldehyde and the hydroxyethyl ethylenediamine into the nano coffee grounds suspension, and placing the nano coffee grounds suspension in a water bath at the temperature of 60-80 ℃ to react for 2-5 hours; then dropwise adding 0.5mol/L hydrochloric acid until the pH value is 5.0-6.0, continuously stirring for 0.5-1 h, filtering while hot to obtain a solid, washing with acetone once, then washing with deionized water to be neutral, and drying in vacuum to obtain a coffee residue activator;
wherein the volume ratio of the cinnamaldehyde to the hydroxyethyl ethylenediamine to the nano coffee grounds suspension is 1: 3-6: 40-60;
s3, weighing ruthenium trichloride trihydrate, adding the ruthenium trichloride trihydrate into deionized water, and stirring until the ruthenium trichloride is dissolved to obtain a ruthenium trichloride solution; adding the coffee grounds activator into the ruthenium trichloride solution, stirring the mixture evenly, placing the mixture in a water bath at the temperature of 40-50 ℃ for reacting for 5-8 hours, cooling the mixture to room temperature, filtering the mixture to obtain a solid, washing the solid for three times by using deionized water, and drying the solid in vacuum to obtain modified coffee grounds;
wherein the mass ratio of the ruthenium trichloride trihydrate to the deionized water is 10-20: 100; the solid-to-liquid ratio of the coffee grounds activator to the ruthenium trichloride solution is 1: 10-20.
6. The method for preparing an environment-friendly plastic toy product as claimed in claim 1 or 2, wherein the modified bagasse fiber is obtained by modifying bagasse fiber with hinoki oil;
the preparation method of the modified bagasse fiber comprises the following steps:
s1, removing impurities from bagasse, cleaning, drying and crushing to obtain bagasse fibers;
s2, adding bagasse fibers into 0.1mol/L sodium hydroxide solution, soaking for 1-5 hours, adding carboxymethyl cellulose, stirring uniformly, dropwise adding Chinese juniper oil, stirring for 1-3 hours at 40-60 ℃ after uniform ultrasonic dispersion, pouring into a reaction kettle, sealing, reacting for 2-10 hours at 80-100 ℃, filtering to obtain solids, washing with acetone for three times, then washing with deionized water to be neutral, and freeze-drying to obtain modified bagasse fibers;
wherein the solid-to-liquid ratio of the bagasse fibers to the sodium hydroxide solution is 1: 10-20; the mass ratio of the carboxymethyl cellulose to the Chinese juniper oil to the bagasse fibers is 0.02-0.05: 0.1-0.3: 1.
7. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the plasticizer is one or more of synthetic vegetable ester, citrate ester and epoxidized soybean oil.
8. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the flame retardant is one or more of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
9. The method for preparing an environment-friendly plastic toy product according to claim 1 or 2, wherein the environment-friendly pigment is an environment-friendly organic pigment and/or an environment-friendly inorganic pigment.
10. The method for preparing an environment-friendly plastic toy product according to claim 1, wherein the barrel is subjected to four temperature ranges, wherein the first temperature range is 170-190 ℃, the second temperature range is 190-210 ℃, the third temperature range is 210-230 ℃, and the fourth temperature range is 230-260 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500688A (en) * | 2020-11-30 | 2021-03-16 | 捷成实业（深圳）有限公司 | Biodegradable antibacterial toy material and preparation method thereof |
| CN112724613A (en) * | 2020-12-10 | 2021-04-30 | 广东格瑞新材料股份有限公司 | Degradable material and preparation method thereof |
| CN117462337A (en) * | 2023-12-06 | 2024-01-30 | 佛山市顺德区州福慈鑫无纺布有限公司 | Coffee sanitary towel and manufacturing process thereof |
-
2020
- 2020-05-12 CN CN202010399575.0A patent/CN111718568A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500688A (en) * | 2020-11-30 | 2021-03-16 | 捷成实业（深圳）有限公司 | Biodegradable antibacterial toy material and preparation method thereof |
| CN112724613A (en) * | 2020-12-10 | 2021-04-30 | 广东格瑞新材料股份有限公司 | Degradable material and preparation method thereof |
| CN117462337A (en) * | 2023-12-06 | 2024-01-30 | 佛山市顺德区州福慈鑫无纺布有限公司 | Coffee sanitary towel and manufacturing process thereof |
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Application publication date: 20200929 |