CN111040400A - Full-biodegradable sheet and preparation method thereof - Google Patents
Full-biodegradable sheet and preparation method thereof Download PDFInfo
- Publication number
- CN111040400A CN111040400A CN201911371367.3A CN201911371367A CN111040400A CN 111040400 A CN111040400 A CN 111040400A CN 201911371367 A CN201911371367 A CN 201911371367A CN 111040400 A CN111040400 A CN 111040400A
- Authority
- CN
- China
- Prior art keywords
- parts
- polylactic acid
- biological
- temperature
- weight
- 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- Withdrawn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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2431/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a full-biodegradable sheet and a preparation method thereof, relating to the technical field of packaging materials, and the technical scheme is characterized in that the full-biodegradable sheet comprises the following components in parts by weight: 70-80 parts of polylactic acid, 10-20 parts of poly butylene succinate, 4-6 parts of a biocompatible agent, 2-4 parts of a biological toughening agent, 0.8-1 part of a slipping agent, 0.8-1.2 parts of calcium carbonate and 0.08-0.12 part of an antioxidant; the biological compatilizer is styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer; the biological toughening agent is vinyl acetate-ethylene-vinyl ester copolymer. The biodegradable sheet of the present invention has excellent degradability, hardness, toughness and processability.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a raw full-biodegradable sheet and a preparation method thereof.
Background
Biodegradable plastics refer to a class of plastics that are degraded by the action of microorganisms such as bacteria, molds (fungi), and algae that exist in nature. Biodegradable plastics can be divided into completely biodegradable plastics and destructive biodegradable plastics, wherein the completely biodegradable plastics are mainly prepared from natural polymers (such as starch, cellulose and chitin) or agricultural and sideline products through microbial fermentation or synthesis of biodegradable polymers, such as thermoplastic starch plastics, aliphatic polyester, polylactic acid, starch/polyvinyl alcohol and the like which belong to the plastics; destructive biodegradable plastics currently mainly comprise starch modified (or filled) polyethylene PE, polypropylene PP, polyvinyl chloride PVC, polystyrene PS, and the like. Polylactic acid is used as a novel biodegradable material, is prepared from starch extracted from renewable plant resources (such as corn), has no pollution in the production process, is biodegradable, is an ideal green high polymer material, and can be used as a packaging material for beverage cups, food trays and the like.
In the prior art, Chinese patent with application number 201410281475.2 discloses a food-grade biodegradable polylactic acid-based composite material and application thereof, wherein the composite material is prepared by drying and mixing four components of 55-85 wt% of polylactic acid, 2-10 wt% of biodegradable polyester, 3-10 wt% of food-grade plasticizer and 10-30 wt% of inorganic filler, and further performing one-step melt blending modification and extrusion granulation by a double-screw extruder; wherein the inorganic filler is an inorganic filler which is not subjected to surface treatment, and has an average particle diameter of 2.7 to 19 micrometers; the weight average molecular weight of the polylactic acid is 10-18 ten thousand, and the molecular weight distribution index is 1.2-2.0.
Although polylactic acid has excellent biodegradability and good machining performance, the polylactic acid contains a large amount of ester bonds, so that the hydrophilicity is poor, the compatibility with other raw materials is reduced, and the processing difficulty is increased; and the polylactic acid is a linear polymer and has high brittleness, so that the toughness of the material is poor. Therefore, there is a need for a degradable material that is easy to process and has high toughness.
Disclosure of Invention
An object of the present invention is to provide a fully biodegradable sheet having excellent degradability, hardness, toughness and processability.
The technical purpose of the invention is realized by the following technical scheme:
the full-biodegradable sheet comprises the following components in parts by weight: 70-80 parts of polylactic acid, 10-20 parts of poly butylene succinate, 4-6 parts of a biocompatible agent, 2-4 parts of a biological toughening agent, 0.8-1 part of a slipping agent, 0.8-1.2 parts of calcium carbonate and 0.08-0.12 part of an antioxidant; the biological compatilizer is styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer; the biological toughening agent is vinyl acetate-ethylene-vinyl ester copolymer.
By adopting the technical scheme, the styrene-acrylonitrile-glycidyl methacrylate terpolymer is selected from SAG-008 type compatilizers which are easy to provide, has good tackifying and chain extending effects on polylactic acid and polybutylene succinate, and can increase melt viscosity and improve processing performance; the vinyl acetate-ethylene-vinyl ester copolymer is selected from the group consisting of the types provided by Wake
The 2505 toughening agent has the advantages that the ethylene content is relatively close, so that the resin is soft and elastic, the resin has good compatibility with polylactic acid and poly butylene succinate, the impact strength, the melt strength and the toughness of the full-biodegradable sheet can be improved, and the mechanical property of the sheet can be improved; through the matching of the biological compatilizer, the biological flexibilizer and the slipping agent, the material taking the polylactic acid and the polybutylene succinate as the base materials has good processing performance and good flexibility.
Further, the paint comprises the following components in parts by weight: 75 parts of polylactic acid, 15 parts of poly butylene succinate, 5 parts of a biological compatilizer, 3 parts of a biological toughening agent, 0.9 part of a slipping agent, 1 part of calcium carbonate and 0.1 part of an antioxidant; the biological compatilizer is styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer; the biological toughening agent is vinyl acetate-ethylene-vinyl ester copolymer.
By adopting the technical scheme, the obtained full-biodegradable sheet has good processing performance and good flexibility at the same time under the above proportion, so that the comprehensive performance of the full-biodegradable sheet is improved.
Further, the polylactic acid needs to be pretreated before use, wherein ① adds 10-15 parts of low molecular weight polyethylene glycol and 1-1.5 parts of stannous octoate catalyst into 100 parts of polylactic acid in parts by weight, the mixture is melted and blended for 8-10 hours at the temperature of 155-165 ℃ to obtain hydroxyl-terminated modified polylactic acid, ② adds 30-40 parts of high molecular weight polyethylene glycol, 6-8 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 3-5 parts of amino acid type surfactant and 3-5 parts of dodecyl glucoside into the hydroxyl-terminated polylactic acid, the mixture is melted and blended for 1-2 hours at the temperature of 180-190 ℃, and then the mixture is extruded and granulated.
By adopting the technical scheme, the polylactic acid reacts with the polyethylene glycol with low molecular weight to obtain the hydroxyl-terminated modified polylactic acid, so that the hydrophilicity of the polylactic acid can be effectively improved, and the compatibility of the polylactic acid with other materials is improved; then, chain extension is carried out on the hydroxyl-terminated modified polylactic acid by adopting high molecular weight polyethylene glycol, ethylene-butyl acrylate-glycidyl methacrylate copolymer, amino acid type surfactant and dodecyl glucoside, so that the brittleness of the polylactic acid can be reduced, and the flexibility of the fully biodegradable sheet can be further improved by matching with a biological toughening agent; and the raw materials of the chain extension reaction are safe and degradable, and the degradability of the polylactic acid is not influenced.
Further, the low molecular weight polyethylene glycol in step ① is one of PEG-400 and PEG-600, and the high molecular weight polyethylene glycol in step ② is PEG-10000.
By adopting the technical scheme, PEG-400 and PEG-600 are transparent liquid, the hydroxyl value is 170-312, the polylactic acid reacts with the polyethylene glycol with low molecular weight to obtain the hydroxyl-terminated modified polylactic acid, the hydrophilicity of the polylactic acid can be effectively improved, the compatibility of the polylactic acid with other raw materials is improved, then the hydroxyl-terminated polylactic acid reacts with the polyethylene glycol-10000 with the hydroxyl value of 8-11mgKOH/g, and after the ethylene-butyl acrylate-glycidyl methacrylate copolymer, the amino acid type surfactant and the dodecyl glucoside are matched, the hydrophilicity of the polylactic acid can be improved, the brittleness of the polylactic acid can be reduced, and the flexibility of the full-biodegradable sheet can be improved by matching with the biological flexibilizer.
Further, the amino acid type surfactant is one of sodium lauroyl sarcosinate and sodium lauroyl glutamate or a compound of the sodium lauroyl sarcosinate and the sodium lauroyl glutamate.
By adopting the technical scheme, sodium lauroyl sarcosinate and sodium lauroyl glutamate are used as a safe surfactant with good biodegradability and are matched with the ethylene-butyl acrylate-glycidyl methacrylate copolymer and the high molecular weight polyethylene glycol, so that on one hand, chain extension can be carried out on polylactic acid, the toughness of the polylactic acid is improved, on the other hand, the compatibility of the polylactic acid with other raw materials can be improved, and the processing performance of the polylactic acid is improved.
Further, the slipping agent is formed by mixing ethylene bis-oleamide and rice bran wax in a weight ratio of 1: 1.
By adopting the technical scheme, the ethylene bis-oleamide is a nonionic surfactant and can be used in food packaging materials, the rice bran wax mainly comprises the myricyl tetracosanoate, and the processing performance of the polylactic acid material can be improved by the slipping agent obtained by compounding the ethylene bis-oleamide with the rice bran wax.
Further, the antioxidant is one of or a compound of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
By adopting the technical scheme, the tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (also called antioxidant 1010) has the characteristics of good volatility, good thermal stability, no toxicity and no pollution, the tri [2, 4-di-tert-butylphenyl ] phosphite (also called antioxidant 168) has the advantages of no pollution and good volatility resistance, the β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol ester (also called antioxidant 1076) has good heat resistance and water extraction resistance, and the thermal degradation and oxidative degradation of the polylactic acid material in the processing process can be prevented by adding a small amount of antioxidant.
The second purpose of the invention is to provide a preparation method of the full-biodegradable sheet.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a full-biodegradable sheet comprises the following steps:
s1, mixing materials: taking polylactic acid, poly (butylene succinate), a biological compatilizer, a biological toughening agent, a slipping agent, calcium carbonate and an antioxidant, and stirring at a high speed for 10-20min under the conditions that the temperature is 60-80 ℃ and the stirring speed is 1000-2000r/min to obtain a mixture;
s2, plasticizing and forming: and putting the mixture into a sheet extruder, and melting and extruding at the temperature of 140-220 ℃ to obtain the fully biodegradable sheet.
By adopting the technical scheme, the full-biodegradable sheet is obtained by mixing, melting and extruding polylactic acid, poly butylene succinate, a biological compatilizer, a biological toughening agent, a slipping agent, calcium carbonate and an antioxidant, and has excellent degradability, good flexibility and good processability.
Furthermore, the polylactic acid of S1 is pretreated before mixing, in parts by weight, ① parts of low molecular weight polyethylene glycol and 1-1.5 parts of stannous octoate catalyst are added into 100 parts of polylactic acid, and melt blending is carried out for 8-10h at the temperature of 155-165 ℃ to obtain hydroxyl terminated modified polylactic acid, ② parts of high molecular weight polyethylene glycol, 6-8 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 3-5 parts of amino acid type surfactant and 3-5 parts of dodecyl glucoside are added into the hydroxyl terminated polylactic acid, and melt blending is carried out for 1-2h at the temperature of 180-190 ℃, and then extrusion and granulation are carried out to obtain the polylactic acid.
Further, the temperatures of the respective zones of the sheet extruder of S2 were: the temperature of the first zone is 180-.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the styrene-acrylonitrile-glycidyl methacrylate terpolymer is selected from good and easily-provided SAG-008 type compatilizers, has good tackifying and chain extending effects on polylactic acid and poly butylene succinate, can increase melt viscosity and improve processability; the vinyl acetate-ethylene-vinyl ester copolymer is selected from the group consisting of the types provided by Wake
The 2505 toughening agent has the advantages that the ethylene content is relatively close, so that the resin is soft and elastic, the resin has good compatibility with polylactic acid and poly butylene succinate, the impact strength, the melt strength and the toughness of the full-biodegradable sheet can be improved, and the mechanical property of the sheet can be improved; through the matching of the biological compatilizer, the biological flexibilizer and the slipping agent, the material taking polylactic acid and polybutylene succinate as the base material has good processing performance and good flexibility;
2. the polylactic acid reacts with the polyethylene glycol with low molecular weight to obtain the hydroxyl-terminated modified polylactic acid, which can effectively improve the hydrophilicity of the polylactic acid, thereby improving the compatibility of the polylactic acid with other raw materials; then, chain extension is carried out on the hydroxyl-terminated modified polylactic acid by adopting high molecular weight polyethylene glycol, ethylene-butyl acrylate-glycidyl methacrylate copolymer, amino acid type surfactant and dodecyl glucoside, so that the brittleness of the polylactic acid can be reduced, and the flexibility of the fully biodegradable sheet can be further improved by matching with a biological toughening agent; the raw materials for the chain extension reaction are safe and degradable, and the degradability of the polylactic acid is not influenced; 3. ethylene bis-oleamide is a nonionic surfactant and can be used in food packaging materials, the rice bran wax mainly comprises myricyl tetracosanoate, and the processing performance of the polylactic acid material can be improved by using the slipping agent obtained by compounding the ethylene bis-oleamide with the rice bran wax.
Detailed Description
The present invention will be described in further detail below.
First, the polylactic acid in the following examples is selected from polylactic acid provided by Hainan, model REVODE 101; the ethylene-butyl acrylate-glycidyl methacrylate copolymer is selected from a model PTW provided by DuPont; PEG-400 and PEG-600 are provided by Nantong Xitai chemical Co., Ltd; PEG-10000 is provided by Nantong Jinlai chemical Co., Ltd; the poly (butylene succinate) is selected from poly (butylene succinate) of Xinjiang blue Tunghe TH 803S; the biological compatilizer is selected from SAG-008 styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer provided by Jiangsu Limited company as a good easy compatilizer; the biological flexibilizer is selected from the type provided by German wakker
2505 of vinyl acetate-ethylene-vinyl ester copolymer; the slipping agent is formed by mixing ethylene bis-oleamide and rice bran wax in a weight ratio of 1: 1; antioxidant 168, antioxidant 1010 and antioxidant 1076 are all provided by basf, germany.
Example 1: the fully biodegradable sheet is prepared by the following method:
s1, mixing materials: taking 75kg of polylactic acid, 15kg of poly butylene succinate, 5kg of a biological compatilizer, 3kg of a biological toughening agent, 0.9kg of a slipping agent, 1.0kg of calcium carbonate and 10100.1 kg of an antioxidant, and stirring at a high speed for 15min under the conditions that the temperature is 70 ℃ and the stirring speed is 1500r/min to obtain a mixture;
s2, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the die head is 240 ℃, and the full-biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Example 2: the fully biodegradable sheet is prepared by the following method:
s1, mixing materials: taking 70kg of polylactic acid, 10kg of poly butylene succinate, 4kg of a biological compatilizer, 2kg of a biological toughening agent, 0.8kg of a slipping agent, 0.8kg of calcium carbonate and 1680.08 kg of an antioxidant, and stirring at a high speed for 10min under the conditions that the temperature is 60 ℃ and the stirring speed is 1000r/min to obtain a mixture;
s2, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the first zone temperature is 180 ℃, the second zone temperature is 185 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 190 ℃, the fifth zone temperature is 200 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 210 ℃, the die head temperature is 220 ℃, and the fully biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Example 3: the fully biodegradable sheet is prepared by the following method:
s1, mixing materials: taking 80kg of polylactic acid, 20kg of poly butylene succinate, 6kg of a biological compatilizer, 4kg of a biological toughening agent, 1kg of a slipping agent, 1.2kg of calcium carbonate and 10760.12kg of an antioxidant, and stirring at a high speed for 20min under the conditions that the temperature is 80 ℃ and the stirring speed is 2000r/min to obtain a mixture;
s2, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the first zone temperature is 200 ℃, the second zone temperature is 210 ℃, the third zone temperature is 220 ℃, the fourth zone temperature is 220 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 230 ℃, the seventh zone temperature is 240 ℃, the die head temperature is 260 ℃, and the fully biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Example 4: the fully biodegradable sheet is prepared by the following method:
s1, preprocessing polylactic acid, namely ① adding 12.5kg of polyethylene glycol-400 and 1.25kg of stannous octoate catalyst into 100kg of polylactic acid, and carrying out melt blending for 9 hours at the temperature of 160 ℃ to obtain hydroxyl-terminated modified polylactic acid, ② adding 35kg of polyethylene glycol-10000, 7kg of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 4kg of sodium lauroyl sarcosinate and 4kg of dodecyl glucoside into the hydroxyl-terminated polylactic acid, carrying out melt blending for 1.5 hours at the temperature of 185 ℃, and then carrying out extrusion and granulation;
s2, mixing materials: taking 75kg of polylactic acid, 15kg of poly butylene succinate, 5kg of a biological compatilizer, 3kg of a biological toughening agent, 0.9kg of a slipping agent, 1.0kg of calcium carbonate and 10100.1 kg of an antioxidant, and stirring at a high speed for 15min under the conditions that the temperature is 70 ℃ and the stirring speed is 1500r/min to obtain a mixture;
s3, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the die head is 240 ℃, and the full-biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Example 5: the fully biodegradable sheet is prepared by the following method:
s1, preprocessing polylactic acid, namely ① adding 10kg of polyethylene glycol-600 and 1kg of stannous octoate catalyst into 100kg of polylactic acid, and carrying out melt blending for 8 hours at the temperature of 155 ℃ to obtain hydroxyl-terminated modified polylactic acid, ② adding 30kg of polyethylene glycol-10000, 6kg of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 3kg of sodium lauroyl glutamate and 3kg of dodecyl glucoside into the hydroxyl-terminated polylactic acid, carrying out melt blending for 1 hour at the temperature of 180 ℃, and then carrying out extrusion and granulation;
s2, mixing materials: taking 75kg of polylactic acid, 15kg of poly butylene succinate, 5kg of a biological compatilizer, 3kg of a biological toughening agent, 0.9kg of a slipping agent, 1.0kg of calcium carbonate and 10100.1 kg of an antioxidant, and stirring at a high speed for 15min under the conditions that the temperature is 70 ℃ and the stirring speed is 1500r/min to obtain a mixture;
s3, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the die head is 240 ℃, and the full-biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Example 6: the fully biodegradable sheet is prepared by the following method:
s1, preprocessing polylactic acid, namely ① adding 15kg of polyethylene glycol-400 and 1.5kg of stannous octoate catalyst into 100kg of polylactic acid, and performing melt blending for 10 hours at the temperature of 165 ℃ to obtain hydroxyl-terminated modified polylactic acid, ② adding 40kg of polyethylene glycol-10000, 8kg of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 2.5kg of sodium lauroyl sarcosinate, 2.5kg of sodium lauroyl glutamate and 5kg of dodecyl glucoside into the hydroxyl-terminated polylactic acid, performing melt blending for 2 hours at the temperature of 190 ℃, and performing extrusion and granulation;
s2, mixing materials: taking 75kg of polylactic acid, 15kg of poly butylene succinate, 5kg of a biological compatilizer, 3kg of a biological toughening agent, 0.9kg of a slipping agent, 1.0kg of calcium carbonate and 10100.1 kg of an antioxidant, and stirring at a high speed for 15min under the conditions that the temperature is 70 ℃ and the stirring speed is 1500r/min to obtain a mixture;
s3, plasticizing and forming: putting the mixture into a sheet extruder, wherein the temperature of each zone is as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 225 ℃, the temperature of the die head is 240 ℃, and the full-biodegradable sheet with the thickness of 1mm is obtained through melting and extrusion molding.
Second, comparative example
Comparative example 1 example 4 of patent application document having application number 201510244607.9 was used, and the raw material components were polylactic acid 65kg, polybutylene succinate 12kg, starch 12kg, dibenzoyl peroxide 1kg, ethylene glycol 3kg, glycerin 4kg, sorbitol 2kg, and antioxidant 1 kg; uniformly mixing starch and a plasticizer in proportion, and sealing the obtained mixture in a plastic bag for storage; and (3) extruding and molding by using a single-screw extruder, wherein the screw temperature of the extruder is 95 ℃, and the screw rotating speed is 220 rpm. The obtained thermoplastic starch granules were dried under vacuum at room temperature for 12 h. PLA and antioxidant were dried under vacuum at 70 ℃ for 15h and cooled under vacuum, and the PBS granules were dried in a common forced air drying oven at 60 ℃ for 15 h. Mixing PLA, PBS, BPO and antioxidant in a high-speed blender uniformly according to the proportion. Then extruding and granulating by utilizing a co-rotating double-screw extruder, wherein the temperature of each section of the extruder screw is as follows: 85 ℃, 95 ℃, 105 ℃, 115 ℃, 125 ℃, 130 ℃, 125 ℃ and the screw rotation speed of 240 rpm. The prepared modified polylactic acid particles are dried for 18 hours in vacuum at the temperature of 60 ℃. Mixing the prepared thermoplastic starch granules and the modified polylactic acid granules according to the proportion, sealing in a plastic bag and standing for 16 hours. Then extruding and granulating by utilizing a co-rotating double-screw extruder, wherein the temperature of each section of the extruder screw is as follows: 125 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 185 deg.C, 180 deg.C, 170 deg.C, and screw rotation speed of 240 rpm. And (3) drying the prepared modified polylactic acid particles at 60 ℃ for 18h in vacuum to obtain the polylactic acid composite granules for plastic uptake. And putting the prepared granules into a casting machine, adjusting parameters of a die head and an air knife, and carrying out melting, plasticizing, calendering, traction, cooling and rolling to obtain the polylactic acid composite sheet for plastic uptake with the thickness of 1 mm.
Comparative example 2: this comparative example differs from example 1 in that the biocompatible agent and the biological toughening agent were replaced with the same amount of polylactic acid.
Comparative example 3: the comparative example is different from example 1 in that the polybutylene succinate is replaced by the same amount of polylactic acid, and the biological toughening agent is replaced by the same amount of polylactic acid.
Comparative example 4 this comparative example is different from example 4 in that ethylene-butyl acrylate-glycidyl methacrylate copolymer, sodium lauroyl sarcosinate, and dodecyl glucoside were not added in step ② of S1.
Comparative example 5 this comparative example is different from example 4 in that polyethylene glycol-10000, sodium lauroyl sarcosinate and dodecyl glucoside were not added to ② of S1.
Comparative example 6: this comparative example differs from example 4 in that the biocompatible and the biological toughener are replaced with the same amount of polylactic acid.
Third, performance test
The sheets prepared in examples 1 to 6 and comparative examples 1 to 6 were tested for their properties in the following manner, and the test results are shown in Table 1.
1. Tensile strength: determination of tensile Properties of plastics according to GB/T1040.3-2006 part 3: test conditions for thin plastics and sheets.
2. Bending strength: the test was carried out according to GB/T1042-1979 "method for Plastic bending test".
3. Impact strength: the test was carried out according to GB/T1843-2008 "determination of impact Strength of Plastic cantilever").
4. Contact angle: the contact angle of the sheet was measured by a liquid drop method using a standard optical contact angle measuring instrument SL200B, the test time was 2s, and the smaller the contact angle, the more hydrophilic the material was, and the better the compatibility with other materials was.
5. The biodegradation rate is as follows: the biodegradation rates after 12 weeks, 16 weeks and 20 weeks were determined according to HJ/T209-2005 "environmental labeling products technical requirements packaging articles".
TABLE 1 Performance test Table for sheets of examples 1-6 and comparative examples 1-6
As can be seen from the data in Table 1, the biodegradation rate of the fully degradable sheets prepared in examples 1-3 reaches more than 80% in 12 weeks, and the fully degradable sheets can reach 100% degradation in 20 weeks, which is obviously superior to the traditional polylactic acid material in comparative example 1, and thus, the sheets prepared in examples 1-3 have excellent degradability; the sheets of examples 1 to 3 have good tensile strength, bending strength and impact strength, which shows that the sheets prepared by examples 1 to 3 have excellent mechanical strength and flexibility; the contact angle of the sheet in the examples 1 to 3 is less than 90 degrees, which shows that the sheet prepared by the examples 1 to 3 has better hydrophilicity, and the polylactic acid has good compatibility with other raw materials in the preparation process.
Compared with example 4, the bending strength and the impact strength of the sheet material in example 4 are obviously improved, the contact angle of the sheet material is obviously reduced, and the biodegradation rate is improved, which shows that the flexibility, the hydrophilicity and the biodegradation rate of the sheet material can be obviously improved by preprocessing polylactic acid before mixing.
In comparative example 2, the biocompatible agent and the biological toughening agent were replaced with the same amount of polylactic acid; the sheet of comparative example 2 was significantly deteriorated in bending strength and impact strength and increased in contact angle compared to example 1, indicating that the addition of the biocompatible and biological toughening agents can improve flexibility and hydrophilicity of the sheet.
Comparative example 3 the poly (butylene succinate) is replaced by the same amount of polylactic acid, and the biological flexibilizer is replaced by the same amount of polylactic acid; compared with example 1, the sheet material in comparative example 3 has obviously poor bending strength and impact strength, which shows that the flexibility of the sheet material can be obviously improved by adding the polybutylene succinate and the biological toughening agent.
In step ② of S1 of comparative example 4, the ethylene-butyl acrylate-glycidyl methacrylate copolymer, sodium lauroyl sarcosinate, and dodecyl glucoside were not added, and the bending strength and the impact strength were significantly deteriorated and the contact angle was significantly increased in comparative example 4 as compared to example 4, indicating that the flexibility and the hydrophilicity of the sheet material were improved by adding the ethylene-butyl acrylate-glycidyl methacrylate copolymer, sodium lauroyl sarcosinate, and dodecyl glucoside.
In the ② of S1 in comparative example 5, polyethylene glycol-10000, sodium lauroyl sarcosinate and dodecyl glucoside are not added, and the bending strength and the impact strength are remarkably deteriorated and the contact angle is remarkably increased in comparative example 5 as compared with example 4, which shows that the addition of polyethylene glycol-10000, sodium lauroyl sarcosinate and dodecyl glucoside can remarkably improve the flexibility and hydrophilicity of the sheet material.
In the raw materials of the comparative example 6, the biocompatible agent and the biological toughening agent are replaced by the same amount of polylactic acid; compared with example 4, the bending strength and the impact strength of comparative example 6 are obviously poor, and the contact angle is obviously increased, which shows that the addition of the biocompatible agent and the biological toughening agent can improve the flexibility and the hydrophilicity of the sheet material.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A fully biodegradable sheet characterized by: the paint comprises the following components in parts by weight: 70-80 parts of polylactic acid, 10-20 parts of poly butylene succinate, 4-6 parts of a biocompatible agent, 2-4 parts of a biological toughening agent, 0.8-1 part of a slipping agent, 0.8-1.2 parts of calcium carbonate and 0.08-0.12 part of an antioxidant;
the biological compatilizer is styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer;
the biological toughening agent is vinyl acetate-ethylene-vinyl ester copolymer.
2. The fully biodegradable sheet according to claim 1, characterized in that: the paint comprises the following components in parts by weight: 75 parts of polylactic acid, 15 parts of poly butylene succinate, 5 parts of a biological compatilizer, 3 parts of a biological toughening agent, 0.9 part of a slipping agent, 1 part of calcium carbonate and 0.1 part of an antioxidant;
the biological compatilizer is styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer;
the biological toughening agent is vinyl acetate-ethylene-vinyl ester copolymer.
3. The fully biodegradable sheet according to claim 1, wherein the polylactic acid is pre-treated before use, wherein ① comprises 8910-15 parts by weight of low molecular weight polyethylene glycol and 1-1.5 parts by weight of stannous octoate catalyst, the mixture is melt blended for 8-10 hours at a temperature of 155-165 ℃ to obtain hydroxyl terminated modified polylactic acid, ② comprises 30-40 parts by weight of high molecular weight polyethylene glycol, 6-8 parts by weight of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 3-5 parts by weight of amino acid type surfactant and 3-5 parts by weight of dodecyl glucoside, the mixture is melt blended for 1-2 hours at a temperature of 180-190 ℃, and the product is obtained by extrusion and granulation.
4. The biodegradable sheet according to claim 3, wherein the low molecular weight polyethylene glycol in step ① is PEG-400 or PEG-600, and the high molecular weight polyethylene glycol in step ② is PEG-10000.
5. The fully biodegradable sheet according to claim 3, characterized in that: the amino acid type surfactant is one or a compound of sodium lauroyl sarcosinate and sodium lauroyl glutamate.
6. The fully biodegradable sheet according to claim 1, characterized in that: the slipping agent is prepared by mixing ethylene bis-oleamide and rice bran wax in a weight ratio of 1: 1.
7. The biodegradable sheet according to claim 1, wherein the antioxidant is one or a combination of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
8. A method for preparing a fully biodegradable sheet according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
s1, mixing materials: taking polylactic acid, poly (butylene succinate), a biological compatilizer, a biological toughening agent, a slipping agent, calcium carbonate and an antioxidant, and stirring at a high speed for 10-20min under the conditions that the temperature is 60-80 ℃ and the stirring speed is 1000-2000r/min to obtain a mixture;
s2, plasticizing and forming: and putting the mixture into a sheet extruder, and melting and extruding at the temperature of 140-220 ℃ to obtain the fully biodegradable sheet.
9. The preparation method of the fully biodegradable sheet according to claim 8, wherein the polylactic acid of S1 is pretreated before mixing, wherein ① parts by weight of low molecular weight polyethylene glycol and 1-1.5 parts by weight of stannous octoate catalyst are added to 100 parts by weight of the polylactic acid, and melt blending is carried out at the temperature of 155-165 ℃ for 8-10h to obtain hydroxyl terminated modified polylactic acid, ② parts by weight of high molecular weight polyethylene glycol, 6-8 parts by weight of ethylene-butyl acrylate-glycidyl methacrylate copolymer, 3-5 parts by weight of amino acid type surfactant and 3-5 parts by weight of dodecyl glucoside are added to the hydroxyl terminated polylactic acid, and melt blending is carried out at the temperature of 180-190 ℃ for 1-2h, and then extrusion and granulation are carried out.
10. The method for preparing a fully biodegradable sheet according to claim 8, wherein the method comprises the following steps: the temperatures of the respective zones of the sheet extruder of S2 were: the temperature of the first zone is 180-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911371367.3A CN111040400A (en) | 2019-12-27 | 2019-12-27 | Full-biodegradable sheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911371367.3A CN111040400A (en) | 2019-12-27 | 2019-12-27 | Full-biodegradable sheet and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111040400A true CN111040400A (en) | 2020-04-21 |
Family
ID=70240306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911371367.3A Withdrawn CN111040400A (en) | 2019-12-27 | 2019-12-27 | Full-biodegradable sheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111040400A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732820A (en) * | 2020-07-13 | 2020-10-02 | 滁州睿兴高分子材料有限公司 | Degradable thermoplastic elastomer composite material and preparation method thereof |
| CN111995848A (en) * | 2020-08-13 | 2020-11-27 | 联泓(江苏)新材料研究院有限公司 | Degradable plastic composition and preparation method and application thereof |
| CN112210200A (en) * | 2020-10-29 | 2021-01-12 | 银金达(上海)新材料有限公司 | Environment-friendly PLA (polylactic acid) film material and application thereof |
| CN112662153A (en) * | 2020-12-23 | 2021-04-16 | 广州赢盛塑料制品有限公司 | Environment-friendly degradable packaging bottle and preparation method thereof |
| CN113789038A (en) * | 2021-09-26 | 2021-12-14 | 厦门市均诚塑胶科技有限公司 | Naturally degradable plastic bag and production process thereof |
| CN114410085A (en) * | 2022-01-13 | 2022-04-29 | 江苏斯尔邦石化有限公司 | Full-biodegradable toughened plasticized polyglycolic acid material and preparation method thereof |
| CN114561065A (en) * | 2021-12-15 | 2022-05-31 | 金发科技股份有限公司 | Polypropylene composite material with biological inductivity and preparation method and application thereof |
| CN114752198A (en) * | 2022-05-13 | 2022-07-15 | 南京工业大学 | High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof |
| CN115521595A (en) * | 2022-09-26 | 2022-12-27 | 浙江播下环保科技有限公司 | Material for leakage-proof lunch box cover and preparation method thereof |
| CN115536999A (en) * | 2022-11-02 | 2022-12-30 | 贵州省材料产业技术研究院 | High-barrier antibacterial biodegradable material and preparation method and application thereof |
| CN115873341A (en) * | 2022-10-19 | 2023-03-31 | 广州悦清再生医学科技有限公司 | Hydrophilic modified toughened polypropylene material and application thereof in preparation of amnioscope |
| WO2023092548A1 (en) * | 2021-11-26 | 2023-06-01 | 安徽江南医疗器械股份有限公司 | Preparation method for disposable infusion hose capable of being completely biodegraded |
| CN116925510A (en) * | 2023-09-12 | 2023-10-24 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
-
2019
- 2019-12-27 CN CN201911371367.3A patent/CN111040400A/en not_active Withdrawn
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732820A (en) * | 2020-07-13 | 2020-10-02 | 滁州睿兴高分子材料有限公司 | Degradable thermoplastic elastomer composite material and preparation method thereof |
| CN111995848A (en) * | 2020-08-13 | 2020-11-27 | 联泓(江苏)新材料研究院有限公司 | Degradable plastic composition and preparation method and application thereof |
| CN112210200A (en) * | 2020-10-29 | 2021-01-12 | 银金达(上海)新材料有限公司 | Environment-friendly PLA (polylactic acid) film material and application thereof |
| CN112662153A (en) * | 2020-12-23 | 2021-04-16 | 广州赢盛塑料制品有限公司 | Environment-friendly degradable packaging bottle and preparation method thereof |
| CN113789038A (en) * | 2021-09-26 | 2021-12-14 | 厦门市均诚塑胶科技有限公司 | Naturally degradable plastic bag and production process thereof |
| CN113789038B (en) * | 2021-09-26 | 2023-10-10 | 厦门市均诚塑胶科技有限公司 | Natural degradable plastic bag and production process thereof |
| WO2023092548A1 (en) * | 2021-11-26 | 2023-06-01 | 安徽江南医疗器械股份有限公司 | Preparation method for disposable infusion hose capable of being completely biodegraded |
| CN114561065A (en) * | 2021-12-15 | 2022-05-31 | 金发科技股份有限公司 | Polypropylene composite material with biological inductivity and preparation method and application thereof |
| CN114410085B (en) * | 2022-01-13 | 2023-08-15 | 江苏斯尔邦石化有限公司 | Full-biodegradation toughened plasticized polyglycolic acid material and preparation method thereof |
| CN114410085A (en) * | 2022-01-13 | 2022-04-29 | 江苏斯尔邦石化有限公司 | Full-biodegradable toughened plasticized polyglycolic acid material and preparation method thereof |
| CN114752198A (en) * | 2022-05-13 | 2022-07-15 | 南京工业大学 | High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof |
| CN115521595A (en) * | 2022-09-26 | 2022-12-27 | 浙江播下环保科技有限公司 | Material for leakage-proof lunch box cover and preparation method thereof |
| CN115521595B (en) * | 2022-09-26 | 2024-03-12 | 浙江播下环保科技有限公司 | Material for leakage-proof lunch box cover and preparation method thereof |
| CN115873341A (en) * | 2022-10-19 | 2023-03-31 | 广州悦清再生医学科技有限公司 | Hydrophilic modified toughened polypropylene material and application thereof in preparation of amnioscope |
| CN115873341B (en) * | 2022-10-19 | 2024-02-20 | 广州悦清再生医学科技有限公司 | Hydrophilic modified toughened polypropylene material and application thereof in preparation of amniotic mirror |
| CN115536999A (en) * | 2022-11-02 | 2022-12-30 | 贵州省材料产业技术研究院 | High-barrier antibacterial biodegradable material and preparation method and application thereof |
| CN116925510A (en) * | 2023-09-12 | 2023-10-24 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
| CN116925510B (en) * | 2023-09-12 | 2023-12-29 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111040400A (en) | Full-biodegradable sheet and preparation method thereof | |
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| CN101475735B (en) | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy | |
| CN111073239A (en) | High-temperature-resistant polylactic acid injection-molded porcelain-like tableware and preparation method thereof | |
| CN101205356A (en) | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid | |
| CN101525487B (en) | Composite material degraded by environment and preparation method thereof | |
| US20200048436A1 (en) | Hydrophobic thermoplastic starch composite and method for manufacturing the same | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| CN113845621B (en) | Compatibilizer and high-starch-content full-biodegradable film adopting compatibilizer | |
| CN103087484A (en) | Biodegradable composite film material of controllable degradation rate and preparation method thereof | |
| CN107603168B (en) | Polylactic acid-based film and preparation method thereof | |
| CN101983986B (en) | Transparent and toughening polylactic acid resin and method for preparing the same | |
| CN113337088B (en) | Preparation method of composite degradable plastic material for injection molding | |
| CN114889285A (en) | Low-temperature heat-sealing biodegradable composite film and preparation process thereof | |
| CN105542365A (en) | Modified PVA composite packaging film and preparation method thereof | |
| CN111907031B (en) | PLA/PBAT film, preparation method and application | |
| CN113956630A (en) | Completely biodegradable film and preparation method thereof | |
| CN111944285A (en) | Polylactic acid composition, toughened transparent material and preparation method thereof | |
| CN113045881A (en) | Thermal-shrinkage degradable environment-friendly film material and preparation method and application method thereof | |
| CN103224697B (en) | PHA/PCL blend of a kind of fully biodegradable and preparation method thereof | |
| CN109504042A (en) | PHA modified TPS/PBAT biodegradable resin and preparation method thereof | |
| CN112341766A (en) | Fully-degradable bio-based composite material product and preparation method thereof | |
| CN115594957B (en) | High-barrier degradable material, high-barrier degradable film and preparation method thereof | |
| CN114031914A (en) | Bio-based plastic uptake material and preparation method thereof | |
| US20230303829A1 (en) | Biodegradable material, preparation method and application thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200421 |