CN115403902B - Biodegradable material and preparation method thereof - Google Patents

Biodegradable material and preparation method thereof Download PDF

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Publication number
CN115403902B
CN115403902B CN202211186367.8A CN202211186367A CN115403902B CN 115403902 B CN115403902 B CN 115403902B CN 202211186367 A CN202211186367 A CN 202211186367A CN 115403902 B CN115403902 B CN 115403902B
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biodegradable
edge sealing
biodegradable material
polylactic acid
material according
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CN115403902A (en
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陈业中
陈平绪
叶南飚
曾祥斌
焦建
麦开锦
董学腾
杨晖
熊凯
李岩
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Zhuhai Jinfa Biomaterials Co ltd
Kingfa Science and Technology Co Ltd
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Zhuhai Jinfa Biomaterials Co ltd
Kingfa Science and Technology Co Ltd
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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • 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
    • C08J2367/02—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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention discloses a biodegradable material and a preparation method thereof, belonging to the field of degradable materials. The biodegradable material provided by the invention is matched with the flexible biodegradable polyester through polylactic acid, has good mechanical strength under the condition of not introducing a non-degradable material, is very suitable for preparing the biodegradable edge sealing bag, and meanwhile, the product effectively solves the delayed edge sealing failure phenomenon of the existing edge sealing bag product, and the delayed edge sealing strength of the prepared biodegradable edge sealing bag can reach more than 70% of the initial edge sealing strength. The invention also discloses a preparation method of the biodegradable material and a biodegradable edge sealing bag prepared by the biodegradable material, and the biodegradable edge sealing bag has good edge sealing performance, high degradability and high mass production cost performance, and can completely replace the existing commercial products of the same type.

Description

Biodegradable material and preparation method thereof
Technical Field
The invention relates to the field of degradable materials, in particular to a biodegradable material and a preparation method thereof.
Background
The edge sealing bags have the characteristics that edge sealing lines are attractive compared with the traditional heat sealing edges, bag making efficiency is high, leftover materials are few, the edge sealing bags are widely applied to packaging in multiple fields such as clothing, tea drinks and express logistics, however, the main body of the existing edge sealing bag materials is PE (polyethylene) and other traditional olefin plastics, the traditional petroleum-based plastics do not have biodegradation characteristics, the use amount of the edge sealing bags is increased along with packaging, the edge sealing bags are mostly disposable, the express edge sealing bags are taken as an example, the edge sealing bags are discarded after being generally used, and various components such as a face sheet, glue and ink are arranged on the surface of the edge sealing bags, so that the recycling difficulty is high, and the problem of ecological pollution is easily caused if the edge sealing bags are not treated in time. On the other hand, studies have been made on biodegradable special materials for special edge sealing bags, which have not only biodegradability but also excellent edge sealing properties. However, the conventional process in the prior art of edge sealing bags sequentially comprises the steps of firstly blowing films to roll, placing in a warehouse, and cutting bags at intervals of about one week. The biodegradable materials are often subjected to natural placement for a period of time after film blowing and then bag cutting, so that the problem of edge sealing brittleness, namely the delayed edge sealing failure phenomenon, seriously affects the use and popularization of the materials and the prepared products.
CN105416797a discloses a processing technology of a three-layer blown film for degrading express bags, which takes PLA, PBAT or PBS as raw materials to directly add color master batch and tackifier, or add filler to modify to improve degradability, but the scheme is mainly researched aiming at the preparation technology, and the added tackifier EAA ethylene-acrylic acid copolymer is a non-degradable material, so that microplastic is still easy to remain, the problem of environmental pollution cannot be solved, and meanwhile, whether the product has delayed edge sealing failure phenomenon is not discussed in the technical scheme.
CN110091564a discloses an edge sealing bag material and a preparation method thereof, the technical scheme is that the composite structure with a three-layer film blowing mode and a PLA outer layer and a PBAT inner layer is designed to achieve ideal performance, however, the inner layer and the outer layer of the composite structure are connected by using polyurethane adhesive, and the adhesive is not a biodegradable material. Meanwhile, the solution is not provided for the delayed edge seal failure phenomenon of the product.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the biodegradable material, and the product has good mechanical strength under the condition of not introducing non-degradable materials by matching polylactic acid with flexible biodegradable polyester, so that the biodegradable material is very suitable for preparing biodegradable edge sealing bags, and meanwhile, the product effectively solves the time delay failure phenomenon and has high time delay strength.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the biodegradable material comprises the following components in parts by weight:
60-90 parts of biodegradable polyester, 2-20 parts of polylactic acid and 2-30 parts of filling material;
the molar content of D-lactic acid in the polylactic acid is 3-15%, and the melt index of the polylactic acid under the load of 2.16kg at 190 ℃ according to ISO 1133-2011 is 1-30 g/10min; the particle size D50 of the filler is less than or equal to 5 mu m.
The polylactic acid is poly L-lactic acid/poly D-lactic acid copolymer, and the molar content of D-lactic acid in the polylactic acid is measured according to the following test mode:
polylactic acid samples were degraded by transesterification with methanol at 150℃in a pressure vessel and analyzed by gas chromatography, wherein the content of D-lactic acid in the polylactic acid was calculated from the ratio of the sum of the peak areas of L-and D-methyl lactate to the peak area of D-methyl lactate, and the specific formula was as follows:
for each GC run, the D-lactic acid content of the sample solution was calculated as follows:
A DML : d-methyl lactate peak area;
A LML : l-methyl lactate peak area;
the average D-lactic acid content of the sample solution was calculated from the obtained single-value D-lactic acid content. The content of D-lactic acid in the PLA sample is reported as the average of the D-lactic acid content found in all sample solutions prepared from the PLA sample.
According to the definition of DIN EN 13432, in general, a material, i.e. a material which is said to be biodegradable, has at least a portion of its mass content, said degradation occurring by enzymatic, hydrolytic or oxidative means and/or by exposure to electromagnetic radiation, such as ultraviolet radiation, most often by exposure to microorganisms, such as bacteria, yeasts, fungi and algae. In order to meet the requirements, some common biodegradable materials such as polylactic acid, polybutylene adipate terephthalate and the like are adopted in the prior art, however, the materials have low strength and large compatibility difference, and on the premise of not introducing additional function strengthening auxiliary agents, the product has poor edge sealing performance when being used as an edge sealing bag, and can also have delayed edge sealing failure. On the basis, the biodegradable material disclosed by the invention takes biodegradable polyester as a main body, and is matched with polylactic acid with the D-lactic acid molar content of more than or equal to 3% and moderate melt index and proper filling materials, so that good biodegradability can be realized, meanwhile, the mechanical strength is higher, after the biodegradable material is naturally placed, the product is obviously improved due to the fact that the compatibility of each component is high, the stability is strong and the delayed failure phenomenon is obviously improved, and when the biodegradable material is used as an edge sealing bag for testing, the edge sealing strength after being naturally placed for a plurality of days can still be kept in a considerable range.
In general, polylactic acid (PLA) is at least one of poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), racemic polylactic acid (PDLLA) and non-optically active polylactic acid (M-PLA), and many of the polylactic acids in the existing degradable materials are mainly PLLA, PDLA or PLLA/PDLA copolymers thereof, and have ideal mechanical strength and degradability, and the inventor finds that when the D-lactic acid content in the polylactic acid is low, the continuity is poor when the D-lactic acid content in the polylactic acid is combined with the biodegradable polyester, the compatibility is poor, not only the mechanical properties are affected, but also defects in the system are gradually increased when the prepared product is naturally placed, so that a significant time-delay failure phenomenon easily occurs to the product, but also the compatibility problem occurs when the content is too high, and the mobility of the polylactic acid itself is too low or too high, the properties of the product during processing and the stability of the continuous phase after processing are directly influenced, and when the D-lactic acid molar content in the polylactic acid is 3-15%, and the melt index is 1-30 g/10min, and the continuous phase of the polylactic acid has high mechanical strength and the continuous phase stability.
On the other hand, the mechanical strength of the biodegradable material can be effectively improved by introducing the filler into the biodegradable material, but because the component is difficult to melt into the system in the processing stage of the product, the inevitable compatibility difference exists between the biodegradable polyester and the polylactic acid, and meanwhile, if the particles of the filler are larger, the continuity of the product is directly deteriorated, the macroscopic use strength is weakened, and meanwhile, the stability of the product system is further reduced, so that the delayed failure phenomenon occurs, so that the inventor finds that only the particle size D50 of the filler is limited to be less than or equal to 5 mu m, and the product can ensure the expected technical effect.
Preferably, the biodegradable material comprises the following components in parts by weight:
80-90 parts of biodegradable polyester, 3-8 parts of polylactic acid and 2-15 parts of filling materials.
The inventor tests show that the product has better comprehensive performance and less filler in the preferred range.
Preferably, the molar content of D-lactic acid in the polylactic acid is 9-12%, and the melt index under the load of 2.16kg at 190 ℃ according to ISO 1133-2011 is 3-10 g/10min.
Through experimental screening of the inventor, the biodegradable material prepared by selecting the polylactic acid in the preferable range has the best mechanical property and time-delay edge sealing strength when an edge sealing test is carried out.
Preferably, the biodegradable polyester comprises at least one of polybutylene adipate terephthalate (PBAT), polybutylene sebacate terephthalate (PBSeT), polyhydroxyalkanoate (PHBV), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene adipate succinate (PBSA).
More preferably, the biodegradable polyester is at least one of polybutylene adipate terephthalate, polybutylene sebacate terephthalate, polybutylene succinate, and polybutylene adipate succinate.
More preferably, the biodegradable polyester is at least one of polybutylene adipate terephthalate, polybutylene sebacate terephthalate, polybutylene adipate succinate.
Polybutylene adipate-terephthalate has good heat resistance and processability, good compatibility with other polyesters when matched, and high degradability, and the component can realize self-decomposition at a certain temperature; polybutylene sebacate is copolyester obtained by esterification and polycondensation of sebacic acid, terephthalic acid and butanediol serving as monomers, and has adjustable thermal performance, mechanical performance and degradation performance due to the difference of raw material proportions, and has wide collocation range and high compatibility with polylactic acid when being used as main polyester; the polybutylene adipate succinate has high degradability. Through the screening of the inventor, when the mass content of the polybutylene adipate terephthalate, the polybutylene sebacate terephthalate and the polybutylene adipate succinate in the biodegradable polyester reaches more than 50%, the product has high mechanical strength and high stability, and even if the product is naturally placed for edge sealing for a long time, the delayed edge sealing failure degree is low.
Preferably, the filler has a particle size d50=1 to 5 μm.
Preferably, the filler is at least one of an organic filler and an inorganic filler.
More preferably, the organic filler is at least one of starch, starch master batch, cellulose fiber and wood powder; the inorganic filler is at least one of talcum powder, calcium carbonate, silicon dioxide, montmorillonite, kaolin, chalk, graphite, gypsum, carbon black, calcium chloride, ferric oxide, dolomite, wollastonite, titanium dioxide, mica and glass fiber.
The particle size D50 of the inorganic filler is measured by the following method:
and (3) placing the biodegradable material sample in a muffle furnace, burning for 30min at 850 ℃, obtaining the residue which is the inorganic filler, washing and drying the inorganic filler by adopting an ethanol solvent, and directly measuring and counting by adopting a laser particle analyzer.
Preferably, the filler is starch.
More preferably, the starch in the filling is added in the form of starch master batches.
Compared with common polyester/polymer organic master batches, the starch master batches have excellent degradability, are generally prepared by taking starch (most corn starch) as a main body and adding a solvent, a compatilizer and a degradable binder, and in the biodegradable material, the inventor finds that compared with inorganic mineral fillers, the compatibility of the organic fillers with biodegradable polyesters and polylactic acid is higher, and in the organic fillers, the use cost performance of the starch is higher, meanwhile, because the starch master batches are subjected to a similar plasticizing preparation process, the system phase continuity is higher, the viscosity is higher, and compared with the combination strength of organic substances of other systems such as cellulose fibers, polyester particles and the like with the biodegradable polyesters and polylactic acid, the obtained product has higher mechanical strength and also has higher delay strength.
More preferably, the starch master batch is prepared from the raw materials including starch, a solvent, a binder and a compatilizer, wherein the mass content of the starch is 80-90%.
It should be noted that the starch master batch of the present invention may be self-made products, or may be common commercial products purchased directly, and the solvents, binders and compatilizers used in the starch master batch may be conventional types, and the main effects of the starch master batch are derived from the starch itself, so long as similar effects can be achieved.
Preferably, the biodegradable material further comprises 0 to 0.95 parts of a processing aid.
More preferably, the processing aid is at least one of a lubricant, an opening agent, a plasticizer, a nucleating agent, and a chain extender.
The compatibility of each component in the product can be higher by proper processing aid, and the mechanical strength is better when the product is used, but because the general processing aid is mostly small molecular compounds, excessive introduction is not needed.
The invention also aims at providing a preparation method of the biodegradable material, which comprises the following steps:
and (3) uniformly mixing the components, and then, putting the mixture into a double-screw extruder for melt extrusion granulation to obtain the biodegradable material.
The preparation method of the biodegradable material has simple operation steps and can realize industrialized mass production.
Preferably, the temperature of the twin-screw extruder is set to 130-220 ℃, the rotating speed is set to 200-400 rpm, and the feeding rate is set to 400-1200 kg/h during the melt extrusion granulation.
It is a further object of the present invention to provide a biodegradable edge-sealing bag prepared from the biodegradable material of the present invention.
The biodegradable edge sealing bag prepared by the biodegradable material has standard biodegradability, high edge sealing strength and delayed edge sealing strength, simple preparation process and wide application range.
Preferably, the preparation method of the biodegradable edge sealing bag comprises the following steps:
(1) Drying the biodegradable material and controlling the moisture content to be less than 500 ppm;
(2) And (3) carrying out film blowing treatment on the dried biodegradable material to obtain a biodegradable film, and then transferring the biodegradable film to an edge sealing machine for edge sealing treatment to obtain the biodegradable edge sealing bag.
Preferably, the temperature of the film blowing treatment in the step (2) is 130-180 ℃, and the width of the obtained biodegradable film is 250-350 mm and the thickness is 20-80 mu m.
Preferably, the temperature of the edge sealing treatment in the step (2) is 200-450 ℃.
The biodegradable material provided by the invention has the beneficial effects that the polylactic acid and the flexible biodegradable polyester are matched, so that the biodegradable material has good mechanical strength under the condition of not introducing a non-degradable material, is very suitable for preparing the biodegradable edge sealing bag, and meanwhile, the product effectively solves the delayed edge sealing failure phenomenon of the existing edge sealing bag product, and the delayed edge sealing strength of the prepared biodegradable edge sealing bag can reach more than 70% of the initial edge sealing strength. The invention also provides a preparation method of the biodegradable material and the prepared biodegradable edge sealing bag, and the biodegradable edge sealing bag has good edge sealing performance, high degradability and high mass production cost performance, and can completely replace the existing commercial products of the same type.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments designed for the implementation of the invention are common reagents and instruments unless otherwise specified.
Examples 1 to 14
In the examples of the biodegradable material and the preparation method thereof according to the present invention, the composition of the biodegradable material is shown in table 1.
TABLE 1
Comparative examples 1 to 6
Each comparative example product differs from the examples only in the components, and the component ingredients of the comparative example product are shown in table 2.
TABLE 2
The components are in parts by weight Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Biodegradable polyester 1 90 90 90 90 90 90
Polylactic acid 1 8
Polylactic acid 6 8
Polylactic acid 7 8
Polylactic acid 8 8
Polylactic acid 9 8
Polylactic acid 10 8
Filler 1 1 1 1 1 1 1
Filler 2 1 1 1 1 1
Filling material 5 1
Processing aid 0.95 0.95 0.95 0.95 0.95 0.95
The raw materials used in each example and comparative example are as follows:
biodegradable polyester 1: PBAT, manufactured by zhuhai gold hair biomaterial limited, a400;
biodegradable polyester 2: PBSeT, manufactured by Pinctada Margaritifera biological materials Co., ltd., A300;
biodegradable polyester 3: PCL, ingeCity, england, capa6500D;
polylactic acid 1: PLLA/PDLA copolymer, produced by Nature works, PLA 4060D, D-lactic acid molar content of 10% and melt index of 5g/10min under 2.16kg load at 190℃according to ISO 1133-2011;
polylactic acid 2: PLLA/PDLA copolymer, produced by Prague, having a molar content of LX930, D-lactic acid of 9% and a melt index of 8g/10min at 190℃under a load of 2.16kg according to ISO 1133-2011;
polylactic acid 3: PLLA/PDLA copolymer, produced by Nature works, 752-27, produced by Prague, LX975, molar content of D-lactic acid 12%, melt index of 4g/10min under 2.16kg load at 190℃according to ISO 1133-2011;
polylactic acid 4: PLLA/PDLA copolymer, produced by Nature works, PLA 4043D, D-lactic acid molar content of 4% and melt index of 4g/10min under 2.16kg load at 190℃according to ISO 1133-2011;
polylactic acid 5: PLLA/PDLA copolymer, produced by Anhuifeng, FY212, molar content of D-lactic acid 15%, melt index of 30g/10min under 2.16kg load at 190℃according to ISO 1133-2011;
polylactic acid 6: PLLA/PDLA copolymer, produced by Nature works, PLA 4032D, D-lactic acid molar content of 1%, melt index at 190℃under 2.16kg load of 2g/10min according to ISO 1133-2011;
polylactic acid 7: PLLA/PDLA copolymer, produced by Nature works, 752-27, having a D-lactic acid molar content of 20% and a melt index of 20g/10min under a load of 2.16kg at 190℃according to ISO 1133-2011;
polylactic acid 8: PLLA, self-made, is prepared by using pure L-lactide, dissolving the pure L-lactide in hexanediol, adding stannous octoate, carrying out ring-opening polymerization, firstly reacting for 3-5 hours at the reaction temperature of 120-150 ℃ and the reaction pressure of 1000-1500 pa, and then reacting for 4-6 hours at the reaction temperature of 160-180 ℃ and the reaction pressure of 50-500 pa to obtain polymer solid. Reflux-dissolving the polymer solid with 5wt% chloroform, filtering the solution, precipitating with ethanol, wherein the volume ratio of ethanol to chloroform is 5:1, and obtaining white flocculent precipitate, wherein the molar content of D-lactic acid is 0%, and the melt index under 2.16kg load is 4.5g/10min at 190 ℃ according to ISO 1133-2011.
Polylactic acid 9: PDLA, self-made, is prepared by using pure D lactide, dissolving the pure D lactide in hexanediol, adding stannous octoate, carrying out ring-opening polymerization, reacting for 3-5 hours at the reaction temperature of 120-150 ℃ and the reaction pressure of 1000-1500 pa, and then reacting for 4-6 hours at the reaction temperature of 160-180 ℃ and the reaction pressure of 50-500 pa to obtain polymer solid. Reflux-dissolving the polymer solid with 5wt% chloroform, filtering the solution, precipitating with ethanol, wherein the volume ratio of ethanol to chloroform is 5:1, and obtaining white flocculent precipitate, wherein the molar content of D-lactic acid is 100%, and the melt index under 2.16kg load is 4g/10min at 190 ℃ according to ISO 1133-2011.
Polylactic acid 10: PDLLA is prepared by self-making, DL lactide with the content of 10% D is dissolved in hexanediol, stannous octoate is added for ring-opening polymerization, the reaction is carried out for 2-3 hours at the reaction temperature of 120-150 ℃ and the reaction pressure of 1000-1500 pa, and then the reaction is carried out for 3-4 hours at the reaction temperature of 160-180 ℃ and the reaction pressure of 50-500 pa, so that polymer solid is obtained. And (3) refluxing and dissolving the polymer solid by using 5wt% chloroform, filtering the solution, and precipitating by using ethanol, wherein the volume ratio of the ethanol to the chloroform is 5:1, so that white flocculent precipitate is obtained. The molar D-lactic acid content of the PDLLA obtained was tested to be 9.4% and the melt index according to ISO 1133-2011 at 190℃under a load of 2.16kg was 38.9g/10min.
Filler 1: talcum powder, liaoning Ai Hai Talc Co., ltd., HTPU, D50 of 1.5 μm;
filling material 2: calcium carbonate, manufactured by omega, 1T-JI, D50 of 2 μm;
and (3) filling material: starch master batch, produced by Shandong Shouguang Co., ltd., TPS-A3, wherein the starch mass content is 85%, and D50 is 2.5 μm after screening;
filling material 4: corn starch, produced by Shandong Shouguang, is selected to have D50 of 2 μm;
and (2) filling material 5: calcium carbonate, manufactured by omega, 5T-JI, D50 of 6 μm;
processing aid: commercially available lubricants, nucleating agents and chain extenders are formulated in a mass ratio of 1:1:1.
The starting materials used in each of the examples and comparative examples were the same as those used in the parallel experiments except for the above specific description.
The preparation method of the biodegradable material comprises the following steps:
and (3) uniformly mixing the components, and then, putting the mixture into a double-screw extruder for melt extrusion granulation to obtain the biodegradable material.
The temperature of the double-screw extruder is set to be 150-200 ℃ during the melt extrusion granulation, the rotating speed is set to be 300rpm, and the feeding speed is set to be 800kg/h.
The products of each example and comparative example were further prepared into biodegradable edge-sealing bags, the preparation method of which comprises the steps of:
(1) Drying the biodegradable material and controlling the moisture content to be within 500 ppm;
(2) Blowing the dried biodegradable material to obtain a biodegradable film, and then transferring the biodegradable film to an edge sealing machine for edge sealing treatment to obtain the biodegradable edge sealing bag;
the temperature of the film blowing treatment in the step (2) is 130-160 ℃, and the width of the obtained biodegradable film is 300mm and the thickness is 60 mu m; the edge sealing treatment is at a temperature of 350 ℃.
And (3) detecting the particle size of the filling material of each prepared biodegradable material, wherein the D50 of the filling material in each product except the product obtained in the comparative example 5 is less than 5 mu m.
Effect example 1
In order to verify the use effect of the biodegradable edge sealing bag prepared by the biodegradable material, the mechanical property test and the edge sealing strength test are carried out on the products of each example and the comparative example, and the test method comprises the following steps:
(1) Tensile strength (elongation) test: according to GB/T1040.3-2006 standard, the test temperature is 23+/-2 ℃, the humidity is 50+/-5 RH%, and the stretching rate is 500mm/min;
(2) Edge seal strength test: the initial edge seal strength was first tested according to the QB/T2358-1998 standard, followed by natural placement of 7d/14d/21d in a standard environment (23.+ -. 2 ℃ C., 50.+ -. 5% RH) using the same procedure.
The test results are shown in tables 3 to 4.
TABLE 3 Table 3
TABLE 4 Table 4
Experimental results Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Tensile Strength (longitudinal/MPa) 22.3 17.3 19.9 19.3 25.3 15.6
Tensile Strength (transverse/MPa) 20.4 15.5 18.7 18.3 23.4 13.4
Elongation (longitudinal/%) 332 354 204 198 298 310
Elongation (transverse/%) 425 478 288 267 368 428
Initial edge seal strength (N/15 mm) 13.8 11.2 8.1 8.3 13.2 11.9
7d edge seal strength (N/15 mm) 7.5 7.6 5.0 5.1 11.6 10.5
14d edge seal strength (N/15 mm) 5.1 4.1 3.0 3.4 8.2 8.6
21d edge seal strength (N/15 mm) 4.1 3.3 1.8 1.9 5.5 5.1
As can be seen from tables 3 and 4, the biodegradable materials obtained in each example are excellent in performance, the longitudinal and transverse tensile strengths of the prepared biodegradable edge sealing bags can reach more than 15MPa, the longitudinal and transverse elongations can reach more than 400%, the service performance is good, the initial edge sealing strength can reach more than 5N/15mm (almost 10N/15 mm) when the edge sealing strength test is carried out, the edge sealing strength of the product can still be kept to be more than 50% of the initial edge sealing strength after 21 days of natural standing, and the delayed edge sealing failure phenomenon is remarkably improved. It can be seen from examples 1, examples 6 to 9 and comparative examples 1 to 4 that the type of polylactic acid has a direct effect on the properties of the biodegradable material, and the products of comparative examples 3 and 4 using unsuitable polylactic acid types cannot achieve the desired mechanical strength, edge seal strength and delayed edge seal strength, while the products of comparative examples 1 and 2 have a low or high D-lactic acid content of polylactic acid, so that the continuous property of the products is reduced or an incompatibility phenomenon occurs during the preparation process, and the properties of the products are impaired. The difference of the properties of the polylactic acid can also directly influence the mechanical strength and the edge sealing performance of the product, and the prepared product has better performance when the D-lactic acid content in the polylactic acid is 3-15% and the melt index under the load of 2.16kg at 190 ℃ is 1-30 g/10min after screening. From the comparison of the properties of the products of examples 1 and 10-12 and comparative example 5, the fillers in the components of the products also affect the continuity, and finally cause the difference of the mechanical strength and edge seal strength of the products, and among the types of fillers, the starch master batch has the best use effect, however, the particle size of the fillers must be strictly controlled, if the product of comparative example 5 uses fillers with large particle size, the edge seal strength of the product is lower, and the obvious delayed edge seal failure phenomenon occurs. In addition, the biodegradable materials prepared in each embodiment are mostly degradable materials, and the content ratio of part of inorganic filling materials also completely accords with DIN EN 13432 definition standard.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (11)

1. The biodegradable material is characterized by comprising the following components in parts by weight:
80-90 parts of biodegradable polyester, 3-8 parts of polylactic acid and 2-15 parts of filler;
the molar content of D-lactic acid in the polylactic acid is 9-12%, and the melt index of the polylactic acid under the load of 2.16kg at 190 ℃ is 3-10 g/10min; the particle size D50 of the filler is less than or equal to 5 mu m.
2. The biodegradable material according to claim 1, characterized in that said biodegradable polyester comprises at least one of polybutylene adipate terephthalate, polybutylene sebacate, polyhydroxyalkanoate, polycaprolactone, polybutylene succinate, polybutylene adipate succinate.
3. The biodegradable material according to claim 2, characterized in that said biodegradable polyester is at least one of polybutylene adipate terephthalate, polybutylene sebacate and polybutylene adipate succinate.
4. The biodegradable material according to claim 1, characterized in that said filler is an organic filler.
5. The biodegradable material according to claim 1, characterized in that the composition of the biodegradable material further comprises 0 to 0.95 parts of a processing aid.
6. The biodegradable material according to claim 5, characterized in that said processing aid is at least one of a lubricant, an opening agent, a plasticizer, a nucleating agent, a chain extender.
7. The method for preparing a biodegradable material according to any one of claims 1 to 6, characterized by comprising the steps of:
and (3) uniformly mixing the components, and then, putting the mixture into a double-screw extruder for melt extrusion granulation to obtain the biodegradable material.
8. The method for producing a biodegradable material according to claim 7, wherein the twin-screw extruder is set to 130 to 220 ℃ in the melt extrusion granulation, the rotational speed is set to 200 to 400rpm, and the feeding rate is set to 400 to 1200kg/h.
9. A biodegradable edge-sealing bag, characterized in that it is prepared from the biodegradable material according to any one of claims 1 to 6.
10. The method of making a biodegradable edge sealing bag according to claim 9, comprising the steps of:
(1) Drying the biodegradable material and controlling the moisture content to be within 500 ppm;
(2) And (3) carrying out film blowing treatment on the dried biodegradable material to obtain a biodegradable film, and then transferring the biodegradable film to an edge sealing machine for edge sealing treatment to obtain the biodegradable edge sealing bag.
11. The method for producing a biodegradable edge sealing bag according to claim 10, wherein the temperature at the time of the film blowing treatment in the step (2) is 130 to 180 ℃, and the thickness of the obtained biodegradable film is 20 to 80 μm; the temperature of the edge sealing treatment is 200-450 ℃.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183483A (en) * 2001-12-25 2003-07-03 Unitika Ltd Biodegradable fertilizer bag
CN1860026A (en) * 2003-10-01 2006-11-08 三菱树脂株式会社 Biodegradable layered sheet
CN101522797A (en) * 2006-09-27 2009-09-02 诺瓦蒙特股份公司 Biodegradable multiphase compositions based on starch
CN103627153A (en) * 2012-08-20 2014-03-12 上海杰事杰新材料(集团)股份有限公司 Entire biodegradation PLA/PBAT composite material and preparing method therefor
CN106471060A (en) * 2014-05-09 2017-03-01 巴斯夫欧洲公司 The product being manufactured by thermoforming
CN113861635A (en) * 2021-10-19 2021-12-31 上海复命新材料科技有限公司 Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005032818A1 (en) * 2003-10-01 2005-04-14 Mitsubishi Plastics, Inc. Biodegradable layered sheet
US9096758B2 (en) * 2011-07-29 2015-08-04 Basf Se Biodegradable polyester foil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183483A (en) * 2001-12-25 2003-07-03 Unitika Ltd Biodegradable fertilizer bag
CN1860026A (en) * 2003-10-01 2006-11-08 三菱树脂株式会社 Biodegradable layered sheet
CN101522797A (en) * 2006-09-27 2009-09-02 诺瓦蒙特股份公司 Biodegradable multiphase compositions based on starch
CN103627153A (en) * 2012-08-20 2014-03-12 上海杰事杰新材料(集团)股份有限公司 Entire biodegradation PLA/PBAT composite material and preparing method therefor
CN106471060A (en) * 2014-05-09 2017-03-01 巴斯夫欧洲公司 The product being manufactured by thermoforming
CN113861635A (en) * 2021-10-19 2021-12-31 上海复命新材料科技有限公司 Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof

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