CN109181254B - Composite material mixed with outdoor degradable polylactic acid and straw and preparation method thereof - Google Patents
Composite material mixed with outdoor degradable polylactic acid and straw and preparation method thereof Download PDFInfo
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- CN109181254B CN109181254B CN201811009182.3A CN201811009182A CN109181254B CN 109181254 B CN109181254 B CN 109181254B CN 201811009182 A CN201811009182 A CN 201811009182A CN 109181254 B CN109181254 B CN 109181254B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a composite material mixed with outdoor degradable polylactic acid and straws and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 50-90 parts of polylactic acid, 10-50 parts of straw powder, 5-15 parts of polyglycolic acid copolyester, 1-4 parts of silane coupling agent, 0.3-0.5 part of grafting promoter, 0.5-1 part of initiator and 0.5-2 parts of catalyst.
Description
Technical Field
The invention belongs to the field of degradable plastics, and particularly relates to a composite material mixed with outdoor degradable polylactic acid and straw and a preparation method thereof.
Background
Polylactic acid (PLA) has good biodegradability, and can be degraded within 3 months, especially in the case of industrial composting. However, in natural environments, such as disposal of polylactic acid (PLA) in domestic yards in the middle of china, polylactic acid (PLA) may not degrade significantly for as long as 2 years. In order to enter the ocean, polylactic acid (PLA) products can not be degraded in years even under the low-temperature environment of the ocean.
Therefore, it has been attempted to increase the degradation rate of polylactic acid (PLA), such as leaving a large amount of carboxyl groups and monomers in the polylactic acid (PLA), which, however, results in a drastic deterioration in the processability of the polylactic acid (PLA).
The patent with publication number CN 101484528B discloses a Polyglycolide (PGA) and polylactic acid (PLA) blended material and a preparation method thereof, but the technical scheme is to simply mix Polyglycolide (PGA) and polylactic acid (PLA), and actually, because the two materials have large polarity difference and poor compatibility, the prepared material can only be applied to the field with low requirements on mechanical properties of the materials, and because of the high melting point of Polyglycolide (PGA), the material processing becomes difficult.
Compared with Polyglycolide (PGA), polyglycolic acid copolyester (PGEA) is a product obtained by copolymerizing glycolic acid or glycolate, adipic acid and ethylene glycol, has a lower melting point and good processability, and on the basis, the copolymer prepared by the glycolic acid, the adipic acid and the ethylene glycol in a molar ratio of 10:1:1 has the characteristic of low melting point, so that the PGEA prepared on the basis of the monomer ratio has obviously reduced crystallinity compared with the Polyglycolide (PGA), and has a higher degradation speed.
In the process of processing and forming polylactic acid (PLA), a polylactic acid product prepared by adopting a normal-temperature mould is in an amorphous state, has no heat resistance, and generally has a heat deformation temperature of not more than 80 ℃. There are therefore generally two methods for obtaining heat-resistant polylactic acid (PLA) articles: one is to directly form the specially modified crystalline polylactic acid by adopting a high-temperature mould; another method is to form crystalline polylactic acid (PLA) by cold die, and then to crystallize the PLA article through a crystallization drying tunnel to impart heat resistance, a technique known in the industry as extra-die crystallization.
Patent publication No. CN 105153659A discloses a heat-resistant polylactic acid composite material and a preparation method thereof, but a polylactic acid product prepared from the material needs to be baked in an oven at 100-105 ℃ after being molded to have heat resistance, and due to the adoption of an external mold crystallization process, the product is easy to deform seriously (mainly influenced by crystallization shrinkage) in the baking process, and a product with a high surface gloss cannot be prepared.
Patent publication No. CN101319032A discloses a method for preparing crosslinked polylactic acid by grafting silane with polylactic acid and then hydrolyzing the silane. However, in the method, the molded polylactic acid needs to be placed in hot water at 30-90 ℃ for 4-96 hours, the heat resistance of the crosslinked polylactic acid can be improved, but the method has a complex processing process, and the degradation performance of the crosslinked and modified polylactic acid is further reduced, so that the crosslinked and modified polylactic acid is difficult to rapidly degrade outdoors (without composting).
Therefore, there is a need to find a polylactic acid composite material which has better processability, heat resistance and can be degraded outdoors.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention adopts the following technical scheme: a composite material mixed with outdoor degradable polylactic acid and straw is characterized in that: the composite material comprises the following components in parts by weight:
50-90 parts of polylactic acid;
10-50 parts of straw powder;
5-50 parts of polyglycolic acid copolyester;
1-4 parts of a silane coupling agent;
0.3-0.5 part of a grafting promoter;
0.5-1 part of an initiator;
0.5-2 parts of a catalyst.
Further, the polyglycolic acid copolyester is copolymerized by glycolic acid, adipic acid and ethylene glycol, wherein the molar ratio of the glycolic acid to the adipic acid to the ethylene glycol monomers is 10:1: 1.
Further, the number average molecular weight of the polyglycolic acid copolyester is 20000-100000.
Further, the silane coupling agent is one or a mixture of two of vinyltrimethoxysilane or vinyltriethoxysilane.
Further, the grafting promoter is tetramethylthiuram disulfide.
Further, the initiator is one or a mixture of more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
Further, the catalyst is a mixture of dimethyl oxalate and bismuth laurate, wherein the molar ratio of dimethyl oxalate to bismuth laurate is 1: 1.
Further, the invention also provides a preparation method of the composite material mixed with the outdoor degradable polylactic acid and the straw, which is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively weighing 50-90 parts by mass of polylactic acid, 10-50 parts by mass of straw powder, 1-4 parts by mass of silane coupling agent, 0.3-0.5 part by mass of grafting promoter and 0.5-1 part by mass of initiator, mixing for 5-10 min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing 5-50 parts of polyglycolic acid copolyester and 0.5-2 parts of catalyst in the same mass part of the particles obtained in the step (1) in a high-speed mixer for 5-10 min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention compounds the straws with polylactic acid (PLA), and the composite material mixed with the PLA and the straws prepared by adopting a special process has excellent mechanical properties.
(2) The invention adds PGEA into the composite material mixed with polylactic acid (PLA) and straw, and combines other auxiliary materials, so that the degradation speed of the PLA is greatly accelerated, and the rapid degradation under the outdoor non-composting condition can be realized.
(3) The composite material mixed with polylactic acid (PLA) and straw fully utilizes the crosslinking characteristic of grafted silane, realizes crosslinking at room temperature and under the condition of common humidity, is convenient to process, and improves the heat resistance of products.
(4) The preparation method of the composite material mixed with the outdoor degradable polylactic acid and the straw is simple, easy to operate and low in cost.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. Unless otherwise specified, the raw material used in the present invention, polylactic acid, was obtained from NatureWorks corporation under the trademark 4032D; PGEA comes from Jiangsu gold polymer materials GmbH, and the synthesis method adopts a patent method with the publication number of CN 103910860A, the number average molecular weight is 2-10 ten thousand, and the copolymerization molar ratio of glycolic acid, adipic acid and glycol is 10:1: 1; the straw powder is commercially available 80-mesh straw powder.
The composite material mixed with the outdoor degradable polylactic acid and the straw is made into a test sample strip after injection molding by an injection molding machine, and if not specially stated, the sample strip used for testing the tensile strength, the elongation at break, the bending strength and the thermal deformation temperature in the invention can become a test standard sample strip used by the invention after being placed in a constant temperature and humidity box (the set temperature is 23 ℃ and the relative humidity is 50%) for 5 days. That is, unless otherwise specified, the test specimens used for the data acquisition in Table 1, namely "tensile strength", "elongation at break", "flexural strength" and "heat distortion temperature", were all specimens obtained after the material was injection-molded by an injection molding machine and placed in a constant temperature and humidity chamber (set temperature 23 ℃ C., 50% relative humidity) for 5 days.
In the invention, the following instruments are used for testing the performance of the material, and the tensile performance test is carried out on an RG1-5 type electronic universal tester (produced by Shenzhen Riger instruments Limited) according to the GB/T1040-; the bending strength test is carried out on an RG1-5 type electronic universal tester (produced by Shenzhen Riger instrument Limited) according to the GB/T9341-; the test is carried out in a ZWY-0318 thermal deformation Vicat temperature tester (produced by Yangzhou pure test mechanical factory) according to the GB/T1634.1-2004 standard.
The invention relates to a constant temperature and humidity 60-day bending strength, which is characterized in that: placing a sample strip obtained after the material is subjected to injection molding in a constant temperature and humidity box (the set temperature is 23 ℃ and the relative humidity is 50%) for 5 days, and then continuously placing the sample strip in the constant temperature and humidity box (the set temperature is 23 ℃ and the relative humidity is 50%) for 60 days, namely testing the obtained bending strength after the sample strip is accumulated and placed in the constant temperature and humidity box for 65 days; the value obtained by dividing the bending strength of the product for 60 days at constant temperature and humidity by the corresponding bending strength is called as the bending strength retention rate in the invention and is used as the reference of the shelf life of the product; the evaluation method of '300-day simulation of outdoor spline disintegration' in the invention refers in particular to: the bending strength test sample strip obtained after injection molding is placed in a constant temperature and humidity box (the set temperature is 23 ℃ and the relative humidity is 50%) for 5 days, then placed in the constant temperature and humidity box (the set temperature is 23 ℃ and the relative humidity is 80%) for 300 days, the outdoor degradation state is simulated, and the disintegration state of the sample strip is observed.
Example 1
The composite material is prepared by the following method:
(1) weighing 90 parts by mass of polylactic acid, 10 parts by mass of straw powder, 4 parts by mass of vinyltrimethoxysilane, 0.3 part by mass of tetramethylthiuram disulfide and 0.5 part by mass of dicumyl peroxide, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing 5 parts of polyglycolic acid copolyester (with the number average molecular weight of 2 ten thousand) and 2 parts of catalyst (a mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) in the same mass part of the particles obtained in the step (1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Table 1 shows the results of the performance tests of the composite obtained in example 1.
Example 2
The composite material is prepared by the following method:
(1) weighing 50 parts by weight of polylactic acid, 50 parts by weight of straw powder, 1 part by weight of vinyl trimethoxy silane, 0.5 part by weight of tetramethyl thiuram disulfide and 1 part by weight of di-tert-butyl peroxide cumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester with the same mass parts of particles obtained in the step (1) (the number average molecular weight is 10 ten thousand) and 0.5 part of catalyst (the mixture of dimethyl oxalate and bismuth laurate with the molar ratio of 1: 1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Table 1 shows the results of the performance tests of the composite obtained in example 2.
Example 3
The composite material is prepared by the following method:
(1) weighing 80 parts by weight of polylactic acid, 50 parts by weight of straw powder, 3 parts by weight of vinyl trimethoxy silane, 0.5 part by weight of tetramethyl thiuram disulfide and 0.6 part by weight of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing 50 parts of polyglycolic acid copolyester (with the number average molecular weight of 10 ten thousand) and 1 part of catalyst (a mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) in the same mass part of the particles obtained in the step (1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Table 1 shows the results of the performance tests of the composite obtained in example 3.
Example 4
The composite material is prepared by the following method:
(1) weighing 90 parts by mass of polylactic acid, 10 parts by mass of straw powder, 2 parts by mass of vinyltriethoxysilane, 2 parts by mass of vinyltrimethoxysilane, 0.4 part by mass of tetramethylthiuram disulfide and 0.6 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester with the same mass fraction of 20 parts (the number average molecular weight is 10 ten thousand) and 2 parts of catalyst (the mixture of dimethyl oxalate and bismuth laurate in the molar ratio of 1: 1) obtained in the step (1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Table 1 shows the results of the performance tests of the composite obtained in example 4.
Example 5
The composite material is prepared by the following method:
(1) weighing 80 parts by mass of polylactic acid, 40 parts by mass of straw powder, 4 parts by mass of vinyltriethoxysilane, 0.5 part by mass of tetramethylthiuram disulfide, 0.5 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by mass of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester with the same mass parts of particles obtained in the step (1) (the number average molecular weight is 10 ten thousand) and 2 parts of catalyst (the mixture of dimethyl oxalate and bismuth laurate in the molar ratio of 1: 1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
Table 1 shows the results of the performance tests of the composite obtained in example 5.
Comparative example 1
The composite material is prepared by the following method:
(1) weighing 80 parts by mass of polylactic acid, 40 parts by mass of straw powder, 4 parts by mass of vinyltriethoxysilane, 0.5 part by mass of tetramethylthiuram disulfide, 0.5 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by mass of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the catalyst (the mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) with the same mass parts of the particles obtained in the step (1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material particles.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 1.
Comparative example 2
The composite material is prepared by the following method:
(1) weighing 80 parts by weight of polylactic acid, 40 parts by weight of straw powder, 4 parts by weight of vinyltriethoxysilane, 0.5 part by weight of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by weight of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester (with the number average molecular weight of 10 ten thousand) in 20 parts by mass of the particles obtained in the step (1) and 2 parts of catalyst (a mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite particles.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 2.
Comparative example 3
The composite material is prepared by the following method:
(1) weighing 80 parts by mass of polylactic acid, 40 parts by mass of straw powder, 4 parts by mass of vinyltriethoxysilane, 0.5 part by mass of tetramethylthiuram disulfide, 0.5 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by mass of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester (with the number average molecular weight of 10 ten thousand) with the same mass parts of the particles obtained in the step (1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite particles.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 3.
Comparative example 4
The composite material is prepared by the following method:
(1) weighing 80 parts by mass of polylactic acid, 40 parts by mass of straw powder, 4 parts by mass of vinyltriethoxysilane, 0.5 part by mass of tetramethylthiuram disulfide, 0.5 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by mass of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester (with the number average molecular weight of 10 ten thousand) in 20 parts by mass of the particles obtained in the step (1) and 2 parts of catalyst (a mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite particles.
However, before testing the tensile strength, flexural strength and heat distortion temperature, the specimens used for the test were not treated in a constant temperature and humidity cabinet (set temperature 23 ℃ C., 50% relative humidity) for 5 days.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 4.
Comparative example 5
The composite material is prepared by the following method:
(1) weighing 80 parts by mass of polylactic acid, 4 parts by mass of vinyltriethoxysilane, 0.5 part by mass of tetramethylthiuram disulfide, 0.5 part by mass of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.5 part by mass of di-tert-butylperoxycumene, mixing for 5min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing the polyglycolic acid copolyester (with the number average molecular weight of 10 ten thousand) in 20 parts by mass of the particles obtained in the step (1) and 2 parts of catalyst (a mixture of dimethyl oxalate and bismuth laurate in a molar ratio of 1: 1) in a high-speed mixer for 5min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite particles.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 5.
Comparative example 6
And (3) performing related tests after directly performing injection molding on the pure polylactic acid 4032D material.
Table 1 shows the results of the performance tests of the composite material obtained in comparative example 6.
TABLE 1
Note: the test specimens used in comparative example 4 in Table 1, which had been subjected to injection molding by an injection molding machine and had not been subjected to a treatment of 5 days in a constant temperature and humidity chamber (set temperature 23 ℃ C., 50% relative humidity), were used for "tensile strength", "elongation at break", "bending strength" and "heat distortion temperature".
In table 1 above, it can be seen from comparative example 1 that polyglycolic acid copolyester plays a very important role in inducing material degradation in the present invention, and the material hardly undergoes disintegration phenomenon in the absence of polyglycolic acid copolyester; it can be seen from the comparative example 2 that without the grafting promoter, the silane coupling agent can not be effectively grafted into the macromolecular chain, and has a large influence on the mechanical property and the heat resistance of the material, and moreover, because the silane coupling agent can not be effectively grafted, the room temperature storage property of the composite material is also influenced, so that the bending strength retention rate is obviously reduced, which indicates that the shelf life of the material can be shortened, and the shelf life of the material can have a large relation with the thermal deformation temperature of the material; as can be seen from the comparative example 3, the addition of the catalyst can greatly improve the crosslinking speed of the composite material in the room temperature environment and also can improve the degradation performance of the composite material, and the degradation of the sample strip is influenced under the condition of no catalyst; as can be seen from the comparison of comparative example 4 and example 5, the composite material of the present invention can be crosslinked by constant temperature and humidity for 5 days, thereby improving the mechanical properties; however, as can be seen from comparison between comparative example 5 and example 5, the straw powder can promote disintegration and degradation of the material, which may be that the straw powder can function as a culture medium to some extent to accelerate disintegration and degradation of the material.
In conclusion, the comparison of the mechanical property, the heat resistance, the degradation property, the storage property and the like of the embodiment and the comparative example shows that the rapidly molded composite material mixed with the outdoor degradable polylactic acid and the straw has the advantages of good mechanical property, good heat resistance, long shelf life, high degradation speed and the like of the product, can realize degradation in an outdoor non-composting environment, and has very high ecological value.
Claims (2)
1. A composite material mixed with outdoor degradable polylactic acid and straw is characterized in that: the composite material comprises the following components in parts by weight:
50-90 parts of polylactic acid;
10-50 parts of straw powder;
5-50 parts of polyglycolic acid copolyester;
1-4 parts of a silane coupling agent;
0.3-0.5 part of a grafting promoter;
0.5-1 part of an initiator;
0.5-2 parts of a catalyst;
the polyglycolic acid copolyester is copolymerized by glycolic acid, adipic acid and ethylene glycol, wherein the molar ratio of the glycolic acid to the adipic acid to the ethylene glycol monomer is 10:1: 1;
the silane coupling agent is one or the mixture of two of vinyltrimethoxysilane or vinyltriethoxysilane;
the grafting accelerator is tetramethyl thiuram disulfide;
the initiator is one or a mixture of more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane;
the catalyst is a mixture of dimethyl oxalate and bismuth laurate, wherein the molar ratio of the dimethyl oxalate to the bismuth laurate is 1: 1;
the preparation method of the composite material mixed with the outdoor degradable polylactic acid and the straw comprises the following steps:
(1) respectively weighing 50-90 parts by mass of polylactic acid, 10-50 parts by mass of straw powder, 1-4 parts by mass of silane coupling agent, 0.3-0.5 part by mass of grafting promoter and 0.5-1 part by mass of initiator, mixing for 5-10 min in a high-speed mixer, and then extruding and granulating in a double-screw extruder at 180-220 ℃;
(2) and (2) mixing 5-50 parts of polyglycolic acid copolyester and 0.5-2 parts of catalyst in the same mass part of the particles obtained in the step (1) in a high-speed mixer for 5-10 min, and then extruding and granulating in a double-screw extruder at 180-205 ℃ to obtain the composite material mixed with the outdoor degradable polylactic acid and the straw.
2. The composite material mixed with the outdoor degradable polylactic acid and the straw as claimed in claim 1, wherein: the number average molecular weight of the polyglycolic acid copolyester is 20000-100000.
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| CN111303457B (en) * | 2020-03-11 | 2023-01-20 | 江苏金聚合金材料有限公司 | Master batch for improving Polyglycolide (PGA) durability and preparation method thereof |
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