CN115011044A - Light/biological dual-degradation PS composite material and preparation method thereof - Google Patents
Light/biological dual-degradation PS composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a light/biological double-degradation PS composite material and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: PS: 55-85 parts; cassava starch: 15-30 parts; plasticizer: 3-5 parts; antioxidant: 0.1-0.5 part; photosensitizer: 0.2-0.6 part; anti-aging agent: 1-3 parts; a compatilizer: 0.5-2 parts. The light/biological double-degradation PS composite material prepared by the invention has excellent degradation performance. The cassava starch and the PS are blended, so that the mechanical property of the composite material can be improved, the biodegradation performance of the composite material can also be improved, the composite material is endowed with excellent photodegradation performance due to the addition of the photosensitizer, and the photodegradation rate of the material can be improved due to the composite use of multiple photosensitizers. The light/biological double-degradation PS composite material can regulate and control the time and period of degradation start, and is a novel environment-friendly degradable material.
Description
Technical Field
The invention relates to a preparation method of a light/biological double-degradation PS composite material, belonging to the technical field of plastics.
Background
Polystyrene, which is a polymer synthesized from styrene monomer by free radical addition polymerization, is a colorless and transparent thermoplastic plastic having a glass transition temperature higher than 100 ℃, and thus is often used to manufacture various disposable containers, disposable foam lunch boxes, and the like, which need to withstand the temperature of boiling water. But the waste polystyrene is difficult to recycle, causes pollution to the ecological environment and causes harm to the health of human bodies. In order to relieve the pollution caused by disposable plastics, China puts forward a plastic limiting order and puts specific requirements on the use of various plastic products. Therefore, the development of degradable composite materials has become a focus of current interest.
A patent with publication number CN112759875A (published Japanese 2021.05.07) reports a degradable polystyrene composite material and a preparation method thereof, the raw materials are PS, PBAT, mineral powder, a toughening agent and a compatilizer, and the degradable polystyrene composite material obtained by blending, extruding and granulating has good processing performance and certain biodegradation performance; the patent of publication No. CN110564070A (published Japanese 2019.12.13) reports a full-biodegradable PS material and a preparation method thereof, the raw materials are PS, styrene butadiene rubber and a biodegradation agent which are blended and granulated to obtain the full-biodegradable PS material, and the degradation rate of the full-biodegradable PS material can reach 65.9 percent in the environment of soil landfill; patent publication No. CN104987609A (published Japanese 2015.10.21) discloses a method for preparing degradable modified starch PS plastic, wherein the starch modified PS plastic prepared by mixing potato starch, PS, a plasticizer, a compatilizer and the like as raw materials, mixing and granulating has certain biodegradability.
However, currently, there are few researches and reports on PS degradable plastics, and most of the existing PS degradable plastics are degraded only by a single biological action, and the degradation speed is slow and the degradation rate is low, which limits the research and development and application of PS degradable plastics.
Therefore, a photo/bio dual-degradable PS composite material and a preparation method thereof are needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a light/biological double-degradation PS composite material, and the composite material is added with starch and a photosensitizer, so that the composite material has the characteristics of double degradation functions, simplicity in preparation, adjustable degradation period and high degradation efficiency.
The invention is realized by the following technical scheme:
a light/biological double-degradation PS composite material comprises the following raw materials in parts by weight:
the light/biological double-degradation PS composite material is characterized in that the plasticizer is glycerol, benzene polyacid ester or diisobutyl phthalate.
The photo/biological double-degradation PS composite material comprises an antioxidant, wherein the antioxidant is one or more of an oxidant 1010, an oxidant 1076, an oxidant 1098, an oxidant 1024, an oxidant AO-80, an antioxidant DLTP, an oxidant DSTP, an antioxidant 168, an oxidant 626 or an oxidant TP 8.
The light/biological double-degradation PS composite material is characterized in that the photosensitizer is one or more of ferric stearate, manganese stearate or cerium stearate.
The light/biological double-degradation PS composite material is characterized in that the anti-aging agent is mono-diglycerol fatty acid ester.
The light/biological double-degradation PS composite material is characterized in that the compatilizer is one or more of POE-g-GMA, EVA-g-MA and silane coupling agent.
The preparation method of the light/biological double-degradation PS composite material comprises the following steps:
(1) drying the cassava starch, uniformly mixing the cassava starch with an anti-aging agent and the like, and adding the cassava starch into a high-speed kneading machine for reaction to obtain thermoplastic starch;
(2) mixing thermoplastic starch with a certain amount of PS, a photosensitizer, an antioxidant and a compatilizer, adding the mixture into an extruder, and performing extrusion granulation to obtain master batches;
(3) and mixing the master batch, the compatilizer and the PS, adding the mixture into an extruder, and carrying out reaction granulation to obtain the light/biological double-degradation PS composite material.
The preparation method of the light/biological double-degradation PS composite material comprises the step (1), wherein the temperature of a high-speed kneader is 120-170 ℃, and the rotating speed is 500-800 RPM.
According to the preparation method of the light/biological double-degradation PS composite material, in the step (2) and the step (3), the temperature of each zone of an extruder is as follows: the first zone temperature is 190 ℃ plus the power, the second zone temperature is 200 ℃ plus the power, the third zone temperature is 200 ℃ plus the power, the fourth zone temperature is 200 ℃ plus the power, the fifth zone temperature is 190 ℃ plus the power, the sixth zone temperature is 190 ℃ plus the power, and the rotation speed is 100 RPM plus 150 RPM.
Polystyrene refers to a polymer synthesized by free radical addition polymerization of styrene monomer, and is a colorless and transparent thermoplastic plastic with a glass transition temperature higher than 100 ℃. The most important feature of polystyrene is that it has excellent thermal stability and fluidity when melted, so that it is easy to mold and process, especially injection molding, and suitable for mass production. When polystyrene is processed and molded, the molding shrinkage rate is small, and the dimensional stability of a molded product is good. Therefore, the product is often used for manufacturing various disposable containers which need to bear the temperature of boiled water, disposable foam lunch boxes and the like.
The cassava starch is powder obtained by extracting cassava starch and then dehydrating and drying. The cassava starch has biodegradability, and the cassava native starch and the modified starch can be mixed with petroleum-based or artificially synthesized high polymer materials to improve the biodegradability of the materials, thereby minimizing the production cost of the environment-friendly materials.
The photosensitizer is one or more of ferric stearate, manganese stearate and cerium stearate. The photosensitizer contains chromophoric groups, so that the photosensitizer can generate primary free radicals after absorbing ultraviolet light, and the primary free radicals become free radical initiation sources, thereby accelerating the photodegradation speed of macromolecules.
The invention achieves the following beneficial effects:
the light/biological double-degradation PS composite material prepared by the invention has excellent degradation performance. The cassava starch and the PS are blended, so that the mechanical property of the composite material can be improved, the biodegradation performance of the composite material can also be improved, the composite material is endowed with excellent photodegradation performance due to the addition of the photosensitizer, and the photodegradation rate of the material can be improved due to the composite use of multiple photosensitizers. The light/biological double-degradation PS composite material can regulate and control the time and period of degradation start, and is a novel environment-friendly degradable material.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (3) blending the modified starch, the antioxidant 1010, the ferric stearate, the cerium stearate, the POE-g-GMA and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, the POE-g-GMA and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
The composite material is prepared by reacting cassava starch and PS as main raw materials through a high-speed kneader and blending and extruding. The cassava starch has wide sources and is biodegradable, but the cassava starch has poor compatibility with weak polar or non-polar resin due to a large amount of polar groups in the molecule. The cassava starch is modified by a simple physical blending method, and the cassava starch, the glycerol and the GMS are reacted in a high-speed kneading machine to obtain the modified starch. And uniformly mixing the modified starch, the antioxidant, the photosensitizer and a small amount of PS, and then carrying out extrusion granulation to obtain the plastic master batch with photo/biological double degradation. And finally, blending and granulating the master batch and the residual PS of the compatilizer to obtain the light/biological double-degradation PS composite material.
The light/biological double-degradation PS composite material has double-degradation function due to the introduction of starch and photosensitizer. And because of the addition of the antioxidant, the induction period of the photosensitizer in the material can be regulated and controlled, and the material is not degraded before the induction period. Therefore, the light/biological double-degradation PS composite material has the characteristics of simple preparation, adjustable degradation period and high degradation efficiency.
Example 2
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (2) blending the modified starch, the antioxidant 1076, the antioxidant 626, ferric stearate, cerium stearate, POE-g-GMA, the silane coupling agent and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, the POE-g-GMA, the silane coupling agent and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Example 3
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (2) blending the modified starch, the antioxidant 1010, the antioxidant 168, the ferric stearate, the cerium stearate, the POE-g-GMA, the silane coupling agent and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, the POE-g-GMA, the silane coupling agent and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Example 4
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (2) blending the modified starch, the antioxidant 1010, the antioxidant 168, the cerium stearate, the POE-g-GMA, the silane coupling agent and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, POE-g-GMA, the silane coupling agent and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Example 5
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (2) blending the modified starch, the antioxidant 1010, the antioxidant 168, the ferric stearate, the POE-g-GMA, the silane coupling agent and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, the POE-g-GMA, the silane coupling agent and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Comparative example 1
Weighing the following raw materials in formula:
modification treatment of cassava starch:
adding the cassava starch, the glycerol and the GMS into a high-speed kneader, wherein the temperature of the high-speed kneader is 120-170 ℃, the rotating speed is 500-800RPM, and reacting for 2.5h to obtain the modified starch.
Preparing plastic master batches:
and (3) blending the modified starch, the antioxidant 1010, the antioxidant 168, the POE-g-GMA, the silane coupling agent and part of PS for extrusion granulation to obtain the plastic master batch. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
Preparing a composite material:
and (3) blending, extruding and granulating the plastic master batch, POE-g-GMA, the silane coupling agent and the residual PS to obtain the light/biological double-degradation PS composite material. The temperatures in the various zones of the extrusion apparatus were: the first zone temperature is 180-.
In the above examples and comparative examples, tapioca starch was dried at a temperature of 70 ℃ for 5 hours. The above examples and comparative examples were placed in ultraviolet light and microbial environments of equal intensity, respectively, and samples were taken at intervals to determine the degradation rate of the samples. The relevant data are shown in tables 1-4.
Tables 1-4 show the degradation profiles of the different samples at 15 days, 30 days, 45 days, and 60 days, respectively. The biodegradation rate is the data obtained by degrading the measured sample under the action of a single microorganism. The photodegradation rate is the data obtained by degrading the sample under the action of single light. The light/biodegradation rate is data obtained by degrading and measuring a sample under the combined action of microorganisms and illumination.
Table 1 degradation performance for 15 days for different example samples.
TABLE 2 30-day degradation behavior of the samples of the different examples
| Biodegradation Rate/% | Percent photodegradation/%) | Light/biodegradation Rate/% | |
| Example 1 | 15.12 | 24.81 | 44.91 |
| Example 2 | 15.24 | 24.95 | 44.68 |
| Example 3 | 15.83 | 25.40 | 45.62 |
| Example 4 | 10.23 | 12.88 | 26.31 |
| Example 5 | 12.64 | 18.32 | 35.98 |
| Comparative example 1 | 7.39 | 1.63 | 9.32 |
TABLE 3 45-day degradation performance of samples of different examples
| Biodegradation Rate/% | Percent photodegradation/%) | Light/biodegradation Rate/% | |
| Example 1 | 22.17 | 39.28 | 64.15 |
| Example 2 | 21.28 | 38.57 | 63.95 |
| Example 3 | 23.38 | 40.59 | 65.37 |
| Example 4 | 18.12 | 24.03 | 45.21 |
| Example 5 | 20.93 | 30.32 | 54.28 |
| Comparative example 1 | 16.92 | 2.45 | 19.39 |
TABLE 4 degradation Properties of the samples of the different examples for 60 days
As can be seen from tables 1 to 4, comparative example 1, in which no photosensitizer was added, had a low photodegradation rate of only 3.98% after 60 days. And the photosensitizer is added in the embodiments 1-5, so that the photodegradation rate of the sample is greatly improved. In example 4, only a single cerium stearate is added as a photosensitizer, in example 5, only a single iron stearate is added as a photosensitizer, and in example 3, both cerium stearate and iron stearate are added as photosensitizers. The rate of photodegradation of example 3 was significantly higher than that of examples 4 and 5, demonstrating that the use of two photosensitizers simultaneously acted synergistically. This is because both photosensitizers can absorb uv light simultaneously, generating more primary radicals, initiating degradation of the material.
The biodegradation rates in examples 1 to 5 are not very different, but there is a large difference in the light/biodegradation rates. Wherein, the light/biodegradation rate of the embodiment 3 is the highest, and the degradation rate after 60 days is as high as 80.13 percent, which exceeds the simple addition of the single biodegradation rate and the light degradation rate. The two actions of photo-degradation and biodegradation are proved to be mutually promoted, so that the degradation speed and the degradation efficiency of the material can be accelerated.
The light/biological dual-degradation PS composite material has excellent degradation performance and can meet the requirements of preparation and use of disposable PS tableware. The method also provides a new idea for the research and production of the PS degradable plastic.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A light/biological double-degradation PS composite material is characterized by comprising the following raw materials in parts by weight:
2. the photo/bio-biodegradable PS composite according to claim 1, wherein said plasticizer is glycerol, benzene polyacid ester or diisobutyl phthalate.
3. The PS composite material of claim 1, wherein the antioxidant is one or more of oxidant 1010, oxidant 1076, oxidant 1098, oxidant 1024, oxidant AO-80, antioxidant DLTP, oxidant DSTP, antioxidant 168, oxidant 626 and oxidant TP 8.
4. The PS composite of claim 1, wherein the photosensitizer is one or more of ferric stearate, manganese stearate or cerium stearate.
5. The photo/bio-degradable PS composite material according to claim 1, wherein said anti-aging agent is a mono-diglycerol fatty acid ester.
6. The PS composite of claim 1, wherein the compatibilizer is one or more of POE-g-GMA, EVA-g-MA, and silane coupling agent.
7. The method for preparing a PS composite material degraded by light and biology according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) drying the cassava starch, uniformly mixing the cassava starch with an anti-aging agent and the like, and adding the cassava starch into a high-speed kneading machine for reaction to obtain thermoplastic starch;
(2) mixing thermoplastic starch with a certain amount of PS, a photosensitizer, an antioxidant and a compatilizer, adding the mixture into an extruder, and performing extrusion granulation to obtain master batches;
(3) and mixing the master batch, the compatilizer and the PS, adding the mixture into an extruder, and carrying out reaction granulation to obtain the light/biological double-degradation PS composite material.
8. The method as claimed in claim 7, wherein the temperature of the high-speed kneader in step (1) is 120-170 ℃, and the rotation speed is 500-800 RPM.
9. The method for preparing a PS composite material based on dual photo/bio degradation as claimed in claim 7, wherein in the step (2) and the step (3), the temperatures of the extruder in the respective zones are as follows: the first zone temperature is 180-.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193026A (en) * | 1997-03-06 | 1998-09-16 | 赵小英 | Base material capable of light degeradation and biological degradation |
| CN103408827A (en) * | 2013-08-29 | 2013-11-27 | 河北奥柯柏环保科技有限公司 | Degradable environmental-friendly mulching film and preparation method thereof |
| CN107400294A (en) * | 2017-08-28 | 2017-11-28 | 台州市苏达山新材料有限公司 | Bio-based degradable material and preparation method thereof, application |
| CN113150396A (en) * | 2021-03-31 | 2021-07-23 | 方龙 | Preparation method of packaging bag capable of being rapidly degraded |
-
2022
- 2022-06-08 CN CN202210642980.XA patent/CN115011044A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193026A (en) * | 1997-03-06 | 1998-09-16 | 赵小英 | Base material capable of light degeradation and biological degradation |
| CN103408827A (en) * | 2013-08-29 | 2013-11-27 | 河北奥柯柏环保科技有限公司 | Degradable environmental-friendly mulching film and preparation method thereof |
| CN107400294A (en) * | 2017-08-28 | 2017-11-28 | 台州市苏达山新材料有限公司 | Bio-based degradable material and preparation method thereof, application |
| CN113150396A (en) * | 2021-03-31 | 2021-07-23 | 方龙 | Preparation method of packaging bag capable of being rapidly degraded |
Non-Patent Citations (1)
| Title |
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| 段予忠等: "《塑料母料生产及应用技术》", vol. 1, 中国轻工业出版社, pages: 134 - 135 * |
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