CN113429635A - High-starch-content film-grade full-biodegradable masterbatch and preparation method thereof - Google Patents
High-starch-content film-grade full-biodegradable masterbatch and preparation method thereof Download PDFInfo
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a high-starch-content film-grade fully biodegradable master batch and a preparation method thereof, wherein the high-starch-content film-grade fully biodegradable master batch comprises the following components in parts by weight: 60-70 parts of corn starch, 10-15 parts of plasticizer, 10-20 parts of PBAT, 5-10 parts of PLA, 0.3-1 part of chain extender, 0.2-0.5 part of aldehyde ketone polymerization inhibitor and 0.05-0.5 part of lubricant. According to the invention, sorbitol and epoxidized soybean oil are used as plasticizers, so that the processing heat resistance of the material can be improved while the processing plasticity of the plasticized starch is ensured, and the surface plasticizer precipitation ratio and speed of the final film bag product are reduced. The ionic liquid aldehyde ketone polymerization inhibitor can effectively prevent the yellowing of the master batch caused by the increase of the content of starch in the master batch, because the polymerization of unsaturated aldehyde or ketone generated by the thermal decomposition of starch is stopped.
Description
Technical Field
The invention relates to the field of biodegradable materials, in particular to a high-starch-content film-grade fully biodegradable masterbatch and a preparation method thereof.
Background
With the development of economy, China has become the largest plastic consumer nations all over the world, and disposable plastic pollution treatment is not slow enough. In 1 month 2020, after the "plastic forbidden orders" are issued from the "opinions on further strengthening the plastic pollution control", local "plastic forbidden orders" are issued successively for each province.
After the policy falls to the ground, the demand of future degradable disposable plastics in the fields of take-out, express delivery and agricultural film can reach 154.53 ten thousand tons. Compared with the current market demand of 4.2 ten thousand tons in China, the market growth space is 36 times.
The existing film bag products in the market are divided into the following parts under the guidance of cost: inorganic filling (calcium carbonate, talc) and organic filling (starch), wherein the organic starch filled film bag products have the following problems: 1. the roughness of the film surface is too large, and the hand feeling is rough; 2. the surface plasticizer is seriously precipitated; 3. the product has yellow color.
Disclosure of Invention
The invention aims to provide a high-starch-content film-grade fully biodegradable master batch and a preparation method thereof, which are used for solving the following problems of organic starch filled film bag products in the prior art: 1. the roughness of the film surface is too large, and the hand feeling is rough; 2. the surface plasticizer is seriously precipitated; 3. the product has yellow color.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a high-starch-content film-grade fully biodegradable masterbatch, which comprises the following components in parts by weight:
60-70 parts of corn starch, 10-15 parts of plasticizer, 10-20 parts of PBAT, 5-10 parts of PLA, 0.3-1 part of chain extender, 0.2-0.5 part of aldehyde ketone polymerization inhibitor and 0.05-0.5 part of lubricant.
Wherein the PBAT is thermoplastic biodegradable plastic and is a copolymer of butanediol adipate and butanediol terephthalate; the PLA is polylactic acid.
Preferably, the high-starch-content film-grade fully biodegradable masterbatch comprises the following components in parts by weight:
60 parts of corn starch, 12 parts of plasticizer, 17 parts of PBAT, 10 parts of PLA, 0.3 part of chain extender, 0.4 part of aldehyde ketone polymerization inhibitor and 0.3 part of lubricant.
Preferably, the high-starch-content film-grade fully biodegradable masterbatch comprises the following components in parts by weight:
70 parts of corn starch, 14 parts of plasticizer, 10 parts of PBAT, 5 parts of PLA, 0.3 part of chain extender, 0.4 part of aldehyde ketone polymerization inhibitor and 0.3 part of lubricant.
Preferably, the plasticizer comprises sorbitol and epoxidized soybean oil mixed in a weight ratio of 4: 1.
Preferably, the chain extender is a basf chain extender ADR-4368 CS.
Preferably, the aldehyde ketone polymerization inhibitor is used to prevent polymerization of unsaturated aldehydes or ketones.
Preferably, the aldehyde ketone polymerization inhibitor is alkyl quaternary ammonium ion [ NR4]+With acetate ion (CH)3COO-) And ionic liquid mixed according to the ionic molar ratio of 1: 1.
Preferably, the alkyl quaternary ammonium ion [ NR ]4]+Is tributylmethylammonium ion or tetramethylammonium ion.
Preferably, the lubricant is obtained by mixing Ethylene Bis Stearamide (EBS) and erucamide in a weight ratio of 2: 1.
In a second aspect, the invention also provides a preparation method of the high-starch-content film-grade fully biodegradable masterbatch, which comprises the following steps:
step 1, corn starch dehydration: placing corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the dried corn starch and the plasticizer in the step 1 into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding PBAT, PLA, a chain extender, an aldehyde ketone polymerization inhibitor and a lubricant according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
The invention has the beneficial effects that:
according to the invention, sorbitol and epoxidized soybean oil are used as plasticizers, so that the processing heat resistance of the material can be improved while the processing plasticity of the plasticized starch is ensured, and the surface plasticizer precipitation ratio and speed of the final film bag product are reduced.
The ionic liquid aldehyde ketone polymerization inhibitor can effectively prevent the yellowing of the master batch caused by the increase of the content of starch in the master batch, because the polymerization of unsaturated aldehyde or ketone generated by the thermal decomposition of starch is stopped.
In addition, the water is removed as much as possible in the process, so that the competition effect of hydrogen bonds between water and the plasticizer in the starch plasticizing process can be reduced, the probability of starch agglomeration and retrogradation can be reduced, and the final reduction of the surface roughness of the film surface and the smooth hand feeling are realized.
Detailed Description
The present invention is further illustrated by the following specific examples. However, the following embodiments are only used for explaining the present invention, and do not constitute any limitation to the actual scope of the present invention in any form, and do not limit the scope of the present invention.
Example 1
A high-starch-content film-grade fully biodegradable film master batch is composed of the following components in parts by weight:
60 parts of corn starch, 9.6 parts of sorbitol, 2.4 parts of epoxidized soybean oil, 17 parts of PBAT, 10 parts of PLA, 0.3 part of BASF chain extender ADR-4368CS, 0.4 part of aldehyde ketone polymerization inhibitor, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The aldehyde ketone polymerization inhibitor is alkyl quaternary ammonium ion [ NR4]+With acetate ion (CH)3COO-) Mixed ionic liquid with ionic molar ratio of 1:1, alkyl quaternary ammonium ion [ NR ]4]+Is tributylmethylammonium ion.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, corn starch dehydration: placing corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the corn starch, the sorbitol and the epoxidized soybean oil dried in the step 1 into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding PBAT, PLA, a BASF chain extender ADR-4368CS, an aldehyde ketone polymerization inhibitor, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
Example 2
A high-starch-content film-grade fully biodegradable film master batch is composed of the following components in parts by weight:
70 parts of corn starch, 11.2 parts of sorbitol, 2.8 parts of epoxidized soybean oil, 10 parts of PBAT, 5 parts of PLA, 0.3 part of BASF chain extender ADR-4368CS, 0.4 part of aldehyde ketone polymerization inhibitor, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The aldehyde ketone polymerization inhibitor is alkyl quaternary ammonium ion [ NR4]+With acetate ion (CH)3COO-) Mixed ionic liquid with ionic molar ratio of 1:1, alkyl quaternary ammonium ion [ NR ]4]+Is tetramethylammonium ion.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, corn starch dehydration: placing corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the corn starch, the sorbitol and the epoxidized soybean oil dried in the step 1 into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding PBAT, PLA, a BASF chain extender ADR-4368CS, an aldehyde ketone polymerization inhibitor, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
Comparative example 1
A high-starch-content film-grade fully biodegradable film master batch is composed of the following components in parts by weight:
70 parts of corn starch, 11.2 parts of sorbitol, 2.8 parts of epoxidized soybean oil, 15 parts of PBAT, 0.3 part of BASF chain extender ADR-4368CS, 0.2 part of aldehyde ketone polymerization inhibitor, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The aldehyde ketone polymerization inhibitor is alkyl quaternary ammonium ion [ NR4]+With acetate ion (CH)3COO-) Mixed ionic liquid with ionic molar ratio of 1:1, alkyl quaternary ammonium ion [ NR ]4]+Is tetramethylammonium ion.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, corn starch dehydration: placing corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the corn starch, the sorbitol and the epoxidized soybean oil dried in the step 1 into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding PBAT, a BASF chain extender ADR-4368CS, an aldehyde ketone polymerization inhibitor, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
In comparative example 1, the tensile strength of the fully biodegradable masterbatch prepared was inferior to that of example 2 and was easily deformed, compared to example 2 without adding PLA.
Comparative example 2
A high-starch-content film-grade fully biodegradable film master batch is composed of the following components in parts by weight:
60 parts of corn starch, 9.6 parts of sorbitol, 2.4 parts of epoxidized soybean oil, 17 parts of PBAT, 10 parts of PLA, 0.3 part of BASF chain extender ADR-4368CS, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, corn starch dehydration: placing corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the corn starch, the sorbitol and the epoxidized soybean oil dried in the step 1 into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding PBAT, a BASF chain extender ADR-4368CS, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
In comparative example 2, compared to example 1, the color of the fully biodegradable masterbatch prepared without the addition of the aldehyde-ketone polymerization inhibitor was yellow and the yellowness index was higher than that of example 1.
Comparative example 3
A high-starch-content film-grade fully biodegradable film master batch is composed of the following components in parts by weight:
60 parts of corn starch, 9.6 parts of sorbitol, 2.4 parts of epoxidized soybean oil, 17 parts of PBAT, 10 parts of PLA, 0.3 part of BASF chain extender ADR-4368CS, 0.4 part of aldehyde ketone polymerization inhibitor, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The aldehyde ketone polymerization inhibitor is alkyl quaternary ammonium ion [ NR4]+With acetate ion (CH)3COO-) Mixed ionic liquid with ionic molar ratio of 1:1, alkyl quaternary ammonium ion [ NR ]4]+Is tributylmethylammonium ion.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, putting the undried corn starch, sorbitol and epoxidized soybean oil into a high-speed mixer in proportion, and stirring for 15 minutes at normal temperature in a sealing manner;
step 2, mixing uniformly: continuously adding PBAT, PLA, a chain extender, an aldehyde ketone polymerization inhibitor, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 3, adding the mixture obtained in the step 2 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃, the screw rotating speed to be 250rpm, and granulating after extrusion and cooling.
In comparative example 3, which omits the first step of drying and dewatering of the preparation method compared to example 1, the surface roughness of the fully biodegradable masterbatch is higher than that of example 1.
Comparative example 4
70 parts of corn starch, 11.2 parts of sorbitol, 2.8 parts of epoxidized soybean oil, 15 parts of PBAT, 0.3 part of BASF chain extender ADR-4368CS, 0.2 part of ethylene bis stearamide and 0.1 part of erucamide.
The preparation method of the high-starch-content film-grade fully biodegradable masterbatch comprises the following steps:
step 1, putting the undried corn starch, sorbitol and epoxidized soybean oil into a high-speed mixer in proportion, and stirring for 15 minutes at normal temperature in a sealing manner;
step 2, mixing uniformly: continuously adding PBAT, a chain extender, ethylene bis stearamide and erucamide according to the proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 3, adding the mixture obtained in the step 2 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃, the screw rotating speed to be 250rpm, and granulating after extrusion and cooling.
In comparative example 4, compared with example 2, the aldehyde ketone polymerization inhibitor and the polylactic acid are not added, and the first step of drying and water removal of the preparation method is omitted, so that the surface roughness of the prepared fully biodegradable master batch is higher than that of example 2, the yellowness value is higher, and the tensile strength is low.
Note: the aldehyde-ketone polymerization inhibitors used in examples 1 to 2 and comparative examples 1 to 4 were prepared by the laboratory, PBAT used for film blowing was 801T purchased from blue mountain tun river, and the remaining materials were conventional products on the market.
In order to more clearly explain the content of the invention, the invention also makes related detection experiments, the master batches prepared in examples 1-2 and comparative examples 1-4 are made into films by the same method, and then related detection is performed, the detection categories and methods are as follows:
1. and (3) detecting the yellowness index of the film:
and testing by using a TS7010 spectral color difference instrument of a 3nh company, placing the single-layer film on a standard white board as a reference after preheating and correcting, and finally taking the b value in the Lab as a reference of the yellow depth.
The data obtained from the final examination are shown in table 1.
TABLE 1 film products yellowness depth b-value test results
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Yellowness (b value) | +13.61 | +13.49 | +13.30 | +18.26 | +13.22 | +17.94 |
As can be seen from Table 1, the film products prepared by using the masterbatches of examples 1 and 2 of the present invention have lower yellowness and whiter color, because the polymerization of aldehyde, ketone and other groups in the high temperature processing process of starch is prevented by the addition of aldehyde and ketone polymerization inhibitors.
2. And (3) detecting the surface roughness of the film:
according to the GB/T1031-2009 standard, a TR surface roughness meter is used for testing, a sampling length (lr) of 0.8mm and a sliding speed (Vt) of 0.5mm/s are selected for testing, and finally, the arithmetic mean deviation (Ra) value of the profile is taken as a reference.
The data obtained from the final examination are shown in table 2.
TABLE 2 surface Friction coefficient test results for film products
As can be seen from Table 2, the film products prepared using the masterbatches of examples 1 and 2 of the present invention had a lower surface coefficient of friction, which means that the filled starch particles had a smaller particle size and the film had a smoother hand, since the dewatering and drying process avoided the competing relationship between water and other polyol plasticizers.
3. And (3) detecting the tensile property of the film:
according to the GB/T1040.3-2006 standard, the sample is type 2, the length is 150mm, the width is 15mm, and the test speed is 200 mm/min. The sample was examined in both the longitudinal and transverse directions and corresponding data was obtained.
The data obtained from the final examination are shown in Table 3.
TABLE 3 mechanical Property test results of film products
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Transverse tensile strength (Mpa) | 25.39 | 23.91 | 20.13 | 23.94 | 18.28 | 14.83 |
| Longitudinal tensile strength (Mpa) | 27.39 | 24.06 | 21.35 | 26.96 | 18.52 | 15.01 |
| Transverse elongation at Break (%) | 455 | 387 | 422 | 448 | 427 | 363 |
| Elongation at Break in longitudinal direction (%) | 420 | 366 | 384 | 401 | 396 | 297 |
As can be seen from table 3, the film products prepared by using the master batches of examples 1 and 2 of the present invention have excellent mechanical properties, which mainly comes from two reasons: (1) the PLA in the formula can play a role in enhancing, but the PLA does not belong to the original innovation point; (2) the island structure formed by the filling material generally reflects the following mechanical properties: the larger the filling starch particles are, the larger the surface friction coefficient is, the poorer the mechanical property is, and the PLA content is difficult to compensate even if the PLA content is increased; the smaller the filling starch particles are, the smaller the surface friction coefficient is, the better the mechanical property is, and the loss of the mechanical property caused by the reduction of the content of part of PLA can be compensated.
Note: the aldehyde-ketone polymerization inhibitors used in examples 1 to 2 and comparative examples 1 to 4 were prepared by the laboratory, PBAT used for film blowing was 801T purchased from blue mountain tun river, and the remaining materials were conventional products on the market.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The high-starch-content film-grade full-biodegradable master batch is characterized by comprising the following components in parts by weight:
60-70 parts of corn starch, 10-15 parts of plasticizer, 10-20 parts of PBAT, 5-10 parts of PLA, 0.3-1 part of chain extender, 0.2-0.5 part of aldehyde ketone polymerization inhibitor and 0.05-0.5 part of lubricant.
2. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the high-starch-content film-grade fully biodegradable masterbatch comprises the following components in parts by weight:
60 parts of corn starch, 12 parts of plasticizer, 17 parts of PBAT, 10 parts of PLA, 0.3 part of chain extender, 0.4 part of aldehyde ketone polymerization inhibitor and 0.3 part of lubricant.
3. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the high-starch-content film-grade fully biodegradable masterbatch comprises the following components in parts by weight:
70 parts of corn starch, 14 parts of plasticizer, 10 parts of PBAT, 5 parts of PLA, 0.3 part of chain extender, 0.4 part of aldehyde ketone polymerization inhibitor and 0.3 part of lubricant.
4. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the plasticizer comprises sorbitol and epoxidized soybean oil mixed in a weight ratio of 4: 1.
5. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the chain extender is a basf chain extender ADR-4368 CS.
6. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the aldehyde-ketone polymerization inhibitor is an ionic liquid in which alkyl quaternary ammonium ions and acetate ions are mixed.
7. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the molar ratio of the alkyl quaternary ammonium ion to the acetate ion is 1: 1.
8. The high-starch-content film-grade fully biodegradable masterbatch according to claim 6, wherein said alkyl quaternary ammonium ions are tributyl methyl ammonium ions or tetramethyl ammonium ions.
9. The high-starch-content film-grade fully biodegradable masterbatch according to claim 1, wherein the lubricant is obtained by mixing ethylene bis stearamide and erucamide in a weight ratio of 2: 1.
10. The preparation method of the high-starch-content film-grade fully biodegradable masterbatch according to any one of claims 1 to 9, comprising the following steps:
step 1, corn starch dehydration: placing the corn starch in an oven, heating to 95 ℃ and drying for 60 minutes;
step 2, plasticizing the corn starch: putting the dried corn starch in the step 1 and the plasticizer into a high-speed mixer in proportion, heating to 95 ℃, keeping sealed stirring for 15 minutes, and cooling to below 45 ℃;
step 3, mixing uniformly: continuously adding the PBAT, the PLA, the chain extender, the aldehyde ketone polymerization inhibitor and the lubricant in proportion, sealing and stirring for 5 minutes, and uniformly mixing;
and 4, adding the mixture obtained in the step 3 into a co-rotating parallel double-screw granulator set, setting the screw temperature to be 90-150 ℃, the die head temperature to be 140 ℃ and the screw rotating speed to be 250rpm, extruding, cooling and granulating to obtain the high-starch-content film-grade fully biodegradable master batch.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656765A (en) * | 2022-04-08 | 2022-06-24 | 宁波昌亚新材料科技股份有限公司 | Full-bio-based heat-resistant polylactic acid composite material and preparation method and application thereof |
| CN116082715A (en) * | 2023-01-30 | 2023-05-09 | 贵州省材料产业技术研究院 | High heat-resistant thermoplastic starch and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656765A (en) * | 2022-04-08 | 2022-06-24 | 宁波昌亚新材料科技股份有限公司 | Full-bio-based heat-resistant polylactic acid composite material and preparation method and application thereof |
| CN116082715A (en) * | 2023-01-30 | 2023-05-09 | 贵州省材料产业技术研究院 | High heat-resistant thermoplastic starch and preparation method thereof |
| CN116082715B (en) * | 2023-01-30 | 2024-02-27 | 贵州省材料产业技术研究院 | High heat-resistant thermoplastic starch and preparation method thereof |
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Application publication date: 20210924 |