CN109679074B - Composite stabilizer for polylactic acid polymerization, and application and use method thereof - Google Patents
Composite stabilizer for polylactic acid polymerization, and application and use method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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Abstract
The invention belongs to the technical field of high polymer chemistry, and the specific composite stabilizer is adopted to reduce the B value in L AB color values of a polylactic acid product obtained by ring-opening polymerization by taking lactide as a raw material, so that the obtained polylactic acid shows more stable performance, and the obtained polylactic acid is suitable for being used as a food packaging material and the like.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and relates to a novel composite stabilizer for polylactic acid polymerization, application thereof and a method for producing polylactic acid by using the composite stabilizer, in particular to the composite stabilizer used for improving the performance stability of the obtained polylactic acid in the process of synthesizing the polylactic acid by lactide ring opening.
Background
At present, the proportion of high polymer materials in daily necessities is leaped forward, metal and other materials are gradually replaced, and the high polymer materials have absolute advantages. However, with the continuous development of social economy and the continuous increase of global population, the earth resources are seriously developed, the environmental and energy problems such as global warming and oil resource exhaustion are more and more severe, and the method for treating both symptoms and root causes is to vigorously develop degradable high molecular materials. Therefore, non-petroleum based degradable materials are receiving increasing attention. Among various biodegradable materials, polylactic acid has been gradually regarded as an environment-friendly polymer material.
Polylactic acid is a biodegradable high molecular material, generally refers to a polymer synthesized by chemical synthesis with lactic acid as a raw material, and belongs to one of aliphatic polyesters. Its raw material is derived from renewable corn and sugar, etc. The polylactic acid has high strength, good biocompatibility and excellent processing performance, and can be used in the fields of fibers, packaging, foaming materials and the like. Meanwhile, polylactic acid is known as a green polymer because of biodegradability, biocompatibility and renewability of raw materials.
The method for synthesizing the polylactic acid mainly comprises a direct polycondensation method and a lactide ring-opening polymerization method, the direct polycondensation method is simple in process and low in cost, the obtained molecular weight is relatively low, the synthesized polylactic acid is not pure enough, yellowish or yellowish-brown polylactic acid is easy to appear, and the application field is narrow. The polylactic acid obtained by the lactide ring-opening method has higher molecular weight, is relatively pure and has wide application, but the synthesis process is complex, the yield is lower and the cost is higher.
In the production of polylactic acid by ring-opening polymerization of lactide, attention is generally paid to the amount and kind of catalyst used therein, the polymerization conditions, and the like. For example, in the research on the synthesis of polylactic acid by lactide ring-opening polymerization, 20(5), 2018, 5 months and 20 days, korea et al (wira korea et al, popular science and technology), the polylactic acid is synthesized by lactide ring-opening polymerization, the polylactic acid is synthesized by taking lactide as a raw material and stannous octoate as a catalyst, the influence of the amount of the catalyst, the polymerization time and the polymerization temperature on the synthesis of the polylactic acid by lactide ring-opening polymerization is considered, and the high molecular weight polylactic acid is obtained under the conditions that the amount of the catalyst accounts for 0.1% of the mass ratio of the monomers, the polymerization temperature is 130 ℃ and the polymerization time is 20 hours.
However, the present inventors have found that when polylactic acid is produced by ring-opening polymerization of lactide by the conventional method, there is a problem that the resulting polylactic acid product is unstable in properties, so that the value of B in the L AB color thereof is too high.
Disclosure of Invention
In view of the above technical problems, the present inventors have found through research that when a specific substance is used as a composite stabilizer in the process of producing polylactic acid by lactide ring-opening polymerization, the properties of the polylactic acid product obtained in the lactide ring-opening polymerization process can be more stabilized, thereby improving the B value of the L AB color value thereof.
In one aspect, the present invention relates to a complex formulation for use as a stabilizer in the ring-opening polymerization of lactide to produce polylactic acid, wherein the complex formulation comprises a stearate and a phenolic antioxidant.
In another aspect, the present invention relates to the use of the above-described complex formulation as a stabilizer in the production of polylactic acid by ring-opening polymerization from lactide as a raw material.
In still another aspect, the present invention relates to a method for producing polylactic acid by ring-opening polymerization using the above-mentioned complex formulation using lactide as a raw material, wherein the complex formulation is added after the ring-opening polymerization reaction of lactide is completed.
The polylactic acid product produced by using the compound preparation as the stabilizer in the process of producing the polylactic acid by ring-opening polymerization by using lactide as a raw material has more stable performance, the B value in L AB color value of the product is obviously improved, and the polylactic acid obtained by the method is suitable for being used as a food packaging material and the like.
Detailed Description
For a better understanding of the present invention, the present invention is further illustrated below with reference to the following embodiments, but these embodiments should not be construed as limiting the present invention in any way.
In the present invention, unless otherwise specified, the L AB color values describe all colors that a normal-sighted person can see, where L represents brightness, a represents the range from red to green, b represents the range from yellow to blue, L has a range from 0 to 100, and a and b have ranges from +127 to-128.
In one embodiment, the present invention relates to a complex formulation for use as a stabilizer in the ring-opening polymerization of lactide to produce polylactic acid, wherein the complex formulation comprises a stearate and a phenolic antioxidant.
In a preferred embodiment, the complex formulation comprises stearate and phenolic antioxidant in a mass ratio of 1:6 to 8:1, preferably 1:4 to 3: 1.
In a preferred embodiment, the stearate may be selected, for example, from magnesium stearate, zinc stearate, calcium stearate and/or barium stearate.
In a preferred embodiment, the phenolic antioxidant may be selected, for example, from antioxidant 1076, antioxidant 2246 and/or antioxidant 330.
In a preferred embodiment, the complex formulation further comprises an organotin stabilizer, such as, but not limited to, methyltin, dimethyltin, dioctyltin, and/or tetraphenyltin.
In a preferred embodiment, in the complex formulation, the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer is 4 to 6:1, for example 5: 1.
In another embodiment, the present invention relates to the use of the above-described complex formulation as a stabilizer in the production of polylactic acid by ring-opening polymerization from lactide as a raw material.
In a preferred embodiment, the amount of the complex formulation is 0.5 to 3 wt%, preferably 1 to 2 wt% of the amount of the lactide.
In still another embodiment, the present invention relates to a method for producing polylactic acid by ring-opening polymerization using the above complex formulation using lactide as a raw material, wherein the complex formulation is added after the ring-opening polymerization reaction of lactide is completed.
In a preferred embodiment, 0.5 to 3 wt%, preferably 1 to 2 wt% of the lactide is added relative to the amount of the lactide.
In a preferred embodiment, the components of the complex formulation are added simultaneously, or sequentially, either continuously or at short intervals.
The ring-opening polymerization of lactide is a conventional reaction in the art, wherein the relevant reaction parameters can be determined by one skilled in the art according to the general technical knowledge in the art. For details or technical details, reference may be made, for example, to the following documents: wajora Han et al, popular science and technology, research on the synthesis of polylactic acid by lactide ring-opening polymerization, 20(5), 5 months and 20 days in 2018; wangshoufeng, the synthetic research of polylactic acid, northwest university, 2007; hujian army, progress of chemical engineering, progress of synthetic techniques of polylactic acid, 31(12), 2012, etc. The contents of the above documents are incorporated herein by reference.
For example, the specific composite stabilizer of the present invention can be used to produce a polylactic acid product from polylactic acid as a raw material by the following exemplary polylactic acid production process, but the scope of the present invention is not limited thereto:
(1) lactide melting
And (2) sucking lactide into a lactide feeding tank by using a vacuum pump under negative pressure, heating and melting the fed lactide in the lactide feeding tank under a micro-vacuum state (for example, introducing heat-conducting oil into a tank jacket for indirect heating), and keeping the lactide in a molten state at the temperature of 100-120 ℃ for later use.
(2) Ring opening polymerization
Adding lactide and a catalyst (such as stannous octoate and the like, but not limited thereto) and an initiator (such as 1, 4-butanediol and the like, but not limited thereto) in a molten state into a polymer preheater under the protection of nitrogen for heating, then pouring the heated lactide and the catalyst into a polymerization reactor, vacuumizing at an exhaust hole, and heating in a closed reactor (such as indirectly heating to 160 ℃ through introducing heat conduction oil into a jacket) for prepolymerization after reaching a high vacuum environment required by the reaction; until a chemical equilibrium between the polymer and the monomer is reached, at which point the ring-opening polymerization of the lactide is complete.
(3) Demonomerization reaction
At a temperature of 200 ℃ a demonomerization reaction was carried out. And then adding the composite stabilizer.
(4) Granulation and crystallization
After the monomer removing reaction, the heat conduction oil is used for cooling, the recovered heat is used for heating the raw material, and the melt enters a granulation system to be extruded to obtain polylactic acid particles.
It will be understood by those skilled in the art that, in the above step (3), the components of the complex formulation of the present invention added as a stabilizer may be added simultaneously or sequentially or consecutively or at short intervals.
For illustration purposes, the solution of the invention can be implemented, for example, by the following paragraphs:
1. a complex formulation for use as a stabilizer in the production of polylactic acid by ring-opening polymerization of lactide, wherein the complex formulation comprises a stearate and a phenolic antioxidant.
2. The complex formulation of paragraph 1, wherein the complex formulation comprises the stearate and the phenolic antioxidant in a mass ratio of 1:6 to 8: 1.
3. The complex formulation of paragraph 2, wherein the complex formulation comprises the stearate and the phenolic antioxidant in a mass ratio of 1:4 to 3: 1.
4. The combination preparation as described in any one of paragraphs 1 to 3, wherein the stearate is selected from magnesium stearate, zinc stearate, calcium stearate and/or barium stearate.
5. The complex formulation of any of paragraphs 1-4, wherein said phenolic antioxidant is selected from antioxidant 1076, antioxidant 2246 and/or antioxidant 330.
6. The complex formulation of any of paragraphs 1-5, wherein the complex formulation further comprises an organotin stabilizer.
7. The composite formulation as described in paragraph 6 wherein the organotin stabilizer is methyltin, dimethyltin, dioctyltin, and/or tetraphenyltin.
8. The complex formulation as described in any of paragraphs 1 to 7, wherein a mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer in the complex formulation is 4 to 6: 1.
9. The complex formulation of paragraph 8, wherein the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer is 5: 1.
10. Use of the complex formulation of any of paragraphs 1-9 as a stabilizer in the production of polylactic acid by ring-opening polymerization from lactide as a starting material.
11. The use of paragraph 10 wherein the amount of the complex formulation is 0.5 wt% to 3 wt% of the amount of lactide.
12. The use of paragraph 11 wherein the amount of the complex formulation is 1 to 2 wt% of the amount of lactide.
13. A method for producing polylactic acid by ring-opening polymerization using the composite preparation described in any of paragraphs 1 to 9, wherein the composite preparation is added after the ring-opening polymerization reaction of lactide is completed.
14. The method of paragraph 13 wherein 0.5 wt% to 3 wt% of the co-formulation is added relative to the amount of lactide.
15. The method of paragraph 14, wherein 1 wt% to 2 wt% of the complex formulation is added relative to the amount of lactide.
16. The method of any of paragraphs 13-15, wherein the components of the co-formulation are added simultaneously or sequentially, either continuously or at short intervals.
Examples
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials, equipment and the like used in the following examples are commercially available unless otherwise specified.
Example 1
50kg of lactide was sucked into a lactide feed tank by a vacuum pump under negative pressure (-0.3MPA), and the lactide was melted by heating for 5min under a slight vacuum (545 to 685torr) and kept in a molten state at a temperature of 110 ℃. Then, lactide in a molten state, stannous octoate in an amount of 2 wt% and 1, 4-butanediol as an initiator in an amount of 0.8 wt% relative to the lactide are added into a polymer preheater under the protection of nitrogen and heated to 140 ℃, then poured into a polymerization reactor, and simultaneously vacuumized at an exhaust hole to reach a high vacuum environment (0.001Pa) required by the reaction, and then pre-polymerized by heating to 160 ℃ in a closed reactor until chemical equilibrium between the polymer and the monomer is reached. Then, when the reaction mixture was further heated to a temperature of about 200 ℃, the demonomerization reaction was carried out. Thereafter, stabilizer methyltin, calcium stearate and antioxidant 2246 (mass ratio 1:3:2) were added thereto in an amount of 1 wt% with respect to the amount of lactide fed, and the melt was fed into a pelletizing system (TDS-75D co-rotating twin screw extruder, nyujingdaxin extrusion equipment ltd) and extruded to obtain polylactic acid pellets.
Example 2
50kg of lactide was sucked into a lactide feed tank by a vacuum pump under negative pressure (-0.3MPA), and the lactide was melted by heating for 5min under a slight vacuum (545 to 685torr) and kept in a molten state at a temperature of 110 ℃. Then, lactide in a molten state, stannous octoate in an amount of 2 wt% and 1, 4-butanediol as an initiator in an amount of 0.8 wt% relative to the lactide are added into a polymer preheater under the protection of nitrogen and heated to 140 ℃, then poured into a polymerization reactor, and simultaneously vacuumized at an exhaust hole to reach a high vacuum environment (0.001Pa) required by the reaction, and then pre-polymerized by heating to 160 ℃ in a closed reactor until chemical equilibrium between the polymer and the monomer is reached. Then, when the reaction mixture was further heated to a temperature of about 200 ℃, the demonomerization reaction was carried out. Thereafter, 1 wt% of stabilizer magnesium stearate and antioxidant 2246 (mass ratio 1:4) with respect to the amount of lactide fed were added thereto, and the melt was fed into a pelletizing system (TDS-75D co-rotating twin screw extruder, nanjing noraxxin industry extrusion equipment limited) and extruded to obtain polylactic acid pellets.
Example 3
50kg of lactide was sucked into a lactide feed tank by a vacuum pump under negative pressure (-0.3MPA), and the lactide was melted by heating for 5min under a slight vacuum (545-685 torr) and kept in a molten state at a temperature of 120 ℃. Then, lactide in a molten state, stannous octoate in an amount of 2 wt% and 1, 4-butanediol as an initiator in an amount of 0.8 wt% relative to the lactide are added into a polymer preheater under the protection of nitrogen and heated to 140 ℃, then poured into a polymerization reactor, and simultaneously vacuumized at an exhaust hole to reach a high vacuum environment (0.001Pa) required by the reaction, and then pre-polymerized by heating to 160 ℃ in a closed reactor until chemical equilibrium between the polymer and the monomer is reached. Then, when the reaction mixture was further heated to a temperature of about 200 ℃, the demonomerization reaction was carried out. Thereafter, 1.5 wt% of stabilizer zinc stearate and antioxidant 330 (mass ratio 3:1) with respect to the amount of lactide fed were added thereto, and the melt was fed into a pelletizing system (TDS-75D co-rotating twin screw extruder, nanjing noraxxin industrial extrusion equipment limited) and extruded to obtain polylactic acid pellets.
Example 4
Sucking 50kg of lactide into a lactide feeding tank by using a vacuum pump under negative pressure, heating the lactide for 5min to melt the lactide in a micro vacuum (545-685 torr) state, and keeping the lactide in a molten state at the temperature of 100 ℃. Then, lactide in a molten state, stannous octoate accounting for 2 wt% of the lactide and 1, 4-butanediol as an initiator accounting for 0.8 wt% of the lactide are added into a polymer preheater under the protection of nitrogen and heated to 140 ℃, then poured into a polymerization reactor, and simultaneously vacuumized at an exhaust hole to reach a high vacuum environment (0.001Pa) required by the reaction, and then prepolymerized by heating to 160 ℃ in a closed reactor until chemical equilibrium between the polymer and the monomer is reached. Then, when the reaction mixture was further heated to a temperature of about 200 ℃, the demonomerization reaction was carried out. After that, 2 wt% of stabilizer barium stearate and antioxidant 1076 (mass ratio of 1:2) with respect to the amount of lactide fed were added thereto, and the melt was fed into a pelletizing system (TDS-75D co-rotating twin screw extruder, nanjing norxin industrial extrusion equipment ltd) and extruded to obtain polylactic acid pellets.
Comparative example 1
Polylactic acid particles were obtained according to the procedure and conditions of example 1, except that no stabilizer was added.
Comparative example 2
Polylactic acid granules were obtained according to the procedure and conditions of example 1, except that magnesium stearate alone was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 3
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that the antioxidant 2246 alone was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 4
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that only calcium stearate was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 5
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that the antioxidant 330 alone was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 6
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that the antioxidant 1076 alone was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 7
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that only barium stearate was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
Comparative example 8
Polylactic acid particles were obtained by following the procedure and conditions of example 1, except that only zinc stearate was used as a stabilizer (the amount of the stabilizer was the same as in example 1).
The polylactic acid pellets obtained in examples 1 to 4 and comparative examples 1 to 8 were subjected to L AB color value detection using L AB value detector (ZB-a colorimeter, hangzhou paho automation technology ltd), wherein the B value was detected as shown in table 1 below:
TABLE 1 detection results of L AB color values of polylactic acids obtained in examples 1 to 4 and comparative examples 1 to 8
| Numbering | Detection index (B value) |
| Example 1 | 8.26 |
| Example 2 | 9.65 |
| Example 3 | 9.81 |
| Example 4 | 9.27 |
| Comparative example 1 | 24.59 |
| Comparative example 2 | 14.23 |
| Comparative example 3 | 14.92 |
| Comparative example 4 | 15.59 |
| Comparative example 5 | 14.37 |
| Comparative example 6 | 15.16 |
| Comparative example 7 | 15.82 |
| Comparative example 8 | 14.65 |
The results in the above table show that the addition of the stabilizer can lower the B value among L AB values of the polylactic acid particles, as compared with comparative example 1 in which no stabilizer is added, and that the addition of the specific composite stabilizer of the present invention (examples 1 to 4) can lower the B value among L AB values of the polylactic acid particles more remarkably, as compared with comparative examples 2 to 8 in which only a single stabilizer is added.
Claims (19)
1. The composite preparation is used as a stabilizer in the process of producing polylactic acid by ring-opening polymerization by taking lactide as a raw material;
wherein the compound preparation comprises stearate and phenolic antioxidant in a mass ratio of 1:6-8: 1;
the phenolic antioxidant is selected from antioxidant 1076, antioxidant 2246 and/or antioxidant 330.
2. The use according to claim 1, wherein the complex formulation comprises stearate and phenolic antioxidant in a mass ratio of 1:4 to 3: 1.
3. Use according to claim 1, wherein the stearate is selected from magnesium stearate, zinc stearate, calcium stearate and/or barium stearate.
4. Use according to any one of claims 1 to 3, wherein the complex formulation further comprises an organotin stabilizer.
5. The use according to claim 4, wherein the complex formulation further comprises methyltin, dimethyltin, dioctyltin and/or tetraphenyltin.
6. The use according to claim 4, wherein the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer in the composite preparation is 4-6: 1.
7. The use according to claim 6, wherein the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer in the complex formulation is 5: 1.
8. The use according to claim 1, wherein the complex formulation is used in an amount of 0.5 to 3 wt% of the amount of lactide.
9. The use according to claim 8, wherein the complex formulation is used in an amount of 1 to 2 wt% of the amount of lactide.
10. A method for producing polylactic acid by using a composite preparation and using lactide as a raw material through ring-opening polymerization, wherein the composite preparation is added after the ring-opening polymerization reaction of the lactide is completed;
wherein the compound preparation comprises stearate and phenolic antioxidant in a mass ratio of 1:6-8: 1;
the phenolic antioxidant is selected from antioxidant 1076, antioxidant 2246 and/or antioxidant 330.
11. The method of claim 10, wherein the co-formulation comprises stearate and phenolic antioxidant in a mass ratio of 1:4 to 3: 1.
12. The process according to claim 10, wherein the stearate is selected from magnesium stearate, zinc stearate, calcium stearate and/or barium stearate.
13. The method of any one of claims 10-12, wherein the co-formulation further comprises an organotin stabilizer.
14. The method of claim 13, wherein the complex formulation further comprises methyltin, dimethyltin, dioctyltin, and/or tetraphenyltin.
15. The method according to claim 13, wherein the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer in the complex formulation is 4-6: 1.
16. The method according to claim 15, wherein the mass ratio of the total mass of the stearate and the phenolic antioxidant to the organotin stabilizer in the co-formulation is 5: 1. .
17. The method according to claim 10, wherein 0.5 to 3 wt% of the complex formulation is added with respect to the amount of lactide.
18. The method of claim 17, wherein 1 to 2 wt% of the complex formulation is added with respect to the amount of the lactide.
19. The method of claim 17, wherein the components of the complex formulation are added simultaneously or sequentially, either continuously or at short intervals.
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| CN101020780B (en) * | 2007-03-15 | 2010-05-19 | 上海交通大学 | Preparation process of polylactic acid-base thermoplastic wood-plastic composite material |
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