CN112980168A - High-impact-resistance full-bio-based polylactic acid/bamboo powder composite material and preparation method thereof - Google Patents
High-impact-resistance full-bio-based polylactic acid/bamboo powder composite material and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention discloses a full-bio-based high-impact polylactic acid/bamboo powder composite material and a preparation method thereof, belonging to the field of bio-based high polymer materials. The epoxidized soybean oil-graft-sebacic acid oligomer obtained by the ring opening reaction of epoxidized soybean oil and sebacic acid under the catalysis can simultaneously solve the problems of poor compatibility, low impact strength, poor processing fluidity and the like of the polylactic acid/bamboo powder composite material. The oligomer is added into a polylactic acid/bamboo powder system to prepare a high-impact polylactic acid/bamboo powder composite material, wherein the tensile strength of the material is 23-36 MPa, the elongation at break is 2.46-11.98%, and the impact strength is 9-16 KJ/m2Compared with polylactic acid/bamboo powder composite material without the oligomer, the impact strength is improved by 3 times after the oligomer is added. In addition, the added ingredients are adopted due to the improvement of processing fluidityThe square injection molding spoon has no defects of cavities, bubbles and the like.
Description
Technical Field
The invention discloses a preparation method of a high-impact-resistance full-bio-based polylactic acid/bamboo powder composite material, belonging to the field of green bio-based composite materials.
Background
Polylactic acid is a thermoplastic bio-based polymer material synthesized from renewable resources, has excellent biocompatibility and compost degradability, and is widely applied to packaging materials and biomedical materials. However, the problems of low heat distortion temperature, high brittleness, high cost and insufficient impact strength of polylactic acid limit the large-scale industrial application thereof. Research on high-performance and low-cost polylactic acid materials has received much attention. The bamboo material belongs to fast growing wood, and the bamboo fiber powder film obtained from the bamboo material has the advantages of high strength, narrow included angle of superfine fibers, low cost and the like. Therefore, the bamboo powder can be used as the reinforcing fiber of the polylactic acid, so that the impact strength and the heat distortion temperature of the polylactic acid are improved, and the material cost is reduced to a certain extent. Compared with the traditional synthetic fiber (such as aramid fiber and glass fiber), the bamboo powder has the advantages of no toxicity, economy, environmental protection and the like. However, the bamboo powder contains a large amount of hydrophilic groups such as alcoholic hydroxyl and phenolic hydroxyl on the surface, so that the polarity and the hydrophilicity of the bamboo powder are high, and when the bamboo powder is compounded with non-polar polylactic acid, the bamboo powder is gathered together and is difficult to uniformly disperse in a polylactic acid matrix. In addition, the unmodified bamboo powder particles have large frictional resistance, so that the melt flowability is poor, and the processing and the forming are difficult. Therefore, the difficulty in developing a high-performance polylactic acid/bamboo powder composite material is to improve the interface compatibility between the polylactic acid matrix and the bamboo powder so as to obtain a product with excellent comprehensive performance.
Methods to improve interfacial compatibility include bamboo powder surface pretreatment (physical or chemical modification) and addition of compatibilizers (reactive and non-reactive). The surface pretreatment of the bamboo powder can change the surface morphology of the fiber and remove components (such as pectin, hemicellulose, lignin, parenchyma cells and the like) which have negative influence on the interface bonding strength. The addition of the compatibilizer can improve the interfacial bonding force among the components and improve the compatibility of the components. At present, the most common method for the surface pretreatment of bamboo powder is alkali treatment. Although the contact area between the blast furnace and the polylactic acid matrix can be effectively improved, more hydrophilic groups can be generated by alkaline hydrolysis, the operation process is time-consuming and complicated, and a large amount of waste liquid can be generated, so that certain pollution is caused to the environment. The addition of the compatibilizer (including reactive and non-reactive compatibilizers) can reduce the processing flow, and is simple and efficient. Therefore, the addition of proper types and dosage of the compatibilizer is the main research and development direction for improving the performance of the polylactic acid/bamboo powder composite material. Inorganic fillers such as talcum powder and a small amount of chitosan, nano clay and the like are added into the polylactic acid/bamboo powder composite material as a compatibilizer, so that the mechanical strength, the thermal property and the crystallization property of the Polymer can be effectively improved (Journal of Applied Polymer Science,2012,123(5): 2828-. Polyethylene glycol, acetyl tributyl citrate, lactide-graft-bamboo powder, etc. can also be used as efficient plasticizers for polylactic acid/bamboo powder (Journal of Applied Polymer Science,2019,136(26): 47709; Journal of Applied Polymer Science,2019,136(26): 477-.
Vegetable oil is a green raw material with rich source and low price, after oxidation reaction, double bonds on a molecular chain are oxidized by oxide epoxy functional groups, and epoxidized soybean oil is often used as a plasticizer of PVC materials. However, the compatibility of the material obtained by directly blending the epoxidized soybean oil with the polylactic acid/bamboo powder is improved to a certain extent, but small molecules of the epoxidized soybean oil migrate to the surface of the material along with the prolonging of time, so that the phenomena of product surface stickiness and the like are caused, and the long-term use of the product is not facilitated. Sebacic acid is a long-chain fatty acid, is obtained by catalytic hydrolysis of castor oil, is a bio-based monomer derived from renewable resources, like epoxidized soybean oil. In the chinese patent CN201610899740.2, epoxy soybean oil, sebacic acid and polylactic acid are simultaneously added into an internal mixer for mixing by using a dynamic vulcanization method, and the tensile property of the obtained polylactic acid material is greatly improved. The dynamic vulcanization method has the advantages of simple method, but simultaneously, because the reaction time is short (if the blending reaction time is prolonged, the polylactic acid is subjected to thermal degradation), a plurality of unreacted monomer molecules exist, and the small molecules can migrate to the surface of the material to cause the loss of the material performance.
Disclosure of Invention
Based on the reasons, the invention adopts a two-step method, firstly, the epoxy soybean oil-graft-sebacic acid oligomer is synthesized, and then, the polylactic acid, the bamboo powder and the epoxy soybean oil-graft-sebacic acid oligomer are mixed to prepare the high-toughness polylactic acid/bamboo powder composite material. The preparation method has the advantages that the molecular weight-controllable oxysoybean oil-graft-sebacic acid oligomer can be prepared by controlling the reaction temperature and the reaction time, so that the polylactic acid/bamboo powder system can be subjected to better toughening modification by selecting the oligomer with proper molecular weight.
1. The material for simultaneously solving the problems of poor compatibility, low impact strength, poor processing fluidity and the like of the polylactic acid/bamboo powder composite material is epoxidized soybean oil-graft-sebacic acid oligomer, and is obtained by ring opening reaction of epoxidized soybean oil and sebacic acid under the catalysis.
The mass ratio of the epoxidized soybean oil to the sebacic acid is 9: 1;
the catalyst is 4-dimethylamino pyridine;
the reaction temperature is 120-200 ℃;
the reaction time is 5-20 min;
the number average molecular weight of the epoxidized soybean oil-graft-sebacic acid oligomer is 2000-4000 g/mol.
2. A high-impact-resistance full-bio-based polylactic acid/bamboo powder composite material is composed of the following raw materials in percentage by weight:
polylactic acid: 50-90 parts;
bamboo powder: 50-10 parts;
epoxidized soybean oil-graft-sebacic acid oligomer: 4-20 parts.
3. The preparation process of the high-impact-resistance full-bio-based polylactic acid/bamboo powder composite material in the step 2 is as follows: firstly, drying polylactic acid and bamboo powder, then adding the polylactic acid, the bamboo powder and the epoxidized soybean oil-graft-sebacic acid oligomer into a high-speed mixer to be uniformly mixed at normal temperature, then adding the mixture into a double-screw extruder to be subjected to melt extrusion, bracing, air cooling and granulation to obtain the full-bio-based polylactic acid/bamboo powder composite material.
4. The temperature of the double-screw extruder in the step 3 is controlled to be 180-190 ℃, and the rotating speed is controlled to be 80-150 rpm; the length-diameter ratio of the screw is 32: 1-45: 1.
The high-impact-resistance full-bio-based polylactic acid/bamboo powder composite material prepared by the invention has excellent mechanical properties and processability, and can be used in the field of food contact materials such as knife, fork and spoon due to the fact that all raw materials are derived from biomass and are non-toxic and green.
Compared with the prior art, the full-bio-based polylactic acid/bamboo powder composite material prepared by the invention has the following outstanding advantages: all the raw materials used in the invention are from bio-based, have the characteristics of environmental protection and degradability after being discarded, and have positive promotion significance for the sustainable development of the environment and the society. The epoxidized soybean oil-graft-sebacic acid oligomer has the functions of a toughening agent, a compatilizer and an impact modifier, and the problems of poor compatibility, low impact strength, poor processing flowability and the like of the polylactic acid/bamboo powder composite material are simply and efficiently solved. Because the epoxidized soybean oil-graft-sebacic acid oligomer in the formed composite material is coated on the surface of the bamboo powder fiber, the defect that the surface of a bamboo-based material is easy to mildew and deteriorate can be effectively overcome.
Drawings
FIG. 1 is a scanning electron micrograph of an impact cross section of comparative example and example;
fig. 2 shows the spoon injection moulded in example 4.
Detailed Description
Comparative examples and preferred examples of the present invention will be described in detail below.
Comparative example 1
Comparative example 1 is a polylactic acid/bamboo powder composite system modified without epoxidized soybean oil-graft-sebacic acid oligomer. The preparation method comprises the following steps: adding polylactic acid and bamboo powder into a double-screw extruder according to the weight ratio of 70:30, carrying out melt extrusion, bracing, air cooling and granulation to obtain the polylactic acid/bamboo powder composite material, wherein the temperature of the double-screw extruder is controlled to be 180-190 ℃. Comparative example 1 had a tensile strength of 38.32MPa, an elongation at break of 1.65%, and an unnotched impact strength of 5.8KJ/m for a simply supported beam2. It can be seen that the polylactic acid/bamboo powder composite material before modification has large brittleness and low impact strength, and is not suitable for production of injection molding parts.
The following examples are to improve the toughness and impact resistance of polylactic acid/bamboo powder composites by adding epoxidized soybean oil-graft-sebacic acid oligomers of different reaction times and weights.
Examples 1-4 the synthesis conditions for the epoxidized soybean oil-graft-sebacic acid oligomer were: adding epoxidized soybean oil and sebacic acid into a reaction container according to the mass ratio of 9:1, adding 1 millimole of catalyst 4-dimethylaminopyridine, reacting at the temperature of 150 ℃ for 12min to obtain epoxidized soybean oil-graft-sebacic acid oligomer (VESO)12) Number-average molecular weight of 2983gmol。
Example 1
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)12) And (3) blending according to the weight ratio of 66:30:4, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 1 had a tensile strength of 35.58MPa, an elongation at break of 2.46% and an unnotched impact strength of 8.93KJ/m for a simply supported beam2。
Example 2
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)12) And (2) blending according to the weight ratio of 62:30:8, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 2 had a tensile strength of 35.54MPa, an elongation at break of 3.42% and an unnotched impact strength of 11.33KJ/m for a simply supported beam2。
Example 3
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)12) And (2) blending according to the weight ratio of 58:30:12, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 3 had a tensile strength of 27.07MPa, an elongation at break of 7.74%, and an unnotched impact strength of 13.73KJ/m for a simply supported beam2。
Example 4
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)12) And (3) blending according to the weight ratio of 54:30:16, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 4 had a tensile strength of 26.88MPa, an elongation at break of 10.8%, and an unnotched impact strength of 16.25KJ/m for a simply supported beam2。
Examples 5-8 Synthesis of epoxidized Soybean oil-graft-sebacic acid oligomer: adding epoxidized soybean oil and sebacic acid into a reaction container according to the mass ratio of 9:1, adding 1 millimole of catalyst 4-dimethylaminopyridine, reacting at the temperature of 150 ℃ for 18min to obtain epoxidized soybean oil-graft-sebacic acid oligomer (VESO)18) The number average molecular weight was 3972 g/mol.
Example 5
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)18) And (3) blending according to the weight ratio of 66:30:4, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 5 had a tensile strength of 35.88MPa, an elongation at break of 2.84%, and an unnotched impact strength of 10.13KJ/m for a simply supported beam2。
Example 6
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)18) And (2) blending according to the weight ratio of 62:30:8, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 6 had a tensile strength of 33.97MPa, an elongation at break of 3.22%, and an unnotched impact strength of 13.23KJ/m for a simply supported beam2。
Example 7
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)18) And (2) blending according to the weight ratio of 58:30:12, adding a double screw, performing melt extrusion, bracing, air cooling and granulation to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, wherein the temperature of a double screw extruder is controlled at 180-190 ℃. Example 7 had a tensile strength of 25.28MPa, an elongation at break of 11.98%, and an unnotched impact strength of 14.55KJ/m for a simply supported beam2。
Example 8
Mixing polylactic acid, bamboo powder and epoxidized soybean oil-graft-sebacic acid oligomer (VESO)18) Blending according to the weight ratio of 54:30:16, adding twin-screw to melt and extrude, bracing, air cooling and granulating to obtain the full bio-based polylactic acid/bamboo powder/VESO composite material, and controlling the temperature of a twin-screw extruderAt 180-190 ℃. Example 8 had a tensile strength of 23.35MPa, an elongation at break of 9.63%, and an unnotched impact strength of 14.23KJ/m for a simply supported beam2。
All the mechanical property data of examples 1 to 8 are shown in table 1. From the results, it can be seen that the molecular weight of the epoxidized soybean oil-graft-sebacic acid oligomer (VESO) gradually increased and the viscosity also increased as the reaction time was prolonged. From the toughening effect point of view, VESO18Toughening effect and VESO12The difference is not large. Therefore, the toughening effect of the final polylactic acid/bamboo powder/VESO system is not obvious due to the prolonged reaction time. However, as the content increases from 4% to 12%, a significant increase in elongation at break and impact strength occurs, and the impact strength of example 4 is almost 3 times that of comparative example 1. As can be seen from FIG. 1, the number of filaments in the impact cross-section increases significantly with increasing addition of VESO, showing significant ductile fracture. Fig. 2 shows that the spoon injection-molded according to the formulation of example 4 has good melt fluidity during injection molding, and the injection-molded part has no defects such as cavities and bubbles due to the change of processing fluidity compared with unmodified polylactic acid/bamboo powder. Therefore, the addition of the VESO obviously improves the interfacial compatibility of the polylactic acid/bamboo powder system, and simultaneously plays a role of a toughening agent, a compatilizer and an impact modifier.
TABLE 1 comparison of mechanical Properties of the examples and comparative examples
Finally, it is noted that the above-mentioned preferred examples are merely intended to illustrate rather than to limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The material for simultaneously solving the problems of poor compatibility, low impact strength, poor processing fluidity and the like of the polylactic acid/bamboo powder composite material is epoxidized soybean oil-graft-sebacic acid oligomer, and is obtained by ring opening reaction of epoxidized soybean oil and sebacic acid under the catalysis.
2. The epoxidized soybean oil and sebacic acid of claim 1 in a mass ratio of 9: 1.
3. The catalyst of claim 1 which is 4-dimethylaminopyridine.
4. The reaction temperature of claim 1 is 120 to 200 ℃.
5. The reaction time of claim 1 is 5 to 20 min.
6. The epoxidized soybean oil-graft-sebacic acid oligomer of claim 1 having a number average molecular weight of 2000 to 4000 g/mol.
7. A high-impact-resistance full-bio-based polylactic acid/bamboo powder composite material is composed of the following raw materials in percentage by weight:
polylactic acid: 50-90 parts;
bamboo powder: 50-10 parts;
epoxidized soybean oil-graft-sebacic acid oligomer: 4-20 parts.
8. The high-impact all-bio-based polylactic acid/bamboo powder composite material of claim 7, which is prepared by the following process: firstly, drying polylactic acid and bamboo powder, then adding the polylactic acid, the bamboo powder and the epoxidized soybean oil-graft-sebacic acid oligomer into a high-speed mixer to be uniformly mixed at normal temperature, then adding the mixture into a double-screw extruder to be subjected to melt extrusion, bracing, air cooling and granulation to obtain the full-bio-based polylactic acid/bamboo powder composite material.
9. The temperature of the twin-screw extruder of claim 7 is controlled to be 180-190 ℃, and the rotating speed is controlled to be 80-150 rpm; the length-diameter ratio of the screw is 32: 1-45: 1.
10. Use of the high impact all bio-based polylactic acid/bamboo powder composite of claim 7 in the preparation of a food contact material for a knife and fork scoop.
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| CN113845648A (en) * | 2021-10-19 | 2021-12-28 | 北京工商大学 | Preparation and application of ESO-SA bio-based plasticizer |
| CN115354446A (en) * | 2022-08-19 | 2022-11-18 | 吉祥三宝高科纺织有限公司 | Polylactic acid thermal insulating flocculus with high fluffiness and high resilience and preparation method thereof |
| CN115558264A (en) * | 2022-09-30 | 2023-01-03 | 福州大学 | Non-reactive compatibilization PLA/PBAT composite material and preparation method thereof |
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