CN112063136B - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN112063136B CN112063136B CN202010808122.9A CN202010808122A CN112063136B CN 112063136 B CN112063136 B CN 112063136B CN 202010808122 A CN202010808122 A CN 202010808122A CN 112063136 B CN112063136 B CN 112063136B
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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
本发明提出了制备聚乳酸复合材料的方法，所述方法包括：将洋麻纤维进行碱处理，以便得到碱处理的洋麻纤维；将所述碱处理的洋麻纤维与丙交酯单体进行第一交联处理，以便得到丙交酯接枝的洋麻纤维；将所述丙交酯接枝的洋麻纤维与环氧大豆油进行第二交联处理，以便得到环氧大豆油‑丙交酯接枝的洋麻纤维；以及将所述环氧大豆油‑丙交酯接枝的洋麻纤维与聚乳酸进行熔融共混处理，以便得到所述聚乳酸复合材料。采用本发明的方法所得到的聚乳酸复合材料具有优良的韧性和耐热性，具有良好的长期稳定性，机械性能良好，制备方法操作简便、快捷、污染小，适于规模化生产和应用。The present invention provides a method for preparing a polylactic acid composite material. The method comprises: subjecting kenaf fibers to alkali treatment to obtain alkali-treated kenaf fibers; and subjecting the alkali-treated kenaf fibers to lactide monomers. The first cross-linking treatment is to obtain the kenaf fiber grafted by lactide; The second cross-linking treatment is carried out to obtain the epoxidized soybean oil-propylene by carrying out the second cross-linking treatment of the lactide-grafted kenaf fiber and epoxidized soybean oil Lactide-grafted kenaf fiber; and the epoxidized soybean oil-lactide-grafted kenaf fiber and polylactic acid are melt-blended to obtain the polylactic acid composite material. The polylactic acid composite material obtained by the method of the present invention has excellent toughness and heat resistance, good long-term stability, good mechanical properties, and the preparation method is simple, fast, and pollution-free, and is suitable for large-scale production and application.
Description
Technical Field
The invention relates to the field of materials. In particular, the invention relates to a polylactic acid composite material and a preparation method thereof.
Background
With the development of the power industry scale and the diversification of power generation and power transmission forms, the requirements of urban power utilization, hydropower output, seabed power transmission and resource environment protection, various cables are increasingly widely applied, at present, the first batch of power equipment insulating materials in China are in aging decommissioning, and crosslinked polyethylene, polyvinyl chloride and the like take fossil energy as raw materials, so that the electrically insulating materials widely used for the power cables have the characteristics of difficult degradation, high recovery processing cost, landfill pollution to the environment and the like. With the increasing awareness of environmental protection, renewable and environmentally friendly materials gradually enter the public, and polylactic acid (PLA) is a biodegradable environmentally friendly material prepared from starch extracted from renewable plant resources (such as corn and soybean). A great deal of research is carried out at home and abroad aiming at the heat resistance and the mechanical property of the material, and the material is widely applied to the fields of automobiles, pharmacy, packaging and the like, the electrical insulation property of the material is equivalent to the performance of the active electrical insulation materials such as crosslinked polyethylene, low-density polyethylene, high-density polyethylene, polypropylene and the like, and part of the performance parameters are slightly superior to the active electrical insulation materials. The problems of poor flexibility of polylactic acid in normal temperature or low temperature environment, poor thermal stability at high temperature, low thermal deformation temperature and the like become a bottleneck for large-scale application of the polylactic acid in cable insulation materials.
Therefore, the polylactic acid composite material and the preparation method thereof still need to be improved.
Disclosure of Invention
The present invention aims to solve at least to some extent at least one of the technical problems of the prior art. Therefore, the invention provides a polylactic acid composite material and a preparation method thereof. The polylactic acid composite material has excellent toughness and heat resistance, good long-term stability, good mechanical property, simple and convenient operation of the preparation method, rapidness, small pollution and suitability for large-scale production and application.
In one aspect of the present invention, a method of preparing a polylactic acid composite is presented. According to an embodiment of the invention, the method comprises: subjecting kenaf fibers to an alkali treatment to obtain alkali-treated kenaf fibers; subjecting the alkali-treated kenaf fiber to a first cross-linking treatment with a lactide monomer to obtain a lactide-grafted kenaf fiber; performing second cross-linking treatment on the lactide-grafted kenaf fiber and epoxidized soybean oil so as to obtain epoxidized soybean oil-lactide-grafted kenaf fiber; and carrying out melt blending treatment on the epoxidized soybean oil-lactide grafted kenaf fiber and polylactic acid so as to obtain the polylactic acid composite material.
The inventor researches a preparation method of the polylactic acid in order to improve the performance of the polylactic acid, and finds that epoxidized soybean oil and kenaf fiber plasticize the polylactic acid under the action of lactide monomers, so that the mechanical performance and the thermal performance of the polylactic acid can be well improved. However, most of the existing methods for preparing polylactic acid composite materials are performed by melt blending a plasticized material and polylactic acid, the process is physical modification, the plasticized material is prone to agglomeration, especially, the invention tries to adopt two raw materials (epoxidized soybean oil and kenaf fiber) and polylactic acid, the three-phase melt blending is prone to agglomeration compared with two phases, and the plasticized material and the polylactic acid have low interfacial compatibility and poor long-term stability.
Further, the inventors found that the toughness and heat resistance of the obtained polylactic acid composite are significantly improved, the stability is strong, and the overall mechanical properties are good, by the two-phase reaction only when the epoxidized soybean oil is connected to the lactide-grafted kenaf fiber through a chemical reaction (cross-linking reaction) and then the epoxidized soybean oil-lactide-grafted kenaf fiber and the polylactic acid are melt-blended. Therefore, the polylactic acid composite material obtained by the method for preparing the polylactic acid composite material has excellent toughness and heat resistance, good long-term stability and good mechanical property, and the preparation method is simple, convenient and quick to operate, has little pollution and is suitable for large-scale production and application.
According to an embodiment of the present invention, the method for preparing a polylactic acid composite material may further have the following additional technical features:
according to an embodiment of the invention, the second cross-linking treatment comprises: mixing and stirring the lactide grafted kenaf fiber, epoxidized soybean oil and a catalyst at 40-70 ℃ for 2-4 hours so as to obtain the epoxidized soybean oil-lactide grafted kenaf fiber. The inventor obtains the better crosslinking reaction condition through a large number of experiments, so that the epoxidized soybean oil and the kenaf fiber can be crosslinked, the crosslinking bond between lactide and the kenaf fiber is not damaged, the agglomeration in the subsequent melt blending process is avoided, the toughness and the heat resistance of the composite material can be effectively improved, and the composite material has good long-term stability and good mechanical property.
According to an embodiment of the present invention, the catalyst is selected from dimethyl sulfoxide and tin tetrachloride, preferably dimethyl sulfoxide and tin tetrachloride, and preferably, the volume ratio of dimethyl sulfoxide to tin tetrachloride is (900-1100): 1. the inventors have found that epoxidized soybean oil can be efficiently crosslinked with lactide using the above catalyst without breaking the crosslink bonds between the lactide and kenaf fibers.
According to the embodiment of the invention, the volume ratio of the lactide grafted kenaf fiber to the epoxidized soybean oil to the catalyst is (1-3): (1-3): (15-20). The proportion is obtained through a large number of experiments by the inventor, so that the epoxidized soybean oil and the kenaf fiber can be effectively crosslinked, and the crosslinking bond between lactide and the kenaf fiber is not damaged, so that agglomeration in the subsequent melt blending process is avoided, the toughness and the heat resistance of the composite material can be effectively improved, and the composite material has good long-term stability and good mechanical properties.
According to an embodiment of the invention, the alkali treatment comprises: mixing kenaf fibers with an alkali solution, mixing with an acid solution until the kenaf fibers are neutral, and then carrying out freeze drying to remove impurities, thereby obtaining the alkali-treated kenaf fibers.
According to an embodiment of the invention, the first cross-linking treatment comprises: mixing the alkali-treated kenaf fiber with toluene and calcium chloride, and heating and refluxing for 20-30 minutes to remove moisture; and (3) mixing the mixed solution from which the water is removed, a lactide monomer and stannous octoate at 130-140 ℃ for 1-2 hours, taking out the kenaf fiber, and extracting and freeze-drying the kenaf fiber to obtain the lactide grafted kenaf fiber. The inventor obtains the preferable reaction condition through a large amount of experiments, thereby effectively crosslinking lactide on the kenaf fiber so as to increase the compatibility when the kenaf fiber is blended with polylactic acid in the following process.
According to an embodiment of the present invention, the lactide monomer and alkali-treated kenaf fiber have a volume ratio of 1: (1-3). The inventor obtains the preferable proportion through a large amount of experiments, thereby effectively crosslinking lactide on the kenaf fiber so as to facilitate the subsequent increase of the compatibility when the kenaf fiber is blended with polylactic acid.
According to an embodiment of the invention, the melt blending process comprises: and mixing the epoxidized soybean oil-lactide grafted kenaf fiber with polylactic acid at 180-190 ℃ for 10-20 minutes to obtain the polylactic acid composite material. The inventors have conducted a large number of experiments to obtain the above-mentioned preferable reaction conditions, whereby epoxidized soybean oil-lactide-grafted kenaf fiber and polylactic acid are more uniformly mixed. In addition, the agglomeration phenomenon is not easy to occur in the process, the toughness and the heat resistance of the obtained composite material are obviously improved, and the composite material has good long-term stability and good mechanical properties.
According to the embodiment of the invention, the mass ratio of the epoxidized soybean oil-lactide grafted kenaf fiber to the polylactic acid is (1-10): (90-99). Therefore, the agglomeration phenomenon can be effectively avoided, the epoxidized soybean oil and the kenaf fiber can be effectively used for plasticizing the polylactic acid, so that the toughness and the heat resistance of the composite material are obviously improved, and the composite material has good long-term stability and good mechanical property.
According to an embodiment of the invention, the method further comprises: and granulating the polylactic acid composite material. Thereby facilitating storage, transport and application.
In another aspect of the present invention, a polylactic acid composite is provided. According to an embodiment of the present invention, the polylactic acid composite material is obtained by the method for preparing a polylactic acid composite material as described above. Therefore, the polylactic acid composite material disclosed by the embodiment of the invention has excellent toughness and heat resistance, good long-term stability and good mechanical properties, and is suitable for large-scale production and application.
It will be appreciated by those skilled in the art that the features and advantages described above in relation to the method of preparing the polylactic acid composite are equally applicable to the polylactic acid composite and will not be described in further detail herein.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
1) Alkali treatment of kenaf fiber:
taking kenaf fiber with the length of 500-800 nm and the diameter of 5-20 nm out, soaking the kenaf fiber in a 15% NaOH solution at the temperature of 25 ℃, continuously stirring the kenaf fiber by using an electromagnetic stirrer or a glass rod for 4 hours, slowly adding glacial acetic acid until the solution is neutral, taking the kenaf fiber out, washing the kenaf fiber by using distilled water, and freeze-drying and storing the kenaf fiber in a freeze dryer.
2) Lactide grafted kenaf fiber:
the alkali-treated kenaf fiber obtained in step 1) was previously dried in a vacuum oven at 80 ℃ for 6 hours. Toluene and CaCl were added to the flask in a ratio of 9:12The reaction system was heated to 110 ℃ and the toluene was boiled and refluxed for 30 minutes to remove water in the reaction system. To the flask was added propane in a ratio of 1:1Lactide monomer and kenaf fiber, and then replacing gas in the reaction system with N by gas replacement2Heating to 130 ℃, adding stannous octoate and lactide monomer in a mass ratio of 1:100, adjusting an inlet valve and an outlet valve to enable the system to be in a decompression state, stirring with an electromagnetic stirrer at an accelerated speed, reacting for 1 hour continuously, taking out the kenaf fibers, extracting the kenaf fibers by a Soxhlet extraction method, and then drying the extracted kenaf fibers in a freeze drying oven for later use.
3) Epoxy soybean oil grafted kenaf fiber:
pouring 1 part of the lactide grafted kenaf fiber obtained in the step 2) and 1 part of epoxidized soybean oil into a flask, pouring a small amount of dimethyl sulfoxide into the flask to fully dissolve the kenaf fiber, heating to raise the temperature of a reaction system to about 60 ℃, keeping the temperature constant, opening an electromagnetic stirrer to stir vigorously, and simultaneously slowly dropwise adding 15 parts of mixed solution of tin tetrachloride and dimethyl sulfoxide with a ratio of 1:1000 through a constant-pressure funnel to be used as a catalyst for reaction, wherein the reaction time is 2 hours. Removing dimethyl sulfoxide to obtain epoxidized soybean oil and lactide grafted kenaf fiber.
4) Preparing a high-toughness heat-resistant environment-friendly polylactic acid material:
placing the epoxidized soybean oil, the lactide grafted kenaf fiber and the polylactic acid particles obtained in the step 3) in an oven at 80 ℃ in advance for drying for 8 hours, heating a double-screw extruder to 190 ℃, preheating for 2 hours, and then proportionally mixing the epoxidized soybean oil-lactide grafted kenaf fiber with the polylactic acid particles to be 1%: putting 99 percent of the mixture into a double-screw extruder, mixing for 20 minutes, and then extruding and granulating. Respectively preparing the epoxidized soybean oil and the lactide grafted kenaf fiber which have the mass fraction of 1 percent and are high-toughness heat-resistant and environment-friendly cable materials.
Example 2
1) Alkali treatment of kenaf fiber:
taking kenaf fiber with the length of 500-800 nm and the diameter of 5-20 nm out, soaking the kenaf fiber in a 15% NaOH solution at the temperature of 25 ℃, continuously stirring the kenaf fiber by using an electromagnetic stirrer or a glass rod for 4 hours, slowly adding glacial acetic acid until the solution is neutral, taking the kenaf fiber out, washing the kenaf fiber by using distilled water, and freeze-drying and storing the kenaf fiber in a freeze dryer.
2) Lactide grafted kenaf fiber:
the alkali-treated kenaf fiber obtained in step 1) was previously dried in a vacuum oven at 80 ℃ for 6 hours. Toluene and CaCl were added to the flask in a ratio of 9:12The reaction system was heated to 110 ℃ and the toluene was boiled and refluxed for 30 minutes to remove water in the reaction system. Adding lactide monomer and kenaf fiber in a ratio of 1:2 into a flask, and then replacing the gas in the reaction system with N by gas replacement2Heating to 130 ℃, adding stannous octoate and lactide monomer in a mass ratio of 1:100, adjusting an inlet valve and an outlet valve to enable the system to be in a reduced pressure state, stirring with an electromagnetic stirrer at an accelerated speed, reacting for 2 hours continuously, taking out the kenaf fibers, extracting the kenaf fibers by a Soxhlet extraction method, and then drying the extracted kenaf fibers in a freeze drying oven for later use.
3) Epoxy soybean oil grafted kenaf fiber:
pouring 2 parts of lactide grafted kenaf fiber obtained in the step 2) and 1 part of epoxidized soybean oil into a flask, pouring a small amount of dimethyl sulfoxide into the flask to fully dissolve the kenaf fiber, heating to raise the temperature of a reaction system to about 60 ℃, keeping the temperature constant, opening an electromagnetic stirrer to stir vigorously, and simultaneously slowly dropwise adding 17 parts of mixed solution of tin tetrachloride and dimethyl sulfoxide with the ratio of 1:1000 through a constant-pressure funnel to serve as a catalyst for reaction, wherein the reaction time is 2 hours. Removing dimethyl sulfoxide to obtain epoxidized soybean oil and lactide grafted kenaf fiber.
4) Preparing a high-toughness heat-resistant environment-friendly polylactic acid material:
placing the epoxidized soybean oil, the lactide grafted kenaf fiber and the polylactic acid particles obtained in the step 3) in an oven at 80 ℃ in advance for drying for 8 hours, heating a double-screw extruder to 190 ℃, preheating for 2 hours, and then proportionally mixing the epoxidized soybean oil-lactide grafted kenaf fiber with the polylactic acid particles to be 5%: putting 95 percent of the mixture into a double-screw extruder, mixing for 20 minutes, and then extruding and granulating. Respectively preparing the epoxidized soybean oil and the lactide grafted kenaf fiber which have the mass fraction of 5 percent and are high-toughness heat-resistant environment-friendly cable materials.
Example 3
1) Alkali treatment of kenaf fiber:
taking kenaf fiber with the length of 500-800 nm and the diameter of 5-20 nm out, soaking the kenaf fiber in a 15% NaOH solution at the temperature of 25 ℃, continuously stirring the kenaf fiber by using an electromagnetic stirrer or a glass rod for 4 hours, slowly adding glacial acetic acid until the solution is neutral, taking the kenaf fiber out, washing the kenaf fiber by using distilled water, and freeze-drying and storing the kenaf fiber in a freeze dryer.
2) Lactide grafted kenaf fiber:
the alkali-treated kenaf fiber obtained in step 1) was previously dried in a vacuum oven at 80 ℃ for 6 hours. Toluene and CaCl were added to the flask in a ratio of 9:12The reaction system was heated to 110 ℃ and the toluene was boiled and refluxed for 30 minutes to remove water in the reaction system. Adding lactide monomer and kenaf fiber in a ratio of 1:3 into a flask, and then replacing the gas in the reaction system with N by gas replacement2Heating to 130 ℃, adding stannous octoate and lactide monomer in a mass ratio of 1:100, adjusting an inlet valve and an outlet valve to enable the system to be in a reduced pressure state, stirring with an electromagnetic stirrer at an accelerated speed, reacting for 2 hours continuously, taking out the kenaf fibers, extracting the kenaf fibers by a Soxhlet extraction method, and then drying the extracted kenaf fibers in a freeze drying oven for later use.
3) Epoxy soybean oil grafted kenaf fiber:
pouring 3 parts of lactide grafted kenaf fiber obtained in the step 2) and 1 part of epoxidized soybean oil into a flask, pouring a small amount of dimethyl sulfoxide into the flask to fully dissolve the kenaf fiber, heating to raise the temperature of a reaction system to about 60 ℃, keeping the temperature constant, opening an electromagnetic stirrer to stir vigorously, and simultaneously slowly dropwise adding 20 parts of mixed solution of tin tetrachloride and dimethyl sulfoxide with the ratio of 1:1000 through a constant-pressure funnel to be used as a catalyst for reaction, wherein the reaction time is 2 hours. Removing dimethyl sulfoxide to obtain epoxidized soybean oil and lactide grafted kenaf fiber.
4) Preparing a high-toughness heat-resistant environment-friendly polylactic acid material:
placing the epoxidized soybean oil, the lactide grafted kenaf fiber and the polylactic acid particles obtained in the step 3) in an oven at 80 ℃ in advance for drying for 8-10 hours, heating a double-screw extruder to 190 ℃, preheating for 2 hours, and then proportionally mixing the epoxidized soybean oil-lactide grafted kenaf fiber with the polylactic acid particles to 10%: putting 90 percent of the mixture into a double-screw extruder, mixing for 20 minutes, and then extruding and granulating. Respectively preparing the epoxidized soybean oil and the lactide grafted kenaf fiber which have the mass fraction of 10 percent and are high-toughness heat-resistant environment-friendly cable materials.
The polylactic acid material of the cable material prepared in the embodiment 1-3 has excellent toughness and heat resistance when being subjected to performance tests.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (12)
1. A method of preparing a polylactic acid composite, comprising:
subjecting kenaf fibers to an alkali treatment to obtain alkali-treated kenaf fibers;
subjecting the alkali-treated kenaf fiber to a first cross-linking treatment with a lactide monomer to obtain a lactide-grafted kenaf fiber;
performing second cross-linking treatment on the lactide-grafted kenaf fiber and epoxidized soybean oil so as to obtain epoxidized soybean oil-lactide-grafted kenaf fiber; and
and carrying out melt blending treatment on the epoxidized soybean oil-lactide grafted kenaf fiber and polylactic acid so as to obtain the polylactic acid composite material.
2. The method according to claim 1, wherein the second crosslinking treatment comprises:
mixing and stirring the lactide grafted kenaf fiber, epoxidized soybean oil and a catalyst at 40-70 ℃ for 2-4 hours so as to obtain the epoxidized soybean oil-lactide grafted kenaf fiber.
3. The method of claim 2, wherein the catalyst is selected from a mixture of dimethyl sulfoxide and tin tetrachloride.
4. The method according to claim 3, wherein the volume ratio of the dimethyl sulfoxide to the tin tetrachloride is (900-1100): 1.
5. the method as claimed in claim 2, wherein the kenaf fiber has a length of 500-800 nm and a diameter of 5-20 nm;
the lactide grafted kenaf fiber, epoxidized soybean oil and the catalyst are in a volume ratio of (1-3): (1-3): (15-20).
6. The method of claim 1, wherein the alkali treatment comprises:
mixing kenaf fibers with an alkali solution, mixing with an acid solution until the kenaf fibers are neutral, and then carrying out freeze drying to obtain the alkali-treated kenaf fibers.
7. The method according to claim 1, wherein the first crosslinking treatment comprises:
mixing the alkali-treated kenaf fiber with toluene and calcium chloride, and heating and refluxing for 20-30 minutes to remove moisture;
and (3) mixing the mixed solution from which the water is removed, a lactide monomer and stannous octoate at 130-140 ℃ for 1-2 hours, taking out the kenaf fiber, and extracting and freeze-drying the kenaf fiber to obtain the lactide grafted kenaf fiber.
8. The method as claimed in claim 1, wherein the kenaf fiber has a length of 500-800 nm and a diameter of 5-20 nm, and the lactide monomer to alkali-treated kenaf fiber volume ratio is 1: (1-3).
9. The method of claim 1, wherein the melt blending process comprises:
and mixing the epoxidized soybean oil-lactide grafted kenaf fiber with polylactic acid at 180-190 ℃ for 10-20 minutes to obtain the polylactic acid composite material.
10. The method according to claim 9, wherein the mass ratio of the epoxidized soybean oil-lactide grafted kenaf fiber to the polylactic acid is (1-10): (90-99).
11. The method of claim 1, further comprising: and granulating the polylactic acid composite material.
12. A polylactic acid composite material, which is obtained by the method for producing a polylactic acid composite material according to any one of claims 1 to 11.
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| US5359026A (en) * | 1993-07-30 | 1994-10-25 | Cargill, Incorporated | Poly(lactide) copolymer and process for manufacture thereof |
| US7553919B2 (en) * | 2005-05-06 | 2009-06-30 | Board Of Trustees Of Michigan State University | Starch-vegetable oil graft copolymers and their biofiber composites, and a process for their manufacture |
| CN101538401A (en) * | 2009-03-13 | 2009-09-23 | 上海大学 | High temperature resistance binary fiber/polylactic acid based composite material and preparation method thereof |
| CN102850740B (en) * | 2012-09-04 | 2014-04-02 | 华南理工大学 | Preparation method of lactide grafted plant fiber reinforced polylactic acid composite material |
| CN110655769A (en) * | 2019-11-08 | 2020-01-07 | 佰信(福建)新材料科技有限公司 | High-toughness fully-degradable composite material |
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