CN112094487A - Easily-cleaned high-temperature-resistant polylactic acid composite material for environment-friendly tableware - Google Patents
Easily-cleaned high-temperature-resistant polylactic acid composite material for environment-friendly tableware Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant polylactic acid composite material for environmental-friendly tableware, which is easy to clean and relates to the technical field of polylactic acid composite materials. The invention discloses an easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware, which is composed of the following raw materials in percentage by mass: the composite material is prepared from the following raw materials in parts by weight: 35-70 parts of modified polylactic acid, 30-65 parts of plant fiber, 0.8-1.5 parts of sodium abietate, 0.1-0.3 part of magnesium aluminum silicate, 10-25 parts of polyethylene glycol and 3-6 parts of lubricant. The polylactic acid composite material is easy to clean, can resist high temperature, has the heat deformation temperature of more than 120 ℃, has excellent mechanical property, high toughness, is not easy to brittle failure, prolongs the service life, has a simple preparation method, is low in cost, is completely biodegradable, and can be widely applied to the fields of food packaging, environment-friendly tableware and the like.
Description
Technical Field
The invention belongs to the technical field of polylactic acid composite materials, and particularly relates to a high-temperature-resistant polylactic acid composite material for environment-friendly tableware, which is easy to clean, and a preparation method thereof.
Background
Today, the environment-friendly biodegradable polymer material is not easily favored by people and becomes a research hotspot in recent years, while the polylactic acid is considered to be one of the most promising traditional plastic substitutes. Polylactic acid (PLA) is biodegradable aliphatic polyester prepared by taking lactic acid formed by fermenting corn or potato starch as a raw material through chemical synthesis, has sufficient and renewable raw material sources, not only gets rid of the dependence on petroleum resources, but also has lower energy consumption in the production and manufacturing process than petroleum-based polymers such as PP and the like, and is a polymer material with low environmental load.
PLA is linear polyester, and ester bonds in a molecular chain of PLA are very sensitive to temperature and moisture, so the PLA is easy to degrade at high temperature in the presence of moisture, and the performance of the PLA can be influenced. PLA has a melting point of around 180 ℃, but when the temperature reaches around 200 ℃, degradation occurs significantly. Compared with common plastics such as PET, PS, PP and PE, PLA has better mechanical property and high transparency, and has good biocompatibility and degradability, so that PLA is generally applied to the fields of environment-friendly tableware, food packaging, films and the like, but the PLA has slow crystallization rate and large heat shrinkage in the processing process, and the PLA product has poor heat resistance, large brittleness and low melt strength, so that the application range of the PLA is limited. The heat distortion temperature of PLA is only about 55-60 ℃, however, when the PLA is used as environment-friendly tableware, the temperature of food can reach about 100 ℃, the use of the PLA as the environment-friendly tableware is severely limited, and the service life is short. The existing PLA material can be recycled as polymer environment-friendly tableware, but can be cleaned only under the action of high temperature and chemical cleaning products during cleaning, the experience feeling is inferior to that of ceramic tableware, the application in family life is limited, and the PLA material is mainly used as disposable tableware at present.
At present, many studies and reports have been made on modification of polylactic acid. Chinese patent CN106221162B discloses a heat-resistant and durable polylactic acid composite material, which is prepared by performing surface activation treatment on shell micro powder, performing thermoplastic modification treatment on sisal fibers, and then performing extrusion granulation on each component through a double-screw extruder, wherein the composite material utilizes natural shell micro powder and sisal fibers to improve the performance, the thermal deformation temperature is higher than 100 ℃, and the composite material has the performances of hydrolysis resistance, aging resistance and the like, but the compatibility of each component of the polylactic acid composite material is poor, so that the formed product of the modified material has poor toughness, large brittleness and easy breakage. The Chinese invention patent CN107201015B discloses an antibacterial heat-resistant polylactic acid tableware, wherein inorganic filler is subjected to in-situ grafting surface modification, and the inorganic filler is subjected to melt blending by a one-step method, and the grafting cross-linking structure among the components can remarkably increase the interface bonding force between the inorganic filler and organisms, so that the mechanical property of the polylactic acid tableware is improved, the temperature resistance is improved, and the polylactic acid tableware has antibacterial property and oxidation resistance.
In summary, there are problems of low efficiency and durability when polylactic acid is modified by some methods at present, and there is no report and research on the performance of polylactic acid products in terms of easy cleaning, so that it is a necessary trend to develop a polylactic acid composite material that is easy to clean and heat resistant with the wide spread of environmentally friendly tableware.
Disclosure of Invention
The invention aims to provide a polylactic acid composite material which is easy to clean, can resist high temperature, has a thermal deformation temperature of over 131 ℃, has excellent mechanical properties, high toughness and difficult brittle fracture, and prolongs the service life. The composite material has the advantages of simple preparation method, low cost and complete biodegradation, and can be widely applied to the fields of food packaging, environment-friendly tableware and the like.
In order to realize the purpose of the invention, the invention provides an easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware, which is composed of the following raw materials in parts by weight: 35-70 parts of modified polylactic acid, 30-65 parts of plant fiber, 0.8-1.5 parts of sodium abietate, 0.1-0.3 part of magnesium aluminum silicate, 10-25 parts of polyethylene glycol and 3-6 parts of lubricant.
Further, the preparation method of the modified polylactic acid comprises the following steps: adding polylactic acid into tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding perfluorooctyl sulfonamide and titanate coupling agent into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely the modified polylactic acid.
Furthermore, the addition amount of the perfluorooctyl sulfonamide is 2.4-3.5 wt% of the polylactic acid, the addition amount of the titanate coupling agent is 0.5-0.8 wt% of the polylactic acid, and a proper amount of tetrahydrofuran solution is obtained. The titanate coupling agent is a chelating titanate coupling agent.
Furthermore, the water content of the plant fibers is lower than 5%, the titer of the plant fibers is 1-5dtex, and the length of the plant fibers is 0.2-0.7 mm.
Further, the plant fiber is derived from one or more of plant straw, bamboo, cotton, algae and aquatic weeds.
Further, the lubricant is one or two of polyethylene wax, N-ethylene bis stearamide, glycerol tristearate and N-butyl stearate.
The preparation method of the high-temperature-resistant polylactic acid composite material for the environment-friendly tableware, which is easy to clean, specifically comprises the following steps: adding weighed plant fibers and polyethylene glycol into a high-speed mixer, stirring for 5-10min, heating, adding weighed sodium abietate and modified polylactic acid at 80-90 ℃, stirring for 1-1.5h, cooling to room temperature, sequentially adding magnesium aluminum silicate and a lubricant, stirring for 10-15min, adding the uniformly stirred mixture into a double-screw extruder, melting and blending, extruding, bracing and granulating to obtain the easily-cleaned high-temperature-resistant polylactic acid composite material for the environment-friendly tableware.
Further, the stirring speed of the high-speed mixer is 320-450 r/min.
Further, the extrusion temperature of the double-screw extruder is 160-195 ℃, the rotating speed of the screw is 80-150r/min, and the length-diameter ratio of the screw is (36-45): 1.
the invention achieves the following beneficial effects:
1. the modified polylactic acid is prepared by crosslinking and compounding polylactic acid and perfluorooctyl sulfonamide under the action of a titanate coupling agent, and the perfluorooctyl sulfonamide is crosslinked with the polylactic acid, so that the crystallization rate and the crystallinity of PLA are improved, and the heat resistance of the PLA is improved; the chelating titanate coupling agent is used, so that the modified polylactic acid has good hydrolytic stability, and the water resistance of the modified polylactic acid is improved.
2. The perfluoro octyl sulfonamide is combined with the polylactic acid interface, so that the toughness of the modified polylactic acid is poorer, the interface binding force of the modified polylactic acid and the plant fiber is improved by adding the sodium abietate, the compatibility of the modified polylactic acid and the plant fiber is improved, the toughness of the polylactic acid composite material is improved, and the heat resistance of the polylactic acid composite material is further improved due to the addition of the plant fiber.
3. The polyethylene glycol is mixed with the plant fiber, so that the plant fiber can be uniformly dispersed in the modified polylactic acid matrix, the compatibility of the plant fiber and the modified polylactic acid is increased, and the toughness of the polylactic acid composite material is improved.
4. The perfluoro octyl sulfonamide and the polylactic acid are compounded, and the perfluoro octyl sulfonamide has excellent hydrophilic capacity, so that the hydrophilic capacity of the modified polylactic acid is greatly improved, oily organic matters are not easy to remain on the surface of the polylactic acid composite material, and the environment-friendly tableware prepared from the polylactic acid composite material is easy to clean.
5. The magnesium aluminum silicate has excellent lubricity, can improve the processability of polylactic acid, has excellent hydrophilic capacity, interacts with perfluorooctyl sulfonamide, greatly improves the hydrophilic capacity of the polylactic acid composite material, has excellent organic matter degradation performance, is easy to take away by oxidizing and degrading oily organic matters and ensures that environment-friendly tableware prepared from the polylactic acid composite material is easy to clean.
6. The fiber length of the plant fiber is controlled between 0.2mm and 0.7mm, the plant fiber can be uniformly dispersed in the modified polylactic acid matrix, and the toughness and the heat resistance of the polylactic acid composite material can be improved. If the plant fiber is 0.2mm, small fiber blocks are easily formed by mixing the plant fiber and the modified polylactic acid, and the plant fiber and the modified polylactic acid cannot be uniformly combined, so that the mechanical property, the toughness and the heat resistance of the polylactic acid composite material are influenced; if the length of the plant fiber exceeds 0.7mm, the gaps formed when the plant fiber and the modified polylactic acid are mixed are large and difficult to be uniform, and the strength and the toughness of the polylactic acid composite material are influenced.
7. The fineness of the plant fiber is controlled to be 1-5dtex, the plant fiber with the fineness is uniformly dispersed in the modified polylactic acid matrix, and the toughness and the heat resistance of the polylactic acid composite material can be improved. If the fineness is too small, the plant fiber and the modified polylactic acid are mixed to easily form a fiber block, and the fiber block cannot be uniformly combined with the modified polylactic acid, so that the mechanical property, the toughness and the heat resistance of the polylactic acid composite material are influenced; if the fineness is too large, the strength of the polylactic acid composite material is influenced.
8. The polylactic acid is modified by using the plant fiber, the raw materials are easy to obtain, the cost is low, the polylactic acid can be completely biodegraded, and the polylactic acid modified by the plant fiber is in line with the environment-friendly development trend.
9. According to the invention, perfluorooctyl sulfonamide is adopted to modify polylactic acid, and the length and fineness of plant fibers are controlled to be blended with raw materials such as sodium abietate and polyethylene glycol to prepare the polylactic acid composite material, wherein the composite material is easy to clean, can resist high temperature, has a thermal deformation temperature of more than 131 ℃, has excellent mechanical properties, high toughness and is not easy to brittle failure, and the service life is prolonged. The polylactic acid composite material has the advantages of easily available raw materials, low cost, no toxicity and degradability, and can be completely biodegraded. The preparation method disclosed by the invention is simple, easy to control, strong in operability and easy for industrial production, and can be widely applied to the fields of food packaging, environment-friendly tableware and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polylactic acid composite material for environmental tableware, which is easy to clean and resistant to high temperature, and the preparation method thereof according to the present invention will be described with reference to the following embodiments.
The titanate coupling agent used in the invention is a chelating titanate coupling agent, namely water-soluble titanate TM-200S of Tianyang chemical company Limited.
The plant fiber in the invention is derived from one or more of plant straw, bamboo, cotton, algae and aquatic weeds.
Example 1
An easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware is composed of the following raw materials in parts by weight: 35 parts of modified polylactic acid, 65 parts of plant fiber, 1.5 parts of sodium abietate, 0.3 part of magnesium aluminum silicate, 25 parts of polyethylene glycol and 3 parts of polyethylene wax, wherein the preparation method comprises the following steps:
adding weighed plant fiber and polyethylene glycol into a high-speed mixer, stirring for 5-10min at the stirring speed of 320-450r/min, heating to 80-90 ℃, adding weighed sodium abietate and modified polylactic acid at 80-90 ℃, stirring for 1-1.5h, cooling to room temperature, sequentially adding magnesium aluminum silicate and polyethylene wax, stirring for 10-15min, adding the uniformly stirred mixture into a double-screw extruder, melting and blending, extruding, bracing and granulating to obtain the easily cleaned high-temperature-resistant polylactic acid composite material for the environment-friendly tableware. Wherein the extrusion temperature of the double-screw extruder is 160-195 ℃, the rotating speed of the screw is 80-150r/min, and the length-diameter ratio of the screw is (36-45): 1.
the preparation method of the modified polylactic acid comprises the following steps:
adding 100 parts of polylactic acid into a proper amount of tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding 3.5 parts of perfluorooctyl sulfonamide (FC-99) and 0.8 part of TM-200S into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely modified polylactic acid.
In this example 1, the water content of the plant fiber is less than 5%, the fineness of the plant fiber is controlled to be 1-5dtex, and the length of the plant fiber is 0.2-0.7 mm.
Example 2
An easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware is composed of the following raw materials in parts by weight: 70 parts of modified polylactic acid, 30 parts of plant fiber, 0.8 part of sodium abietate, 0.1 part of magnesium aluminum silicate, 10 parts of polyethylene glycol, 3 parts of polyethylene wax and 3 parts of N, N-ethylene bis stearamide, and the preparation method is the same as that in example 1, with specific reference to example 1, except that the polyethylene wax (i.e. lubricant) is replaced by the polyethylene wax and the N, N-ethylene bis stearamide.
The preparation method of the modified polylactic acid comprises the following steps:
adding 100 parts of polylactic acid into a proper amount of tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding 2.4 parts of FC-99 and 0.5 part of TM-200S into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely modified polylactic acid.
In the embodiment, the water content of the plant fiber is lower than 5%, the fineness of the plant fiber is controlled to be 1-5dtex, and the length of the plant fiber is 0.2-0.7 mm.
Example 3
An easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware is composed of the following raw materials in parts by weight: 45 parts of modified polylactic acid, 55 parts of plant fiber, 1.2 parts of sodium abietate, 0.2 part of magnesium aluminum silicate, 20 parts of polyethylene glycol and 4 parts of glycerol tristearate, wherein the preparation method is the same as that in example 1, and the difference is that polyethylene wax (namely lubricant) is replaced by glycerol tristearate with specific reference to example 1.
The preparation method of the modified polylactic acid comprises the following steps:
adding 100 parts of polylactic acid into a proper amount of tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding 3.0 parts of FC-99 and 0.7 parts of TM-200S into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely modified polylactic acid.
In the embodiment, the water content of the plant fiber is lower than 5%, the fineness of the plant fiber is controlled to be 1-5dtex, and the length of the plant fiber is 0.2-0.7 mm.
Example 4
An easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware is composed of the following raw materials in parts by weight: 55 parts of modified polylactic acid, 45 parts of plant fiber, 1 part of sodium abietate, 0.2 part of magnesium aluminum silicate, 15 parts of polyethylene glycol and 5 parts of glycerol tristearate, wherein the preparation method is the same as that in example 1, and the difference is that polyethylene wax (namely a lubricant) is replaced by n-butyl stearate.
The preparation method of the modified polylactic acid comprises the following steps:
adding 100 parts of polylactic acid into a proper amount of tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding 3.2 parts of FC-99 and 0.6 part of TM-200S into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely modified polylactic acid.
In the embodiment, the water content of the plant fiber is lower than 5%, the fineness of the plant fiber is controlled to be 1-5dtex, and the length of the plant fiber is 0.2-0.7 mm.
Comparative example 1
The raw materials and the preparation method of the polylactic acid composite material are the same as those in the embodiment 4, and the embodiment 4 is specifically referred. The only difference was that FC-99 was not added to the modified polylactic acid in this comparative example.
Comparative example 2
The raw materials and the preparation method of the polylactic acid composite material are the same as those in the embodiment 4, and the embodiment 4 is specifically referred. The only difference was that no sodium abietate was added in this comparative example.
Comparative example 3
The raw materials and the preparation method of the polylactic acid composite material are the same as those in the embodiment 4, and the embodiment 4 is specifically referred. The only difference is that no magnesium aluminum silicate was added in this comparative example.
The above examples 1 to 4 and comparative examples 1 to 3 were subjected to the performance test, and the test results thereof are shown in the following table 1.
TABLE 1 detection results of the properties of the polylactic acid composite materials of examples 1-4 and comparative examples 1-3
As shown in the detection result table of the polylactic acid composite material in the table 1, the polylactic acid composite material has the heat deformation temperature of more than 131 ℃, good high temperature resistance and good mechanical property, and has the tensile strength of 78.5-98.4MPa and the impact strength of 20.8-31.7kJ/m2And the elongation at break is 139.8-394.2%. After the polylactic acid is modified by FC-99, the strength, toughness and high temperature resistance of the polylactic acid composite material are improved; when the polylactic acid composite material is added with sodium abietate or magnesium aluminum silicate, the strength, toughness and high temperature resistance of the polylactic acid composite material are correspondingly improved.
Comparative example 4
A polylactic acid polymer material, the starting materials and the production method thereof are the same as those in example 4, with specific reference to example 4. The only difference is that the length of the plant fiber in this comparative example is 0.1mm and less.
Comparative example 5
A polylactic acid polymer material, the starting materials and the production method thereof are the same as those in example 4, with specific reference to example 4. The only difference is that the length of the plant fiber in this comparative example is 0.8mm and more.
Comparative example 6
A polylactic acid polymer material, the starting materials and the production method thereof are the same as those in example 4, with specific reference to example 4. The only difference is that the fineness of the plant fiber in this comparative example was 0.9dtex or less.
Comparative example 7
A polylactic acid polymer material, the starting materials and the production method thereof are the same as those in example 4, with specific reference to example 4. The only difference is that the fineness of the plant fiber in this comparative example was 6dtex or more.
The above example 4 and comparative examples 4 to 7 were subjected to the performance test, and the test results thereof are shown in the following table 2.
TABLE 2 detection results of the properties of the polylactic acid composite materials of example 4 and comparative examples 4 to 7
As can be seen from the table of the detection results of the polylactic acid composite material in Table 2, the fiber length of the plant fiber of the invention is controlled to be 0.2-0.7mm, and the fineness of the plant fiber is controlled to be 1-5dtex, so that the plant fiber can be uniformly dispersed in the modified polylactic acid matrix, and the toughness and the heat resistance of the polylactic acid composite material can be improved.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. An easy-to-clean high-temperature-resistant polylactic acid composite material for environment-friendly tableware is characterized by comprising the following raw materials in parts by weight: 35-70 parts of modified polylactic acid, 30-65 parts of plant fiber, 0.8-1.5 parts of sodium abietate, 0.1-0.3 part of magnesium aluminum silicate, 10-25 parts of polyethylene glycol and 3-6 parts of lubricant.
2. The easy-to-clean high-temperature-resistant polylactic acid composite material for the environment-friendly tableware according to claim 1, wherein the preparation method of the modified polylactic acid comprises the following steps: adding polylactic acid into tetrahydrofuran solution, stirring at 50 ℃ until the polylactic acid is dissolved, adding perfluorooctyl sulfonamide and titanate coupling agent into the mixed solution at constant temperature, stirring for 2.5-4h, then heating to 70-80 ℃, stirring for 0.5h, washing, centrifugally separating, drying, crushing and granulating to obtain a PLA/FC compound, namely the modified polylactic acid.
3. The polylactic acid composite material with easy cleaning and high temperature resistance for the environmental-friendly tableware according to claim 2, wherein the addition amount of the perfluorooctyl sulfonamide is 2.4-3.5 wt% of the polylactic acid, the addition amount of the titanate coupling agent is 0.5-0.8 wt% of the polylactic acid, and the tetrahydrofuran solution is in a proper amount.
4. The easy-to-clean high-temperature-resistant polylactic acid composite material for the environment-friendly tableware according to claim 1, wherein the water content of the plant fibers is lower than 5%, the titer of the plant fibers is 1-5dtex, and the length of the plant fibers is 0.2-0.7 mm.
5. The polylactic acid composite material with easy cleaning and high temperature resistance for the environmental tableware according to claim 3, wherein the plant fiber is derived from one or more of plant straw, bamboo, cotton, algae and aquatic weed.
6. The easy-to-clean high-temperature-resistant polylactic acid composite material for the environment-friendly tableware according to claim 1, wherein the lubricant is one or two of polyethylene wax, N-ethylene bis stearamide, glycerol tristearate and N-butyl stearate.
7. The preparation method of the polylactic acid composite material with easy cleaning and high temperature resistance for the environment-friendly tableware according to the claims 1 to 6 is characterized by comprising the following steps: adding weighed plant fibers and polyethylene glycol into a high-speed mixer, stirring for 5-10min, heating, adding weighed sodium abietate and modified polylactic acid at 80-90 ℃, stirring for 1-1.5h, cooling to room temperature, sequentially adding magnesium aluminum silicate and a lubricant, stirring for 10-15min, adding the uniformly stirred mixture into a double-screw extruder, melting and blending, extruding, bracing and granulating to obtain the easily-cleaned high-temperature-resistant polylactic acid composite material for the environment-friendly tableware.
8. The method for preparing the polylactic acid composite material with easy cleaning and high temperature resistance for the environmental tableware according to claim 7, wherein the stirring speed of the high-speed mixer is 320-450 r/min.
9. The preparation method of the polylactic acid composite material with easy cleaning and high temperature resistance for the environmental-friendly tableware according to claim 7, wherein the extrusion temperature of the twin-screw extruder is 160-195 ℃, the screw rotation speed is 80-150r/min, and the screw length-diameter ratio is (36-45): 1.
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