Disclosure of Invention
In order to solve the problems mentioned in the background art, the present invention aims to provide an environment-friendly material for outdoor seats and a production process thereof.
The aim of the invention can be achieved by the following technical scheme:
an environment-friendly material for outdoor seats comprises, by weight, 70-90 parts of polylactic acid, 20-50 parts of polycarbonate, 2-5 parts of a compatilizer, 1-4 parts of a lubricant, 1-3 parts of an antioxidant, 3-6 parts of a functional fibrous filler and 2-5 parts of an antibacterial and mildew-proof component.
Further, the compatilizer is ethylene-methyl acrylate-glycidyl methacrylate, the lubricant is polyethylene wax, and the antioxidant is antioxidant 1010 or antioxidant 168.
Further, the preparation method of the functional fiber filler comprises the following steps:
S1, mixing quartz fibers with N, N-dimethylformamide, raising the temperature to 60-80 ℃, adding chloroethyl isocyanate and a catalyst A, reacting for 2-4 hours, and performing suction filtration, washing and drying to obtain modified quartz fibers;
S2, adding the modified quartz fiber into toluene, uniformly mixing, introducing nitrogen, raising the temperature to 70-80 ℃, adding 2, 6-tetramethyl-4-piperidinol and an alkaline catalyst, reacting for 3-5 hours, and performing suction filtration, washing and drying to obtain the functional fiber filler.
By adopting the technical scheme, under the action of the catalyst, the hydroxyl groups on the surface of the quartz fiber can react with isocyanate in a chloroethyl isocyanate structure, so that chlorine substituents are introduced into the surface of the quartz fiber to obtain the modified quartz fiber, and under the action of the acid binding agent, the chlorine substituents on the surface of the modified quartz fiber can react with the hydroxyl groups in the 2, 6-tetramethyl-4-piperidinol structure in a substitution manner to obtain the functional fiber filler.
Further, in S1, the catalyst a is dibutyltin dilaurate or stannous octoate.
Further, in S2, the alkaline catalyst is a sodium carbonate solution or a potassium carbonate solution.
Further, the preparation method of the antibacterial mildew-proof component comprises the following steps:
Adding polyamide amine into toluene, stirring uniformly, adding an anhydride modifier, reacting for 1-3 hours at room temperature, increasing the temperature to 80-100 ℃, adding diniconazole and a catalyst B, reacting for 3-5 hours at a constant temperature, cooling to room temperature, and discharging to obtain the antibacterial mildew-proof component.
By adopting the technical scheme, the amino in the polyamidoamine structure can react with the anhydride modifier, so that carboxyl groups are introduced into the structure, and the carboxyl groups can perform esterification reaction with the hydroxyl in the diniconazole structure under the action of the catalyst B, so that the antibacterial mildew-proof component is obtained.
Further, the anhydride modifier is succinic anhydride or glutaric anhydride.
Further, the catalyst B is p-toluenesulfonic acid.
The production process of the environment-friendly material for the outdoor seat comprises the following steps of:
Step one, adding polylactic acid, polycarbonate, a compatilizer, a lubricant, an antioxidant, a functional fiber filler and an antibacterial and mildew-proof component into a high-speed mixer, raising the temperature to 60-90 ℃, and mixing for 1-2 hours to obtain a premix;
and secondly, placing the premix into a double-screw extruder, and performing melt extrusion granulation to obtain the environment-friendly material.
Further, in the second step, the extrusion temperature of the double-screw extruder is 180-220 ℃, and the screw rotating speed is 100-400r/min.
The invention has the beneficial effects that:
(1) According to the functional fiber filler prepared by the invention, the quartz fiber is used as a matrix, after the quartz fiber is organically modified, the compatibility problem between the quartz fiber and the polylactic acid matrix is improved, the functional fiber filler can be uniformly dispersed in the polylactic acid matrix, the interface bonding effect with the polylactic acid matrix is further enhanced, the reinforcing effect is exerted in the polylactic acid matrix, the mechanical property of the polylactic acid matrix is improved, in addition, small molecules containing hindered amine groups are grafted on the surface of the functional fiber filler, the migration and precipitation of a small-molecule ultraviolet resistant agent can be avoided, the functional fiber filler can be permanently acted in the polylactic acid matrix, the ultraviolet resistant performance of an environment-friendly material is enhanced, the aging phenomenon of the environment-friendly material is prevented from being irradiated by ultraviolet rays for a long time in an outdoor environment, the performance of the environment-friendly material is reduced, and the service life of an outdoor seat is influenced.
(2) The polyamide with branched structure in the antibacterial mildew-proof component prepared by the invention has a great amount of amide bonds in the branched structure, can interact with polylactic acid matrix molecular chain groups, increases entanglement with polylactic acid molecular chains, promotes crystallization nucleation of a system, improves crystallization rate of the system, enhances compactness of the polylactic acid matrix, can effectively disperse and transfer stress, enhances impact toughness of the polylactic acid matrix, prevents materials from being damaged when being impacted by external force, improves the impact toughness of an environment-friendly material, and has high-efficiency broad-spectrum antibacterial mildew-proof effect by micromolecule antibacterial mildew-proof matter diniconazole.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation methods of the functional fibrous fillers and the antibacterial and mildew-proof components in the following examples and comparative examples are as follows:
Preparation of functional fibrous fillers
S1, mixing 3.2g of quartz fiber with N, N-dimethylformamide, raising the temperature to 70 ℃, adding 2.6g of chloroethyl isocyanate and 0.2g of dibutyltin dilaurate, reacting for 3 hours, and performing suction filtration, washing and drying to obtain modified quartz fiber;
S2, adding 2.8g of modified quartz fiber into toluene, uniformly mixing, introducing nitrogen, raising the temperature to 75 ℃, adding 2g of 2, 6-tetramethyl-4-piperidinol and 0.3g of potassium carbonate solution, reacting for 4 hours, and performing suction filtration, washing and drying to obtain the functional fiber filler.
The sample was prepared by potassium bromide tabletting, and infrared test was performed on the functional fiber filler by using an AVATAR-370FT type infrared spectrometer, and as shown in FIG. 1, analysis revealed that in the infrared spectrum of the functional fiber filler, an absorption peak of C=O in carbamate appeared at 1709cm-1, an absorption peak of N-H in carbamate appeared at 1540cm-1, an absorption peak of piperidine ring appeared at 1465cm-1、1383cm-1、1366cm-1, an absorption peak of ether bond C-O appeared at 1132cm-1, and an absorption peak of Si-O-Si appeared at 1086cm-1.
Preparation of antibacterial mildew-proof component
Adding 6g of polyamidoamine into toluene, uniformly stirring, adding 2.2g of succinic anhydride, reacting at room temperature for 2 hours, raising the temperature to 95 ℃, adding 1.6g of diniconazole and 0.5g of p-toluenesulfonic acid, reacting at the temperature for 5 hours, cooling to the room temperature, and discharging to obtain the antibacterial mildew-proof component.
The sample was prepared by potassium bromide tabletting, and infrared test was performed on the antibacterial and mildew-proof component by using an AVATAR-370FT type infrared spectrometer, and as shown in FIG. 2, analysis revealed that in the infrared spectrum of the antibacterial and mildew-proof component, an absorption peak of C-H in olefin appeared at 3054cm-1, an absorption peak of C-H in benzene ring appeared at 3029cm-1, an absorption peak of C=O in ester group appeared at 1733cm-1, an absorption peak of C=O in amide appeared at 1649cm-1, and an absorption peak of C=N appeared at 1560cm-1.
Example 1
Preparation of environment-friendly material
Step one, adding 70g of polylactic acid, 20g of polycarbonate, 2g of ethylene-methyl acrylate-glycidyl methacrylate, 1g of polyethylene wax, 1g of antioxidant 1010, 3g of functional fiber filler and 2g of antibacterial and mildew-proof components into a high-speed mixer, raising the temperature to 60 ℃, and mixing for 1h to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 180 ℃, and performing melt extrusion granulation at the screw speed of 100r/min to obtain the environment-friendly material.
Example 2
Preparation of environment-friendly material
Step one, adding 80g of polylactic acid, 30g of polycarbonate, 3g of ethylene-methyl acrylate-glycidyl methacrylate, 2g of polyethylene wax, 2g of antioxidant 1010, 4g of functional fiber filler and 3g of antibacterial and mildew-proof components into a high-speed mixer, raising the temperature to 70 ℃, and mixing for 1.5 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 190 ℃, and performing melt extrusion granulation at the screw speed of 200r/min to obtain the environment-friendly material.
Example 3
Preparation of environment-friendly material
Step one, adding 85g of polylactic acid, 40g of polycarbonate, 4g of ethylene-methyl acrylate-glycidyl methacrylate, 3g of polyethylene wax, 2.5g of antioxidant 1010, 5g of functional fiber filler and 4g of antibacterial and mildew-proof components into a high-speed mixer, raising the temperature to 80 ℃, and mixing for 2 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 200 ℃, and performing melt extrusion granulation at the screw speed of 300r/min to obtain the environment-friendly material.
Example 4
Preparation of environment-friendly material
Step one, adding 90g of polylactic acid, 50g of polycarbonate, 5g of ethylene-methyl acrylate-glycidyl methacrylate, 4g of polyethylene wax, 3g of antioxidant 1010, 6g of functional fiber filler and 5g of antibacterial and mildew-proof components into a high-speed mixer, raising the temperature to 90 ℃, and mixing for 2 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 220 ℃, and performing melt extrusion granulation at the screw speed of 400r/min to obtain the environment-friendly material.
Comparative example 1
Preparation of environment-friendly material
Step one, adding 80g of polylactic acid, 30g of polycarbonate, 3g of ethylene-methyl acrylate-glycidyl methacrylate, 2g of polyethylene wax, 2g of antioxidant 1010 and 4g of functional fiber filler into a high-speed mixer, raising the temperature to 70 ℃, and mixing for 1.5 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 190 ℃, and performing melt extrusion granulation at the screw speed of 200r/min to obtain the environment-friendly material.
Comparative example 2
Preparation of environment-friendly material
Step one, adding 80g of polylactic acid, 30g of polycarbonate, 3g of ethylene-methyl acrylate-glycidyl methacrylate, 2g of polyethylene wax, 2g of antioxidant 1010 and 3g of antibacterial and mildew-proof components into a high-speed mixer, raising the temperature to 70 ℃, and mixing for 1.5 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 190 ℃, and performing melt extrusion granulation at the screw speed of 200r/min to obtain the environment-friendly material.
Comparative example 3
Preparation of environment-friendly material
Step one, adding 80g of polylactic acid, 30g of polycarbonate, 3g of ethylene-methyl acrylate-glycidyl methacrylate, 2g of polyethylene wax, 2g of antioxidant 1010, 4g of 2, 6-tetramethyl-4-piperidinol and 3g of antibacterial mildew-proof components into a high-speed mixer, raising the temperature to 70 ℃, and mixing for 1.5 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 190 ℃, and performing melt extrusion granulation at the screw speed of 200r/min to obtain the environment-friendly material.
Comparative example 4
Preparation of environment-friendly material
Step one, adding 80g of polylactic acid, 30g of polycarbonate, 3g of ethylene-methyl acrylate-glycidyl methacrylate, 2g of polyethylene wax, 2g of antioxidant 1010, 4g of functional fiber filler and 3g of diniconazole into a high-speed mixer, raising the temperature to 70 ℃, and mixing for 1.5 hours to obtain a premix;
And secondly, placing the premix into a double-screw extruder, setting the extrusion temperature to be 190 ℃, and performing melt extrusion granulation at the screw speed of 200r/min to obtain the environment-friendly material.
Performance detection
Preparing environment-friendly materials prepared in examples 1-4 and comparative examples 1-4 into samples meeting test conditions, testing the tensile strength of the samples according to GB/T1040.1-2018 standards, judging the mechanical properties of the samples, testing the impact strength of the samples according to GB/T1043.2-2018 standards, judging the impact toughness of the samples, performing ultraviolet resistance detection on the samples by adopting the following methods, namely performing ultraviolet resistance detection on the samples according to GB/T16422.2-2022 standards by using FLB40T12E/90D type ultraviolet fluorescent tubes, calculating the delta E value of chromatic aberration by using a formula delta E= [ (DELTAL)2+(△a)2+(△b)2]1/2, and performing antibacterial and mildew resistance detection on the samples by adopting the following methods, namely performing antibacterial and mildew resistance detection on the samples by using the following methods, namely placing 1mL of staphylococcus aureus in a nutrient agar medium for 8 hours at 36 ℃, diluting the concentration of the bacterial liquid to 1X 10-5 CFU/mL, taking 1mL of bacterial liquid drop, adding the bacterial liquid to the surface of the bacterial liquid for a sterilizing culture medium for 20 ℃ at the following conditions of 36 ℃ for 20 ℃ by using the following statistical test results, and performing uniform statistics on the bacterial liquid to obtain the bacterial liquid, and performing a blank test table at the same time of the following conditions:
TABLE 1
As can be seen from the above table, the environment-friendly material prepared by the invention has excellent mechanical properties, impact toughness, ultraviolet resistance and antibacterial mildew resistance, wherein the test effect of the example 2 is optimal, the comparative example 1 is added with functional fiber filler, has excellent mechanical properties and ultraviolet resistance, no antibacterial mildew resistance is added with the antibacterial mildew resistance, the impact toughness and the antibacterial mildew resistance are poor, the comparative example 2 is added with the antibacterial mildew resistance, the impact toughness and the antibacterial mildew resistance are excellent, no functional fiber filler is added, the ultraviolet resistance and the mechanical properties are poor, the comparative example 3 is added with 2, 6-tetramethyl-4-piperidinol and the antibacterial mildew resistance are poor, the small molecular hindered amine 2, 6-tetramethyl-4-piperidinol can migrate and precipitate to cause the ultraviolet resistance, the impact toughness and the antibacterial mildew resistance are excellent, the impact toughness and the antibacterial mildew resistance are not improved, the mechanical properties of a polylactic acid matrix can not be enhanced by adding the functional fiber filler and the diniconazole, but the ultraviolet resistance and the mechanical properties are poor, and the polylactic acid matrix cannot be mutually deformed due to the fact that the small molecular mildew resistance and the polylactic acid chain is poor in the mutual toughness are mutually transferred, and the polylactic acid matrix is poor in the mechanical properties are improved.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.