CN109880180B - Nano-cellulose/cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof - Google Patents
Nano-cellulose/cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof Download PDFInfo
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- 238000010146 3D printing Methods 0.000 title claims abstract description 53
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Images
Abstract
The invention belongs to the fields of polymer composite materials and 3D printing materials, and particularly relates to a nanocellulose/cellulose composite for polylactic acid 3D printing materials and a related reinforced 3D printing material. The invention takes natural cellulose, acid, silane coupling agent and polylactic acid as raw materials, and obtains the nano-cellulose/cellulose compound and the reinforced polylactic acid 3D printing material thereof through constant-temperature water bath reaction and blending extrusion. The preparation process comprises raw material pretreatment, mixing, water bath heating, drying, blending extrusion, wire drawing and the like, the whole preparation process is simple, the repeatability is high, the mechanical property of the prepared 3D printing material is remarkably improved compared with pure polylactic acid, the processing performance is good, compared with the common natural cellulose reinforced polylactic acid 3D printing material, the transparency is high, plugs and raised edges are not easy to occur during printing, and the preparation method has higher application value in the fields of home furnishing, decoration, lamps, art, model design and the like.
Description
Technical Field
The invention belongs to the field of polymer composite materials and 3D printing materials, and particularly relates to a nanocellulose/cellulose composite, a reinforced polylactic acid 3D printing material and a preparation method thereof.
Background
Cellulose is a multipurpose biological polymer, cannot be dissolved in a conventional solvent, only a high-concentration zinc chloride aqueous solution, a copper ammonia solution, an ionic liquid and the like can destroy the crystal structure of the cellulose to dissolve the cellulose, and the cellulose has a complex structure and various interactions, so that the research on the monomer synthetic polymer material derived from the cellulose still faces a plurality of difficulties. The nano material has special properties such as high specific surface area, high Young's modulus, high mechanical strength, high biocompatibility and the like, and has a nano size effect, which is the leading direction of material development. The nano-cellulose has a good fluffy three-dimensional network structure, and can promote the polymer matrix and the filler to be mechanically combined, so that the performance of the polymer is enhanced, and the nano-cellulose which is extracted as a cellulose main body material is more in line with the development trend of high-performance green composite materials.
Chinese patent CN108239379A discloses a method for preparing a nano-cellulose composite material, which is to make natural cotton into nano-microfiber, and then blend the nanofiber with polylactic acid to prepare an injection molding material, but in the process of preparing nano-cellulose with cotton, strong alkali and hydrogen peroxide are used for cooking, and then a TEMPO oxidation system is used for oxidation and then centrifugal separation is performed, the process uses a lot of expensive reagents, the process is long, the yield of the obtained nano-cellulose is low, and a large amount of natural cellulose is wasted. Chinese patent CN104292439A discloses a preparation method of a sisal cellulose nanowhisker/polylactic acid biological composite material, wherein polylactic acid oligomer is grafted on the surface of the sisal cellulose nanowhisker to form interface bonding with good compatibility, and an in-situ composite technology is adopted to prepare the sisal cellulose nanowhisker/polylactic acid biological composite material, wherein the method uses safe and environment-friendly reagents, but needs conditions of high temperature of 400 ℃, vacuum cooling, reduced pressure distillation and the like, and the polymerization process has higher requirements on equipment. Chinese patent CN108219404A discloses a preparation method of a nano microcrystalline cellulose reinforced polylactic acid 3D printing material, which comprises the steps of carrying out acidolysis on needle-leaved wood cellulose by 98% sulfuric acid, carrying out ultrasonic treatment, carrying out high-speed centrifugation, adding zinc oxide, carrying out high-pressure homogenization to prepare a dispersion liquid, and finally blending the dispersion liquid with a polylactic acid-trichloromethane solution for drawing. The material has good fluidity and mechanical property, but toxic hazardous reagents such as 98% sulfuric acid, trichloromethane and the like have high risk in the production process, have extremely high requirements on production equipment and storage equipment, are difficult to produce in large scale in batch, and cause great pollution to the environment in the production process.
In the FDM type 3D printing technology, theoretically, cellulose is used as a natural long fiber and can be dispersed in a high polymer matrix through doping, and the internal friction force of the matrix is increased, so that the mechanical property, particularly the tensile property, of the material is improved, and the application value of the material is improved. However, untreated cellulose has a very large molecular weight, a large number of surface hydroxyl groups, and a very stable structure, and often cannot be compatible with a polymer matrix, but the untreated cellulose destroys the regular structure in the polymer and lowers the overall mechanical properties. Meanwhile, cellulose incompatible with the matrix is easy to agglomerate and deposit on the printing nozzle in the 3D printing process, so that the phenomena of unsmooth printing, plug and the like are caused, and the printing cannot be continuously carried out. The nano-cellulose has small size, relatively low molecular weight and higher activity, can be well infiltrated and combined with a high molecular matrix, but is often required to be separated and purified in the preparation process, and has long required period and higher cost.
Disclosure of Invention
In order to overcome the defects and shortcomings of poor compatibility of cellulose and high molecular polymer, complex preparation process of nano cellulose, difficulty in full utilization and the like in the prior art, the invention mainly aims to: a nanocellulose/cellulose compound which can be used for enhancing polylactic acid 3D printing materials is prepared by carrying out a series of simpler and safer process treatments on cellulose. The method is realized by the following technical scheme:
a nanocellulose/cellulose composite made by a process comprising the steps of:
(1) pulverizing a certain amount of cellulose, treating with inorganic acid (at 45-60 deg.C in thermostatic water bath for 1-5 hr) until the solution turns yellow, diluting with water (10-20 times volume of the obtained solution), standing for layering, and collecting the mixed solution containing flocculent cellulose;
(2) centrifuging the mixed solution containing the flocculent cellulose obtained in the step (1) at a high speed (for 5-20 min) at 8000-;
(3) crushing and sieving a certain amount of cellulose to obtain cellulose powder with uniform particle size or microcrystalline cellulose powder with the same particle size purchased in the market as cellulose powder for later use; uniformly mixing a certain amount of the nano cellulose sol obtained in the step (2) with the cellulose powder;
(4) placing the mixture prepared in the step (3) under the water bath condition of 75-85 ℃ (0.5-1 h) to constant temperature, and then adding the mixture which is mixed with the cellulose powder in a mass ratio of (1-10): (1-10) stirring and reacting the silane coupling agent for 4-5 hours under the constant-temperature sealing condition to obtain product precipitate; washing the obtained product (with water), filtering, removing residual silane coupling agent and other substances in the reaction to obtain the nano-cellulose/cellulose compound, and drying (at 80 ℃).
Preferably, the inorganic acid in the step (1) is one or more of hydrochloric acid with the mass fraction of 20-38%, sulfuric acid with the mass fraction of 50-64%, oleic acid and phosphoric acid; the cellulose can be one or more of cotton, flax, jute, softwood, hardwood and filter paper pulp cellulose;
preferably, the particle size of the cellulose powder in the step (3) is 50-250 meshes, and more preferably 100-150 meshes.
Preferably, the mass ratio of the nano-cellulose sol to the cellulose powder in the step (3) is (10-500): 1; preferably (50-100): 1.
Preferably, the silane coupling agent in the step (4) is a KH series silane coupling agent, more preferably one of gamma-aminopropyltriethoxysilane (KH 550), gamma-glycidoxypropyltrimethoxysilane (KH 560) and gamma- (methacryloyloxy) propyltrimethoxysilane (KH 570), and most preferably gamma-aminopropyltriethoxysilane (KH 550).
The invention also aims to provide a nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material, which can remarkably improve the bending property, the tensile property and the impact resistance of the material while maintaining the excellent 3D printing property of PLA.
The reinforced polylactic acid 3D printing material comprises the nano-cellulose/cellulose compound as a raw material, and is preferably obtained by blending polylactic acid, an inorganic nano-material, a toughening agent and a plasticizer.
Preferably, the reinforced polylactic acid 3D printing material comprises the following raw materials in percentage by mass: 0.1-2% of nano-cellulose/cellulose compound, 90-98% of polylactic acid, 0.1-3% of inorganic nano-material, 0.1-5% of toughening agent and 0.1-5% of plasticizer.
More preferably, the polylactic acid has a molecular weight of 1.0 × 106-3.0×106. The inorganic nano material is one of nano silicon dioxide, nano titanium dioxide, nano zirconium dioxide and nano calcium carbonate. The toughening agent is one of SEBS (styrene-butadiene-styrene block copolymer), SBS (thermoplastic polystyrene-polybutadiene-polystyrene block copolymer), TPU (thermoplastic polyurethane elastomer) and TPEE (thermoplastic polyester elastomer). The plasticizer is polyethylene glycol (PEG) with a molecular weight of 1000-20000.
The preparation method of the reinforced polylactic acid 3D printing material comprises the following steps:
(1) mixing the nano-cellulose/cellulose composite with polylactic acid, inorganic nano-materials, a toughening agent and a plasticizer at a high speed according to a proportion to form a blend;
(2) melting and extruding the obtained mixture by a double-screw extruder, and pelletizing, wherein the temperatures of the 1-6 sections of the extruder are respectively 170-175 ℃, 170-177 ℃, 175-180 ℃, 180-185 ℃ and 185-190 ℃ to obtain granules, and fully drying at 80-85 ℃;
(3) and extruding, drawing and winding the obtained granules by a single-screw extruder to prepare the 3D printing wire rod, wherein the temperature of 1-4 sections of the extruder is respectively 170-180 ℃, 175-185 ℃, 180-190 ℃ and 180-190 ℃, the drawing speed is 50-60mm/s, and the obtained wire rod is about 1.75mm or 3mm in diameter, and the diameter error is within +/-5%.
The invention has the following positive and beneficial effects:
the nano-cellulose/cellulose composite has good compatibility with polylactic acid. The composite has the long fiber-shaped structure of natural large cellulose and the large specific surface and nano size effects of nano cellulose. Different from common cellulose, the mechanical property of the polylactic acid can be obviously improved by doping a small amount of polylactic acid, a high-performance 3D printing wire rod is manufactured, the transparent or semitransparent appearance of the polylactic acid 3D printing material can be kept, and the polylactic acid 3D printing wire rod can be applied to the fields of polymer 3D printing, particularly 3D printing decoration and the like.
(1) The cellulose is used as natural biomass, has wide source and is easy to obtain, and the raw materials of the natural cellulose, the microcrystalline cellulose, the silane coupling agent, the inorganic nano material, the toughening agent, the plasticizer and the like adopted by the invention all belong to industrial grade, are safe and nontoxic, and have low requirements on the raw materials. And the preparation period is short, the repeatability is high, and the preparation method is convenient for production and application.
(2) The cellulose is subjected to size nanocrystallization and then is compounded with the cellulose, so that the cellulose is attached to the surface of natural cellulose, the defect of poor compatibility between the cellulose and polylactic acid is overcome by utilizing a nanometer size effect, meanwhile, the silane coupling agent can reduce hydroxyl groups rich on the surface of the cellulose, the compatibility between the cellulose and polylactic acid is further improved, the mechanical strength of the polylactic acid 3D printing wire rod can be enhanced, and the phenomenon of blocking of the product in the printing process is avoided.
(3) The nano-cellulose solution obtained in the process can participate in the next reaction without separation and purification, the performance of the nano-cellulose solution is not influenced, and the long period and high cost required by dialysis after centrifugation of the traditional acidolysis nano-cellulose are reduced.
(4) The 3D printing material is composed of cellulose and polylactic acid, is an environment-friendly degradable material, does not generate secondary pollution such as white pollution and the like, and can be decomposed after being simply treated under appropriate conditions.
Drawings
Figure 1 SEM image of nanocellulose/microcrystalline cellulose composite at 1200 x magnification.
Figure 2 SEM image of nanocellulose/microcrystalline cellulose composite at 12000 magnification.
Figure 3 SEM image of nanocellulose/microcrystalline cellulose composite at 65000 x magnification.
Fig. 4a nanocellulose/microcrystalline cellulose composite reinforced polylactic acid 3D printing wire.
Fig. 5 a reinforced polylactic acid 3D printing wire printing finished product model.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples of the present invention are commercially available reagents or starting materials unless otherwise specified, and the test methods used in the examples are those conventionally used in the art unless otherwise specified. The specific method for testing the mechanical property of the material is as follows: the tensile test is executed according to the national standard GB/T1040-; the bending test is executed according to the national standard GB/T9341-; the notch impact test is carried out according to the national standard GB/T1043-2008 standard.
Example 1
A reinforced polylactic acid 3D printing material is prepared by the following steps:
(1) crushing 2g of cotton cellulose, treating the crushed cotton cellulose with 25 ml of acid mixed by 64 percent sulfuric acid and 25 ml of oleic acid in a thermostatic water bath at 50 ℃ for 2 hours until the solution turns yellow, stopping the reaction, and diluting the solution with 500 ml of water; standing for layering, and taking the mixed solution containing flocculent cellulose at the lower layer for later use;
(2) centrifuging the mixed solution containing the flocculent cellulose at a high speed of 8000 r/m for 15 minutes, collecting the upper layer of turbid solution, adding water into the flocculent cellulose at the bottom, uniformly mixing the water and the turbid solution to obtain turbid solution, centrifuging the turbid solution again, circulating the turbid solution for multiple times until the turbid solution is not uniformly mixed with the water into the flocculent cellulose at the bottom after separation, and combining the obtained turbid solution to obtain stable nano-cellulose sol solution;
(3) crushing 2g of cotton cellulose, and sieving the crushed cotton cellulose with a 150-mesh sieve to obtain 150-mesh cellulose powder;
(4) 200ml of prepared nano cellulose sol liquid is taken to be evenly mixed with 2g of cellulose powder;
(5) placing the mixture prepared in the step (4) in a water bath at 80 ℃ for 0.5h to a constant temperature, then adding 1g of silane coupling agent KH550 at the constant temperature, stirring under a constant-temperature sealing condition, and reacting for 5 h;
(6) after the reaction is stopped, the mixed solution can be observed to turn from turbid to clear, then the product obtained by the reaction in the step (5) is washed by water and filtered to remove the residual silane coupling agent and other substances in the reaction to obtain the nano-cellulose/cellulose compound, and then the nano-cellulose/cellulose compound is dried at the temperature of 80 ℃, and the utilization rate of the cellulose reaches 86.2 percent. The scanning electron microscope image of the prepared nano-cellulose/cellulose compound is shown in the attached figure 1 of the specification;
(7) weighing 0.5% of nano-cellulose/cellulose composite, 98% of polylactic acid, 0.5% of nano-silicon dioxide, 0.5% of SEBS and 0.5% of PEG-100000.5% by mass, putting the components together into a high-speed mixer, mixing for 5 min, and taking out to obtain a mixture;
(8) extruding and blending the mixture prepared in the step (7) by a double-screw extruder, cooling by water, cutting into granules to obtain composite master batches, drying at 80 ℃ for 24 hours, and sealing for later use, wherein the temperatures of all zones of the extruder are respectively set to be 170 ℃, 175 ℃, 180 ℃, 185 ℃, and the rotating speeds of a host machine and a feeding machine are respectively 20 r/min and 10 r/min;
(9) drying the granules prepared in the step (8), and adding the granules into a single-screw extruder, wherein the temperatures of a feeding section, a compression section, a metering section and a cylinder of the extruder are respectively set to be 170 ℃, 175 ℃, 180 ℃ and 185 ℃; cooling and air-drying the extruded melt through a water tank, preparing the melt into monofilaments with the diameter of about 1.75mm or 3.0 mm through a traction machine, and rolling the monofilaments;
(10) testing after the monofilament after rolling is printed a standard spline through FDM type 3D printer, printing temperature (nozzle) is 200 ℃ (can be adjusted according to actual conditions), nozzle diameter is 0.4mm, printing speed is 60mm/min, and print platform temperature is not fixed.
Mechanical property tests are carried out on the prepared material standard sample strips according to national standards, and the detection results of the mechanical property and the 3D printing property of the nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material prepared in the embodiment are shown in Table 1.
Example 2
A reinforced polylactic acid 3D printing material is prepared by the following steps:
(1) crushing 2g of flax cellulose, treating the flax cellulose with 35ml of 64 percent sulfuric acid in a constant-temperature water bath at 45 ℃ for 1h until the solution is slightly yellow, stopping the reaction, and diluting the flax cellulose with 700ml of water; standing for layering, and taking the mixed solution containing flocculent cellulose at the lower layer for later use;
(2) centrifuging the mixed solution containing the flocculent cellulose at a high speed of 8000 r/m for 20 minutes, collecting the upper layer of turbid solution, adding water into the flocculent cellulose at the bottom, uniformly mixing the water and the turbid solution to obtain turbid solution, centrifuging the turbid solution again, circulating the turbid solution for multiple times until the turbid solution is not uniformly mixed with the water into the flocculent cellulose at the bottom after separation, and combining the obtained turbid solution to obtain stable nano-cellulose sol solution;
(3) crushing 2g of flax cellulose, and sieving the flax cellulose with a 150-mesh sieve to obtain 150-mesh cellulose powder;
(4) 200ml of prepared nano cellulose sol liquid is taken to be evenly mixed with 2g of cellulose powder;
(5) placing the mixture prepared in the step (4) in a water bath at 75 ℃ for 0.5h to a constant temperature, then adding 1g of silane coupling agent KH560 at the constant temperature, stirring under a constant-temperature sealing condition, and reacting for 5 h;
(6) after the reaction is stopped, the mixed solution can be observed to turn from turbid to clear, then the product obtained by the reaction in the step (5) is washed by water and filtered to remove the residual silane coupling agent and other substances in the reaction to obtain a nano-cellulose/cellulose compound, and then the nano-cellulose/cellulose compound is dried at the temperature of 80 ℃, wherein the utilization rate of the cellulose reaches 85.3 percent;
(7) weighing 0.5% of nano-cellulose/cellulose composite, 97% of polylactic acid, 0.5% of nano-silicon dioxide, 1% of SEBS and PEG-100001% in percentage by mass, putting the components together into a high-speed mixer, mixing for 5 min, and taking out to obtain a mixture; the remaining steps (8), (9) and (10) are the same as in example 1.
Mechanical property tests are carried out on the prepared material standard sample strips according to national standards, and the detection results of the mechanical property and the 3D printing property of the nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material prepared in the embodiment are shown in Table 1.
Example 3
A reinforced polylactic acid 3D printing material is prepared by the following steps:
(1) pulverizing 2g of jute cellulose, treating with 40ml of 30% hydrochloric acid in a constant temperature water bath at 60 ℃ for 1h until the solution is slightly yellow, stopping the reaction, and diluting with 600ml of water; standing for layering, and taking the mixed solution containing flocculent cellulose at the lower layer for later use;
(2) centrifuging the mixed solution containing the flocculent cellulose at a high speed of 12000 r/m for 10 minutes, collecting the upper layer of turbid solution, adding water into the flocculent cellulose at the bottom, uniformly mixing the water and the turbid solution to obtain turbid solution, centrifuging the turbid solution again, circulating the turbid solution for multiple times until the turbid solution is not changed after the water is added into the flocculent cellulose at the bottom and the turbid solution is uniformly mixed, and combining the obtained turbid solution to obtain stable nano-cellulose sol solution;
(3) pulverizing 2g of jute cellulose, and sieving with 150 mesh sieve to obtain 150 mesh cellulose powder.
(4) 200ml of prepared nano cellulose sol liquid is taken to be evenly mixed with 2g of cellulose powder;
(5) placing the mixture prepared in the step (4) in a water bath at 80 ℃ for 0.5h to a constant temperature, then adding 1g of silane coupling agent KH570 at the constant temperature, stirring under a constant-temperature sealing condition, and reacting for 5 h;
(6) after the reaction is stopped, the mixed solution can be observed to turn from turbid to clear, then the product obtained by the reaction in the step (5) is washed by water and filtered to remove the residual silane coupling agent and other substances in the reaction to obtain a nano-cellulose/cellulose compound, and then the nano-cellulose/cellulose compound is dried at the temperature of 80 ℃, and the utilization rate of the cellulose reaches 86.7 percent;
(7) weighing 0.5% of nano-cellulose/cellulose composite, 96% of polylactic acid, 0.5% of nano titanium dioxide, 1.5% of SEBS and PEG-80001.5% by mass percent, putting the components together into a high-speed mixer, mixing for 5 min, and taking out to obtain a mixture; the experimental procedures for the rest of (8), (9) and (10) were the same as those of example 1.
Mechanical property tests are carried out on the prepared material standard sample strips according to national standards, and the detection results of the mechanical property and the 3D printing property of the nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material prepared in the embodiment are shown in Table 1. The 3D printing wire rod and the printing finished product prepared by the embodiment are shown in the attached figure 2 of the specification.
Example 4
A reinforced polylactic acid 3D printing material is prepared by the following steps:
(1) crushing 2g of microcrystalline cellulose, treating the crushed microcrystalline cellulose with 40ml of phosphoric acid in a constant-temperature water bath at 45 ℃ for 1h until the solution is slightly yellow, stopping the reaction, and diluting the solution with 400ml of water; standing for layering, and taking the mixed solution containing flocculent cellulose at the lower layer for later use;
(2) centrifuging the mixed solution containing the flocculent cellulose at a high speed of 10000 r/m for 15 minutes, collecting the upper layer of turbid solution, adding water into the flocculent cellulose at the bottom, uniformly mixing the water and the turbid solution to be turbid, centrifuging again, circulating for many times until the flocculent cellulose at the bottom is uniformly mixed and does not become turbid after separation, and combining the obtained turbid solutions to obtain a stable nano-cellulose sol solution;
(3) crushing 2g of microcrystalline cellulose, and sieving the crushed microcrystalline cellulose with a 100-mesh sieve to obtain 100-mesh cellulose powder;
(4) uniformly mixing 200ml of prepared nano cellulose sol liquid with 2g of microcrystalline cellulose powder;
(5) placing the mixture prepared in the step (4) in a water bath at 80 ℃ for 0.5h to a constant temperature, then adding 1g of silane coupling agent KH550 at the constant temperature, stirring under a constant-temperature sealing condition, and reacting for 5 h;
(6) after the reaction is stopped, the mixed solution can be observed to turn from turbid to clear, then the product obtained by the reaction in the step (5) is washed by water and filtered to remove the residual silane coupling agent and other substances in the reaction to obtain a nano-cellulose/microcrystalline cellulose compound, and then the nano-cellulose/microcrystalline cellulose compound is dried at 80 ℃, wherein the utilization rate of the cellulose reaches 90.5 percent;
(7) weighing 0.5% of nano-cellulose/cellulose composite, 96% of polylactic acid, 0.5% of nano titanium dioxide, 1.5% of SEBS and PEG-40001.5% by mass percent, putting the components together into a high-speed mixer, mixing for 5 min, and taking out to obtain a mixture; the experimental procedures for the rest of (8), (9) and (10) were the same as those of example 1.
Mechanical property tests are carried out on the prepared material standard sample strips according to national standards, and the detection results of the mechanical property and the 3D printing property of the nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material prepared in the embodiment are shown in Table 1.
Example 5
A reinforced polylactic acid 3D printing material is prepared by the following steps:
(1) crushing 2g of needle-leaved wood cellulose, treating the crushed needle-leaved wood cellulose with acid mixed by 20 ml of phosphoric acid and 20 ml of oleic acid in a constant-temperature water bath at 50 ℃ for 1 hour until the solution is slightly yellow, stopping the reaction, and diluting the solution with 400ml of water; standing for layering, and taking the mixed solution containing flocculent cellulose at the lower layer for later use;
(2) centrifuging the mixed solution containing the flocculent cellulose at a high speed of 8000 r/m for 15 minutes, collecting the upper layer of turbid solution, adding water into the flocculent cellulose at the bottom, uniformly mixing the water and the turbid solution to obtain turbid solution, centrifuging the turbid solution again, circulating the turbid solution for multiple times until the turbid solution is not uniformly mixed with the water into the flocculent cellulose at the bottom after separation, and combining the obtained turbid solution to obtain stable nano-cellulose sol solution;
(3) 2g of filter paper pulp cellulose is crushed and sieved by a 150-mesh sieve to obtain 150-mesh cellulose powder.
(4) 200ml of the prepared nano cellulose sol solution is taken and mixed with 2g of cellulose powder evenly.
(5) And (3) placing the mixture prepared in the step (4) in a water bath condition at 85 ℃ for 0.5h to a constant temperature, then adding 1g of silane coupling agent KH570 at the constant temperature, stirring under a constant-temperature sealing condition, and reacting for 5 h.
(6) After the reaction is stopped, the mixed solution can be observed to turn from turbid to clear, then the product obtained by the reaction in the step (5) is washed by water and filtered to remove the residual silane coupling agent and other substances in the reaction to obtain a nano-cellulose/cellulose compound, and then the nano-cellulose/cellulose compound is dried at 80 ℃, wherein the utilization rate of the cellulose reaches 90.6 percent;
(7) weighing 0.5% of nano-cellulose/cellulose composite, 96% of polylactic acid, 0.5% of nano titanium dioxide, 1.5% of SEBS and PEG-4001.5% by mass percent, putting the components together into a high-speed mixer, mixing for 5 min, and taking out to obtain a mixture; the experimental procedures for the rest of (8), (9) and (10) were the same as those of example 1.
Mechanical property tests are carried out on the prepared material standard sample strips according to national standards, and the detection results of the mechanical property and the 3D printing property of the nano-cellulose/cellulose composite reinforced polylactic acid 3D printing material prepared in the embodiment are shown in Table 1.
Comparative example 1
This comparative example was the same as example 1 except that the filler was 150 mesh microcrystalline cellulose which was not modified with nanocellulose (nanocellulose/cellulose composite was replaced with 150 mesh microcrystalline cellulose). The mechanical property and 3D printing performance results of the microcrystalline cellulose reinforced polylactic acid 3D printing material prepared by the comparative example are shown in Table 1.
Comparative example 2
This comparative example was conducted under the same process conditions and in the same manner as in example 1 except that the filler was commercially available cotton nanocellulose (the nanocellulose/cellulose composite was replaced with commercially available cotton nanocellulose). The mechanical property and printing performance results of the cotton nanocellulose-reinforced polylactic acid 3D printing material prepared by the comparative example are shown in table 1.
Appearance and properties of printed product of nanocellulose/cellulose polylactic acid 3D printing material obtained in Table 1
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. The reinforced polylactic acid 3D printing material is characterized by comprising the following raw materials: 0.1-2% of nano-cellulose/cellulose compound, 90-98% of polylactic acid, 0.1-3% of inorganic nano-material, 0.1-5% of toughening agent and 0.1-5% of plasticizer;
the nano-cellulose/cellulose composite is prepared by a method comprising the following steps:
(1) crushing cellulose, performing acidolysis treatment in a constant-temperature water bath, diluting with water, standing for layering, and taking a mixed solution containing flocculent cellulose in a lower layer for later use;
(2) performing high-speed centrifugation, separation and water adding on the mixed solution containing the flocculent cellulose obtained in the step (1) for multiple times, mixing the mixed solution and the upper turbid solution obtained each time to obtain stable nano cellulose sol;
(3) uniformly mixing the nano cellulose sol obtained in the step (2) with a certain amount of cellulose powder;
(4) adding a silane coupling agent into the mixture prepared in the step (3), reacting to obtain a precipitate, washing and drying to obtain a nano-cellulose/cellulose compound;
the cellulose and cellulose powder are natural cellulose or microcrystalline cellulose; the acid is one or more of inorganic strong acid, medium strong acid and organic acid; the silane coupling agent is a KH-series silane coupling agent;
the condition of the constant-temperature water bath used in the step (1) is 45-60 ℃; the water consumption for dilution is 10-20 times of the volume of the obtained solution; acidolysis treatment is carried out until the solution turns yellow; the step (2) of high-speed centrifugation is to centrifuge for 5-20 min at 12000 r/min of 8000-; in the reaction in the step (4), the mixture is firstly placed under the water bath condition of 75-85 ℃ to be constant temperature, and then the mixture is added with the cellulose powder according to the mass ratio of (1-10): (1-10) stirring and reacting the silane coupling agent for 4-5 hours under the constant-temperature sealing condition;
the mass ratio of the nano-cellulose sol to the cellulose powder used in the step (3) is (10-500): 1.
2. The reinforced polylactic acid 3D printed material according to claim 1, wherein: the acid is one or more of hydrochloric acid with the mass fraction of 20-38%, sulfuric acid with the mass fraction of 50-64%, oleic acid and phosphoric acid.
3. The reinforced polylactic acid 3D printed material according to claim 1, wherein: the silane coupling agent is one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
4. The reinforced polylactic acid 3D printing material according to claim 1, wherein the molecular weight of the polylactic acid is 1.0 x 106-3.0×106(ii) a The inorganic nano material is one of nano silicon dioxide, nano titanium dioxide, nano zirconium dioxide and nano calcium carbonate; the toughening agent is one of styrene-ethylene-butadiene-styrene block copolymer, thermoplastic polystyrene-polybutadiene-polystyrene block copolymer, thermoplastic polyurethane elastomer and thermoplastic polyester elastomer; the plasticizer is polyethylene glycol with the molecular weight of 1000-20000.
5. The preparation method of the reinforced polylactic acid 3D printing material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) mixing the nano-cellulose/cellulose composite with polylactic acid, inorganic nano-materials, a toughening agent and a plasticizer at a high speed according to a proportion to form a blend;
(2) melting and extruding the obtained mixture by a double-screw extruder, and pelletizing, wherein the temperatures of the 1-6 sections of the extruder are respectively 170-175 ℃, 170-177 ℃, 175-180 ℃, 180-185 ℃ and 185-190 ℃ to obtain granules, and fully drying at 80-85 ℃;
(3) and extruding, drawing and winding the obtained granules by a single-screw extruder to prepare the 3D printing wire, wherein the temperatures of 1-4 sections of the extruder are respectively 170-180 ℃, 175-185 ℃, 180-190 ℃ and the drawing speed is 50-60 mm/s.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
| EP2661462A1 (en) * | 2011-01-05 | 2013-11-13 | Teknologian tutkimuskeskus VTT | Method of producing composite materials |
| CN104910422A (en) * | 2015-06-29 | 2015-09-16 | 中国林业科学研究院林产化学工业研究所 | High-length-diameter-ratio nano-cellulose-reinforced polylactic acid composite material and preparation method thereof |
| CN106893284A (en) * | 2017-04-01 | 2017-06-27 | 浙江大学宁波理工学院 | The preparation method of polylactic acid/nano-cellulose composite material |
| CN109054323A (en) * | 2018-08-23 | 2018-12-21 | 华南农业大学 | Lignin/Microcrystalline cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof |
-
2019
- 2019-03-13 CN CN201910186916.3A patent/CN109880180B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2661462A1 (en) * | 2011-01-05 | 2013-11-13 | Teknologian tutkimuskeskus VTT | Method of producing composite materials |
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
| CN104910422A (en) * | 2015-06-29 | 2015-09-16 | 中国林业科学研究院林产化学工业研究所 | High-length-diameter-ratio nano-cellulose-reinforced polylactic acid composite material and preparation method thereof |
| CN106893284A (en) * | 2017-04-01 | 2017-06-27 | 浙江大学宁波理工学院 | The preparation method of polylactic acid/nano-cellulose composite material |
| CN109054323A (en) * | 2018-08-23 | 2018-12-21 | 华南农业大学 | Lignin/Microcrystalline cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof |
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