CN114634630B - Modified camellia oleifera shell powder, filled polylactic acid 3D printing material and preparation method thereof - Google Patents

Modified camellia oleifera shell powder, filled polylactic acid 3D printing material and preparation method thereof Download PDF

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CN114634630B
CN114634630B CN202210301867.5A CN202210301867A CN114634630B CN 114634630 B CN114634630 B CN 114634630B CN 202210301867 A CN202210301867 A CN 202210301867A CN 114634630 B CN114634630 B CN 114634630B
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camellia oleifera
shell powder
oleifera shell
polylactic acid
solution
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CN114634630A (en
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董先明
肖嘉林
关丽涛
冼敏祺
吴锦尧
洪崇竣
李知远
周武艺
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South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention belongs to the field of high polymer materials, and relates to a method for preparing nano/micron CaCO by crushing waste oil tea shells, treating with alkali, silane coupling agent and the like and adopting an in-situ deposition method 3 Or SiO 2 Or TiO 2 The modified camellia oleifera hull powder is deposited on the surface of the camellia oleifera hull powder, and then the polylactic acid 3D printing material is prepared by blending, melt grafting, extruding and wire drawing the modified camellia oleifera hull powder and the polylactic acid. The prepared modified camellia oleifera shell powder filled polylactic acid 3D printing material has good mechanical property, interface compatibility and antibacterial property, has excellent 3D printing property, can be used for replacing general fused deposition molding 3D printing plastic consumables, is green and environment-friendly, has wood texture, and can be widely applied to the fields of toys, music equipment, individual artworks, furniture, building decoration and the like.

Description

Modified camellia oleifera shell powder, filled polylactic acid 3D printing material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials and fused deposition modeling 3D printing, and particularly relates to a modified camellia oleifera shell powder and filled polylactic acid 3D printing material and a preparation method thereof.
Background
The plant waste is a renewable resource in the nature and is a preferred reinforcing material of the composite material. The commonly used plant wastes include agricultural product processing wastes such as crop straws, chaffs, shells, bagasse and the like. The camellia oleifera shells are used as byproducts in the camellia oleifera oil industry, the yield is high, the camellia oleifera shells contain rich tea saponin, tea seed polysaccharide, tea seed protein and the like, and are raw materials of products in chemical industry, fertilizer industry, food industry, feed industry and the like, and meanwhile, the camellia oleifera shells also have a plurality of excellent characteristics of antibiosis, light weight, high strength, ultraviolet resistance, oxidation resistance and the like, so the camellia oleifera shells have considerable economic value. However, most of the oil-tea camellia shells are not fully utilized at present and are usually burnt as fuels or directly discarded, so that not only is the resource waste caused, but also the environmental pollution is caused. Because the camellia oleifera shells contain a large amount of pectin, lignin and the like, the content of the lignin reaches 40-60%, the content of the cellulose is low and is only 20-30%, and the camellia oleifera shells contain a large amount of pore structures, the strengthening effect of the camellia oleifera shells on polymers is not obvious. Therefore, few reports are reported on the camellia oleifera shell powder reinforced polymer composite material, and the prepared camellia oleifera shell particle board or camellia oleifera shell-based composite material can hardly reach the mechanical index of the wood-plastic composite material specified by the national standard.
Polylactic acid (PLA) is a relatively common Fused Deposition (FDM) type 3D printing high polymer material, and has the advantages of no bad smell, complete biodegradation, no toxicity or harm to human bodies and the like during melting. But the defects of poor toughness, easy fracture, low melting point, poor thermal stability and other mechanical properties limit the application range of the 3D printing material. Therefore, the mechanical properties and thermal stability of the fiber are usually improved by adding reinforcing materials such as carbon fiber and plant fiber, wherein the plant fiber is paid attention to due to the advantages of wide sources, low price, environmental protection and the like. However, when the plant fiber reinforced polylactic acid 3D printing material is prepared, the plant fiber is long, so that the 3D printing wire cannot be stably molded, and a printer plug is easily caused in the printing process. In addition, most plant fiber reinforced polylactic acid 3D printing materials lack certain functions, such as bacteriostasis, ultraviolet resistance, oxidation resistance, etc., which results in limited application.
Disclosure of Invention
In order to overcome the defects of poor mechanical property, single function and the like of a composite material in the existing oil-tea camellia shell powder filling polylactic acid 3D printing material technology, the invention mainly aims to carry out chemical modification treatment on waste oil-tea camellia shell powder and deposit a nano inorganic material on the surface of the oil-tea camellia shell powder, thereby providing a method for treating the oil-tea camellia shell powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for modifying camellia oleifera shell powder comprises the following steps:
(1) Soaking oil tea shell in hot water (90-100 deg.C), removing part of small molecular compounds, pigment, pectin, etc., washing with water until the filtrate is nearly colorless, and oven drying at 60-80 deg.C;
(2) Crushing the oil-tea camellia shells obtained in the step (1), grinding the obtained powder for 1-2 hours by a ball mill at the grinding speed of 400-600rpm, and sieving the powder by a 40-200-mesh sieve to obtain oil-tea camellia shell powder with uniform particle size;
(3) Uniformly mixing the camellia oleifera shell powder obtained in the step (2) with an alkali solution, washing the obtained mixture with water to be neutral, filtering and drying (in a drying oven at 60-80 ℃ for 12-24 h) to obtain alkali-treated camellia oleifera shell powder;
the mass ratio of the oil-tea camellia shell powder to the alkali solution is 1 (4-6); the alkali solution is one of sodium hydroxide, calcium hydroxide or potassium hydroxide water solution, and the mass percentage is 1-10%;
(4) Uniformly mixing the alkali-treated camellia oleifera shell powder obtained in the step (3) with an alcohol solution, adding a silane coupling agent accounting for 8-12% of the mass of the alkali-treated camellia oleifera shell, and stirring and reacting for 4-6 hours at 70-90 ℃ under a sealed condition; washing the mixture obtained by the reaction with water or ethanol, filtering (removing residual silane coupling agent and the like), and drying (in a drying oven at 60-80 ℃ for 12-24 h) to obtain the camellia oleifera shell powder treated by the silane coupling agent;
the mass ratio of the alkali-treated camellia oleifera shell powder to the alcoholic solution is 1 (4-6), and the volume ratio of alcohol to water in the alcoholic solution is (3-5): 1;
the alcohol is at least one of ethanol, propanol, butanol and n-propanol; the silane coupling agent is one of gamma-aminopropyltriethoxysilane (KH 550), gamma-glycidoxypropyltrimethoxysilane (KH 560) and gamma- (methacryloyloxy) propyltrimethoxysilane (KH 570);
(5) Adding the silane coupling agent treated camellia oleifera shell powder obtained in the step (4) into a calcium solution, stirring for 0.25-0.5h at normal temperature, then adding a carbonate solution, stirring for 0.5-1h at room temperature, washing and filtering the mixture obtained by reaction with water, and drying in a 60-80 ℃ oven for 12-24h to obtain CaCO 3 Depositing the camellia oleifera shell powder in situ;
the calcium solution is an aqueous solution of calcium chloride or calcium nitrate, the concentration is 0.2-0.5 mol/L, and the mass ratio of the used silane coupling agent treated camellia oleifera shell powder to the calcium solution is 1: (4-6); the carbonate solution is an aqueous solution of sodium carbonate or potassium carbonate, and the concentration of the carbonate solution is 0.2-0.5 mol/L; a dispersant is also dissolved in the carbonate solution, and the dispersant is dipotassium ethylenediamine tetraacetate or disodium ethylenediamine tetraacetate with the concentration of 1 multiplied by 10 －3 g/mL-5×10 －3 g/mL; the volume ratio of the carbonate solution to the calcium solution is 1 (0.8-1.2).
Or adding the silane coupling agent treated camellia oleifera hull powder obtained in the step (4) into a certain amount of alcohol solution (the volume ratio of alcohol to water in the alcohol solution is 1 (1.6-2.4), the mass ratio of the silane coupling agent treated camellia oleifera hull powder to the alcohol solution is 1 (4-6)), stirring for 0.5-1h at 30-50 ℃ in a sealed environment, then adding orthosilicate (one of methyl orthosilicate and ethyl orthosilicate, the volume ratio of the orthosilicate to the alcohol solution is 1 (1.3-1.6)), stirring for 0.5-1h, then slowly adding alkali solution (one of ammonia water, sodium hydroxide, potassium hydroxide and barium hydroxide aqueous solution, the concentration is 1-3mol/L, and the volume ratio of the alkali solution to the alcohol solution is 1 (1.3-1.6)), adding 40-60% alkali solution, then performing ultrasonic oscillation for 0.5-1h at 30-50 ℃, and then addingAdding residual alkali solution, ultrasonic oscillating for 0.5-1h, transferring to 30-50 deg.C water bath, stirring for 10-15h, washing reaction product with water, filtering, and oven drying at 60-80 deg.C for 12-24h to obtain SiO 2 Depositing the camellia oleifera shell powder in situ.
Or adding the silane coupling agent treated camellia oleifera hull powder obtained in the step (4) into a certain amount of alcohol (one of ethanol, propanol, butanol and n-propanol, wherein the mass ratio of the camellia oleifera hull to the alcohol is 1 (4-6)), then adding titanate (one of tetraethyl titanate, isopropyl titanate and tetrabutyl titanate) accounting for 20-30% of the volume of the alcohol, and stirring for 0.5-1h at 30-50 ℃ in a sealed environment to obtain a mixed solution A; mixing alcohol with the volume of 80-120% of that of the mixed solution A, deionized water with the volume of 40-60% of that of the mixed solution A, glacial acetic acid with the volume of 8-15% of that of the mixed solution A and dilute hydrochloric acid (with the concentration of 1-4 mol/L) with the volume of 3-8% of that of the mixed solution A under the stirring condition, and violently stirring for 5-10min at the temperature of 30-50 ℃ to obtain a mixed solution B; adding the mixed solution B into the mixed solution A, strongly stirring for 1-2h at 30-50 ℃, washing with deionized water after stirring, filtering, and drying (in an oven at 60-80 ℃ for 12-24 h) to obtain TiO 2 Depositing the camellia oleifera shell powder in situ.
The invention also aims to provide the modified camellia oleifera shell powder filled polylactic acid 3D printing material, which improves the mechanical property of the material on the basis of keeping the excellent 3D printing performance of PLA, endows the polylactic acid 3D printing material with natural wood texture and has good antibacterial, ultraviolet-resistant and antioxidant functions. The method is realized by the following technical scheme:
a modified camellia oleifera abel shell powder filled polylactic acid 3D printing material is a blend containing modified camellia oleifera abel shell powder, polylactic acid and nano montmorillonite; the modified oil-tea camellia shell powder is the alkali-treated oil-tea camellia shell powder and the silane coupling agent-treated oil-tea camellia shell powder and CaCO 3 Depositing the oil-tea camellia shell powder and SiO 2 Sedimented Camellia oleifera shell powder and TiO 2 One of the deposited camellia oleifera shell powder.
Preferably, the material comprises the following raw materials in percentage by mass: 1-60% of modified camellia oleifera shell powder, 30-95% of polylactic acid (PLA), 1-10% of nano montmorillonite and 0.1-3% of antioxidant.
In a preferred embodiment of the method of the invention,the molecular weight of the polylactic acid is 1 multiplied by 10 6 -5×10 6 。
Preferably, the purity of the nano montmorillonite is more than 95%.
Preferably, the antioxidant is one of an antioxidant 1010 (pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]), an antioxidant 138 ([ tris (1, 4-di-tert-butylphenyl) phosphite ]), and an antioxidant 618 ([ bis (octadecyl) pentaerythritol diphosphite ester ]).
The preparation method of the modified camellia oleifera shell powder filled polylactic acid 3D printing material comprises the following steps:
(1) Uniformly mixing the modified camellia oleifera shell powder, polylactic acid, nano montmorillonite and antioxidant at a high speed according to a proportion to form a blend, and drying (at the temperature of 60-80 ℃ for 12-24 hours) for later use;
(2) Melting and extruding the blend obtained in the step (1) by a double-screw extruder, cooling and granulating, and drying the obtained granules (at 60-80 ℃ for 4-12 h) for later use;
wherein the temperature of the twin-screw extruder is as follows: the first zone is 160-165 ℃, the second zone is 160-165 ℃, the third zone is 165-170 ℃, the fourth zone is 165-170 ℃, the fifth zone is 170-175 ℃, the head is 170-175 ℃, and the rotating speeds of the main machine and the granulator are respectively 9-11r/min and 6-8 r/min;
(3) Extruding, drawing and forming the granules obtained in the step (2) by a single-screw extruder, and rolling to obtain the modified camellia oleifera shell powder filled polylactic acid 3D printing material; wherein the temperature of 1-4 sections of the single screw extruder is 165-170 ℃, 165-170 ℃ and 170-175 ℃, the temperature of the water tank 1 area and the water tank 2 area is 40-45 ℃ and 35-40 ℃, the extrusion speed is 10-20mm/s, and the traction speed is 5-10 mm/s.
The diameter of the obtained wire is about 1.75mm, and the diameter error is within +/-0.05 mm; the rolled wire is subjected to printing test by a desktop FDM type 3D printer, the temperature of a printing nozzle is 180-200 ℃ (the temperature can be adjusted according to actual conditions), the diameter of the nozzle is 0.4 mm, the printing speed is 50-60 mm/min, and the temperature of a printing platform is 50-60 ℃.
Compared with the prior art, the invention has the following advantages and effects:
(1) The invention deposits CaCO on the surface of the oil-tea camellia shell powder 3 、SiO 2 And TiO 2 2 The preparation method can make up for the defects of the surface microporous structure of the oil-tea camellia shell, plays a role in filling rigid particles, simultaneously increases the compatibility of the oil-tea camellia shell powder and polylactic acid, and can improve the mechanical property of the polylactic acid 3D printing material.
(2) The modified camellia oleifera shell powder filled polylactic acid 3D printing material prepared by the invention has good antibacterial property and mechanical property, has natural wood texture, is not suitable for discoloration and fading, is resistant to illumination, is resistant to oxidation and the like, is suitable for an FDM rapid forming technology, and can be widely applied to the fields of toys, music equipment, individual artworks, furniture, building decoration and the like.
Drawings
Fig. 1 is an infrared spectrum of the modified camellia oleifera shell powder prepared in each embodiment;
fig. 2 is a thermogravimetric analysis TG diagram of the modified camellia oleifera hull powder prepared in each embodiment;
FIG. 3 is a chart of thermogravimetric analysis (DTG) of modified Camellia shell meal prepared in accordance with various embodiments;
fig. 4 is a graph illustrating the antibacterial effect of the 3D printed material prepared according to each embodiment;
fig. 5 is a photograph of a 3D printing material wire prepared according to each embodiment after being wound;
fig. 6 is a product model printed by the 3D printing material prepared in each embodiment.
Detailed Description
The following examples further illustrate the present invention in detail, but the embodiments of the present invention are not limited to these examples.
The reagents used in the examples of the present invention are conventional raw materials or reagents unless otherwise specified, and the experimental methods used are conventional in the art unless otherwise specified. The specific method for testing the mechanical property of the composite material is as follows: the tensile test is executed according to the national standard GB/T1040-2006, and the tensile speed is 5 mm/min; the bending test is carried out according to the national standard GB/T9341-2008, and the bending speed is 5 mm/min. The composite material is subjected to antibacterial performance test according to the national standard GB/T21510-2008.
Example 1
A preparation method of a silane coupling agent KH550 treated camellia oleifera shell powder filled polylactic acid 3D printing material comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 2h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Mixing the oil tea shell powder obtained in the step (1) with a 5% NaOH solution by mass, wherein the mass ratio of the oil tea shell powder to the NaOH solution is 1:5, stirring for 24 hours at normal temperature, washing the obtained mixture to be neutral by water, filtering, and drying for 24 hours in an oven at 80 ℃ to obtain alkali-treated camellia oleifera shell powder;
(3) Uniformly mixing the alkali-treated camellia oleifera shell powder obtained in the step (2) with an ethanol solution, wherein the mass ratio of the alkali-treated camellia oleifera shell powder to the ethanol solution is 1:5, the volume ratio of ethanol to water in the ethanol solution is 8:2; then adding a silane coupling agent KH550 with the mass of 10 percent of that of the alkali-treated camellia oleifera shell powder, and stirring for 4 hours at the temperature of 80 ℃ under a sealed condition; washing the mixture with water, filtering, removing residual silane coupling agent and other substances in the reaction, and drying in an oven at 80 ℃ for 12h to obtain alkali and silane coupling agent KH550 treated camellia oleifera shell powder;
(4) Uniformly mixing 5% of the alkali obtained in the step (3) and 5% of the oil-tea camellia shell powder treated by the silane coupling agent KH550, 92% of polylactic acid, 2% of nano-montmorillonite and 1% of antioxidant 1010 at a high speed by a high-speed mixer to form a mixed material, and drying for 4 hours at the temperature of 80 ℃;
(5) Melting and extruding the blend obtained in the step (4) by a double-screw extruder, cooling and granulating, and drying the obtained granules at 80 ℃ for 24 hours for later use; wherein the temperature of the twin-screw extruder is as follows: the rotating speeds of the main machine and the granulator are respectively 10 r/min and 7 r/min at 160 ℃ in the first area, 160 ℃ in the second area, 165 ℃ in the third area, 165 ℃ in the fourth area, 170 ℃ in the fifth area, 170 ℃ in the machine head and 170 ℃ in the main machine and the granulator;
(6) And (3) extruding, drawing and forming the granules obtained in the step (5) by a single-screw extruder, rolling and processing into a 3D printing wire, wherein the temperatures of sections 1 to 4 of the single-screw extruder are 165 ℃, 168 ℃ and 170 ℃, the temperatures of a water tank 1 area and a water tank 2 area are 40 ℃ and 35 ℃, the extrusion speed is 15mm/s, and the drawing speed is 7.5 mm/s.
(7) And (3) carrying out a standard spline printing test on the coiled wire rod through a desktop FDM type 3D printer, wherein the printing temperature (nozzle) is 200 ℃, the diameter of the nozzle is 0.4 mm, the printing speed is 50 mm/min, and the temperature of a printing platform is 50 ℃.
The infrared spectrum of the oil-tea camellia shell powder treated by the alkali and the silane coupling agent KH550 of the embodiment is shown in curve 3 in FIG. 1, and the thermogravimetric analysis and related data are shown in curve 3 in FIG. 2, curve 3 in FIG. 3 and Table 1. Mechanical property tests are carried out on the alkali prepared by 3D printing and a standard sample strip of the KH550 treated camellia oleifera hull powder/polylactic acid 3D printing material according to national standards, and the mechanical property test results and the printing effect are shown in Table 2. The antibacterial effect is shown in table 2 and fig. 4.
Example 2
CaCO (calcium carbonate) 3 The preparation method of the deposited camellia oleifera shell powder filled polylactic acid 3D printing material comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 2h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Mixing the oil tea shell powder obtained in the step (1) with a 5% NaOH solution, wherein the mass ratio of the oil tea shell powder to the NaOH solution is 1:5, stirring for 24 hours at normal temperature, washing the obtained mixture to be neutral by water, filtering, and drying for 24 hours in an oven at 80 ℃ to obtain alkali-treated camellia oleifera shell powder;
(3) Uniformly mixing the alkali-treated camellia oleifera shell powder obtained in the step (2) with an ethanol solution, wherein the mass ratio of the alkali-treated camellia oleifera shell powder to the ethanol solution is 1:5, the volume ratio of ethanol to water in the ethanol solution is 4:1; then adding a silane coupling agent KH550 with the mass of 10 percent of that of the alkali-treated camellia oleifera shell powder, and stirring for 4 hours at the temperature of 80 ℃ under a sealed condition; washing the mixture with water, filtering, removing residual silane coupling agent and other substances in the reaction, and drying in an oven at 80 ℃ for 12h to obtain silane coupling agent KH550 treated camellia oleifera shell powder;
(4) Treating the camellia oleifera shell powder treated by the silane coupling agent KH550 obtained in the step (3) according to a mass ratio of 1:5 adding 0.5mol/L CaCl 2 Stirring the solution at normal temperature for 0.5h, and adding CaCl at a rate of 25ml/min 2 Solution of equal volume of 0.5mol/L Na 2 CO 3 Solution, na 2 CO 3 The solution contains 5 × 10 -3 g/mL of dispersant EDTA-2Na, and continuously stirring for 0.5h at 25 ℃; washing the mixture with water, filtering, and oven drying at 60 deg.C for 24 hr to obtain CaCO 3 Depositing the camellia oleifera shell powder in situ.
(5) CaCO obtained in the step (5) according to mass percent 3 Uniformly mixing 5% of deposited camellia oleifera shell powder, 92% of polylactic acid, 2% of nano montmorillonite and 1% of antioxidant 1010 at a high speed through a high-speed mixer to form a blend, and drying for 4 hours at 80 ℃;
the remaining experimental procedures were the same as in steps (5), (6) and (7) of example 1.
CaCO of the example 3 The infrared spectrum of the sedimentary oil tea shell powder is shown as curve 4 in figure 1, and the thermogravimetric analysis and related data are shown as curve 4 in figure 2, curve 4 in figure 3 and table 1. CaCO prepared by 3D printing 3 The deposited camellia oleifera hull powder/polylactic acid 3D printing material standard sample strip is subjected to mechanical property test according to the national standard, and the mechanical property test result and the printing effect are shown in table 2. The antibacterial effect is shown in table 2 and fig. 4.
Example 3
SiO (silicon dioxide) 2 The preparation method of the enhanced polylactic acid 3D printing material with deposited camellia oleifera shell powder comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 2h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Mixing the oil tea shell powder obtained in the step (1) with a 5% NaOH solution, wherein the mass ratio of the oil tea shell powder to the NaOH solution is 1:5, stirring for 24 hours at normal temperature, washing the obtained mixture to be neutral by using tap water, filtering, and drying for 24 hours in an oven at the temperature of 80 ℃ to obtain alkali-treated camellia oleifera shell powder;
(3) Mixing and stirring the alkali-treated camellia oleifera shell powder obtained in the step (2) and a certain amount of ethanol solution at 40 ℃ for 1h, wherein the mass ratio of the camellia oleifera shell powder to the ethanol solution is 1:5, the volume ratio of ethanol to water in the ethanol solution is 4:1; then adding a silane coupling agent KH560 accounting for 10% of the weight of the alkali-treated camellia oleifera shell powder, stirring for 4 hours at 80 ℃ under a sealed condition, washing and filtering the mixture with water, removing substances such as the silane coupling agent and the like remained in the reaction, and drying for 12 hours in an oven at 80 ℃ to obtain the silane coupling agent KH 560-treated camellia oleifera shell powder;
(4) Adding the silane coupling agent KH560 treated camellia oleifera shell powder obtained in the step (3) into a certain amount of ethanol solution (the volume ratio of ethanol to water in the ethanol solution is 1 2 Depositing the camellia oleifera shell powder in situ.
(5) According to the mass percentage, the SiO obtained in the step (4) is 2 Uniformly mixing 5% of the deposited camellia oleifera shell powder, 92% of polylactic acid, 2% of nano montmorillonite and 1% of antioxidant 138 at a high speed through a high-speed mixer to form a blend, and drying for 4 hours at 80 ℃;
the remaining experimental procedures were the same as in steps (5), (6) and (7) of example 1.
SiO in the present example 2 The infrared spectrum of the sedimentary oil Camellia shell powder is shown as curve 5 in FIG. 1, and the thermogravimetric analysis and related data are shown as curve 5 in FIG. 2, curve 5 in FIG. 3 and Table 1. SiO prepared by 3D printing 2 The deposited camellia oleifera hull powder/polylactic acid 3D printing material standard sample strip is subjected to mechanical property test according to the national standard, and the mechanical property test result and the printing effect are shown in table 2. The antibacterial effect is shown in table 2 and fig. 4.
Example 4
TiO 2 2 The preparation method of the enhanced polylactic acid 3D printing material with deposited camellia oleifera shell powder comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 2h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Mixing the camellia oleifera shell powder obtained in the step (1) with a calcium hydroxide solution with the concentration of 5%, wherein the mass ratio of the camellia oleifera shell powder to the calcium hydroxide solution is 1:5, stirring for 24 hours at normal temperature, washing the obtained mixture to be neutral by using tap water, filtering, and drying for 24 hours in an oven at the temperature of 80 ℃ to obtain alkali-treated camellia oleifera shell powder;
(3) Mixing and stirring the alkali-treated camellia oleifera shell powder obtained in the step (2) and a certain amount of ethanol solution at 40 ℃ for 1h, wherein the mass ratio of the camellia oleifera shell powder to the ethanol solution is 1:5, the volume ratio of ethanol to water in the ethanol solution is 4:1; then adding a silane coupling agent KH550 with the mass being 10% of that of the alkali-treated camellia oleifera shell powder, stirring for 4 hours at the temperature of 80 ℃ under a sealed condition, washing and filtering the mixture with water, removing substances such as the silane coupling agent and the like remained in the reaction, and drying for 12 hours in an oven at the temperature of 80 ℃ to obtain the silane coupling agent KH 550-treated camellia oleifera shell powder;
(4) Adding the silane coupling agent KH550 treated camellia oleifera shell powder obtained in the step (3) into a certain amount of ethanol (the mass ratio of the camellia oleifera shells to the ethanol is 1; mixing 100% ethanol volume of ethanol in the mixed solution A, 50% deionized water volume of ethanol in the mixed solution A, 12% glacial acetic acid volume of ethanol in the mixed solution A and 5% 2mol/L diluted hydrochloric acid volume of ethanol in the mixed solution A under the condition of stirring, and violently stirring for 10min at 40 ℃ to obtain mixed solution B;
(5) Adding the mixed solution B in the step (4) into the mixed solution A, strongly stirring for 1h at 40 ℃, washing with deionized water, filtering, and drying in an oven at 80 ℃ for 12h to obtain TiO 2 Depositing the camellia oleifera shell powder in situ.
(6) Mixing the TiO obtained in the step (5) according to the mass percentage 2 Uniformly mixing 5% of deposited camellia oleifera shell powder, 92% of polylactic acid, 2% of nano-montmorillonite and 1% of antioxidant 618 at a high speed through a high-speed mixer to form a blend, and drying for 4 hours at 80 ℃;
the remaining experimental procedures were the same as in steps (5), (6) and (7) of example 1.
TiO of this example 2 The infrared spectrum of the sedimentary oil tea shell powder is shown as curve 6 in figure 1, and the thermogravimetric analysis and related data are shown as curve 6 in figure 2, curve 6 in figure 3 and table 1. TiO prepared by 3D printing 2 The deposited camellia oleifera hull powder/polylactic acid 3D printing material standard sample strip is subjected to mechanical property test according to the national standard, and the mechanical property test result and the printing effect are shown in table 2. The antibacterial effect is shown in table 2 and fig. 4.
Comparative example 1
A preparation method of an oil-tea camellia shell powder reinforced polylactic acid 3D printing material without chemical treatment comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 2h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Uniformly mixing 5% of the camellia oleifera shell powder obtained in the step (1), 92% of polylactic acid, 2% of nano montmorillonite and 1% of antioxidant 1010 by mass percent at a high speed through a high-speed mixer to form a mixture, and drying at 80 ℃ for 4 hours;
the remaining experimental procedures were the same as in steps (5), (6) and (7) of example 1.
The infrared spectrum of the non-chemically treated oil-tea camellia shell powder of the comparative example is shown in a curve 1 in fig. 1, and thermogravimetric analysis and related data are shown in a curve 1 in fig. 2, a curve 1 in fig. 3 and table 1. And (3) performing mechanical property test on the standard sample strip of the oil-tea camellia shell powder/polylactic acid 3D printing material which is prepared by 3D printing and is not subjected to chemical treatment according to the national standard, wherein the mechanical property test result and the printing effect are shown in Table 2. The antibacterial effect is shown in table 2 and fig. 4.
Comparative example 2
A preparation method of an alkali-treated camellia oleifera shell powder filled polylactic acid 3D printing material comprises the following steps:
(1) Soaking a certain amount of camellia oleifera shells in 100 ℃ water for 10min, washing with water, filtering, drying in an oven at 80 ℃ for 24h, crushing at a high speed for 5min to obtain crude camellia oleifera shell powder, ball-milling the obtained powder by a ball mill at a speed of 500rpm for 1.5h, and sieving by a sieve of 140-160 meshes to obtain camellia oleifera shell powder with uniform particle size;
(2) Mixing the oil tea shell powder obtained in the step (1) with a 5% NaOH solution, wherein the mass ratio of the oil tea shell powder to the NaOH solution is 1:5, stirring for 24 hours at normal temperature, washing the obtained mixture to be neutral by using tap water, filtering, and drying for 24 hours in an oven at the temperature of 80 ℃ to obtain alkali-treated camellia oleifera shell powder;
(3) Uniformly mixing 5% of the alkali-treated camellia oleifera shell powder obtained in the step (2) with 92% of polylactic acid, 2% of nano montmorillonite and 1% of antioxidant 1010 at a high speed by a high-speed mixer to form a mixed material, and drying at 80 ℃ for 4 hours;
the remaining experimental procedures were the same as in steps (5), (6) and (7) of example 1.
The infrared spectrum of the alkali-treated oil-tea camellia shell powder of the comparative example is shown in a curve 2 in fig. 1, and thermogravimetric analysis and related data are shown in a curve 2 in fig. 2, a curve 2 in fig. 3 and table 1. And (3) performing mechanical property test on the alkali-treated camellia oleifera hull powder/polylactic acid 3D printing material standard sample strip prepared by 3D printing according to the national standard, wherein the mechanical property test result and the printing effect are shown in Table 2. The antibacterial effect is shown in table 2 and fig. 4.
TABLE 1 thermogravimetric data of Camellia oleifera shell meal obtained by various treatment modes
Figure RE-181896DEST_PATH_IMAGE001
Table 2 various performance indexes of camellia oleifera shell reinforced polylactic acid 3D printing material
Figure RE-567878DEST_PATH_IMAGE002
。
The detection result shows that the modified oil tea shell/polylactic acid 3D printing material prepared by the invention has excellent mechanical property and thermal stability, is green, environment-friendly and degradable, has good printing effect and antibacterial effect, meets the mechanical strength and appearance requirements of the polylactic acid 3D printing material required in the market, and meets the technical requirements of FDM type 3D printing. Fig. 5 is the resulting unmodified (left panel) and modified (right panel) camellia oleifera shell/polylactic acid composite wires for 3D printing, and fig. 6 is a sample printed with the modified camellia oleifera shell/polylactic acid composite wires (example 1).
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Other variations will be anticipated by those skilled in the art in view of the description of the invention, and such variations are intended to be included within the scope of the invention.

Claims (3)

1. The preparation method of the modified camellia oleifera shell powder filled polylactic acid 3D printing material is characterized by comprising the following steps:
1. uniformly mixing the modified camellia oleifera shell powder, the polylactic acid, the nano montmorillonite and the antioxidant at a high speed according to a ratio to form a blend, and drying for later use;
2. melting and extruding the blend obtained in the step one through a double-screw extruder, cooling and granulating, and drying the obtained granules for later use;
wherein the temperature of the twin-screw extruder is as follows: the first zone is 160-165 ℃, the second zone is 160-165 ℃, the third zone is 165-170 ℃, the fourth zone is 165-170 ℃, the fifth zone is 170-175 ℃, the head is 170-175 ℃, and the rotating speeds of the main machine and the granulator are respectively 9-11r/min and 6-8 r/min;
3. extruding, drawing and forming the granules obtained in the second step by a single-screw extruder, and rolling to obtain the modified camellia oleifera shell powder filled polylactic acid 3D printing material; wherein the temperature of 1-4 sections of the single screw extruder is 165-170 ℃, 165-170 ℃ and 170-175 ℃, the temperature of the water tank 1 area and the water tank 2 area is 40-45 ℃ and 35-40 ℃, the extrusion speed is 10-20mm/s, and the traction speed is 5-10 mm/s;
the modified camellia oleifera shell powder filled polylactic acid 3D printing material is a blend containing modified camellia oleifera shell powder, polylactic acid and nano montmorillonite; the material comprises the following raw materials in percentage by mass: 1-60% of modified camellia oleifera shell powder, 30-95% of polylactic acid, 1-10% of nano montmorillonite and 0.1-3% of antioxidant;
the modified oil-tea camellia shell powder is prepared by the following steps:
(1) Soaking oil tea shells in hot water, then washing the oil tea shells until filtrate is nearly colorless, and drying the oil tea shells;
(2) Crushing the camellia oleifera shells obtained in the step (1), grinding the obtained powder for 1-2 hours by using a ball mill, and sieving to obtain camellia oleifera shell powder with uniform particle size;
(3) Uniformly mixing the camellia oleifera shell powder obtained in the step (2) with an alkali solution, washing the obtained mixture with water to be neutral, filtering and drying to obtain alkali-treated camellia oleifera shell powder;
(4) Uniformly mixing the alkali-treated camellia oleifera shell powder obtained in the step (3) with an alcohol solution, adding a silane coupling agent accounting for 8-12% of the weight of the alkali-treated camellia oleifera shell, and stirring and reacting for 4-6 hours at 70-90 ℃ under a sealed condition; washing the mixture obtained by the reaction with water or ethanol, filtering and drying to obtain the silane coupling agent treated camellia oleifera shell powder;
(5) Adding the silane coupling agent treated camellia oleifera shell powder obtained in the step (4) into a certain amount of alcohol, then adding titanate with the volume of 20-30% of that of the alcohol, and stirring for 0.5-1h at 30-50 ℃ in a sealed environment to obtain a mixed solution A; mixing alcohol with the volume of 80-120% of that of the mixed solution A, deionized water with the volume of 40-60% of that of the mixed solution A, glacial acetic acid with the volume of 8-15% of that of the mixed solution A and dilute hydrochloric acid with the volume of 3-8% of that of the mixed solution A under the condition of stirring, and violently stirring for 5-10min at 30-50 ℃ to obtain a mixed solution B; then adding the mixed solution B into the mixed solution A for 30-50%Stirring strongly for 1-2h, washing with deionized water, filtering, and oven drying to obtain TiO 2 Depositing the camellia oleifera shell powder in situ;
the alcohol in the step (5) is one of ethanol, propanol, butanol and n-propanol, and the mass ratio of the silane coupling agent treated camellia oleifera shell powder to the alcohol is 1: (4-6); the titanate is one of tetraethyl titanate, isopropyl titanate and tetrabutyl titanate; the concentration of the dilute hydrochloric acid is 1-4mol/L.
2. The method of claim 1, wherein: the mass ratio of the camellia oleifera shell powder to the alkali solution used in the step (3) is 1 (4-6); the alkali solution is one of sodium hydroxide, calcium hydroxide or potassium hydroxide water solution, and the mass concentration is 1-10%.
3. The method of claim 1, wherein: the mass ratio of the alkali-treated camellia oleifera shell powder to the alcoholic solution in the step (4) is 1 (4-6), and the volume ratio of alcohol to water in the alcoholic solution is (3-5): 1, the alcohol is at least one of ethanol, propanol, butanol and n-propanol.
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