CN108641319A - A kind of polylactic acid wood plastic composite and preparation method, application for 3D printing musical instrument - Google Patents
A kind of polylactic acid wood plastic composite and preparation method, application for 3D printing musical instrument Download PDFInfo
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- CN108641319A CN108641319A CN201810433720.5A CN201810433720A CN108641319A CN 108641319 A CN108641319 A CN 108641319A CN 201810433720 A CN201810433720 A CN 201810433720A CN 108641319 A CN108641319 A CN 108641319A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/04—Impregnating in open tanks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/001—Heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention discloses a kind of polylactic acid wood plastic composite for 3D printing musical instrument and preparation method, application, above-mentioned polylactic acid wood plastic composite is blended by the component of following mass percent：Modified wood powder 5wt% ~ 30wt%, polylactic acid 62wt% ~ 86wt%, toughener 5wt% ~ 10wt%, nano-inorganic filler 2wt% ~ 5wt%, lubricant 1wt% ~ 3wt%.There is the polylactic acid wood plastic composite stretch-proof, resist bending, impact-resistant good characteristic, impact resistance to be tested by FDM type 3D printers, and composite material surface polishing, japanning, entirely appropriate to be used for 3D printing musical instrument.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of polylactic acid wood moulding for 3D printing musical instrument is multiple
Condensation material and preparation method, application.
Background technology
Polylactic acid（PLA）As common FDM types 3D printing high molecular material, it is advantageous that without unpleasant different when melting
Taste derives from biomass and fully biodegradable, non-toxic to humans, and extrusion, blowing, injection molding may be used etc. often
Processing method is advised, processing technology is simple, thus application is very extensive.But its mechanical property is bad, poor toughness, easy fracture, and molten
The shortcomings of point is relatively low, thermal stability is poor significantly limits the application range as 3D printing material.Therefore, generally use is added
Reinforcing material such as carbon fiber, glass fibre, plant fiber etc. improves the mechanical property and thermal stability of PLA, and wherein plant is fine
Dimension due to having many advantages, such as to derive from a wealth of sources, it is cheap, environmentally protective thus receive people's favor.
In 104356618 A of Chinese invention patent application CN, a kind of biomass wood plastics composite for 3D printing
Material is raw material by PLA, wood powder/bamboo powder/powdered rice hulls, paper pulp, UHMWPE, cenosphere and other auxiliary agents, first through planetary-screw
Extruder extruding pelletization, again through conical double screw extruder wire-drawing shape prepare.
105820527 A of Chinese invention patent application CN disclose one kind with PLA, wood moulding powder, coupling agent etc. as raw material system
It is ready for use on the Biocomposite material of 3D printing.But above-mentioned two patent does not provide prepared 3D printing material mechanical performance number
According to.104448738 A of Chinese patent CN are original with PLA, thermoplastic starch, toughener, crosslinking agent, filler and other auxiliary agents
Material is prepared for a kind of biology base 3D printing material, and tensile strength is between 20 ~ 80 Mpa, and impact strength is in 3 ~ 7 KJ/m2
In range.
106380652 A of Chinese invention patent application CN disclose one kind with plant fiber powder, polyolefin plastics powder, PLA
And other auxiliary agents are HI high impact high tenacity wood plastic composite prepared by raw material, tensile strength is up to 52.48 MPa, is bent
Maximum intensity is 62.67 MPa, and bending modulus is up to 2311 MPa, and notch impact strength is up to 4.39 KJ/m2。
Traditional musical instrument（Such as guitar, violin）Production method generally use timber manually and mechanical processing, processing
Period is long, to the mechanical property of timber（Especially bending strength and bending modulus）It is more demanding and only for some shapes
Special, the personalized more difficult making of musical instrument.3D printing technique（That is rapid shaping technique）Be one kind using digital three-dimemsional model as base
Plinth constructs the technology of object, the skill by layer-by-layer printing with materials such as plastics, photosensitive resin, metal, ceramics
Art is widely used to the fields such as industrial design and manufacture, aerospace, medical treatment, education, jewelry, footwear, automobile, gun.3D
Printing technique also provides possibility for unique, the personalized musical instrument making of shape.But FDM type 3D printing materials on the market
Most of to be prepared for a small amount of auxiliary agent of the plastics such as ABS, PLA, PC, POM addition, colorant, the works printed have apparent modeling
Material sense, and can not polish, japanning, be not suitable for printing musical instrument.
Invention content
Present invention seek to address that the device that in the prior art prepared by wooden lactic acid composite material 3D printing can not polish, on
The problem of painting, not being suitable for printing musical instrument provides the device that a kind of toughness is strong, prepares and is suitble to the polylactic acid of polishing, japanning wooden
Plastic composite materials；
Another object of the present invention is to provide the preparation methods of the above-mentioned polylactic acid wood plastic composite for 3D printing musical instrument；
The application of musical instrument is prepared another object of the present invention is to provide above-mentioned polylactic acid wood plastic composite in 3D printing.
Above-mentioned purpose of the present invention is achieved by the following technical programs：
A kind of polylactic acid wood plastic composite for 3D printing musical instrument is blended by the component of following mass percent：Change
Property 5 wt% of wt % ~ 30 of wood powder, the polylactic acid wt% of 62 wt% ~ 86, the toughener wt% of 5 wt% ~ 10, nano-inorganic filler
The wt% of 2wt% ~ 5, lubricant 1 wt% ~ 3 wt%.
Further, the composite material has the component of following mass percent to be blended：Modified wood powder 10wt % ~
20 wt%, the polylactic acid wt% of 70 wt% ~ 80, toughener 5 wt% ~ 8 wt%, 4 wt% of nano-inorganic filler ~ 4.5wt%,
1 wt% of lubricant ~ 2wt%.
In above-mentioned formula, added so as to improve the interface compatibility of itself and polylactic acid matrix by the way that modified wood powder is added
Add lubricant that extrusion can be made more smooth, surface smoothness improves, and addition nano-inorganic filler can not only significantly increase curved
Qu Qiangdu and bending modulus, tensile strength and impact strength have also obtained improving by a relatively large margin, utilize the composite material of the formula
The device of 3D printing is more suitable in the polishing of its surface, coloring and japanning, and the device surface of lacquer painting and polishing has stronger compatible
Property, to make the device surface of the polishing of japanning be not easy paint, which prepares the pleasure such as piano, violin suitable for 3D printing
Device.
Preferably, the modified wood powder is spruce wood, maple, mahogany, rose wood, one kind in Acacia or more
Kind, wood powder particle size is the mesh of 120 mesh ~ 300.
Preferably, the toughener is SEBS（The one embedding copolymer of benzene second of styrene-butadiene）、SBS（Thermoplasticity polyphenyl
Ethylene-polybutadienes-polystyrene block copolymer）、TPU（Thermoplastic polyurethane elastomer）、TPEE（Thermoplastic polyester elastomer
Body）In one or more mixtures.
Preferably, the nano-inorganic filler be nano silicon dioxide, nano-titanium dioxide, one kind in carbon nanotube or
Two kinds；The lubricant is zinc stearate.
Wherein, the method for the above-mentioned polylactic acid wood plastic composite for 3D printing musical instrument, includes the following steps：
S1. wood powder is prepared into modified wood powder using chemical modifier.
S2. modified wood powder, polylactic acid, toughener, nano-inorganic filler, lubricant obtained by step S1 are passed through into mixed at high speed
Machine, which be blended, forms blend composition.
S3. the blend composition double helix extrusion melt blending obtained by step S2 is squeezed out and is granulated, repeated to squeeze out 2 times, obtain institute
State polylactic acid wood plastic composite master batch.
S4. after the polylactic acid wood plastic composite master batch prepared in step S3 being dried, wire drawing is squeezed out, the polylactic acid is obtained
Wood plastic composite.
In the above preparation method, dispersion process of the modified wood powder in polylactic acid matrix mainly uses twin-screw extrusion
Machine is realized by melt blending repeated processing.
Preferably, in the step S1, the chemical modifier is sodium hydroxide, gamma-amino propyl-triethoxysilicane
Alkane（KH550）, γ-glycidyl ether oxygen propyl trimethoxy silicane（KH560）、γ-（Methacryloxypropyl）Propyl trimethoxy
Base silane（KH570）, γ-mercaptopropyl trimethoxysilane（KH590）, it is one or more in maleic anhydride.
In the step S3,1 ~ 6 section of temperature that the double helix squeezes out is respectively 150 ~ 165 DEG C, 150 ~ 165 DEG C, 160
~170℃、170~175℃、165~175℃、165~175℃。
In the step S4, the filament diameter of the wire drawing is the mm of 1.75 mm ~ 3.0；The diameter error is ± 5%
Within.
Preferably, in the above-mentioned methods, step S1 is carried out in accordance with the following methods：
S11. wood powder is impregnated with the sodium hydroxide solution of the wt% of 5 wt% ~ 10 at room temperature, then stirs 12 ~ 24 h, used
The strainer filtering of 400 mesh is simultaneously washed with clear water to neutrality repeatedly, in 80 ~ 90 DEG C of fully dry 12 ~ 24 h, is obtained dry
Alkali process wood powder；Wherein, the mixing quality of the wood powder and sodium hydroxide solution ratio is 1:15.
S12. the alkali process wood powder obtained by step S11 is put into molten equipped with the wt% of 5 wt% ~ 10 maleic anhydrides-absolute ethyl alcohol
In the reaction vessel of liquid, 10 ~ 20 min of hydrolysis are stood in 20 ~ 30 DEG C, are then returned through row stirring in water bath at 80 ~ 90 DEG C
Stream process reacts 3 ~ 4 h, filters, and is placed on 70 ~ 90 DEG C of 12 ~ 24 h of drying of baking oven, obtains the modified wood powder；Wherein,
The absolute dry mass of the maleic anhydride and wood powder ratio is 1 % of % ~ 2.
Preferably, the step S12 is carried out in accordance with the following methods：
Alkali process wood powder obtained by the step S11 is put into the reaction vessel equipped with the wt% silane coupling agents of 5 wt% ~ 10
In, 10 ~ 20 min of hydrolysis are stood in 20 ~ 30 DEG C, then at 80 ~ 90 DEG C through row stirring in water bath reflow treatment, reaction 3
~ 4 h are filtered, and are placed on 70 ~ 90 DEG C of 12 ~ 24 h of drying of baking oven, are obtained the modified wood powder；Wherein, the silane coupling agent
Absolute dry mass ratio with wood powder is the % of 1 % ~ 2；The silane coupling agent is γ aminopropyltriethoxy silane（KH550）、
γ-glycidyl ether oxygen propyl trimethoxy silicane（KH560）、γ-（Methacryloxypropyl）Propyl trimethoxy silicane
（KH570）, γ-mercaptopropyl trimethoxysilane（KH590）It is one or more.
Application of the above-mentioned polylactic acid wood plastic composite in 3D printing prepares musical instrument.
Compared with prior art, technical solution of the present invention has the advantages that：
（1）The above-mentioned polylactic acid wood plastic composite tensile strength for 3D printing musical instrument can reach 75.4 Mpa, bending
Intensity is up to 124.4 Mpa, and bending modulus can reach 7535 Mpa, and notch impact strength is up to 9.5 KJ/m2, made
Standby polylactic acid wood plastic composite wire rod is tested by FDM type 3D printers, is completely suitable for 3D printing technique.It is above-mentioned compound
Material not only has good mechanical strength and toughness, mechanical strength to be far above common polylactic acid printed material, be especially bent
Intensity, bending modulus and impact strength, make it be more widely applied.And preparation method is simple and practicable, is suitble to industrialized production,
And it is biodegradable, belong to a kind of green material.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Reagent used in the embodiment of the present invention is all conventional reagent or raw material purchased in market, embodiment institute unless stated otherwise
The test method used is all this field conventional method unless stated otherwise.The tool of Mechanics Performance Testing is carried out to composite material
Body method is as follows：Tension test is executed with reference to national standard GB 1040-2006 standards, and tensile speed is 5 mm/min；Bend test is joined
It is executed according to national standard GB 9341-2008 standards, rate of bending is 5 mm/min；Nick break test is with reference to national standard GB 1043-
2008 standards execute.
Embodiment 1
A kind of polylactic acid wood plastic composite for 3D printing musical instrument is blended by the component of following mass percent：It is modified
5 wt% of rose wood powder, 86 wt% of polylactic acid, 5 wt % of toughener, nano-inorganic filler 3 wt% %, 1 wt% of lubricant；
Wherein, the nano-inorganic filler preferably be nano silicon dioxide, nano-titanium dioxide, one kind in carbon nanotube or
Two kinds.The lubricant is preferably zinc stearate.
The toughener is preferably SEBS（The one embedding copolymer of benzene second of styrene-butadiene）、SBS（Thermoplasticity polyphenyl second
Alkene-polybutadienes-polystyrene block copolymer）、TPU（Thermoplastic polyurethane elastomer）、TPEE（Thermoplastic polyester elastomer
Body）In one or more mixtures.
Above-mentioned polylactic acid wood plastic composite is prepared by the following method：
S1. wood powder is prepared into modified wood powder using chemical modifier, be as follows：
120 mesh rose wood powders are immersed in 10 wt% NaOH aqueous solutions（Rose wood powder is 1 with NaOH aqueous solution mass ratioes:15）
After 12 h of middle stirring at normal temperature, rose wood powder is washed to neutrality with deionized water, wood powder is placed in 80 DEG C with after strainer filtering
Continuous drying 24 h in baking oven；Taking-up is crushed with high speed disintegrator afterwards, obtains modified rose wood powder；
S2. modification rose wood powder, polylactic acid, lubricant after will be dry obtained by S1, inorganic filler be mixed in high speed in proportion together
It is taken out after mixing 8 min in conjunction machine, obtains mixture.
S3. extruder is added in the mixture prepared in step S2 to squeeze out, repeats to squeeze out 2 times, obtains polylactic acid wood plastics composite
Material granule, wherein extruder each area's temperature setting be respectively 150 DEG C, 160 DEG C, 160 DEG C, 170 DEG C, 165 DEG C,
165 DEG C, host and feeder rotating speed are respectively 13 r/min and 7.5 r/min.
S4. the polylactic acid wood plastic composite particle drying that will be prepared in step S3 is added single screw extrusion machine and squeezes out drawing
The temperature of silk, the feeding section of extruder, compression section, metering section and cylindrical mouth mold be respectively set as 175 DEG C, 180 DEG C, 185
DEG C and 185 DEG C（It can be adjusted according to actual conditions）；The melt of extrusion is prepared into through water-carrying groove cooling air-drying using dragger
Diameter is about the monofilament of 1.75 mm or 3.0 mm, and winds.
Monofilament after winding can be directly used for FDM type 3D printings, and print temperature is 180 ~ 200 DEG C, print platform temperature
It is not fixed.
A kind of mechanical property of polylactic acid wood plastic composite for 3D printing musical instrument manufactured in the present embodiment is joined respectively
It examines GB 1040-2006, GB 9341-2008 and GB 1043-2008 is tested, testing result is shown in Table 1.
Embodiment 2
The present embodiment difference from example 1 is that：Polylactic acid wood plastic composite for 3D printing musical instrument is by following
The component of mass percent is blended：Modified yearning between lovers wood powder 20wt%, 62 wt% of polylactic acid, 10 wt% of toughener, nano inorganic
5 wt% of filler, 3 wt% of lubricant.
Above-mentioned steps S1 is carried out in accordance with the following methods：
300 mesh yearning between lovers wood powders are immersed in 5wt% NaOH aqueous solutions by S11. alkali process wood powder（Yearning between lovers wood powder and NaOH aqueous solutions
Mass ratio is 1:15）Middle stirring at normal temperature for 24 hours after, dragon spruce wood powder is washed to neutrality with deionized water, with will be wooden after strainer filtering
Powder is placed in continuous drying 12 h in 90 DEG C of baking oven；Obtain alkali process wood powder.
S12. the alkali process wood powder obtained by step S11 is put into equipped with the wt% of 5 wt% ~ 10 maleic anhydrides-absolute ethyl alcohol
In the reaction vessel of solution, 20 min of hydrolysis are stood in 30 DEG C, then at 90 DEG C through row stirring in water bath reflow treatment, reaction 4
H is filtered, and is placed on 90 DEG C of 24 h of drying of baking oven, is obtained the modified wood powder；Wherein, the absolute dry mass of the maleic anhydride and wood powder
Than for 2 %；
In addition to this, other processing step methods are the same as embodiment 1；
A kind of mechanics properties testing result of polylactic acid wood plastic composite for 3D printing musical instrument manufactured in the present embodiment is shown in
Table 1.
Embodiment 3
The present embodiment difference from example 1 is that：Polylactic acid wood plastic composite for 3D printing musical instrument is by following
The component of mass percent is blended：Modified maple powder 15.5wt%, polylactic acid 70 wt%, toughener 8wt%, nano inorganic are filled out
Expect 4.5wt%, lubricant 2wt%.
Above-mentioned steps S1 is carried out in accordance with the following methods：
300 mesh maple powder are immersed in 5wt% NaOH aqueous solutions by S11. alkali process wood powder（Yearning between lovers wood powder and NaOH aqueous solution matter
Amount is than being 1:15）Middle stirring at normal temperature for 24 hours after, dragon spruce wood powder is washed to neutrality with deionized water, with after strainer filtering by wood powder
It is placed in continuous drying 12 h in 90 DEG C of baking oven；Obtain alkali process wood powder.
S12. the alkali process wood powder obtained by step S11 is put into equipped with 10 wt% silane coupling agents-ethanol solution
In reaction vessel, 10 min of hydrolysis are stood in 30 DEG C, are then reacted 4 h through row stirring in water bath reflow treatment at 85 DEG C, are filtered,
80 DEG C of 24 h of drying of baking oven are placed on, the modified wood powder is obtained；Wherein, the absolute dry mass of the silane coupling agent and wood powder ratio is 1
%；
The silane coupling agent is preferably γ aminopropyltriethoxy silane（KH550）, γ-glycidyl ether oxygen propyl
Trimethoxy silane（KH560）、γ-（Methacryloxypropyl）Propyl trimethoxy silicane（KH570）, γ-mercapto propyl trimethoxy
Base silane（KH590）It is one or more；
In addition to this, other processing step methods are the same as embodiment 1；
A kind of mechanics properties testing result of polylactic acid wood plastic composite for 3D printing musical instrument manufactured in the present embodiment is shown in
Table 1.
Embodiment 4
The present embodiment difference from example 1 is that：Polylactic acid wood plastic composite for 3D printing musical instrument is by following
The polylactic acid wood plastic composite is blended by the component of following mass percent：Modified dragon spruce wood powder 30wt%, polylactic acid
62 wt%, toughener 10 wt%, nano-inorganic filler 2wt%, 1 wt% of lubricant；
In addition to this, other processing step methods are the same as embodiment 1；
A kind of mechanics properties testing result of polylactic acid wood plastic composite for 3D printing musical instrument manufactured in the present embodiment is shown in
Table 1.
Embodiment 5
The present embodiment and embodiment 2 the difference is that：Wood powder selects mahogany powder, and the grain size of wood powder is 120 mesh,
Above-mentioned steps S1 is followed the steps below：
300 mesh yearning between lovers wood powders are immersed in 5wt% NaOH aqueous solutions by S11. alkali process wood powder（Yearning between lovers wood powder and NaOH aqueous solutions
Mass ratio is 1:15）Middle stirring at normal temperature for 24 hours after, dragon spruce wood powder is washed to neutrality with deionized water, with will be wooden after strainer filtering
Powder is placed in continuous drying 12 h in 90 DEG C of baking oven；Obtain alkali process wood powder.
S12. a 500g alkali process wood powder, maleic anhydride and diformazan are added in the 250 mL boiling flasks equipped with condenser pipe
Benzene is placed in oil bath, is warming up to 105 DEG C, heat preservation 4h dischargings.Incline supernatant liquor, is washed with toluene, then centrifuges, by institute
It obtains product to centrifuge 3 times, washs again with acetone to 4 h of product Soxhlet extraction, be finally dried to products therefrom in 100 DEG C
Constant weight.Remaining process conditions and step are identical as embodiment 2.
A kind of mechanics properties testing knot of polylactic acid wood plastic composite for musical instrument 3D printing manufactured in the present embodiment
Fruit is shown in Table 1.
Embodiment 6
The present embodiment difference from example 1 is that：Polylactic acid wood plastic composite for 3D printing musical instrument is by following
The polylactic acid wood plastic composite is blended by the component of following mass percent：Modified spruce wood-Acacia mixing wood
Powder 10wt%, polylactic acid 80wt%, toughener 5 wt%, nano-inorganic filler 4wt%, 1 wt% of lubricant；
In addition to this, other processing step methods are the same as embodiment 1；
A kind of mechanics properties testing result of polylactic acid wood plastic composite for 3D printing musical instrument manufactured in the present embodiment is shown in
Table 1.
Comparative example 1
Other than each component mass percent difference of lactic acid wood plastic composite and embodiment 1, the same embodiment of other conditions
1；The component of specific mass percent is changed into：Modified rose wood powder 4wt%, polylactic acid 87wt%, toughener 4wt%, nano inorganic
Filler 1wt%, 4 wt% of lubricant；
The mechanics properties testing of composite material prepared by this comparison the results are shown in Table 1.
Comparative example 2
Other than each component mass percent difference of lactic acid wood plastic composite and embodiment 1, the same embodiment of other conditions
1；The component of specific mass percent is changed into：Modified rose wood powder 31wt%, polylactic acid 61wt%, toughener 4wt%, nanometer nothing
Machine filler 1wt%, lubricant 3wt%；
The mechanics properties testing of composite material prepared by this comparison the results are shown in Table 1.
Comparative example 3
This comparative example by wood powder in addition to being changed to rose wood powder, and not chemically modified processing, toughener are changed to outside SBS, remaining is matched
Side and process conditions are identical as embodiment.The mechanics properties testing of composite material prepared by this comparative example the results are shown in Table 1.
The Mechanics Performance Testing knot of 1 embodiment 1 ~ 6 of table, 1 ~ 2 composite material polylactic acid wood plastic composite of comparative example
Fruit
Testing result shows：A kind of mechanical property of polylactic acid wood plastic composite can be used for musical instrument 3D printing prepared by the present invention
It can protrude very much, wherein bending strength can reach 90 ~ 124 Mpa, and bending modulus can reach 5208 ~ 7532 Mpa, stretch
Intensity can reach 60 ~ 75 Mpa, and notch impact strength can reach 6.9 ~ 9.5 KJ/m2, elongation at break improve 60 % ~
95 % meet the required mechanical strength of general musical instrument, and meet FDM type 3D printing conditions.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of polylactic acid wood plastic composite for 3D printing musical instrument, which is characterized in that the polylactic acid wood and plastic composite
Material is blended by the component of following mass percent：5 wt% of wt % ~ 30 of modified wood powder, 62 wt% ~ 86 of polylactic acid
Wt%, the toughener wt% of 5 wt% ~ 10, the nano-inorganic filler wt% of 2 wt% ~ 5, lubricant 1 wt% ~ 3 wt%.
2. the polylactic acid wood plastic composite according to claim 1 for 3D printing musical instrument, which is characterized in that described multiple
Condensation material has the component of following mass percent to be blended：Modified wood powder the 10wt wt% of % ~ 20,70 wt% of polylactic acid ~
80 wt%, toughener 5 wt% ~ 8 wt%, 4 wt% of nano-inorganic filler ~ 4.5wt%, 1 wt% of lubricant ~ 2wt%.
3. the polylactic acid wood plastic composite for 3D printing musical instrument according to claim, which is characterized in that described to change
Property wood powder be spruce wood, it is maple, mahogany, rose wood, one or more in Acacia, wood powder particle size be 120 mesh ~
300 mesh.
4. the polylactic acid wood plastic composite for 3D printing musical instrument according to claim, which is characterized in that the increasing
Tough dose is SEBS（The one embedding copolymer of benzene second of styrene-butadiene）、SBS（Thermoplastic polystyrene-polybutadienes-polystyrene
Block copolymer）、TPU（Thermoplastic polyurethane elastomer）、TPEE（Thermoplastic polyester elastomer）In one or more mixing
Object.
5. the polylactic acid wood plastic composite for 3D printing musical instrument according to claim, which is characterized in that described to receive
Rice inorganic filler is one or both of nano silicon dioxide, nano-titanium dioxide, carbon nanotube；The lubricant is tristearin
Sour zinc.
6. a kind of method preparing the polylactic acid wood plastic composite for 3D printing musical instrument as described in claim 1 ~ 5,
It is characterized in that, includes the following steps：
S1. wood powder is prepared into modified wood powder using chemical modifier；
S2. by modified wood powder, polylactic acid, toughener, nano-inorganic filler, lubricant obtained by step S1 by high-speed mixer into
Row is blended and forms blend composition；
S3. the blend composition double helix extrusion melt blending obtained by step S2 is squeezed out and is granulated, repeat to squeeze out 2 times, obtained described poly-
Lactic acid wood plastic composite master batch；
S4. after the polylactic acid wood plastic composite master batch prepared in step S3 being dried, wire drawing is squeezed out, the polylactic acid wood moulding is obtained
Composite material.
7. the method according to claim 6 for preparing the polylactic acid wood plastic composite for 3D printing musical instrument, feature
It is, in the step S1, the chemical modifier is sodium hydroxide, γ aminopropyltriethoxy silane（KH550）、
γ-glycidyl ether oxygen propyl trimethoxy silicane（KH560）、γ-（Methacryloxypropyl）Propyl trimethoxy silicane
（KH570）, γ-mercaptopropyl trimethoxysilane（KH590）, it is one or more in maleic anhydride；
In the step S3,1 ~ 6 section of temperature that the double helix squeezes out is respectively 150 ~ 165 DEG C, 150 ~ 165 DEG C, 160 ~ 170
℃、170~175℃、165~175℃、165~175℃；
In the step S4, the filament diameter of the wire drawing is the mm of 1.75 mm ~ 3.0；The diameter error be ± 5% with
It is interior.
8. the method according to claim 7 for preparing the polylactic acid wood plastic composite for 3D printing musical instrument, feature
It is, the step S1 is carried out in accordance with the following methods：
S11. wood powder is impregnated with the sodium hydroxide solution of the wt% of 5 wt% ~ 10 at room temperature, then stirs 12 ~ 24 h, used
The strainer filtering of 400 mesh is simultaneously washed with clear water to neutrality repeatedly, in 80 ~ 90 DEG C of fully dry 12 ~ 24 h, is obtained dry
Alkali process wood powder；Wherein, the mixing quality of the wood powder and sodium hydroxide solution ratio is 1:15；
S12. the alkali process wood powder obtained by step S11 is put into equipped with the wt% of 5 wt% ~ 10 maleic anhydrides-ethanol solution
In reaction vessel, in 20 ~ 30 DEG C stand hydrolysis 10 ~ 20 min, then at 80 ~ 90 DEG C through row stirring in water bath reflux at
Reason reacts 3 ~ 4 h, filters, and is placed on 70 ~ 90 DEG C of 12 ~ 24 h of drying of baking oven, obtains the modified wood powder；Wherein, described
The absolute dry mass of maleic anhydride and wood powder ratio is 1 % of % ~ 2.
9. the method for polylactic acid wood plastic composite of the preparation for 3D printing musical instrument according to claim,
It is characterized in that, the step S12 is carried out in accordance with the following methods：
Alkali process wood powder obtained by the step S11 is put into the reaction vessel equipped with the wt% silane coupling agents of 5 wt% ~ 10
In, 10 ~ 20 min of hydrolysis are stood in 20 ~ 30 DEG C, then at 80 ~ 90 DEG C through row stirring in water bath reflow treatment, reaction 3
~ 4 h are filtered, and are placed on 70 ~ 90 DEG C of 12 ~ 24 h of drying of baking oven, are obtained the modified wood powder；Wherein, the silane coupling agent
Absolute dry mass ratio with wood powder is the % of 1 % ~ 2；The silane coupling agent is γ aminopropyltriethoxy silane（KH550）、
γ-glycidyl ether oxygen propyl trimethoxy silicane（KH560）、γ-（Methacryloxypropyl）Propyl trimethoxy silicane
（KH570）, γ-mercaptopropyl trimethoxysilane（KH590）It is one or more.
10. a kind of such as claim 1~9 any one of them polylactic acid wood plastic composite answering in 3D printing prepares musical instrument
With.
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