CN108676336A - Lactic acid composite material and preparation method thereof applied to FDM forming techniques - Google Patents
Lactic acid composite material and preparation method thereof applied to FDM forming techniques Download PDFInfo
- Publication number
- CN108676336A CN108676336A CN201810524178.4A CN201810524178A CN108676336A CN 108676336 A CN108676336 A CN 108676336A CN 201810524178 A CN201810524178 A CN 201810524178A CN 108676336 A CN108676336 A CN 108676336A
- Authority
- CN
- China
- Prior art keywords
- parts
- lactic acid
- composite material
- powder
- forming techniques
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
Abstract
The present invention relates to a kind of lactic acid composite materials and preparation method thereof applied to FDM forming techniques.The lactic acid composite material is made of polylactic resin, metal powder, toughener and other auxiliary agents；It calculates in parts by mass, including 3~10 parts of 100 parts of polylactic resin, 10~30 parts of metal powder, 2~15 parts of toughener and other auxiliary agents.The preparation method includes the steps that dry raw material, handles metal powder and prepare mixed liquor, by after drying the polylactic resin, treated, and the metal powder is added that 2~15 parts of the toughener is mixed in 3~10 parts of other auxiliary agents, and mixing extrusion in rotating Vortex mixing double screw extruder is added in the mixed liquor.Using the preparation method application and preparation in the lactic acid composite material of FDM forming techniques, the modification performance of polylactic acid can be effectively promoted, to meet 3D printing product high-precision requirement.
Description
Technical field
The present invention relates to FDM printed materials fields, compound more particularly to a kind of polylactic acid applied to FDM forming techniques
Material and preparation method thereof.
Background technology
FDM（Fused Deposition Modeling, fused glass pellet）Technology is current most widely used 3D
One of printing technique.However the heavy difficult point for being selected to limitation 3D printing development of the printed material in FDM forming techniques is asked
Topic.Mainly there is acrylonitrile-butadiene-styrene copolymer suitable for the material of FDM forming techniques at present（ABS）, polylactic acid tree
Fat（PLA）, makrolon（PC）, polyphenylsulfone（PPSF）With polyethylene terephthalate -1,4-CHDM ester
（PETG）, polyether-ether-ketone（PEEK）Deng.Wherein, polylactic resin（PLA）Nontoxic, without pungent smell, biodegradability is excellent
It is good, easily decomposed and replace by the enzyme in the multiple-microorganism or animal and plant body in nature, ultimately form water and carbon dioxide, not dirty
Many advantages, such as contaminating environment, therefore by most commonly used concern.But since the key technology of FDM techniques is how to keep material
Half mobility and the even solidification molding of material, and polylactic acid is a kind of crystal structure, and when heating directly turns from solid to liquid
Printing nozzle phase change is big when changing, temperature reduction then quickly solidification, therefore cooling down, and is easy to block printing nozzle, the product of formation
There are buckling deformations.And it is easy-to-draw to lack toughness due to the crystallographic rigidity of polylactic acid, when leading to polylactic acid as 3D printing consumables
It is disconnected, can not long-time stable molding, cause printing to have some setbacks, molding product lacking toughness and intensity make polylactic acid print
The product come is very restricted in terms of precision, intensity.
Currently, having larger demand for high performance 3D printing material in the market, wherein FDM forming techniques can be used for
Polylactic acid modification data it is less.And according to, to the blending and modifying of polylactic acid, mainly passing through increasing in existing technology
Add toughening material that its toughness is made to be improved, but thermal transition characteristic is not substantially change, because polylactic acid is specifically solid when heating
Determine fusing point, directly converted from solid to liquid, is easily trickled when being successively molded, and temperature reduces then quickly solidification, therefore be heat-shrinked
Deformation is big, it is difficult to print high-precision product.
Invention content
Based on this, it is necessary to can not for the performance of selected polydactyl acid in FDM forming techniques in the prior art
The problem of meeting 3D printing product high-precision requirement, polylactic acid modified performance can effectively be promoted by providing one kind, be beaten with meeting 3D
Print the lactic acid composite material and preparation method thereof applied to FDM forming techniques of product high-precision requirement.
A kind of poly-lactic acid material applied to FDM forming techniques, by polylactic resin, metal powder, toughener and other
Auxiliary agent forms；Calculate in parts by mass, including 100 parts of polylactic resin, 10~30 parts of metal powder, 2~15 parts of toughener and
3~10 parts of other auxiliary agents.
The polylactic resin is l-lactic acid in one of the embodiments,.
The molecular weight of the l-lactic acid is 10~200,000 in one of the embodiments,.
In one of the embodiments, the metal powder be the aluminium powders of 2500~8000 mesh, it is iron powder, copper powder, zinc powder, stainless
At least one of comminuted steel shot, nickel powder, titanium valve, tungsten powder, lead powder or zinc aluminium alloy powder.
The toughener is that end ring oxygen liquid reaction type nitrile rubber or end carboxyl liquid are anti-in one of the embodiments,
Answer formula nitrile rubber.
Other auxiliary agents are at least one of coupling agent, anti-hydrolysis agent or compatilizer in one of the embodiments,.
The coupling agent is KH-550 silane coupling agents, KH-560 silane coupling agents or titanium in one of the embodiments,
At least one of sour coupling agent.
The anti-hydrolysis agent is polycarbodiimide and/or single second carbide imine compound in one of the embodiments,.
The compatilizer is maleic anhydride grafting polymer, methyl methacrylate-fourth two in one of the embodiments,
In the terpolymer of alkene-styrene or the terpolymer of glycidyl methacrylate-ethylene-methyl acrylate extremely
Few one kind.
A method of it being used to prepare the lactic acid composite material applied to FDM forming techniques, is included the following steps：It is dry
Raw material carry out high temperature drying processing to the polylactic resin；Metal powder is handled, acetic acid is added simultaneously in coupling agent aqueous solution
PH value is adjusted to 5, the aqueous solution that pH value is 5 is sprayed in the metal powder and carries out mixing dispersion；Mixed liquor is prepared, it will
The polylactic resin after drying, treated the metal powder is added 2~15 parts the toughener and its of 3~10 parts
It is mixed in its auxiliary agent；The mixed liquor is added rotating Vortex and is kneaded mixing extrusion in double screw extruder, obtained by molding
The lactic acid composite material applied to FDM forming techniques
Above application is in the lactic acid composite material and preparation method thereof of FDM forming techniques, by introducing metal in polylactic acid
Powder is semifluid using the thermal capacitance of metal powder to change the hot property of polylactic acid, when polylactic acid melted extrusion modeling being made to be molded,
It prevents from trickling, when being molded cooling, solidification is uniform, and thermal contraction becomes smaller, and prevents warpage；And since metal powder has good sliding
Property and flexibility, can promote polylactic acid Uniform Flow in 3D printing, in addition, by the polylactic acid added with metal powder
Introduce toughener and other auxiliary agents, can significantly improve poly-lactic acid material fracture toughness and it is flexible, increase substantially polylactic acid
The impact strength of material, cryogenic mechanics performance, to realize efficient toughening, the enhancing purpose of poly-lactic acid material, Er Qiezeng
By force, the stabilization that works well of toughening is adapted to printing high-precision product.
Description of the drawings
Fig. 1 is the method for being used to prepare the lactic acid composite material applied to FDM forming techniques of an embodiment
Flowage structure schematic diagram.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Specific implementation mode be described in detail.Many details are elaborated in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case of violating intension of the present invention, therefore the present invention is not limited by following public specific embodiment.
In one embodiment, a kind of lactic acid composite material applied to FDM forming techniques, by polylactic resin, metal
Powder, toughener and other auxiliary agents composition；It calculates in parts by mass, including 100 parts of polylactic resin, 10~30 parts of metal powder, increasing
Tough dose 2~15 parts and 3~10 parts of other auxiliary agents.I.e. based on 100 parts of polylactic resin, the addition of other materials is carried out,
To obtain the lactic acid composite material.For example, the polylactic resin is l-lactic acid.Further, described left-handed poly-
The molecular weight of lactic acid is 10~200,000.Preferably, the molecular weight of the l-lactic acid is 150,000.The experimental results showed that passing through
In the range by the molecular weight control of selected polylactic acid, toughness, intensity and melting viscosity polylactic acid appropriate be can get
Composite material.And since polylactic acid molecule amount is too high, then its melting viscosity is big, can influence extrusion and print speed；If polylactic acid
Molecular weight is too low, then influences the mechanical properties such as toughness, the intensity of modified material.In a preferred embodiment, the polylactic acid
The melt flow index of resin is 10~40g/10min.Preferably, the melt flow index of the polylactic resin be 15~
25g/10min.In this way by selecting the polylactic resin of the melt flow index in OK range, may make using this kind
It is more smooth when lactic acid composite material is printed.It should be noted that when the metal powder addition is less than 10 parts, it is right
The rigid of composite material, heat resistance are not obviously improved；When addition is more than 30 parts, because the dispersion unevenness of material causes
The interface connectivity of composite material is deteriorated, elongation at break and degraded toughness.Therefore, in the present embodiment, by the metal
The addition of powder is controlled at 10~30 parts.For example, the addition of the metal powder can be 10 parts, 11 parts, 12 parts, 13 parts, 14
Part, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts
And 30 parts.Preferably, the addition of the metal powder is controlled at 15~20 parts, further, the addition of the metal powder
It is 16 parts or 17 parts.When the addition of the metal powder controls within this range, the rigid of the composite material obtained
And toughness can reach best condition.In addition, when the toughener addition is very few, then the purpose for increasing toughness is not had；
When the toughener addition is excessive, can make under intensity, rigidity, heat resistance and the other mechanical properties of the composite material
Drop.Therefore, in selection, the addition of the toughener is 2~15 parts；Preferably, the addition of the toughener is 5~10
Part, for example, the addition of the toughener can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.And due to the polylactic acid
Resin itself has environment-protecting and non-poisonous effect, therefore by the way that metal powder, toughener and other are added in told polylactic resin
Auxiliary agent, can be obtained that safety coefficient is high, product surface is bright and clean, dimensionally stable, and the 3D printer for being suitable for FDM forming techniques uses.
In a wherein embodiment, the metal powder be the aluminium powders of 2500~8000 mesh, iron powder, copper powder, zinc powder, stainless steel powder,
At least one of nickel powder, titanium valve, tungsten powder, lead powder or zinc aluminium alloy powder.The i.e. described metal powder be 2500~8000 mesh aluminium powder,
It is one or more kinds of mixed in iron powder, copper powder, zinc powder, stainless steel powder, nickel powder, titanium valve, tungsten powder, lead powder or zinc aluminium alloy powder
Close object.It should be noted that being shown when the grain size of the metal powder is less than 2500 mesh, with polylactic acid tree by actual experiment
Amalgamation is poor when fat mixes, and causes the toughness of composite material, intensity machine heat resistance poor；When the grain size of the metal powder is more than
When 8000 mesh, it is unfavorable for dispersion of the metal powder in polylactic resin, so as to cause the toughness of composite material, intensity and other power
Learn degradation.Preferably, the grain size of the metal powder is 2500~5000 mesh；Further, the grain size of the metal powder is
3000~4000 mesh.In this way, there is the flexible and good metal powder of thermal capacitance by being introduced in polylactic resin, metal powder is utilized
Thermal capacitance to change the hot property of polylactic acid, and since metal powder has flexibility, so that the toughness of polylactic acid is improved, together
When can also improve the intensity and heat resistance of polylactic resin, realize that toughening enhancing is carried out at the same time.
In a wherein embodiment, the toughener is end ring oxygen liquid reaction type nitrile rubber or end carboxyl liquid reaction
Formula nitrile rubber.Wherein, the end ring oxygen liquid reaction type nitrile rubber abbreviation " ETBN ", the end carboxyl liquid reaction formula fourth
Nitrile rubber is referred to as " CTBN ".Wherein ETBN and CTBN has heat resistance, oil resistivity, resistance to ag(e)ing, the flexibility of nitrile rubber
And caking property.And since ETBN and CTBN are liquid, it is easy to it be made to be uniformly mixed with polylactic resin.And due to butyronitrile rubber
Active function groups in the active end group and polylactic resin at glue both ends are easier to react, and foundation is connected chemically, can will be rich
In elasticity rubber particles be brought into polylactic resin main body, to significantly improve polylactic resin material fracture toughness and
Flexibility, the impact strength for increasing substantially polylactic resin material, cryogenic mechanics performance, to realize polylactic resin material
Efficient toughening, enhancing purpose, and enhance, the stabilization that works well of toughening.
In a wherein embodiment, other auxiliary agents are at least one of coupling agent, anti-hydrolysis agent or compatilizer.Tool
The selection species number of other auxiliary agents described in body can select one such or a variety of auxiliary agents to match according to actual product performance needs
Close addition.Preferably, other auxiliary agents are made of coupling agent, anti-hydrolysis agent and compatilizer.I.e. described other auxiliary agents are by three
Kind material composition, may make the performance by compound poly-lactic acid material more balanced in this way.One example is the coupling agent
For at least one of KH-550 silane coupling agents, KH-560 silane coupling agents or metatitanic acid coupling agent；The i.e. described coupling agent can be with
Selection one of which coupling agent or several coupling agents are mixed.Another example is that the anti-hydrolysis agent is that poly- carbonization two is sub-
Amine and/or single second carbide imine compound；The i.e. described anti-hydrolysis agent can be by polycarbodiimide and single second carbide imine chemical combination
Object forms, and the anti-hydrolysis agent can also be made of a kind of substance in polycarbodiimide or single second carbide imine compound.
Preferably, the anti-hydrolysis agent is made of polycarbodiimide and single second carbide imine.Further, polycarbodiimide and list
The mixed proportion of carbodiimides is 1:9~9:1.For example, the mixed proportion of polycarbodiimide and single second carbide imine is 5:
5.Another example is that the compatilizer is maleic anhydride grafting polymer, methyl methacrylate-butadiene-styrene
At least one of the terpolymer of terpolymer or glycidyl methacrylate-ethylene-methyl acrylate.That is institute
It is maleic anhydride grafting polymer, the terpolymer of methyl methacrylate-butadiene-styrene, methyl-prop to state compatilizer
One or several kinds of mixtures in the terpolymer of olefin(e) acid ethylene oxidic ester-ethylene-methyl acrylate.Preferably, institute
Compatilizer is stated by maleic anhydride grafting polymer, the terpolymer and methyl of methyl methacrylate-butadiene-styrene
The terpolymer of glycidyl acrylate-ethylene-methyl acrylate forms.It should be noted that methyl methacrylate-
The terpolymer of butadiene-styrene is polymerized by methyl methacrylate, butadiene and styrene three；First
The terpolymer of base glycidyl acrylate-ethylene-methyl acrylate, i.e., by glycidyl methacrylate, ethylene
And methyl acrylate three is polymerized.
Above application is in the lactic acid composite material of FDM forming techniques, by introducing metal powder in polylactic acid, utilizes gold
Belong to the thermal capacitance of powder to change the hot property of polylactic acid, be semifluid when polylactic acid melted extrusion modeling being made to be molded, prevent from trickling,
When being molded cooling, solidification is uniform, and thermal contraction becomes smaller, and prevents warpage；And since metal powder has good sliding and flexible
Property, polylactic acid Uniform Flow in 3D printing can be promoted, in addition, by introducing toughening in the polylactic acid added with metal powder
Agent and other auxiliary agents, can significantly improve poly-lactic acid material fracture toughness and it is flexible, increase substantially the anti-of poly-lactic acid material
Impact strength, cryogenic mechanics performance to realize efficient toughening, the enhancing purpose of poly-lactic acid material, and enhance, toughening
It works well to stablize and is adapted to printing high-precision product.
In another embodiment, a method of being used to prepare the lactic acid composite material applied to FDM forming techniques, wrap
Include following steps：
S110：Dry raw material carry out high temperature drying processing to the polylactic resin.
High temperature drying processing is carried out before adding other components to spare to 100 parts of polylactic resin.
Specifically, polylactic resin is dry in the environment of temperature is 80~100 DEG C, drying time is 4~6h.It is preferred that
Ground, polylactic resin is dry under environment at a temperature of 90 °C, dry 5h.It may make the moisture of polylactic resin abundant in this way
It is removed, to enhance its structural stability, in order to be kneaded twin-screw in rotating Vortex after subsequently being mixed with other components
It is sufficiently mixed in extruder.I.e. by being pre-processed in advance to metal powder, polylactic resin material and metal are increased
Amalgamation between powder and other auxiliary agents makes the mechanical performance of polylactic resin material significantly improve.
S120：Metal powder is handled, acetic acid is added in coupling agent aqueous solution and adjusts pH value to 5, is described in 5 by pH value
Aqueous solution, which is sprayed in the metal powder, carries out mixing dispersion.
Specifically, then the aqueous solution 0.3~2.5 part of coupling agent being made into is added acetic acid and adjusts in the aqueous solution
Then solution is added in the form of spraying in metal powder by the pH value of solution to 5.Further, using high-speed mixer pair
The metal powder for being sprayed with coupling agent aqueous solution is disperseed.For example, dispersion temperature is 80~100 DEG C；For example, the mixed at high speed
The speed of machine is 1200~1500rpm.For example, jitter time is 5~10min.It may make metal powder dispersion more equal in this way
It is even, obtain active metal-powder.
S130：Prepare mixed liquor, by after drying the polylactic resin, treated, and the metal powder is added to 2~
15 parts of the toughener is mixed with 3~10 parts of other auxiliary agents.
Specifically, using high-speed mixer to after drying the polylactic resin, treated the metal powder, 2~
15 parts of the toughener and 3~10 parts of other auxiliary agents are mixed.For example, mixing temperature is 40~50 DEG C；For example, mixed
Sum velocity is 300~1200rpm；Incorporation time is 10-20min.Blowing after each component carries out being completely dispersed mixing, it is to be added
Work is molded.
S140：The mixed liquor is added rotating Vortex and is kneaded mixing extrusion in double screw extruder, obtains application by molding
In the lactic acid composite material of FDM forming techniques.
Specifically, at 160~220 DEG C, the screw speed is 40~100rpm for the temperature control of the extruder.Wherein
The rate of feeding of extruder is 5~15rpm.Further, the material squeezed out by the extruder carries out tie rod, cold successively
But, the lactic acid composite material for being applied to FDM forming techniques is made in drying and granulating working procedure.Using the present embodiment
In preparation method acquired in the diameter of the lactic acid composite material applied to FDM forming techniques be usually 1.75mm
Or 3mm.It should be noted which kind of model the lactic acid composite material applied to FDM forming techniques is processed into, institute is had no effect on
The performance of the lactic acid composite material prepared, whether being only in that easy to use.Experimental data shows by polylactic acid
The middle tensile strength height for adding treated metal powder, the lactic acid composite material that toughener and various other auxiliary agents are obtained
Up to 90Mpa, bending strength is up to 120Mpa, and notch impact strength 30KJ/m2, elongation at break is up to 50%.
The above-mentioned method for being used to prepare the lactic acid composite material applied to FDM forming techniques, by dry by high temperature
The metal powder with good thermal capacitance is added in polylactic resin after dry, is formed when being not only molded polylactic acid melted extrusion modeling
Semifluid structure to effectively prevent material to trickle, and can solidify uniformly when being molded cooling, and thermal contraction becomes smaller, to very
Prevent product from leading to the problem of alice well；Further pass through the polylactic resin after drying, treated the metal
Powder is added to 2~15 parts of the toughener and is mixed with 3~10 parts of other auxiliary agents, then mixed liquor is added in the same direction
Mixing extrusion is to obtain the lactic acid composite material for being used for FDM forming techniques in rotation mixing double screw extruder.
Required equipment requirement is relatively simple and easy to operate in the preparation process, can be widely used in large-scale industrial production.
Below by specific several examples, the technical solutions of the present invention will be further described：
1 each component list of table
In above-described embodiment 1 to 10, other auxiliary agents use preferred embodiment, i.e., described other auxiliary agents are by the coupling agent, institute
State anti-hydrolysis agent and compatilizer composition.Specifically to the concrete composition of other auxiliary agents described in each embodiment at defending oneself
It is bright as follows：
Other auxiliary agents described in example 1 are respectively：0.5 part of KH-560 silane coupling agents, 1.0 parts of polycarbodiimide compound,
0.5 part of single second carbide imine compound, 3.0 parts of maleic anhydride grafting polymer.
Other auxiliary agents described in example 2 are respectively：0.8 part of KH-560 silane coupling agents, polycarbodiimide compound 1.2
Part, 0.8 part of single second carbide imine compound, by the terpolymer of Methyl Methacrylate-Butadiene-Styrene Copolymer
3.5 part.
Other auxiliary agents described in example 3 are respectively：1.5 parts of metatitanic acid coupling agent, 1.5 parts of polycarbodiimide compound, list
4.0 parts of the terpolymer of 0.3 part of carbodiimide compound, GMA- ethylene-methyl acrylates.
Other auxiliary agents described in example 4 are respectively：1.0 parts of metatitanic acid coupling agent, 0.8 part of polycarbodiimide compound, list
1.0 parts of carbodiimide compound, 4 parts of maleic anhydride grafting polymer.
Other auxiliary agents described in example 5 are respectively：2.0 parts of KH-560 silane coupling agents, polycarbodiimide compound 0.6
Part, 1.5 parts of single second carbide imine compound, MMB methyl methacrylate butadiene styrene 4.0 parts of terpolymer.
Other auxiliary agents described in example 6 are respectively：0.5 part of KH-550 silane coupling agents, polycarbodiimide compound 0.5
Part, 1.2 parts of single second carbide imine compound, GMA- ethylene-methyl acrylates 3.5 parts of terpolymer.
Other auxiliary agents described in example 7 are respectively：2.0 parts of metatitanic acid coupling agent, 0.7 part of polycarbodiimide compound, list
0.5 part of carbodiimide compound, 4.0 parts of maleic anhydride grafting polymer.
Other auxiliary agents described in example 8 are respectively：1.0 parts of silane coupling agent KH-560, polycarbodiimide compound
1.2 parts, 4.0 parts of the terpolymer of 0.4 part of single second carbide imine compound, methyl methacrylate-butadiene-styrene.
Other auxiliary agents described in example 9 are respectively：1.5 parts of KH-550 silane coupling agents, polycarbodiimide compound 0.5
Part, 1.5 parts of single second carbide imine compound, GMA- ethylene-methyl acrylates 3.0 parts of terpolymer.
Other auxiliary agents described in example 10 are respectively：0.8 part of metatitanic acid coupling agent, 1.0 parts of polycarbodiimide compound, list
0.8 part of carbodiimide compound, 3.5 parts of maleic anhydride grafting polymer.
Accordingly, in above-described embodiment 1 to 10, the performance indicator of gained lactic acid composite material is as shown in table 2 below.
| It is anti-to stretch intensity/MPa | Bending strength/MPa | Notch impact strength/KJ/m2 | Elongation at break/% | |
| Example 1 | 85.6 | 118.8 | 28.5 | 45.5 |
| Example 2 | 75.3 | 119.2 | 26.8 | 46.3 |
| Example 3 | 75.6 | 115.6 | 27.3 | 47.2 |
| Example 4 | 85.4 | 115.5 | 27.6 | 48.3 |
| Example 5 | 82.6 | 117.8 | 29.2 | 46.6 |
| Example 6 | 86.7 | 116.3 | 24.9 | 46.5 |
| Example 7 | 88.5 | 120.5 | 30.0 | 50.3 |
| Example 8 | 90.3 | 117.4 | 26.6 | 48.3 |
| Example 9 | 82.1 | 118.1 | 28.8 | 45.4 |
| Example 10 | 85.6 | 119.5 | 27.6 | 48.8 |
2 performance indicator list of table
Shown by being pre-processed in advance to the metal powder by above table comparing result, it is poly- so as to greatly enhance
Amalgamation between lactic acid resin and metal powder and other auxiliary agents makes the mechanical performance of polylactic resin material significantly improve.Wherein
The tensile strength of composite material is up to 90Mpa, and bending strength is up to 120Mpa, and notch impact strength reaches 30KJ/m2, extension at break
Rate is up to 50%.So as to be effectively adapted to printing high-precision product.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of lactic acid composite material applied to FDM forming techniques, which is characterized in that by polylactic resin, metal powder, increasing
Tough dose and other auxiliary agents composition；It calculates in parts by mass, including 100 parts of polylactic resin, 10~30 parts of metal powder, toughener 2
~15 parts and 3~10 parts of other auxiliary agents.
2. the lactic acid composite material according to claim 1 applied to FDM forming techniques, which is characterized in that described poly-
Lactic acid resin is l-lactic acid.
3. the lactic acid composite material according to claim 2 applied to FDM forming techniques, which is characterized in that the left side
The molecular weight for revolving polylactic acid is 10~200,000.
4. the lactic acid composite material according to claim 1 applied to FDM forming techniques, which is characterized in that the gold
Belong to aluminium powder, iron powder, copper powder, zinc powder, stainless steel powder, nickel powder, titanium valve, tungsten powder, lead powder or zinc-aluminium that powder is 2500~8000 mesh to close
At least one of bronze.
5. the lactic acid composite material according to claim 1 applied to FDM forming techniques, which is characterized in that the increasing
Tough dose is end ring oxygen liquid reaction type nitrile rubber or end carboxyl liquid reaction formula nitrile rubber.
6. the lactic acid composite material according to claim 1 applied to FDM forming techniques, which is characterized in that it is described its
Its auxiliary agent is at least one of coupling agent, anti-hydrolysis agent or compatilizer.
7. the lactic acid composite material according to claim 6 applied to FDM forming techniques, which is characterized in that the idol
Connection agent is at least one of KH-550 silane coupling agents, KH-560 silane coupling agents or metatitanic acid coupling agent.
8. the lactic acid composite material according to claim 6 applied to FDM forming techniques, which is characterized in that described anti-
Hydrolytic reagent is polycarbodiimide and/or single second carbide imine compound.
9. the lactic acid composite material according to claim 6 applied to FDM forming techniques, which is characterized in that the phase
Appearance agent be maleic anhydride grafting polymer, methyl methacrylate-butadiene-styrene terpolymer or methacrylic acid
At least one of the terpolymer of ethylene oxidic ester-ethylene-methyl acrylate.
10. a kind of polylactic acid being used to prepare as claimed in any one of claims 1-9 wherein applied to FDM forming techniques is compound
The method of material, which is characterized in that include the following steps：
Dry raw material carry out high temperature drying processing to the polylactic resin；
Metal powder is handled, acetic acid is added in coupling agent aqueous solution and adjusts pH value to 5, the aqueous solution that pH value is 5 is sprayed
It spills and carries out mixing dispersion into the metal powder；
Mixed liquor is prepared, by the polylactic resin after drying, treated the metal powder is added 2~15 parts of the increasing
It is mixed in tough dose of other auxiliary agents with 3~10 parts；
The mixed liquor is added rotating Vortex and is kneaded mixing extrusion in double screw extruder, obtained and be molded applied to FDM by molding
The lactic acid composite material of technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810524178.4A CN108676336A (en) | 2018-05-29 | 2018-05-29 | Lactic acid composite material and preparation method thereof applied to FDM forming techniques |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810524178.4A CN108676336A (en) | 2018-05-29 | 2018-05-29 | Lactic acid composite material and preparation method thereof applied to FDM forming techniques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108676336A true CN108676336A (en) | 2018-10-19 |
Family
ID=63807012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810524178.4A Pending CN108676336A (en) | 2018-05-29 | 2018-05-29 | Lactic acid composite material and preparation method thereof applied to FDM forming techniques |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108676336A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845300A (en) * | 2015-03-26 | 2015-08-19 | 成都新柯力化工科技有限公司 | Polylactic acid composite material used for three-dimensional printing and preparation method therefor |
| KR20150098142A (en) * | 2014-02-19 | 2015-08-27 | (주)비앤케이 | Complex filament composition for fdm type 3d printer containing metal powder |
| CN107686638A (en) * | 2017-07-21 | 2018-02-13 | 宁夏共享模具有限公司 | A kind of PLA for 3D printing is material modified and preparation method |
-
2018
- 2018-05-29 CN CN201810524178.4A patent/CN108676336A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150098142A (en) * | 2014-02-19 | 2015-08-27 | (주)비앤케이 | Complex filament composition for fdm type 3d printer containing metal powder |
| CN104845300A (en) * | 2015-03-26 | 2015-08-19 | 成都新柯力化工科技有限公司 | Polylactic acid composite material used for three-dimensional printing and preparation method therefor |
| CN107686638A (en) * | 2017-07-21 | 2018-02-13 | 宁夏共享模具有限公司 | A kind of PLA for 3D printing is material modified and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102632B (en) | Chlorinated polyvinyl chloride is material modified and preparation method thereof | |
| CN107903540A (en) | A kind of polychloroethylene pipes material and preparation method thereof | |
| CN107022190B (en) | A kind of graphene microchip masterbatch and preparation method for engineering plastics enhancing | |
| CN105907069A (en) | Plant powder modified polylactic acid 3d printing material and preparation method thereof | |
| CN104830040A (en) | Polycarbonate composition for 3D printing technology and preparation method thereof | |
| CN107686638A (en) | A kind of PLA for 3D printing is material modified and preparation method | |
| CN105542379B (en) | A kind of high-impact resists cold ABS tank materials and the preparation method and application thereof | |
| CN108659421A (en) | Chliorinated polyvinyl chloride composition and tubing preparation method | |
| CN104592730A (en) | Polylactic acid/polyester alloy and preparation method thereof | |
| CN110343332A (en) | A kind of high-toughness polypropylene/elastic composite and preparation method | |
| CN108456422A (en) | Show business chip high density thermoplastic plastics and preparation method thereof | |
| CN105623106B (en) | Rub resistance, the modified random copolymerization of resistance to scratch polypropylene material and preparation method thereof | |
| CN109796704A (en) | A kind of hard ABS/PVC alloy and preparation method thereof improving mobility | |
| CN108384229A (en) | A kind of composite fibre reinforced nylon 6 reworked material and preparation method thereof | |
| CN108676336A (en) | Lactic acid composite material and preparation method thereof applied to FDM forming techniques | |
| CN108059744A (en) | A kind of material for manufacturing phone housing and preparation method thereof | |
| CN104327446A (en) | Waste ABS/PP (acrylonitrile butadiene styrene/polypropylene) composite material and preparation method thereof | |
| CN104610505B (en) | High toughening efficiency and the nylon toughener of high fluidity and preparation method thereof | |
| CN109796740A (en) | A kind of resistant PC/PET alloy and preparation method thereof | |
| CN108129789A (en) | A kind of ABS composite material of 3D printing and preparation method thereof | |
| CN108239390A (en) | A kind of PA6 alloy materials of toughening modifying and preparation method thereof | |
| CN105273325A (en) | Cold-resistant wear-resistant polyvinyl chloride composition and preparation method thereof | |
| CN110128748A (en) | A kind of high-toughness polypropylene material and preparation method thereof | |
| CN104817719B (en) | A kind of graphene modifying agent, graphene enhancing complex material and preparation method thereof | |
| CN104177793A (en) | PBT (polybutylene terephthalate) toughener as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181019 |