CN106751607A - A kind of FDM printings use graininess PLA material modified and preparation method - Google Patents
A kind of FDM printings use graininess PLA material modified and preparation method Download PDFInfo
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- CN106751607A CN106751607A CN201611090958.XA CN201611090958A CN106751607A CN 106751607 A CN106751607 A CN 106751607A CN 201611090958 A CN201611090958 A CN 201611090958A CN 106751607 A CN106751607 A CN 106751607A
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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
- 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
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention discloses a kind of FDM printings with graininess PLA is material modified and preparation method.Present invention relates particularly to a kind of large scale industry with the novel environment friendly PLA that FDM is printed is material modified and preparation method, including following weight portion component：100 parts of polylactic resin, 10~30 parts of inorganic fillers, 5~30 parts of polymer elastomers, 1~10 part of other auxiliary agent.PLA is made by the granulation of mixing extrusion technique material modified.Product of the present invention is degradable, environment-protecting asepsis, printing are smooth, odorlessness, pollution-free, and safety coefficient is high, and printout has any surface finish, and outward appearance is beautiful, well-balanced, dimensionally stable, the good characteristics such as is difficult to shrink, and is highly suitable for FDM 3D printers and uses.And the PLA waste materials of production process can recovery and reusing and recycling completely.The present invention makes the durability of product of PLA material printing of the invention considerably beyond conventional PLA material, and can also bear bigger pressure and abrasion by adding polymer elastomer.
Description
Technical field
The present invention relates to technical field of polymer materials, 3D printing technique field, used more particularly, to a kind of large scale industry
FDM printings novel environment friendly PLA is material modified and preparation method.
Background technology
FDM technology is most widely used, most vital 3D printing technique, is a kind of quick, safe, cheap fast
Fast moulding process, its easy operation, equipment cost is low, concise in technology.Printed material is the main skill that 3D printing further develops
Art bottleneck, it is adaptable to the consumptive material of FDM 3D printers, will not only meet high mechanical properties, low-shrinkage, be adapted to melt temperature etc.
It is required that, and more to meet the environmental requirement such as safe and nontoxic, nonirritant.
The consumptive material suitable for FDM printing techniques mainly has acrylonitrile-butadiene-styrene copolymer (ABS), poly- breast at present
Sour (PLA), makrolon (PC), PPSU (PPSF) etc..But, these materials have certain defect, such as ABS materials in itself
Material contract on cooling rate is big, and the easy contraction distortion of product easily occurs splitting and warpage etc., limits its application.Simultaneously as
ABS print temperatures are up to more than 230 DEG C, cause the decomposed of material and produce peculiar smell.
PLA and its copolymer are a kind of synthesis macromolecule materials with excellent biocompatibility and biodegradable
Material.It has strong nontoxic, nonirritant, plasticity, easy processing shaping, easily by the multiple-microorganism or animal and plant body in nature
Interior enzyme is decomposed and replaced, and ultimately forms water and carbon dioxide, free from environmental pollution, thus is considered as that most promising biology can drop
Solution macromolecular material, new century most rising new material is defined as by materialogy.
But, there are some defects in PLA, so as to have impact on its processing characteristics and application, such as due to itself：Itself
Intensity is not high, fragility, the poor, poor heat resistance of barrier etc..With tensile strength higher, modulus of compressibility, but matter is hard toughness compared with
Difference, lacks flexible and elasticity, easily flexural deformation；In addition, the chemical constitution of PLA lacks reactive functional groups, also without parent
Aqueous, degradation speed needs control, it is therefore necessary to which PLA is modified.
In the prior art for the modified often just for the improvement of single performance of PLA.As individually changed to toughness
Property, individually heat resistance is modified or individually anti-flammability is modified；In addition, by changing that toughness and heat resistance combine
Property patent also has been reported.At present, the PLA of market sale it is material modified be essentially all for desktop level 3D printer wire
Material, the PLA of few granular large scale industry levels is material modified；And, current these material modified products for printing
All all kinds of corrupt practices creep in for product, such as, and warpage, cracking, bad adhesion, later stage deformation etc..
At present, printed material has seriously hindered 3D printing industry and has further developed；Accordingly, it would be desirable to develop one kind not
It is only cheap, green low-carbon environment-friendly, good stability of the dimension, intensity are high, in process not plug-hole, not fracture of wire, become without warpage
The PLA of the FDM 3D printings of the advantages of shape is material modified.This popularization and application for widening the species and PLA of 3D printing consumptive material has
There is larger realistic meaning, and this application to improving 3D printing technique is significant.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of cheap, green low-carbon environment-friendly, easily drop
Solution, product size stabilization, intensity is high, shrinkage factor is small, in process not plug-hole, not fracture of wire, without buckling deformation, without cracking, viscous
The material modified techniques of novel environment friendly PLA of the graininess FDM 3D printings of the advantages of knot property is good.
In order to realize foregoing invention purpose, the present invention is realized in the following way：
A kind of FDM 3D printings of excellent performance are material modified with PLA, including following mass parts component：100 parts of poly- breasts
Acid resin, 10~30 parts of inorganic fillers, 5~30 parts of polymer elastomers, 1~10 part of other auxiliary agent.
1st, four kinds of preferred schemes of component are as follows：
Polylactic resin species can also be able to be the mixture of the two for left-handed or dextrorotation, and molecular weight 5~200,000 are melted
10~20g/10min of body flow index；
Inorganic filler is preferably one or two mixing for being formed in titanium dioxide, talcum powder, calcium carbonate, calcium sulfate crystal whiskers
Thing, the mesh number of inorganic filler is preferably 2500~5000 mesh.Inorganic filler can not only improve the rigidity of PLA, while can be with
The toughness of PLA is improved, realizes that toughness reinforcing increases just while carrying out；
Polymer elastomer is ethylene-vinyl acetate copolymer (EVA), ethylene acrylic acid co polymer (EAA), styrene
Analog thermoplastic elastomer (TPS), polyurethane-type thermoplastic elastomer (TPU), olefin hydrocarbons thermoplasticity elastic body (TPO), poly- carbonic acid
One or two mixtures for being formed in ester elastomer.Polymer elastomer can not only increase the toughness of PLA, improve anti-impact
Performance is hit, the situation easily stuck up, easily split of product is reduced, but also the compatibility of PLA and other materials can be increased；
Other auxiliary agents are included in plasticizer, toughener, coupling agent, antioxidant, hydrolysis-resisting agent, compatilizer, lubricant
One or more.Those skilled in the art can select one or more auxiliary agent therein to match somebody with somebody according to actual product performance need
Close addition.Preferably 7 kinds auxiliary agents are all used, and the performance of resulting materials is more balanced.
2nd, the preferred scheme of various auxiliary agents is as follows described in other auxiliary agents：
The toughener be poly butylene succinate, polycaprolactone, poly adipate succinic acid ester in one or two
Composition；
The plasticizer is at least in dioctyl phthalate, tributyl 2-acetylcitrate, tricresyl phosphate
Kind.The plasticity and mobility of PLA can be increased, improve processability, and make product that there is pliability；
The coupling agent is one or more in silane resin acceptor kh-550, KH-560 and metatitanic acid coupling agent；
The chain extender is ADR, can both compensate plastics due to problem that is dry bad or not bringing thoroughly to processing
Process brings benefit, it is also possible to the rheological property of PLA and mechanical performance has been reached desirable balance；
The antioxidant has two classes, and a class is tetrapentaerythritol ester and triphosphite ester mixture, and mass ratio is 1:
2；Another kind of is antioxidant 1010 and the compound composition of antioxidant 215, and mass ratio is 1:3~3:1；
The hydrolysis-resisting agent is one kind or at least two formation in polycarbodiimide and single second carbide imine compound
Mixture, the mixture of particularly preferred polycarbodiimide and single second carbide imine.Further, it is preferable to polycarbodiimide
It is 1 with the mixed proportion of single second carbide imine:9~9:1；
The compatilizer is maleic anhydride grafting polymer, common by methyl methacrylate, butadiene, styrol copolymer
Use cooperatively for one or more in poly- ternary polymerization, the terpolymer of GMA- ethylene-methyl acrylates；
The lubricant is the mixing of one or more in atoleine, Tissuemat E, zinc stearate.
3. preparation method
A kind of FDM 3D printings of excellent performance material modified techniques of PLA, comprise the following steps：
A. raw material drying：By PLA, polymer elastomer etc. at 80~100 DEG C, 4~6h is dried, it is standby；
B. it is blended：All material is proportionally added into mixed at high speed mixer, is stirred.
C. it is molded：By mixing extrusion in the above-mentioned mixture addition rotating Vortex mixing double screw extruder for stirring,
Extruder temperature control be followed successively by 165~180 DEG C, 170~185 DEG C, 175~190 DEG C, 180~195 DEG C, 185~200 DEG C,
180~195 DEG C；Screw speed is 80~200rpm, and rate of feeding is 5~15rpm.Extruded material successively through tie rod, cool down, blow
It is dry, that granulating working procedure is made PLA is material modified.Two kinds of a diameter of 1.75mm or 3mm of usual product.Product processing is into which kind of type
Number, the material modified performance prepared by the present invention is had no effect on, whether easy to use it is only.
The present invention has the advantages that：
1. this product is degradable, environment-protecting asepsis, printing are smooth, odorlessness, pollution-free, and safety coefficient is high, printout tool
There is any surface finish, outward appearance is beautiful, well-balanced, dimensionally stable, be difficult the good characteristics such as contraction, sticking up for printed product is solved well
The defect such as song, cracking, bad adhesion, is highly suitable for FDM 3D printers and uses.
2. the PLA waste materials of this product can recovery and reusing and recycling completely, not only reduce cost, improve resource utilization,
And serve key effect in today's society advocates the strategy of sustainable development of " low-carbon (LC), energy-saving and environmental protection ".
3. polymer elastomer is added in the present invention, not only increase amalgamation between PLA and filler, and make PLA
The mechanical performances such as the toughness of material, impact resistance are significantly improved；It is anti-to stretch intensity up to 75Mpa；Elastic modelling quantity is up to 1800-
3500Mpa；Notch impact strength 18KJ/m2；Dimension card softens (B50) 105 DEG C of temperature.Expect printing using PLA of the invention
The durability of product can also bear bigger pressure and abrasion considerably beyond conventional PLA material.
4. present invention process flow is short, equipment requirement is simple, manufacturing process is easy, it is easy to operate, without reference to harsh
Chemical technology is operated, and production efficiency is high, is very suitable for large-scale industrial production.
Specific embodiment
The following examples can make those skilled in the art that the present invention is more fully understood, but limit never in any form
The present invention.Table 1 is the preferred embodiments of the present invention.
Table 1
In above-described embodiment one to ten, described other auxiliary agents use preferred scheme, i.e. plasticizer, toughener, coupling agent, anti-
Oxidant, hydrolysis-resisting agent, compatilizer, 7 kinds of auxiliary agent raw materials of lubricant are all used.
In above-described embodiment one to ten, the material modified performance indications of gained are as shown in table 2：
Table 2
Specifically：
Other auxiliary agents are respectively described in example one：1 part of dioctyl phthalate, 1 part of polycaprolactone, KH-550 0.5
Part, ADR0.2 parts, tetrapentaerythritol ester and 0.3 part of triphosphite ester mixture, 0.5 part of polycarbodiimide compound, single carbon
Change 0.2 part of diimine compounds, 0.5 part of maleic anhydride grafting polymer, 0.5 part of atoleine.
Other auxiliary agents are respectively described in example two：1 part of tributyl 2-acetylcitrate, 1 part of poly adipate succinic acid ester,
1 part of KH-560, ADR0.2 parts, tetrapentaerythritol ester and 0.5 part of triphosphite ester mixture, polycarbodiimide compound 0.6
Part, 0.3 part of single second carbide imine compound, 0.8 part of maleic anhydride grafting polymer, 0.3 part of zinc stearate.
Other auxiliary agents are respectively described in example three：1 part of tricresyl phosphate, 1 part of poly butylene succinate, metatitanic acid idol
2 parts of agent of connection, 0.2 part of ADR, tetrapentaerythritol ester and 0.8 part of triphosphite ester mixture, polycarbodiimide compound 0.5
Part, 0.5 part of single second carbide imine compound, 1 part of maleic anhydride grafting polymer, 0.5 part of Tissuemat E.
Other auxiliary agents are respectively described in example four：1 part of tricresyl phosphate, 1.5 parts of poly adipate succinic acid ester, KH-
560 1.5 parts, 0.2 part of ADR, tetrapentaerythritol ester and 1 part of triphosphite ester mixture, polycarbodiimide compound 0.8
Part, 0.4 part of single second carbide imine compound, methyl methacrylate, butadiene, benzene second thing, the three of alkene copolymer copolymerization
0.8 part of membered copolymer, 0.8 part of Tissuemat E.
Other auxiliary agents are respectively described in example five：0.5 part of dioctyl phthalate, poly adipate succinic acid ester 0.8
Part, 0.5 part of KH-560,0.2 part of ADR, antioxidant 1010 and antioxidant 215 compound composition 0.4 part, polycarbodiimide chemical combination
0.5 part of thing, 0.5 part of single second carbide imine compound, methyl methacrylate, the ternary polymerization of GMA- ethylene-methyl acrylates
0.5 part of thing, 0.2 part of atoleine.
Other auxiliary agents are respectively described in example six：2 parts of tricresyl phosphate, 1 part of poly adipate succinic acid ester, metatitanic acid idol
1.5 parts of agent of connection, 0.2 part of ADR, antioxidant 1010 and antioxidant 215 compound composition 0.6 part, polycarbodiimide compound 0.4
Part, 1 part of the terpolymer of 0.8 part of single second carbide imine compound, methyl methacrylate, GMA- ethylene-methyl acrylates,
0.5 part of zinc stearate.
Other auxiliary agents are respectively described in example seven：1.5 parts of tributyl 2-acetylcitrate, 1 part of poly butylene succinate,
0.8 part of KH-550,0.2 part of ADR, antioxidant 1010 and antioxidant 215 compound composition 0.7 part, polycarbodiimide compound
0.6 part, 1 part of single second carbide imine compound, methyl methacrylate, butadiene, benzene second thing, the three of alkene copolymer copolymerization
0.5 part of membered copolymer, 0.8 part of Tissuemat E.
Other auxiliary agents are respectively described in example eight：1 part of dioctyl phthalate, 0.5 part of poly butylene succinate,
1.5 parts of KH-550,0.2 part of ADR, antioxidant 1010 and antioxidant 215 compound composition 0.5 part, polycarbodiimide compound 1
Part, 0.5 part of single second carbide imine compound, methyl methacrylate, butadiene, benzene second thing, the three of alkene copolymer copolymerization
0.8 part of membered copolymer, 0.5 part of Tissuemat E.
Other auxiliary agents are respectively described in example nine：2 parts of tributyl 2-acetylcitrate, 1.5 parts of polycaprolactone, metatitanic acid coupling
1 part of 0.5 part of agent, 0.2 part of ADR, tetrapentaerythritol ester and triphosphite ester mixture, 0.5 part of polycarbodiimide compound,
0.5 part of single second carbide imine compound, 0.8 part of maleic anhydride grafting polymer, 0.8 part of atoleine.
Other auxiliary agents are respectively described in example ten：1.5 parts of dioctyl phthalate, 2 parts of polycaprolactone, metatitanic acid coupling
Compound 0.8 part of the composition of 1.5 parts of agent, 0.2 part of ADR, antioxidant 1010 and antioxidant 215,0.5 part of polycarbodiimide compound,
0.5 part of single second carbide imine compound, 1 part of maleic anhydride grafting polymer, 0.6 part of atoleine.
It will be understood by those skilled in the art that above example is only exemplary embodiment, without departing substantially from spirit of the invention
In the case of scope, various changes, replacement can be carried out and changed.
Claims (9)
1. a kind of FDM printing is material modified with graininess PLA, it is characterised in that raw materials used including following proportion by weight
Component：
100 parts of polylactic resin, 10~30 parts of inorganic fillers, 5~30 parts of polymer elastomers, 1~10 part of other auxiliary agent；
Described other auxiliary agents are in plasticizer, toughener, coupling agent, antioxidant, hydrolysis-resisting agent, compatilizer, lubricant
Plant or various mixtures.
2. FDM printings according to claim 1 are material modified with graininess PLA, it is characterised in that the polylactic resin
It is PLLA resin or dextrorotation polylactic resin, or the mixture of the two.
3. FDM printings according to claim 2 are material modified with graininess PLA, it is characterised in that the polylactic resin
Index is molecular weight 5~200,000,10~20g/10min of melt flow index.
4. FDM according to claim 1 printing is material modified with graininess PLA, it is characterised in that the inorganic filler is
One or two mixture in titanium dioxide, talcum powder, calcium carbonate, calcium sulfate crystal whiskers.
5. FDM printings according to claim 1 are material modified with graininess PLA, it is characterised in that the inorganic filler
Mesh number is 2500~5000 mesh.
6. FDM printings according to claim 1 are material modified with graininess PLA, it is characterised in that the polymer elasticity
Body is ethylene-vinyl acetate copolymer, ethylene acrylic acid co polymer, styrene analog thermoplastic elastomer, polyurethanes thermoplastic
Property elastomer, olefin hydrocarbons thermoplasticity elastic body, one or two mixtures for being formed in polycarbonate elastomer body.
7. FDM printings according to claim 1 are material modified with graininess PLA, it is characterised in that described other auxiliary agents
In,
The toughener is one or two compositions in poly butylene succinate, polycaprolactone, poly adipate succinic acid ester；
The plasticizer is at least one in dioctyl phthalate, tributyl 2-acetylcitrate, tricresyl phosphate；
The coupling agent is one or more in silane resin acceptor kh-550, KH-560 and metatitanic acid coupling agent；
The chain extender is ADR；
The antioxidant is the one kind in two classes, and a class is tetrapentaerythritol ester and triphosphite ester mass ratio is 1:2 it is mixed
Compound；It is another kind of be by antioxidant 1010 and antioxidant 215 in mass ratio be 1:3~3:1 compound composition；
The hydrolysis-resisting agent is the mixture of the one or both in polycarbodiimide and single second carbide imine compound；
The compatilizer is maleic anhydride grafting polymer, by methyl methacrylate, butadiene, styrol copolymer copolymerization and
Into ternary polymerization, the terpolymer of GMA- ethylene-methyl acrylates in one kind or at least two mixture；
The lubricant is the mixing of one or more in atoleine, Tissuemat E, zinc stearate.
8. FDM according to claim 7 printing is material modified with graininess PLA, it is characterised in that the hydrolysis-resisting agent is
The mass ratio of polycarbodiimide and single second carbide imine is 1:9~9:1 mixture.
9. a kind of FDM printing graininess PLA prepared any one of claim 1 to 8 material modified technique, it is special
Levy and be, comprise the following steps：
A. raw material drying：By the dry raw material of needs such as PLA, polymer elastomer at 80~100 DEG C, dry 4~
6h, it is standby；
B. it is blended：All material is proportionally added into mixed at high speed mixer, is stirred；
C. it is molded：By mixing extrusion, extrusion in the above-mentioned mixture addition rotating Vortex mixing double screw extruder for stirring
Machine temperature control be followed successively by 165~180 DEG C, 170~185 DEG C, 175~190 DEG C, 180~195 DEG C, 185~200 DEG C, 180
~195 DEG C；Screw speed is 80~200rpm, and rate of feeding is 5~15rpm；Extruded material successively through tie rod, cooling, drying,
It is material modified that granulating working procedure is made PLA.
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