CN105419266A - 3D (three dimensional) printing material and preparation method thereof - Google Patents
3D (three dimensional) printing material and preparation method thereof Download PDFInfo
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The invention discloses a 3D (three dimensional) printing material and a preparation method thereof, and the technical problem needed to be solved is to improve the strength and toughness of a polylactic acid material. The 3D printing material disclosed by the invention is prepared from the following raw materials in percentage by mass: 45.0 to 95.0 percent of polylactic acid, 1.5 to 20.0 percent of nano flexibilizer, 1.5 to 20.0 percent of coupling agent and 2.0 to 15.0 percent of surfactant. The preparation method disclosed by the invention comprises the steps of drying the polylactic acid, pre-processing a modification reagent, blending the polylactic acid and the modification reagent, performing extrusion molding and cutting into pellets. Compared with the prior art, the nano flexibilizer can effectively improve the hardness, tensile strength, bending strength, and notch impact strength of the polylactic acid material, thus the mechanical property of the 3D material is improved, the accuracy of printed products is increased, and the preparation cost of the polylactic acid material can be greatly reduced, degradability of the polylactic acid can not be affected by calcium carbonate, the preparation method is simple in process, and is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of 3D material and preparation method thereof, particularly a kind of modified polylactic acid material for 3D printing and preparation method thereof.
Background technology
3D prints (increasing material manufacture), and method refers to based on digital model, uses the material such as metal-powder or plastic powders, by successively bonding the method printing and manufacture object.Different from conventional cast industry, 3D Method of printing without the need to design in advance and mfg. moulding die, need not subtract a large amount of material of consumption in formed product process, also need not through traditional casting technique and flow process.In material usage, save material, improve its utilization ratio.In formed product process, optimize structure, reduce the consumption of Mould design and manufacturing link, reducing the difficulty manufacturing and there is complicated shape part, creating condition for realizing appearance design inspection, fit-up inspection and rapid reaction engineering.By the successively superposition of material, 3D prints the increasing material process forming method of 3D solid material being become some two dimensional surfaces, achieves the designability of product philosophy, prints the intention product and industrial devices with multiple geometrical shape.
As a kind of manufacture based on material addition pattern, the core of 3D Method of printing is digitized intelligence manufacture.By changing the process for processing pattern of cutting starting material, assembling, achieve the production as required towards any complex construction, by the design to product, manufacture, material, form and even whole traditional manufacturing system of manufacturing enterprise produce deep effect.The digitizing being representative with 3D Method of printing, intellectuality, individual character manufacturing and service, not only likely reinvent the relation of production and service sector, also reinvents the economic means advantage of countries and regions in a sense, and then reinvent Economic development general layout.
In recent years, 3D Method of printing progressively enters Application Areas, obtains apply more and more widely in fields such as aerospace, furniture item, biologic medical, Large-Scale Equipments.Development 3D Method of printing, can produce the various personalized product with specific function, and the large batch of personalized customization of promotion is become important production model, improving product development level, accelerate the development of advanced manufacturing industry, promote industrial repositioning upgrading, form new growth engines.Development 3D Method of printing also promotes its industrialized development, to strengthening enterprise, area, the production innovation ability of country, cultivation new industry, extremely important meaning of having optimized the structure of production.
The core that 3D prints is its overturning traditional manufacturing mode.Therefore, 3D prints the material development process that the process of most critical is to be based upon in Fundamental Course of Mechanic Manufacturing.In 3D print procedure, after material melts under driven by program, be extruded or tile, being frozen into each lamella, making material recombine by such method, completing shaping.Relate to the thawing of material due to whole process and the change such as to solidify, the requirement for material is high, thus the cost of material is remained high.Therefore, the following target increasing material manufacturing industry will be: " developing the material of more type ", " material and technology is mated more ", " improve material technology precision and reduce material price " and " 3D Method of printing is applied to more wide field ".
Point out according to the up-to-date report of the portion of RnRmarketResearch.com, 3D prints primarily of polymeric film and fibrous materials such as acrylonitrile-butadiene-styrene copolymer ABS, polylactic acid PLA, nylon, the metal-powders such as titanium or titanium alloy, duralumin, cast magnesium alloys, the compositions such as aluminum oxide, silicon carbide ceramics particle.Wherein the demand of polymer materials is apparently higher than other materials, again maximum with the consumption of polylactic acid PLA material, purposes is the most extensive.Compared to metal powder material, poly(lactic acid) fusing point T
mbe 180 DEG C, second-order transition temperature T
gbe 60 DEG C, meet the contour machining procedure of material well.Material is applicable to the various working method such as blowing, thermoplastic.Poly(lactic acid) has good mechanical property and physicals, and by means of good tensile strength and ductility, poly-lactic acid products can carry out various processing, such as, melt extrude shaping, injection molding, ejection formation, blowfilm shaping, foaming and vacuum forming.Compared to traditional polymer materials, the most important performance of poly(lactic acid) is to have degradability.As a kind of new bio degradable material, poly(lactic acid) is prepared from by lactic acid ring-opening polymerization technique.In physical environment, water and carbonic acid gas can be decomposed into completely by microorganism, without the pollutant byproducts of nitrogen sulphur.In processing and burning process, also can not produce sharp aroma, can not damage human body and biology, be current optimal organic environmental-protection material.
China Patent Publication No. CN103467950A discloses a kind of 3D and prints modified polylactic acid material and preparation method thereof, for the defect of 3D printing poly-lactic acid material in shock strength, toughness and resistance toheat, proposition low temperature planetary ball mill is by linking agent, chainextender, nucleator reagent and polylactic acid blend, grafting, cross-linking modified, and shaping consumptive material is prepared in final utilization granulation, drawing process.Although this invention solves in plurality of reagents mixing process the uneven and level of response problem not completely existed, but the mechano-degradation that under also there is Strong shear, polylactic acid molecule splitting of chain causes, be unfavorable for toughness and the intensity of improving poly(lactic acid), be more not suitable for making 3D printed material.
China Patent Publication No. CN103665802A discloses a kind of preparation method of the poly-lactic acid material for 3D printing, utilize ultrasonic wave, grinding distribution method and extruding pelletization, wire drawing, achieve and nano inorganic toughner and coupling agent are carried out surface modification, and with polylactic acid blend, be polymerized, prepare 3D printing toughening modified polylactic acid material.Compared to traditional modified technique, this invention significantly improves tensile strength and the elongation at break of material, and meanwhile, the mobility of material does not occur significantly to change, and shows good processing characteristics.But tooling cost is higher, the cycle is long, is unfavorable for towards industrialization future development.
China Patent Publication No. CN104357953A discloses a kind of preparation method of toughening type PLA Composite Fiber, the feature of, poor toughness low for poly-lactic acid material intensity, adopt hydroxylation multi-walled carbon nano-tubes to carry out the method for finishing, chemical graft, make toughening type lactic acid composite material through granulation, melt-spinning technology.Although the even carbon nanotube processed is dispersed in poly(lactic acid) matrix, there is not agglomeration, art breading difficulty is large, batch output is low, preparation cost is low, significantly cannot improve output in a short time, be difficult to meet the market requirement that 3D prints consumption.
At present, domestic existence has paper about poly(lactic acid) production, spinning, film forming and patent in a large number.Part is test-manufactured, but is present in the poly(lactic acid) in market and limits due to the factor of its intensity, toughness, still can not as the consumptive material of large-scale 3D printing device.
Summary of the invention
The object of this invention is to provide a kind of 3D printed material and preparation method thereof, the technical problem that solve improves intensity and the toughness of poly-lactic acid material, meets the demand of technical grade 3D printing consumables, reduce costs.
The present invention is by the following technical solutions: a kind of 3D printed material, is made up of the raw material of following mass percent: poly(lactic acid) 45.0 ~ 95.0%, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%.
Poly(lactic acid) of the present invention is Poly-L-lactic acid PLLA, dextrorotation poly(lactic acid) PDLA or vertical structure poly(lactic acid) PDLLA, and weight-average molecular weight is 8 ~ 200,000.
Nanometer toughner of the present invention is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders.
Coupling agent of the present invention is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate.
Tensio-active agent of the present invention is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
A preparation method for 3D printed material, comprises the following steps:
One, by mass percentage, poly(lactic acid) 45.0 ~ 95.0% is taken, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%;
Poly(lactic acid) is 40 ~ 100 DEG C at drying temperature by two, dry poly(lactic acid), and dry 1 ~ 50h, obtains dried poly(lactic acid);
Three, pretreatment modification reagent, by tensio-active agent and nanometer toughner under rotating speed is 4000 ~ 20000rpm condition, with the heat-up rate of 2 ~ 10 DEG C, from room temperature to 145 ~ 165 DEG C, insulation 5 ~ 30min, Temperature fall to 25 ~ 80 DEG C, obtain the blended reagent of modification;
Four, blended poly(lactic acid) and modifying agent, by dried poly(lactic acid), the blended reagent of modification and coupling agent under rotating speed is 300 ~ 7000rpm condition, with the heat-up rate of 0.5 ~ 5 DEG C/min, from room temperature to 180 ~ 250 DEG C, insulation 0.1 ~ 2.0h, Temperature fall to 25 ~ 80 DEG C, obtain blended product;
Five, extrusion moulding and be cut into material grain, the time that blended product extrudes stop is 3 ~ 15min, extrusion temperature section temperature is followed successively by: 170 ~ 175 DEG C, 175 ~ 180 DEG C, 180 ~ 190 DEG C, 185 ~ 195 DEG C, 180 ~ 185 DEG C, die head temperature is 195 ~ 205 DEG C, cooling temperature is followed successively by 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C and 20 DEG C, being cut into diameter is 1.75mm, and length is the thin short silk of 3.00mm, obtains 3D printed material.
Method poly(lactic acid) of the present invention is Poly-L-lactic acid PLLA, dextrorotation poly(lactic acid) PDLA or vertical structure poly(lactic acid) PDLLA, and weight-average molecular weight is 8 ~ 200,000; Described nanometer toughner is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders; Described coupling agent is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate; Described tensio-active agent is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
Step 2 of the present invention dried poly(lactic acid) biodiversity content is not higher than 0.05%.
The dry poly(lactic acid) of method steps two of the present invention, puts into drying machine inner drying by poly(lactic acid); Described step 3 pretreatment modification reagent and the blended poly(lactic acid) of step 4 and modifying agent, adopt the high-speed mixer of JB200; Described step 5 extrusion moulding be cut into material grain, adopt SHJ-36 equidirectional parallel double-screw extruder, screw diameter is 45 ~ 75mm, and length-to-diameter ratio is 15 ~ 40:1, and compression ratio is 1 ~ 5:1.
After method steps five of the present invention cools, do dry and waterproof and dampproof process.
3D printed material quality moisture content≤0.05% after the dry and waterproof of method of the present invention.
The present invention compared with prior art, nanometer toughner can significantly improve hardness, tensile strength, flexural strength, the notched Izod impact strength of poly-lactic acid material, thus improve the mechanical property of 3D material, improve the precision of printed product, nanometer toughner is as modifying agent, the preparation cost of poly-lactic acid material can also be reduced significantly, calcium carbonate can not bring pollution to environment, also the degradability of poly(lactic acid) can not be affected, preparation method's technique is simple, and raw material is easy to get, with short production cycle, efficiency is high, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.3D printed material of the present invention, is made up of the raw material of following mass percent: poly(lactic acid) 45.0 ~ 95.0%, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%.
Poly(lactic acid) is Poly-L-lactic acid PLLA, dextrorotation poly(lactic acid) PDLA or vertical structure poly(lactic acid) PDLLA, and its weight-average molecular weight is 8 ~ 200,000.
Nanometer toughner is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders.
Coupling agent is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate.
Tensio-active agent is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
The preparation method of 3D printed material of the present invention, comprises the following steps:
One, by mass percentage, poly(lactic acid) 45.0 ~ 95.0% is taken, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%.
Poly(lactic acid) is Poly-L-lactic acid PLLA, dextrorotation poly(lactic acid) PDLA or vertical structure poly(lactic acid) PDLLA, and its weight-average molecular weight is 8 ~ 200,000.Poly-L-lactic acid PLLA, dextrorotation poly(lactic acid) PDLA and vertical structure poly(lactic acid) PDLLA are respectively by L ~ rac-Lactide, D ~ rac-Lactide and D, L ~ lactide isomer ring-opening polymerization prepares, L ~ rac-Lactide, D ~ rac-Lactide and D, L ~ rac-Lactide crystallinity is different, the regularity of molecular chain and the change of canoe can be caused, affect the fusing point of synthetic materials poly(lactic acid), intensity, toughness.
Nanometer toughner is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders.
Coupling agent is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate.
Tensio-active agent is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
Poly(lactic acid) in 3D printed material as skeleton and body material.The regularity acting as reduction polylactic acid molecule chain of nanometer toughner.The foot that act as of coupling agent makes polylactic acid molecule and nanometer toughner carry out chemical reaction.Tensio-active agent act as the consistency improving poly(lactic acid) and nanometer toughner, coupling agent.Nanometer toughner is inorganic particulate, and active tie point rare with polylactic acid molecule chain, adds coupling agent and tensio-active agent, improve the consistency of poly(lactic acid) and nanometer toughner.
Two, dry poly(lactic acid), puts into drying machine and carries out drying by poly(lactic acid), drying temperature is 40 ~ 100 DEG C, and time of drying is 1 ~ 50h, is controlled by poly(lactic acid) biodiversity content, not higher than 0.05%, to obtain dried poly(lactic acid).
Containing carboxyl, hydroxyls dehydrate group in polylactic acid molecule chain, easy and water molecules generation hydrolytic side reactions in the course of processing.Close to second-order transition temperature T
gtime, moisture content is directly proportional to molecular chain depolymerization behavior.Moisture all can produce considerable influence to polylactic acid molecule amount, mechanical property, thermal stability.Too high water content is unfavorable for the stable of machine-shaping and mechanical property.
Three, pretreatment modification reagent, tensio-active agent and nanometer toughner are placed in the high-speed mixer that model is JB200, under rotating speed is 4000 ~ 20000rpm condition, with the heat-up rate of 2 ~ 10 DEG C, be warming up to 145 ~ 165 DEG C from room temperature (20 DEG C), insulation 5 ~ 30min, keep rotating speed constant, Temperature fall to 25 ~ 80 DEG C, obtain the blended reagent of modification.
It is more even that pre-treatment makes modifying agent mix, active group in surfactant structure is exposed, simultaneously the nanoparticle of nanometer toughner and the living chain of tensio-active agent are able to island structure and exist, and add the stability of nanometer toughner in polylactic acid blend material system.
Four, blended poly(lactic acid) and modifying agent, it is in the high-speed mixer of JB200 that dried poly(lactic acid), the blended reagent of modification and coupling agent are joined model successively, under rotating speed is 300 ~ 7000rpm condition, with the heat-up rate of 0.5 ~ 5 DEG C/min, from room temperature to 180 ~ 250 DEG C, insulation 0.1 ~ 2.0h, keeps rotating speed constant, Temperature fall to 25 ~ 80 DEG C, obtain blended product.
Blendedly make nanometer toughner, coupling agent and polylactic acid blend, produce the molten state of poly(lactic acid), make modifying agent nanometer toughner and coupling agent be embedded in poly(lactic acid) structure, the segment distribution characteristics of change polylactic acid molecule chain.
In blended product, coupling agent can improve the interface performance of poly(lactic acid) and nanometer toughner, improves dispersity and the processing characteristics of nanometer toughner.Meanwhile, nanometer toughner particle causes poly(lactic acid) matrix crazingization to absorb energy, thus improves the toughening effect of 3D material.
Five, extrusion moulding and be cut into material grain, adopts SHJ-36 equidirectional parallel double-screw extruder to carry out extruding pelletization.The time that blended product stops in an extruder is 3 ~ 15min, and being cut into diameter is 1.75mm, and length is the thin short silk of 3.00mm.Concrete technology requires: extruder screw diameter is 45 ~ 75mm, length-to-diameter ratio is 15 ~ 40:1, compression ratio is 1 ~ 5:1, forcing machine extrusion temperature section temperature is set as successively: 170 ~ 175 DEG C, 175 ~ 180 DEG C, 180 ~ 190 DEG C, 185 ~ 195 DEG C, 180 ~ 185 DEG C, and die head temperature is 195 ~ 205 DEG C.In order to the diameter error of conservative control processing filament, adopt the mode of sub-sectional cooling after die head, cooling temperature is followed successively by 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C and 20 DEG C, a temperature section cooling after moving to from last temperature section, to the temperature of a rear temperature section, then move the cooling of next temperature section.Then the wire rod extruded is cut into pellet, does dry and waterproof and dampproof process, quality moisture content≤0.05% after drying and waterproof, packs, obtains 3D printed material.
The present invention adopts the method for modifying of physical blending, is mixed by the nano inorganic toughner through surface preparation, be issued to homodisperse effect in Action of Surfactant with dried poly(lactic acid).On the basis of prior art polydactyl acid method, by the addition of optimized choice modifying agent, improve the intensity of material, toughness and elongation at break physicals.
The 3D printed material that the inventive method prepares, carry out mechanical property and processing characteristics test, the penetration hardness (shore hardness) of sclerometer test 3D printed material is used by GB/T2411-2008 plastics and vulcanite, tensile property and the elongation at break of 3D printed material is tested by GB/T1040.1-2006 plastic tensile performance and elongation at tear tests method, by the flexural strength of GB/T9341-2008 plastics flexural strength testing method test 3D printed material, by the cantilever beam impact strength of the test 3D printed material of GB/T1843-2008 plastics cantilever beam impact strength, by the bending load heat-drawn wire of GB/T1634-1979 plastics bending load heat-drawn wire measurement of test method 3D printed material, by GB3682-83 plastic melt flow rate MFR, MVR tests the melt flow rate (MFR) of 3D printed material.
The DSC1 type differential scanning calorimeter of Mei Tele company of Switzerland is adopted to measure the fusing point of 3D printed material.First, in chamber, pass into nitrogen protection, control pressure is 0.1MPa, and opens refrigerator power supply; Meanwhile, according to system suggestion, after stove lid is opened, the blank crucible made is placed on inside stove, then load weighted 3D printed material sample crucible is put in outside; Build bell, arranging temperature rise rate is 0.5 DEG C/min, starts test.End to be tested, reads out fusing point.
Embodiment 1
One, take the Poly-L-lactic acid PLLA that 12.6Kg weight-average molecular weight is 8.0 ten thousand, mass percent is 45.0%; 5.6Kg polynite, mass percent is 20.0%; The stearic ester group isopropyl titanate of 5.6Kg tri-, mass percent is 20.0%; 4.2Kg calcium stearate, mass percent is 15.0%.
Two, dry poly(lactic acid), is placed on Poly-L-lactic acid in drying machine, and dry 1h at 40 DEG C, obtains dried Poly-L-lactic acid.
Three, calcium stearate and polynite are put into the high-speed mixer of JB200, rotating speed is 4000rpm, with the heat-up rate of 2 DEG C/min from room temperature to 145 DEG C, is incubated 5min, and keep rotating speed constant, Temperature fall to 25 DEG C, obtains the blended reagent of modification.
Four, dried Poly-L-lactic acid, the blended reagent of modification and three stearic ester group isopropyl titanates are put into high-speed mixer successively, rotating speed is 300rpm, with the heat-up rate of 0.5 DEG C/min from room temperature to 180 DEG C, insulation 0.1h, keep rotating speed constant, Temperature fall to 25 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 45mm, the length-to-diameter ratio of forcing machine is 15:1, compression ratio is 1:1, it is 3min that blended product extrudes the residence time in an extruder, each section of temperature of forcing machine is respectively 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, die head temperature is 195 DEG C, shaping rear cooling, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 1 prepared is made batten.According to the testing standard of GB/T1040-2006 plastic tensile batten, use cutting or method for die cutting, prepare the rectangular sample that width is 10.0 ± 0.2mm, length is not less than 150mm, thickness is 4.0 ± 0.2mm, should have the sample being spaced apart 50mm two parallel lines in the middle part of sample, length 80 ± 2mm, width 10.0 ± 0.2mm, thickness are the rectangle batten of 4.0 ± 0.2mm.Adopt the stamping knife after polishing, ensure sample the smooth of the edge non-notch.Carry out mechanical property and processing characteristics test.Test result is: hardness (SD) 92, tensile strength 43.3MPa, notched Izod impact strength 8.1kJ/m
2, flexural strength 99.4MPa, elongation at break 260%.Be 0.03% through the dried moisture content of step 2, the modification of this index to material has a direct impact, the too high meeting Partial digestion in the course of processing of material moisture also reduces bulk strength, the heat-drawn wire of polydactyl acid is 92 DEG C, fusing point is 185 DEG C, and melt flow index is 4.9g/min.As shown in Table 1 and Table 2.
Embodiment 2
One, take the Poly-L-lactic acid PLLA that 19.6Kg weight-average molecular weight is 8.0 ten thousand, mass percent is 70.0%; 3.08Kg talcum powder, mass percent is 11.0%; 3.08Kg hydramine lipid acid titanic acid ester, mass percent is 11.0%; 2.24Kg amino acid calcium, mass percent is 8.0%.
Two, dry poly(lactic acid), is placed on Poly-L-lactic acid in drying machine, and dry 25h at 100 DEG C, obtains dried Poly-L-lactic acid.
Three, amino acid calcium and talcum powder are put into the high-speed mixer of JB200, rotating speed is 12000rpm, with the heat-up rate of 2 DEG C/min from room temperature to 145 DEG C, is incubated 30min, and keep rotating speed constant, Temperature fall to 80 DEG C, obtains the blended reagent of modification.
Four, dried Poly-L-lactic acid, the blended reagent of modification and hydramine lipid acid titanic acid ester are put into high-speed mixer successively, rotating speed is 3650rpm, with the heat-up rate of 0.5 DEG C/min from room temperature to 180 DEG C, insulation 2.0h, keep rotating speed constant, Temperature fall to 80 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 75mm, the length-to-diameter ratio of forcing machine is 40:1, compression ratio is 5:1, the residence time is 15min to blended product in an extruder, each section of temperature of forcing machine is respectively 175 DEG C, 180 DEG C, 190 DEG C, 195 DEG C, 185 DEG C, die head temperature is 205 DEG C, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 2 prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Test result is: hardness (SD) 110, tensile strength 47.8MPa, notched Izod impact strength 18.4kJ/m
2, flexural strength 112.3MPa, elongation at break 200%.Be 0.03% through the dried moisture content of step 2, the heat-drawn wire of polydactyl acid is 86 DEG C, and fusing point is 193 DEG C, and melt flow index is 5.2g/min.As shown in Table 1 and Table 2.
Embodiment 3
One, take the vertical structure poly(lactic acid) PDLLA that 26.6Kg weight-average molecular weight is 20.0 ten thousand, mass percent is 95.0%; 0.42Kg calcium carbonate, mass percent is 1.5%; 0.42Kg isopropyl tri (dioctylphosphato)titanate, mass percent is 1.5%; 0.56Kg calcium stearate, mass percent is 2.0%.
Two, dry poly(lactic acid), is placed in drying machine by vertical structure poly(lactic acid), and dry 25h at 70 DEG C, obtains dried Poly-L-lactic acid.
Three, calcium stearate and calcium carbonate are put into the high-speed mixer of JB200, rotating speed is 12000rpm, with the heat-up rate of 10 DEG C/min from room temperature to 155 DEG C, is incubated 18min, and keep rotating speed constant, Temperature fall to 25 DEG C, obtains the blended reagent of modification.
Four, dried vertical structure poly(lactic acid), the blended reagent of modification and isopropyl tri (dioctylphosphato)titanate are put into high-speed mixer successively, rotating speed is 3650rpm, with the heat-up rate of 5 DEG C/min from room temperature to 250 DEG C, insulation 0.1h, keep rotating speed constant, Temperature fall to 25 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 60mm, the length-to-diameter ratio of forcing machine is 25:1, compression ratio is 1:1, the residence time is 10min to blended product in an extruder, each section of temperature of forcing machine is respectively 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, die head temperature is 205 DEG C, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 3 prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Test result is: hardness (SD) 103, tensile strength 45.6MPa, notched Izod impact strength 15.8kJ/m
2, flexural strength 109.9MPa, elongation at break 230%.Be 0.02% through the dried moisture content of step 2, the heat-drawn wire of polydactyl acid is 109 DEG C, and fusing point is 238 DEG C, and melt flow index is 5.4g/min.As shown in Table 1 and Table 2.
Embodiment 4
One, take the vertical structure poly(lactic acid) PDLLA that 12.6Kg weight-average molecular weight is 20.0 ten thousand, mass percent is 45.0%; 5.6Kg calcium carbonate, mass percent is 20.0%; 5.6Kg hydramine lipid acid titanic acid ester, mass percent is 20.0%; 4.2Kg calcium dodecylbenzene sulphonate, mass percent is 15.0%.
Two, dry poly(lactic acid), is placed in drying machine by vertical structure poly(lactic acid), and dry 50h at 100 DEG C, obtains dried Poly-L-lactic acid.
Three, calcium dodecylbenzene sulphonate and calcium carbonate are put into the high-speed mixer of JB200, rotating speed is 20000rpm, with the heat-up rate of 10 DEG C/min from room temperature to 155 DEG C, insulation 18min, keep rotating speed constant, Temperature fall to 80 DEG C, obtains the blended reagent of modification.
Four, dried vertical structure poly(lactic acid), the blended reagent of modification and hydramine lipid acid titanic acid ester are put into high-speed mixer successively, rotating speed is 7000rpm, with the heat-up rate of 5 DEG C/min from room temperature to 250 DEG C, insulation 2.0h, keep rotating speed constant, Temperature fall to 80 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 60mm, the length-to-diameter ratio of forcing machine is 25:1, compression ratio is 5:1, the residence time is 10min to blended product in an extruder, each section of temperature of forcing machine is respectively 175 DEG C, 180 DEG C, 190 DEG C, 195 DEG C, 185 DEG C, die head temperature is 195 DEG C, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 4 prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Test result is: hardness (SD) 99, tensile strength 44.9MPa, notched Izod impact strength 12.5kJ/m
2, flexural strength 107.7MPa, elongation at break 240%.Be 0.02% through the dried moisture content of step 2, the heat-drawn wire of polydactyl acid is 97 DEG C, and fusing point is 190 DEG C, and melt flow index is 5.0g/min.As shown in Table 1 and Table 2.
Embodiment 5
One, take the dextrorotation poly(lactic acid) PDLA that 19.6Kg weight-average molecular weight is 15.0 ten thousand, mass percent is 70.0%; 3.08Kg calcium carbonate, mass percent is 11.0%; 3.08Kg three stearic ester group isopropyl titanates, mass percent is 11.0%; 2.24Kg calcium dodecylbenzene sulphonate, mass percent is 8.0%.
Two, dry poly(lactic acid), is placed on Poly-L-lactic acid in drying machine, and dry 1h at 40 DEG C, obtains dried Poly-L-lactic acid.
Three, calcium dodecylbenzene sulphonate and calcium carbonate are put into the high-speed mixer of JB200, rotating speed is 4000rpm, with the heat-up rate of 6 DEG C/min from room temperature to 165 DEG C, insulation 5min, keep rotating speed constant, Temperature fall to 55 DEG C, obtains the blended reagent of modification.
Four, dried Poly-L-lactic acid, the blended reagent of modification and three stearic ester group isopropyl titanates are put into high-speed mixer successively, rotating speed is 300rpm, with the heat-up rate of 3 DEG C/min from room temperature to 210 DEG C, insulation 1.0h, keep rotating speed constant, Temperature fall to 55 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 45mm, the length-to-diameter ratio of forcing machine is 15:1, compression ratio is 3:1, the residence time is 3min to blended product in an extruder, each section of temperature of forcing machine is respectively 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, die head temperature is 195 DEG C, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 5 prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Test result is: hardness (SD) 106, tensile strength 47.0MPa, notched Izod impact strength 17.2kJ/m
2, flexural strength 111.2MPa, elongation at break 220%.Be 0.02% through the dried moisture content of step 2, the heat-drawn wire of polydactyl acid is 102 DEG C, and fusing point is 235 DEG C, and melt flow index is 5.2g/min.As shown in Table 1 and Table 2.
Embodiment 6
One, take the vertical structure poly(lactic acid) (PDLLA) that 26.6Kg weight-average molecular weight is 15.0 ten thousand, mass percent is 95.0%; 0.42Kg polynite, mass percent is 1.5%; 0.42Kg isopropyl tri (dioctylphosphato)titanate, mass percent is 1.5%; 0.56Kg calcium dodecylbenzene sulphonate, mass percent is 2.0%.
Two, dry poly(lactic acid), is placed on Poly-L-lactic acid in drying machine, and dry 50h at 70 DEG C, obtains dried Poly-L-lactic acid.
Three, calcium dodecylbenzene sulphonate and polynite are put into the high-speed mixer of JB200, rotating speed is 20000rpm, with the heat-up rate of 6 DEG C/min from room temperature to 165 DEG C, insulation 30min, keep rotating speed constant, Temperature fall to 55 DEG C, obtains the blended reagent of modification.
Four, dried vertical structure poly(lactic acid), the blended reagent of modification and isopropyl tri (dioctylphosphato)titanate are put into high-speed mixer successively, rotating speed is 7000rpm, with the heat-up rate of 3 DEG C/min from room temperature to 210 DEG C, insulation 1.0h, keep rotating speed constant, Temperature fall to 55 DEG C, obtains blended product.
Five, blended product being joined screw diameter is in the hopper of the twin screw extruder of 60mm, the length-to-diameter ratio of forcing machine is 25:1, compression ratio is 3:1, the residence time is 10min to blended product in an extruder, each section of temperature of forcing machine is respectively 175 DEG C, 180 DEG C, 190 DEG C, 195 DEG C, 185 DEG C, die head temperature is 205 DEG C, and cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in, obtains 3D printed material.
3D printed material embodiment 6 prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Hardness (SD) 100, tensile strength 43.9MPa, notched Izod impact strength 13.6kJ/m
2, flexural strength 104.6MPa, elongation at break 220%.Be 0.03% through the dried moisture content of step 2, the heat-drawn wire of polydactyl acid is 94 DEG C, and fusing point is 230 DEG C, and melt flow index is 5.3g/min.As shown in Table 1 and Table 2.
Comparative example
Weigh the Poly-L-lactic acid PLLA that 20.0Kg weight-average molecular weight is 20.0 ten thousand, be placed in drying machine and carry out drying first, dry 50h at 100 DEG C.Dry thing is placed in high-speed mixer, and control rotating speed is 7000rpm, and with the ramp to 180 DEG C of 0.5 DEG C/min, insulation 2.0h, keeps rotating speed constant, Temperature fall to 25 DEG C.Material being joined screw diameter is extrusion moulding in the hopper of the twin screw extruder of 60mm, the length-to-diameter ratio of forcing machine is 25:1, compression ratio is 5:1, material residence time in whole forcing machine is 10min, each section of temperature of forcing machine is respectively 175 DEG C, 180 DEG C, 190 DEG C, 195 DEG C, 185 DEG C, and die head temperature is 195 DEG C.Processing cooling temperature is set as successively: 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C, 20 DEG C.The raw material extruded is cut to material grain, again joins drying in drying machine and to dewater dehumidifying, packaging warehouse-in.
Material grain comparative example prepared is made batten by the method for embodiment 1, carries out mechanical property and processing characteristics test.Hardness (SD) 88, tensile strength 40.3MPa, notched Izod impact strength 3.0kJ/m
2, flexural strength 93.9MPa, elongation at break 290%.Dried moisture content is 0.04% first, and the heat-drawn wire of polydactyl acid is 59 DEG C, and fusing point is 180 DEG C, and melt flow index is 5.6g/min.As shown in Table 1 and Table 2.
Table 1. embodiment 1 ~ 6 and comparative example quantitative measurement result
Table 2. embodiment 1 ~ 6 and comparative example processing characteristics test result
Learnt with comparing of comparative example by embodiment 1-6:
(1) from detected result, nanometer toughner can significantly improve hardness, tensile strength, flexural strength, the notched Izod impact strength of poly-lactic acid material, thus improves the mechanical property of 3D printed material.From the service condition of 3D printed material, nanometer toughner reduces the mobility of material, thus improves the precision of printed product.
(2) use toughner as modifying agent, the preparation cost of poly-lactic acid material can be reduced significantly, be convenient to promote to intention product and industrial circle, promote profit margin.Calcium carbonate can not cause environmental problem, also can not affect the degradability of poly(lactic acid), ensure that the environment friendly of 3D printed material.
(3) method of the present invention is simple, and raw material is easy to get, with short production cycle, and efficiency is high, is applicable to suitability for industrialized production.
Claims (10)
1. a 3D printed material, is characterized in that: described 3D printed material is made up of the raw material of following mass percent: poly(lactic acid) 45.0 ~ 95.0%, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%.
2. 3D printed material according to claim 1, is characterized in that: described poly(lactic acid) is Poly-L-lactic acid (PLLA), dextrorotation poly(lactic acid) (PDLA) or vertical structure poly(lactic acid) (PDLLA), and weight-average molecular weight is 8 ~ 200,000.
3. 3D printed material according to claim 1, is characterized in that: described nanometer toughner is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders.
4. 3D printed material according to claim 1, is characterized in that: described coupling agent is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate.
5. 3D printed material according to claim 1, is characterized in that: described tensio-active agent is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
6. a preparation method for 3D printed material, comprises the following steps:
One, by mass percentage, poly(lactic acid) 45.0 ~ 95.0% is taken, nanometer toughner 1.5 ~ 20.0%, coupling agent 1.5 ~ 20.0%, tensio-active agent 2.0 ~ 15.0%;
Poly(lactic acid) is 40 ~ 100 DEG C at drying temperature by two, dry poly(lactic acid), and dry 1 ~ 50h, obtains dried poly(lactic acid);
Three, pretreatment modification reagent, by tensio-active agent and nanometer toughner under rotating speed is 4000 ~ 20000rpm condition, with the heat-up rate of 2 ~ 10 DEG C, from room temperature to 145 ~ 165 DEG C, insulation 5 ~ 30min, Temperature fall to 25 ~ 80 DEG C, obtain the blended reagent of modification;
Four, blended poly(lactic acid) and modifying agent, by dried poly(lactic acid), the blended reagent of modification and coupling agent under rotating speed is 300 ~ 7000rpm condition, with the heat-up rate of 0.5 ~ 5 DEG C/min, from room temperature to 180 ~ 250 DEG C, insulation 0.1 ~ 2.0h, Temperature fall to 25 ~ 80 DEG C, obtain blended product;
Five, extrusion moulding and be cut into material grain, the time that blended product extrudes stop is 3 ~ 15min, extrusion temperature section temperature is followed successively by: 170 ~ 175 DEG C, 175 ~ 180 DEG C, 180 ~ 190 DEG C, 185 ~ 195 DEG C, 180 ~ 185 DEG C, die head temperature is 195 ~ 205 DEG C, cooling temperature is followed successively by 110 DEG C, 90 DEG C, 70 DEG C, 50 DEG C, 35 DEG C and 20 DEG C, being cut into diameter is 1.75mm, and length is the thin short silk of 3.00mm, obtains 3D printed material.
7. the preparation method of 3D printed material according to claim 6, it is characterized in that: described poly(lactic acid) is Poly-L-lactic acid (PLLA), dextrorotation poly(lactic acid) (PDLA) or vertical structure poly(lactic acid) (PDLLA), and weight-average molecular weight is 8 ~ 200,000; Described nanometer toughner is polynite, calcium carbonate, talcum powder, hydrotalcite particle, brucite fiber or calcium carbonate crystal whisker, and purity is not less than 98%, and granularity is 600 ~ 1500 orders; Described coupling agent is the stearic ester group isopropyl titanate of titanate ester three, hydramine lipid acid titanic acid ester or isopropyl tri (dioctylphosphato)titanate; Described tensio-active agent is amino acid calcium, calcium stearate or calcium dodecylbenzene sulphonate.
8. the preparation method of 3D printed material according to claim 6, is characterized in that: described step 2 dried poly(lactic acid) biodiversity content is not higher than 0.05%.
9. the preparation method of 3D printed material according to claim 6, is characterized in that: the dry poly(lactic acid) of described step 2, poly(lactic acid) is put into drying machine inner drying; Described step 3 pretreatment modification reagent and the blended poly(lactic acid) of step 4 and modifying agent, adopt the high-speed mixer of JB200; Described step 5 extrusion moulding be cut into material grain, adopt SHJ-36 equidirectional parallel double-screw extruder, screw diameter is 45 ~ 75mm, and length-to-diameter ratio is 15 ~ 40:1, and compression ratio is 1 ~ 5:1.
10. the preparation method of 3D printed material according to claim 6, is characterized in that: after described step 5 cooling, do dry and waterproof and dampproof process; 3D printed material quality moisture content≤0.05% after described drying and waterproof.
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Application publication date: 20160323 |