CN105585720A - Polylactic resin powder for selective laser sintering and a preparation method thereof - Google Patents
Polylactic resin powder for selective laser sintering and a preparation method thereof Download PDFInfo
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- CN105585720A CN105585720A CN201410577740.1A CN201410577740A CN105585720A CN 105585720 A CN105585720 A CN 105585720A CN 201410577740 A CN201410577740 A CN 201410577740A CN 105585720 A CN105585720 A CN 105585720A
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- polylactic resin
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Abstract
The invention provides a preparation method of a polylactic resin powder for selective laser sintering. The preparation method includes the following steps: a) at a heating temperature, dissolving polylactic resin in an organic solvent composed of at least one of acetone, butanone, 2-pentanone, 3-pentanone, cyclopentanone, methyl isopropyl ketone, tetrahydrofuran and dioxane to obtain a polylactic resin solution; and b) decreasing the temperature of the polylactic resin solution to separate out a solid precipitate. In the method, a proper solvent is firstly selected, and then proper temperature increasing and decreasing methods are designed at certain temperature and under certain pressure, thereby preparing the polylactic resin powder raw material which is very suitable for the selective laser sintering in shape, characters and the like. The method is free of other additives and can be used for producing the polylactic resin powder, which is moderate in size, has a smooth surface, is good in dispersibility, is small in particle size distribution and has proper bulk density, for the selective laser sintering.
Description
Technical field
The present invention relates to technical field of polymer processing, say further, relate to one and be applicable to selective laserThe method of the polylactic resin powder of sintering.
Background technology
Selective laser sintering (SelectiveLaserSintering, SLS) technology is a kind of rapid shaping technique, isThe technology that increases at present most widely used general and tool market prospects in material manufacturing technology, presents fast development in recent yearsTrend. SLS technology is first 3D solid to be scanned by computer, then shines by high intensity laser beamPenetrate optionally molten sintering layer by layer of the material powder spread in advance on workbench or parts,And then realize the technology of successively moulding. SLS technology has the design flexibility of height, can produce accurate mouldType and prototype, can moulding have the parts that can directly use of reliable structure, and with short production cycle,Technique is simple, is therefore particularly suitable for the exploitation of new product.
The moulding material kind that can be used in SLS technology is comparatively extensive, comprises macromolecule, paraffin, metal, potteryPorcelain and their composite. But the performance of moulding material, proterties are again that SLS technology sintering is successfulA key factor, it also directly affects shaping speed, the precision of profiled member, and physics, chemical property andIts combination property. Although applicable moulding material is of a great variety, can directly apply at present SLS technologyAnd the polymer powder powder stock that successfully produces the moulded work that scale error is little, surface is regular, porosity is low is freshFew. In prior art, conventionally adopt comminuting method, prepare the powder stock that SLS uses as deep cooling crush method, thisNot only need particular device, the powder stock particle surface for preparing is more coarse, particle diameter not evenly, shapeIrregular, be unfavorable for the formation of sintered moulded body, and affect the performance of formed body. Be applicable in the market SLSThe polymer powder scarcity of raw material of technology, therefore the corresponding pressed powder raw material of various type of polymer is urgently openedSend out.
PLA (PLA) is a kind of biodegradable resin material, has good mechanical performance, hotEnergy and optical property, therefore develop the PLA pressed powder with biocompatibility for SLS, can meet individual characterThe demand of the bio-medical carrier material application of changing.
Summary of the invention
For defect and the deficiency of prior art, the invention provides a kind of the poly-of selective laser sintering that be applicable toLactic acid toner with and preparation method thereof. There is suitable chi according to polylactic resin powder provided by the inventionVery little size, suitable bulk density, well-balanced particle profile and particle diameter are evenly distributed, powder flowbility is good, thisThe inventor of invention finds that such polylactic resin powder is particularly useful for selective laser sintering and prepares respectivelyPlant moulded work.
According to the present invention, first provide a kind of preparation of the polylactic resin powder for selective laser sinteringMethod, said method comprising the steps of: a) under heating-up temperature, by polylactic resin be dissolved in by acetone,In butanone, 2 pentanone, propione, cyclopentanone, methyl isopropyl ketone, oxolane and dioxane extremelyIn the organic solvent of few a kind of formation, obtain polylactic resin solution; B) PLA tree step a) being obtainedLipoprotein solution cooling, separates out solids of sedimentation.
In a preferred embodiment, described organic solvent is preferably acetone and/or butanone.
Although organic solvent deposit technology has been used to separate and purification biochemical substances, especially protein, orPerson is used for separating out and prepares crystal. But, at present about adopting organic solvent precipitation method for the preparation of selective laserThe report of the resin material powder of sintering technology is also little. Especially not yet there is report to select for the preparation of being applicable toThe laser sintered polylactic resin powder of property. For organic solvent deposit technology, being selected from of solvent species is most important.For specific macromolecular material polylactic resin, the present inventor is by constantly attempting and exploration is groundStudy carefully, find to use organic solvent as above, especially acetone and/or butanone as organic solvent dissolution and fallWhen temperature precipitation polylactic resin, can advantageously obtain the PLA powder stock that is suitable for selective laser sintering.
According to the present invention, preferably step a) in, taking polylactic resin as 100 parts by weight, described in haveMachine solvent is 600～1200 parts by weight, is preferably 800～1000 parts by weight.
The present inventor further finds by a large amount of experimental exploring, organic molten as mentioned above when usingAgent, for example acetone be during as the solvent of polylactic resin, can make polylactic resin with spherical and/or class is sphericalProterties is separated out, and has the particle diameter of 20～125 μ m, and surface is round and smooth, good dispersion, and distribution of sizes is little, spyBe not applicable to Selective Laser Sintering.
The consumption of organic solvent is in aforementioned range time, can obtain pattern, dispersed polylactic resin preferablyPowder.
In a preferred embodiment of the invention, step a) in, described temperature is 120～160 DEG C, preferablyIt is 130～140 DEG C. Preferably, step a) heats under inert gas, for example nitrogen atmosphere. PreferablyGround, step b) is carried out under self-generated pressure.
Preferably, step a) in, by polylactic resin solution heating-up temperature keep 30～90 minutes.
The method according to this invention, preferred steps average rate of temperature fall b) is 0.1 DEG C/min～1 DEG C/min.
Preferably, step b) in, polylactic resin solution is cooled to cooling target temperature, and coolingTarget temperature keeps 30～90 minutes; Described cooling target temperature is preferably 10～30 DEG C, for example room temperature.
In method provided by the invention, the temperature-fall period of polylactic resin solution can at the uniform velocity be lowered the temperature, and also canInterim cooling. The present inventor is through a large amount of experimental exploring, finds that preferred more of the present inventionIn embodiment, step b) in, polylactic resin solution is cooled to one or more medium temperatures, andKeep 30～90 minutes in described medium temperature; Described medium temperature is preferably 80～110 DEG C, is preferably 90～100DEG C. Easily understand, described medium temperature refers to step heating-up temperature and step cooling target temperature b) a)Between temperature. Further, in the time that medium temperature is for example any one temperature in 80～110 DEG C, stepA) temperature in should be greater than this medium temperature. For example,, in a specific embodiment, by polylactic resinWhen solution is down to 100 DEG C from 130 DEG C of heating-up temperatures, keep temperature 60 minutes at 100 DEG C; Or be directly down toRoom temperature. In other preferred embodiments, in the time that polylactic resin solution is down to 90～100 DEG C from heating-up temperature,Be incubated 30～90 minutes, can obtain and separate out preferably effect.
By the heating cooling method of invention, can ensure to obtain the powder particle that particle diameter is evenly distributed, thereby specialBe not suitable for selective laser sintering application.
According to the present invention, preferably optical purity >=92% of polylactic resin. Select such polylactic resin,Obtain better selective laser sintering effect and sintered products.
The present invention also provides the PLA for selective laser sintering preparing according to above method treeCosmetics end, the particle of described powder is spherical and/or class is spherical, and the particle size of particle is 20～125 μ m, grainDistribution D10=26～46, footpath μ m, D50=50～67 μ m, D90=80～110 μ m. Be somebody's turn to do according to provided by the inventionPolylactic resin powder is particularly useful for Selective Laser Sintering, sinters power into high, and the sintering obtaining producesProduct and predetermined prod scale error are little, and section cavity is few.
In addition, the present invention further provides a kind of selective laser sintering method, described method comprises by as aboveDescribed method is prepared polylactic resin powder, using as sintered powder raw material. By this choosing provided by the inventionSelecting property laser sintering processes, can prepare there is regular profile, surface well-balanced smooth, satisfactory mechanical propertyPLA moulded work.
The preparation method of the polylactic resin powder for selective laser sintering provided by the invention, operating procedureSimply, easy operating, by selecting suitable solvent, be chosen under specific temperature and pressure, it is suitable to designIntensification and cooling method, thereby obtain form, proterties etc. and be particularly suitable for the PLA of selective laser sinteringToner raw material. In addition, another outstanding advantage of the present invention is, without using other auxiliary agents or interpolationAgent, just can obtain that size is moderate, round and smooth, the dispersiveness in surface and good fluidity, particle diameter are evenly distributed,The polylactic resin powder that bulk density is suitable, when for Selective Laser Sintering, can easily prepare chiVery little error is little, hole is few, profile is well-balanced, the moulded work of good mechanical property. Thus, the invention provides oneWell behaved polylactic resin powder stock that is applicable to selective laser sintering and preparation method thereof, is not onlySelective laser sintering provides new qualified raw materials for sintering, also for processing and the application of polylactic resin provideNew direction.
Brief description of the drawings
Fig. 1 schemes according to the SEM of polylactic resin powder provided by the invention (SEM).
Fig. 2 is the scanning electron microscope diagram of the commercially available polyamide powder for selective laser sintering.
Detailed description of the invention
To be described further the present invention by specific embodiment below, but should be understood that scope of the present inventionBe not limited to this.
In following examples polylactic resin used with the 2002D of NatureWorksLLC company of the U.S. andThe polylactic resin of 1510 trades mark of the 4032D trade mark and PURAC company is raw material, and wherein L-type lactic acid containsAmount (optical purity) is respectively 96%, 98% and 99%. In following examples, acetone used, butanone are BeijingChemical plant produces.
In following examples, use SEM (XL ?30, FEI Co. of the U.S.) to characterize institute and obtainThe pattern of the polylactic resin powder obtaining and the commercially available polyamide powder for selective laser sintering. Adopt and swashLight particle size analyzer (Mastersizer2000, Malvern company of Britain) characterizes the polylactic resin powder obtainingParticle size and particle diameter distribute.
Embodiment 1
The acetone of 1510 polylactic resin of 100 weight portions and 1000 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.2MPa; Be warming up to subsequently 135 DEG C, constant temperature 60 minutes at this temperature; Constant temperature knotShu Houjing cooling water is down to 100 DEG C with the speed of 1.0 DEG C/min, constant temperature 60 minutes at this temperature; Continue withThe speed of 1.0 DEG C/min is down to room temperature. Material is obtained being applicable to after centrifugation and vacuum drying selective sharpThe polylactic resin powder of light sintering.
Adopt SEM to characterize the pattern (seeing accompanying drawing 1) of the polylactic resin powder obtaining. AdoptThe particle size that characterizes the polylactic resin powder obtaining with laser particle analyzer is 30～90 μ m, and particle diameter is distributed asD10＝41μm，D50＝50μm，D90＝80μm。
Embodiment 2
The acetone of the 4032D polylactic resin of 100 weight portions and 800 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.1MPa; Be warming up to subsequently 140 DEG C, constant temperature 30 minutes at this temperature; Constant temperature knotShu Houjing cooling water is down to 95 DEG C with the speed of 1.0 DEG C/min, constant temperature 75 minutes at this temperature; With 1.0 DEG CThe speed of/min is down to 20 DEG C, and keeps 60 minutes at 20 DEG C. By material after centrifugation and vacuum dryingObtain being applicable to the polylactic resin powder of selective laser sintering.
Adopt SEM to characterize pattern (result and the embodiment 1 of the polylactic resin powder obtainingSimilar, not shown at this SEM figure). Measure the polylactic resin that the present embodiment obtains through laser particle analyzerThe particle size of powder is 30～100 μ m, and particle diameter is distributed as D10=44 μ m, D50=58 μ m, D90=88 μ m.
Embodiment 3
The acetone of the 2002D polylactic resin of 100 weight portions and 1200 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.3MPa; Be warming up to subsequently 130 DEG C, constant temperature 90 minutes at this temperature; With 0.1 DEG CThe speed of/min is down to room temperature. Material being obtained being applicable to after centrifugation and vacuum drying selective laser burnsThe polylactic resin powder of knot.
Adopt SEM to characterize pattern (result and the embodiment 1 of the polylactic resin powder obtainingSimilar, not shown at this SEM figure). Measure the polylactic resin that the present embodiment obtains through laser particle analyzerThe particle size of powder is 20～120 μ m, and particle diameter is distributed as D10=30 μ m, D50=67 μ m, D90=105 μ m.
Embodiment 4
The acetone of the 2002D polylactic resin of 100 weight portions and 1200 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.3MPa; Be warming up to subsequently 130 DEG C, constant temperature 90 minutes at this temperature; Constant temperature knotShu Houjing cooling water is down to 95 DEG C with the speed of 0.5 DEG C/min, constant temperature 60 minutes at this temperature; With 0.1 DEG CThe speed of/min is down to room temperature, keeps at room temperature 30 minutes. By material after centrifugation and vacuum dryingObtain being applicable to the polylactic resin powder of selective laser sintering.
Adopt SEM to characterize pattern (result and the embodiment 1 of the polylactic resin powder obtainingParticle proterties similar and the polycaprolactone toner that discovery the present embodiment obtains than embodiment 3 is evenerClaim, surface is more smooth; Not shown at this SEM figure). Measure through laser particle analyzer, the present embodiment obtainsThe particle size of polylactic resin powder is 235～100 μ m, and particle diameter is distributed as D10=41 μ m, D50=70 μ m,D90＝85μm。
Embodiment 5
The acetone of the 4032D polylactic resin of 100 weight portions and 1000 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.1MPa; Be warming up to subsequently 140 DEG C, constant temperature 30 minutes at this temperature; Constant temperature knotShu Houjing cooling water is down to 30 DEG C with the speed of 0.5 DEG C/min, and keeps 60 minutes at 30 DEG C. By material warpAfter centrifugation and vacuum drying, obtain being applicable to the polylactic resin powder of selective laser sintering.
Adopt SEM to characterize pattern (result and the embodiment 1 of the polylactic resin powder obtainingSimilar, not shown at this SEM figure). Measure the polylactic resin that the present embodiment obtains through laser particle analyzerThe particle size of powder is 20～125 μ m, and particle diameter is distributed as D10=26 μ m, D50=60 μ m, D90=110 μ m.
Embodiment 6
The butanone of 1510 polylactic resin of 100 weight portions and 1200 weight portions is placed in to autoclave.Pass into high pure nitrogen to 0.2MPa; Be warming up to subsequently 130 DEG C, constant temperature 90 minutes at this temperature; Constant temperature knotShu Houjing cooling water is down to 90 DEG C with the speed of 0.5 DEG C/min, constant temperature 90 minutes at this temperature; With 0.2 DEG CThe speed of/min is down to room temperature. Material being obtained being applicable to after centrifugation and vacuum drying selective laser burnsThe polylactic resin powder of knot.
Adopt SEM to characterize pattern (result and the embodiment 1 of the polylactic resin powder obtainingSimilar, not shown at this SEM figure). Measure the polylactic resin that the present embodiment obtains through laser particle analyzerThe particle size of powder is 35～100 μ m, and particle diameter is distributed as D10=46 μ m, D50=54 μ m, D90=90 μ m.
The proterties of the polylactic resin powder that as seen from Figure 1, the method according to this invention prepares be spherical and/ or class is spherical, for example potato proterties, and the surface of particle is more smooth, better dispersed, the gathering caking of particleFew, be therefore specially adapted to selective laser sintering. From granulometry result, the method according to this inventionThe polylactic resin powder diameter obtaining distributes more even. Fig. 2 is commercially available for selective laser sinteringThe scanning electron microscope diagram of polyamide powder. From Fig. 2 and Fig. 1 to recently, commercially available polyamide powderThe proterties of particle is not as polycaprolactone resinous powder particles rule provided by the invention, well-balanced, and particle is stickyShown serious of continued proportion Fig. 1. As can be seen here, generally, for polylactic resin material, by the present inventionMethod for the preparation of the polylactic resin powder of selective laser sintering, obtained good effect.
Although the present invention is described in detail, for a person skilled in the art, at spirit of the present invention and modelAmendment in enclosing will be apparent. In addition, should be understood that each side, difference that the present invention recordsThe each several part of detailed description of the invention and the various features of enumerating can be combined or all or part of exchange. Above-mentionedEach detailed description of the invention in, those embodiments with reference to another detailed description of the invention can be suitably and itsThe combination of its embodiment, this is by understand by those skilled in the art. In addition those skilled in the art,Will be understood that, description is above only the mode of example, is not intended to limit the present invention.
Claims (10)
1. for the preparation method of the polylactic resin powder of selective laser sintering, described method comprise withLower step:
A), under heating-up temperature, polylactic resin is dissolved in by acetone, butanone, 2 pentanone, propione, ringIn the organic solvent of at least one formation in pentanone, methyl isopropyl ketone, oxolane and dioxane,Obtain polylactic resin solution;
B) polylactic resin solution cooling step a) being obtained, separates out solids of sedimentation.
2. method according to claim 1, is characterized in that, step a) in, with polylactic resinBe 100 parts by weight meters, described organic solvent is 600～1200 parts by weight, is preferably 800～1000 weightUmber.
3. method according to claim 1 and 2, is characterized in that, step a) in, described temperatureBe 120～160 DEG C, be preferably 130～140 DEG C.
4. according to the method described in any one in claim 1-3, it is characterized in that, step a) in,Polylactic resin solution is kept 30～90 minutes in heating-up temperature.
5. according to the method described in any one in claim 1-4, it is characterized in that, step b) in,Average rate of temperature fall is 0.1 DEG C/min～1 DEG C/min.
6. according to the method described in any one in claim 1-5, it is characterized in that, step b) in,Polylactic resin solution is cooled to cooling target temperature, and keeps 30～90 minutes at cooling target temperature; InstituteState cooling target temperature and be preferably 10～30 DEG C.
7. according to the method described in any one in claim 1-6, it is characterized in that, step b) in,Polylactic resin solution is cooled to one or more medium temperatures, and keeps 30～90 points in described medium temperatureClock; Described medium temperature is preferably 80～110 DEG C, is preferably 90～100 DEG C.
8. according to the method described in any one in claim 1-7, it is characterized in that described polylactic resinOptical purity >=92%.
9. burning for selective laser of preparing according to method described in any one in claim 1-8The polylactic resin powder of knot, the particle of described powder is spherical and/or class is spherical, and the particle size of particle is20～125 μ m, particle diameter distribution D10=26～46 μ m, D50=50～67 μ m, D90=80～110 μ m.
10. a selective laser sintering method, described method comprises by as any one in claim 1-8Described method is prepared polylactic resin powder, using as sintered powder raw material.
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Cited By (3)
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| CN106566212A (en) * | 2015-10-13 | 2017-04-19 | 中国石油化工股份有限公司 | Antibacterial polylactic acid resin powder for selective laser sintering and preparation therefor |
| WO2017063352A1 (en) * | 2015-10-13 | 2017-04-20 | 中国石油化工股份有限公司 | Aliphatic polyester powder applicable for selective laser sintering, and preparation method thereof |
| CN107189087A (en) * | 2017-06-01 | 2017-09-22 | 深圳市业天科技有限公司 | A kind of preparation method and applications of PLA powder for selective laser sintering |
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