CN106589858B - For the fiberglass reinforced polylactic resin powder of selective laser sintering and its preparation - Google Patents
For the fiberglass reinforced polylactic resin powder of selective laser sintering and its preparation Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 95
- 229920005989 resin Polymers 0.000 title claims abstract description 95
- 239000000843 powder Substances 0.000 title claims abstract description 84
- 239000011152 fibreglass Substances 0.000 title claims abstract description 33
- 238000000110 selective laser sintering Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 150000002576 ketones Chemical class 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 33
- 238000009826 distribution Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 11
- 102220043159 rs587780996 Human genes 0.000 claims description 9
- 102220042174 rs141655687 Human genes 0.000 claims description 8
- 102220076495 rs200649587 Human genes 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- -1 alkane monocarboxylic acid Chemical class 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229940114926 stearate Drugs 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of preparation methods of the fiberglass reinforced polylactic resin powder for selective laser sintering, the described method comprises the following steps：A) at the heating temperature, polylactic resin is dissolved in ketone and/or ether organic solvent, obtains polylactic resin solution；B) the polylactic resin solution for obtaining step a) cools down, and makes solid Precipitation；C) it is uniformly mixed after auxiliary agent is added in the solidliquid mixture that step b) is obtained, is drying to obtain the powder, wherein auxiliary agent includes ultrashort glass fibre, antioxidant and separator powder.This method is easy to operate, easily operated, and only selective laser sintering does not provide the excellent raw materials for sintering of processing performance, also provides new direction for the processing of functional polylactic resin and application.The present invention still further provides the fiberglass reinforced polylactic resin powder prepared according to this method and the selective laser sintering method with it as sintering powder raw material.
Description
Technical field
The present invention relates to technical field of polymer processing, and in particular to a kind of fiberglass reinforced for selective laser sintering
Polylactic resin powder and preparation method thereof and the application in terms of selective laser sintering.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) technology is a kind of rapid shaping technique,
It is most widely used in current increases material manufacturing technology and most market prospects technologies, shows becoming for fast development in recent years
Gesture.SLS technologies are scanned first to 3D solid by computer, are then irradiated in advance in workbench by high intensity laser beam
Or the material powder spread on parts selectively molten sintering layer by layer, and then realize successively molding skill
Art.SLS technologies have the design of height flexible, can produce accurate model and prototype, can be molded with reliable structure
The parts that can directly use, and it is with short production cycle, it is simple for process, be therefore particularly suited for the exploitation of new product.
The moulding material type that can be used in SLS technologies is relatively broad, including macromolecule, paraffin, metal, ceramics and it
Composite material.However, the performance of moulding material, character, which are SLS technologies again, is sintered a successful key factor, it is also straight
Connect shaping speed, precision and the physics for influencing molded part, chemical property and its comprehensive performance.Although applicable moulding material
Type is various, but can directly apply to SLS technologies at present and successfully produce that scale error is small, surface is regular, porosity
The polymer powder powder stock of low moulded work is fresh few.In the prior art, prepared by generally use comminuting method, such as deep cooling crush method
The powder raw material of SLS, this not only needs particular device, and the particles of powdered ingredient surface being prepared is rougher, grain size is inadequate
Uniformly, in irregular shape, it is unfavorable for the formation of sintered moulded body, and influence the performance of formed body.It is suitable for SLS currently on the market
The polymer powder scarcity of raw material of technology, therefore the corresponding solid powder raw material of various type of polymer is urgently developed.
Polylactic acid (PLA) is the biodegradable polymer through high-tech preparation using biomass starch as raw material.
PLA has excellent biological degradability, in two years can be degradable by the microorganism in soil after discarding, and generates CO2And H2O is right
Environment does not generate pollution.However, its physical mechanical property is poor, it is restricted in application process.
Invention content
In view of the drawbacks of the prior art and insufficient, the present invention provides a kind of fiberglass reinforced polylactic resin powder and its systems
Preparation Method and application.According to fiberglass reinforced polylactic resin powder provided by the invention, with suitably sized size, suitably
Heap density, well-balanced particle shape and particle diameter distribution is uniform, powder flowbility is good, prepare suitable for selective laser sintering
The various moulded works that biodegradable is required, be especially added to including ultrashort glass fibre, antioxidant and powder every
After the auxiliary agent including agent, the machinery and mechanical property of product can be enhanced, improve its dispersibility and stability.
According to the present invention, a kind of system of the fiberglass reinforced polylactic resin powder for selective laser sintering is provided first
Preparation Method the described method comprises the following steps：A) at the heating temperature, polylactic resin is dissolved in ketone and/or ethers has
In solvent, polylactic resin solution is obtained；B) the polylactic resin solution for obtaining step a) cools down, and makes solid precipitation analysis
Go out；C) it is uniformly mixed after auxiliary agent is added in the solidliquid mixture that step b) is obtained, is drying to obtain the powder；Wherein, described
Auxiliary agent includes ultrashort glass fibre, antioxidant and separator powder.
In the preferred embodiment of the present invention, the ketone and/or ether organic solvent be acetone, butanone,
At least one of 2 pentanone, propione, cyclopentanone, methyl isopropyl ketone, tetrahydrofuran and dioxane.
In the preferred embodiment of the present invention, the ketone and/or ether organic solvent for acetone and/or
Butanone.
Although organic solvent sedimentation has been used for detaching and purifying biochemical substances, especially protein, Huo Zheyong
Crystal is prepared in precipitation.But at present about the tree prepared using organic solvent precipitation method for Selective Laser Sintering
The report of fat material powder is also seldom.Especially not yet it is used to prepare the polylactic resin powder suitable for selective laser sintering
End.For organic solvent deposit technology, the selection of solvent type is most important.For specific high molecular material polylactic acid tree
Fat, the present inventor have found to use organic solvent as described above, especially third by being constantly trying to and exploratory development
When ketone and/or butanone are as organic solvent dissolving and cryoprecipitation polylactic resin, it is laser sintered being suitably selected for property can be obtained
Polylactic acid powder raw material.
The further exploration discovery through a large number of experiments of the present inventor, when using organic solvent as described above, example
When such as solvent of the acetone as polylactic resin, polylactic resin can be made to be precipitated with spherical and/or spherical character, and
With 20-125 μm of grain size, surface is round and smooth, and good dispersion, Size Distribution is small, especially suitable for Selective Laser Sintering.
, according to the invention it is preferred in step a), by polylactic resin in terms of 100 parts by weight, the organic solvent is
600-1200 parts by weight, preferably 800-1000 parts by weight.
When the dosage of organic solvent is in aforementioned range, the preferable polylactic resin powder of pattern, dispersibility can be obtained.
, according to the invention it is preferred in step a), polylactic resin solution is kept for 30-90 minutes in heating temperature, institute
It is 120-160 DEG C, preferably 130-140 DEG C to state heating temperature.
Preferably, step a) is heated under inert gas, such as nitrogen atmosphere.
Preferably, step b) is carried out at autogenous pressures, preferably 0.1-0.3MPa.
, according to the invention it is preferred in step b), polylactic resin solution is cooled to cooling target temperature, and cooling down
Target temperature is kept for 30-90 minutes；The cooling target temperature is 10-30 DEG C, average rate of temperature fall is 0.1 DEG C/min-1 DEG C/
min。
Preferably, in step b), polylactic resin solution is cooled to one or more medium temperatures, and in described
Between temperature keep 30-90 minutes；The medium temperature between step a) heating temperature and step b) cooling target temperature it
Between, preferably 80-110 DEG C, more preferably 90-100 DEG C.
In method provided by the invention, the temperature-fall period of polylactic resin solution can at the uniform velocity cool down, can also the stage
Property cooling.The present inventor passes through a large amount of experimental exploring, finds in some preferred embodiments of the present invention,
In step b), polylactic resin solution is cooled to one or more medium temperatures, and kept for 30-90 points in the medium temperature
Clock；The medium temperature is preferably 80-110 DEG C, more preferably 90-100 DEG C.It is readily appreciated that, the medium temperature refers to step
A) temperature between the cooling target temperature of heating temperature and step b).For example, in a specific embodiment, by poly- breast
When acid resin solution is down to 100 DEG C from 130 DEG C of heating temperature, temperature is kept at 100 DEG C 60 minutes；Or directly it is down to 10-30
℃.In other preferred embodiments, when polylactic resin solution is down to 90-110 DEG C from heating temperature, 30-90 is kept the temperature
Minute, preferable precipitation effect can be obtained.
Heating cooling method through the invention can ensure the acquisition uniform powder particle of particle diameter distribution, thus especially
The laser sintered application of being suitably selected for property.
, according to the invention it is preferred to optical purity >=92% of the polylactic resin.The such polylactic resin of selection, is obtained
Obtain the laser sintered effect of better choice and sintered products.
, according to the invention it is preferred in step c), be 100 parts by weight by polylactic resin in terms of, the ultrashort glass fibers
Dimension is 5-60 parts by weight, preferably 10-50 parts by weight.
The features such as ultrashort glass fibre has good dispersion, and mobility is excellent, is conducive to powder sintering process.In resin-oatmeal
Ultrashort glass fibre is added in end, on the one hand can reduce product cost, on the other hand can enhance polylactic resin powder
Intensity and wearability can obtain under the premise of not influencing product biodegradation with certain mechanical strength, good dispersion, property
The fiberglass reinforced polylactic resin powder that matter is stablized.
In a preferred embodiment, the ultrashort glass fibre is 5-20 μm of diameter, 100-1000 μm of length
Glass fibre, preferably 5-15 μm of diameter, the glass fibre of 100-500 μm of length, more preferably 5-15 μm of diameter, length 100-
500 μm of alkali-free glass fibre.
According to the present invention, by polylactic resin in terms of 100 parts by weight, the antioxidant is 0.1-0.5 parts by weight, excellent
It is selected as 0.2-0.4 parts by weight.
It can be prevented using antioxidant or delay polylactic resin that oxidative degradation occurs, to extend its service life.
Especially its dosage can obtain that property is stable, the longer polylactic resin powder of service life in aforementioned range.
In a preferred embodiment, the antioxidant be antioxidant 1330, antioxidant 1010, antioxidant 1790,
Irgasfos 168, antioxidant 622, more preferably antioxidant 1330.
According to the present invention, by polylactic resin in terms of 100 parts by weight, the separator powder is 0.01-10 parts by weight
Number, preferably 0.1-5 parts by weight, more preferably 0.5-1 parts by weight.
It on the one hand can prevent from bonding between polylactic resin powder particle using separator powder, so that influencing
On the other hand processing performance is also possible to prevent the bonding of fiberglass reinforced agent, its being dispersed in polylactic resin evenly is made to send out
Fiberglass reinforced performance is waved, further, separator powder can also act synergistically with fiberglass reinforced agent, and especially its dosage is aforementioned
In range, dispersibility and good fluidity, the polylactic resin powder for being suitable for selective laser sintering can be obtained.
In a preferred embodiment, the separator powder is based on the alkali of alkane monocarboxylic acid or dimeric dibasic acid gold
Category or alkaline-earth metal, more preferably from least one in odium stearate, potassium stearate, zinc stearate, calcium stearate and lead stearate
Kind.
In another preferred embodiment, the separator powder be nano-oxide or nano metal salt, it is more excellent
Selected from nano silicon dioxide, nano-titanium dioxide, nano aluminium oxide, nano zine oxide, nano zircite, nano-calcium carbonate and receive
At least one of nano-barium sulfate.
The present invention also provides the poly- breasts of the fiberglass reinforced for selective laser sintering being prepared according to the above method
The particle of acid resin powder, the powder is spherical and/or spherical, and the grain size of particle is 20-125 μm, particle diameter distribution D10=
26-46 μm, D50=50-67 μm, D90=80-110 μm.It is particularly suitable for according to the polylactic resin powder provided by the invention
Selective Laser Sintering, sintering success rate is high, and obtained sintered products and predetermined prod scale error are small, section cavity
Few, fiberglass reinforced is had excellent performance.
The present invention still further provides a kind of selective laser sintering method, and the method includes passing through above method system
Standby fiberglass reinforced polylactic resin powder, using as sintering powder raw material.The selection provided through the invention is laser sintered
Method can be prepared and gather with what irregular figure, the well-balanced smooth, satisfactory mechanical property in surface, fiberglass reinforced were had excellent performance
Lactic acid moulded work.
Provided by the present invention for the preparation method of the fiberglass reinforced polylactic resin powder of selective laser sintering, operation
Step is simple, easily operated, by selecting suitable solvent, selects under specific temperature and pressure, designs suitable heating
And cooling method, to obtain the fiberglass reinforced polylactic resin powder particularly suitable for selective laser sintering such as form, character
Powder stock, with powder size is of moderate size, surface is round and smooth, dispersed and good fluidity, particle diameter distribution are uniform, heap appropriate density
The features such as, especially after the auxiliary agent being added to including ultrashort glass fibre, antioxidant and separator powder, for selecting
Property laser sintering technology when, can easily prepare scale error is small, hole is few, shape is well-balanced, volume resistance significantly reduce, glass
Enhance the moulded work haveing excellent performance.The present invention provides a kind of glass of good performance suitable for selective laser sintering as a result,
Fibre enhancing polylactic resin powder raw material and preparation method thereof, only selective laser sintering does not provide new qualified sintering
Raw material also provides new direction for the processing of functional polylactic resin and application.
Specific implementation mode
The present invention will be described further by specific embodiment below, it should be appreciated that the scope of the present invention is not
It is limited to this.
In the examples below that, polylactic resin used is with the 2002D trade mark (light of Nature Works LLC companies of the U.S.
Learn purity 96%) and the 4032D trades mark (optical purity 98%) and 1510 trades mark (optical purity 99%) of PURAC companies gather
Lactic acid resin is raw material.Acetone used, butanone are Beijing Chemical Plant's production in following embodiment.
Polylactic resin powder is prepared according to the scheme of embodiment 1-6, but does not add ultrashort glass fibre, using laser grain
Degree instrument (Mastersizer 2000, Malvern companies of Britain) characterizes its particle size and particle diameter distribution to get embodiment 1-6
The grain size and particle diameter distribution of the particle of the fiberglass reinforced polylactic resin powder obtained.
Embodiment 1
The acetone of the polylactic resin (optical purity 96%) of 1510 trades mark of 100 parts by weight and 1000 parts by weight is set
In autoclave.High pure nitrogen is passed through to 0.2MPa；135 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes；Constant temperature
100 DEG C are down to the rate of 1.0 DEG C/min through cooling water after end, at this temperature constant temperature 60 minutes；Continue with 1.0 DEG C/min
Rate be down to 25 DEG C, constant temperature 60 minutes at this temperature.5 μ of diameter of 10 weight fractions is added in obtained solidliquid mixture
M, the ultrashort glass fibre of 150 μm of length, the antioxidant 1330 of 0.25 weight fraction and the calcium stearate of 0.5 weight fraction
Afterwards, the fiberglass reinforced polylactic resin powder suitable for selective laser sintering is obtained after being centrifuged and be dried in vacuo.It should
The grain size of the particle of fiberglass reinforced polylactic resin powder be 30-90 μm, particle diameter distribution be D10=41 μm, D50=50 μm, D90
=80 μm.
Embodiment 2
The acetone of the polylactic resin (optical purity 98%) of the 4032D trades mark of 100 parts by weight and 800 parts by weight is set
In autoclave.High pure nitrogen is passed through to 0.1MPa；140 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes；Constant temperature
20 DEG C are down to the rate of 1.0 DEG C/min through cooling water after end, and is kept for 60 minutes at 20 DEG C.In obtained solidliquid mixture
It is added 10 μm of the diameter of 25 weight fractions, the ultrashort glass fibre of 250 μm of length, the antioxidant 1330 of 0.5 weight fraction, and
After the zinc stearate of 1 weight fraction, it is centrifuged and obtains increasing suitable for the glass of selective laser sintering after being dried in vacuo
Strong polylactic resin powder.The grain size of the particle of the fiberglass reinforced polylactic resin powder is 30-100 μm, particle diameter distribution D10
=44 μm, D50=58 μm, D90=88 μm.
Embodiment 3
The acetone of the 2002D polylactic resin (optical purity 96%) of 100 parts by weight and 1200 parts by weight is placed in height
It presses in reaction kettle.High pure nitrogen is passed through to 0.3MPa；130 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes；Constant temperature terminates
25 DEG C are down to the rate of 0.1 DEG C/min by cooling water, at this temperature constant temperature 90 minutes.Add in obtained solidliquid mixture
Enter 15 μm of the diameter of 10 weight fractions, the ultrashort glass fibre of 200 μm of length, the antioxidant 1330 of 0.25 weight fraction, and
After the nano silicon dioxide of 0.75 weight fraction, it is centrifuged and is obtained after being dried in vacuo suitable for selective laser sintering
Fiberglass reinforced polylactic resin powder.The grain size of the particle of the fiberglass reinforced polylactic resin powder is 20-120 μm, grain size point
Cloth is D10=30 μm, D50=67 μm, D90=105 μm.
Embodiment 4
The acetone of the 2002D polylactic resin (optical purity 96%) of 100 parts by weight and 1200 parts by weight is placed in height
It presses in reaction kettle.High pure nitrogen is passed through to 0.3MPa；130 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes；Constant temperature terminates
95 DEG C are down to the rate of 0.5 DEG C/min by cooling water, at this temperature constant temperature 60 minutes；Continue with the speed of 0.1 DEG C/min
Rate is down to 25 DEG C, is kept for 30 minutes at this temperature.5 μm of diameter, the length of 50 weight fractions are added in obtained solidliquid mixture
The carbon nanotube of the ultrashort glass fibre and 0.05 weight fraction of 150 μm of degree, the antioxidant 1330 of 0.25 weight fraction, and
After the nano zine oxide of 0.9 weight fraction, the glass suitable for selective laser sintering is centrifuged and obtained after being dried in vacuo
Fibre enhancing polylactic resin powder.The grain size of the particle of the fiberglass reinforced polylactic resin powder is 25-100 μm, particle diameter distribution
It is D10=41 μm, D50=70 μm, D90=85 μm.
Embodiment 5
By the acetone of polylactic resin (optical purity 98%) and 1000 parts by weight of the 4032D trades mark of 100 parts by weight
It is placed in autoclave.High pure nitrogen is passed through to 0.1MPa；120 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes；It is permanent
Temperature through cooling water is down to 30 DEG C after terminating with the rate of 0.5 DEG C/min, at this temperature constant temperature 30 minutes.Obtained solid-liquid mixing
15 μm of the diameter of 35 weight fractions, the ultrashort glass fibre of 500 μm of length, the antioxidant of 0.25 weight fraction are added in object
After the nano-calcium carbonate of 1330 and 0.6 weight fraction, it is centrifuged and obtains being suitable for selective laser after being dried in vacuo
The fiberglass reinforced polylactic resin powder of sintering.The grain size of the particle of the fiberglass reinforced polylactic resin powder is 20-125 μm,
Particle diameter distribution is D10=26 μm, D50=60 μm, D90=110 μm.
Embodiment 6
The butanone of the polylactic resin (optical purity 99%) of 1510 trades mark of 100 parts by weight and 1200 parts by weight is set
In autoclave.High pure nitrogen is passed through to 0.2MPa；130 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes；Constant temperature
90 DEG C are down to the rate of 0.5 DEG C/min through cooling water after end, at this temperature constant temperature 90 minutes；Continue with 0.2 DEG C/min
Rate be down to 25 DEG C, constant temperature 30 minutes at this temperature.5 μ of diameter of 25 weight fractions is added in obtained solidliquid mixture
M, the ultrashort glass fibre of 150 μm of length, the antioxidant 1330 of 0.1 weight fraction and the odium stearate of 0.8 weight fraction
Afterwards, the fiberglass reinforced polylactic resin powder suitable for selective laser sintering is obtained after being centrifuged and be dried in vacuo.It should
The grain size of the particle of fiberglass reinforced polylactic resin powder be 35-100 μm, particle diameter distribution be D10=46 μm, D50=54 μm,
D90=90 μm.
The particle for the polylactic resin powder that the method for the present invention is prepared is spherical and/or spherical, such as Ma Ling
The surface of potato character, particle is more smooth, and preferably, the aggregation caking of particle is few, is therefore particularly suitable for selective laser for dispersibility
Sintering.From the point of view of granulometry result, the polylactic resin powder diameter distribution obtained according to the method for the present invention is relatively uniform.
Comparative example 1
The acetone of the polylactic resin (optical purity 99%) of 1510 trades mark of 100 parts by weight and 1000 parts by weight is set
In autoclave.High pure nitrogen is passed through to 0.2MPa；135 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes；Constant temperature
100 DEG C are down to the rate of 1.0 DEG C/min through cooling water after end, at this temperature constant temperature 60 minutes；Continue with 1.0 DEG C/min
Rate be down to 25 DEG C, constant temperature 60 minutes at this temperature.The antioxygen of 0.25 weight fraction is added in obtained solidliquid mixture
After the calcium stearate of agent 1330 and 0.5 weight fraction, it is centrifuged and obtains being suitable for selective laser after being dried in vacuo
The polylactic resin powder of sintering.Laser particle analyzer is used to characterize the particle size of obtained polylactic resin powder as 30-
90 μm, particle diameter distribution is D10=39 μm, D50=48 μm, D90=78 μm.
By the fiberglass reinforced polylactic resin powder of embodiment 1-6 and the polylactic resin powder of comparative example 1 in SLS powder
In sinter molding equipment, require that dumbbell shape test sample is made according to 527 test bars of national standard ISO.It is pressed using universal testing machine
The mechanical property of said products is tested according to national standard ISO 527, measurement result is as shown in table 1.
The tensile strength of 1 embodiment 1-6 of table and the powder sintered product of polylactic resin of comparative example 1
As can be seen from Table 1, the powder sintered product of polylactic resin itself has higher tensile strength, 35MPa is can reach, especially
It is that the tensile strength of the powder sintered product of fiberglass reinforced polylactic resin of 1-6 of the embodiment of the present invention increases substantially, power
It learns performance to significantly improve, reaches 45MPa or more.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, different specific implementation mode that the present invention records
Each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific implementation mode, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, this is will be by this field skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode, not purport
In the limitation present invention.
Claims (18)
1. a kind of preparation method of fiberglass reinforced polylactic resin powder for selective laser sintering, the method includes with
Lower step：
A) at the heating temperature, polylactic resin is dissolved in ketone and/or ether organic solvent, it is molten obtains polylactic resin
Liquid；
B) the polylactic resin solution for obtaining step a) cools down, and makes solid Precipitation；
C) it is uniformly mixed after auxiliary agent is added in the solidliquid mixture that step b) is obtained, is drying to obtain the powder；
Wherein, the auxiliary agent includes ultrashort glass fibre, antioxidant and separator powder；
Wherein, by polylactic resin in terms of 100 parts by weight, the ultrashort glass fibre is 5-60 parts by weight；And
The ultrashort glass fibre is 5-20 μm of diameter, the glass fibre of 100-500 μm of length.
2. according to the method described in claim 1, it is characterized in that, in step a), with polylactic resin for 100 parts by weight
Meter, the organic solvent are 600-1200 parts by weight.
3. according to the method described in claim 2, it is characterized in that, in step a), with polylactic resin for 100 parts by weight
Meter, the organic solvent are 800-1000 parts by weight.
4. method according to claim 1 or 2, which is characterized in that in step a), polylactic resin solution is being heated
Temperature is kept for 30-90 minutes, and the heating temperature is 120-160 DEG C.
5. according to the method described in claim 4, it is characterized in that, the heating temperature is 130-140 DEG C.
6. method according to claim 1 or 2, which is characterized in that in step b), polylactic resin solution is cooled to
Cool down target temperature, and is kept for 30-90 minutes in cooling target temperature；The cooling target temperature is 10-30 DEG C, average to cool down
Rate is 0.1 DEG C/min-1 DEG C/min.
7. method according to claim 1 or 2, which is characterized in that in step b), polylactic resin solution is cooled to
One or more medium temperatures, and kept for 30-90 minutes in the medium temperature；Heating of the medium temperature between step a)
Between temperature and the cooling target temperature of step b).
8. the method according to the description of claim 7 is characterized in that the medium temperature is 80-110 DEG C.
9. according to the method described in claim 8, it is characterized in that, the medium temperature is 90-100 DEG C.
10. method according to claim 1 or 2, which is characterized in that optical purity >=92% of the polylactic resin.
11. method according to claim 1 or 2, which is characterized in that by polylactic resin be 100 parts by weight in terms of, it is described
Ultrashort glass fibre is 10-50 parts by weight；The antioxidant is 0.1-0.5 parts by weight；The separator powder is 0.01-
10 parts by weight.
12. according to the method for claim 11, which is characterized in that described anti-in terms of being 100 parts by weight by polylactic resin
Oxygen agent is 0.2-0.4 parts by weight；The separator powder is 0.1-5 parts by weight.
13. according to the method for claim 12, which is characterized in that by polylactic resin be 100 parts by weight in terms of, the powder
Last interleaving agent is 0.5-1 parts by weight.
14. method according to claim 1 or 2, which is characterized in that the ultrashort glass fibre is 5-15 μm of diameter, long
The alkali-free glass fibre of 100-250 μm of degree.
15. method according to claim 1 or 2, which is characterized in that the separator powder is based on alkane monocarboxylic acid
Or at least one of alkali or alkaline earth metal, nano-oxide and the nano metal salt of dimeric dibasic acid.
16. according to the method for claim 15, which is characterized in that the separator powder is selected from odium stearate, stearic acid
It is potassium, zinc stearate, calcium stearate, lead stearate, nano silicon dioxide, nano-titanium dioxide, nano aluminium oxide, nano oxidized
At least one of zinc, nano zircite, nano-calcium carbonate and nano barium sulfate.
17. a kind of glass for selective laser sintering being prepared according to any one of claim 1-16 the methods
Enhance polylactic resin powder, the particle of the powder is spherical and/or spherical, and the grain size of particle is 20-125 μm, grain size
D10=26-46 μm, D50=50-70 μm, D90=80-110 μm of distribution.
18. a kind of selective laser sintering method, the method includes passing through the side as described in any one of claim 1-16
Method prepares fiberglass reinforced polylactic resin powder, using as sintering powder raw material.
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| CN101392064A (en) * | 2008-11-07 | 2009-03-25 | 东华大学 | A kind of preparation method of monodisperse polylactic acid microsphere |
| CN103172876A (en) * | 2011-12-26 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Polylactic acid microsphere and preparation method thereof |
| CN103509197A (en) * | 2012-06-14 | 2014-01-15 | 东丽先端材料研究开发（中国）有限公司 | Preparation method of polylactic acid particles |
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| CN101392064A (en) * | 2008-11-07 | 2009-03-25 | 东华大学 | A kind of preparation method of monodisperse polylactic acid microsphere |
| CN103172876A (en) * | 2011-12-26 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Polylactic acid microsphere and preparation method thereof |
| CN103509197A (en) * | 2012-06-14 | 2014-01-15 | 东丽先端材料研究开发（中国）有限公司 | Preparation method of polylactic acid particles |
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