CN106674552A - Polyformaldehyde resin powder used for selective laser sintering and preparation and application thereof - Google Patents
Polyformaldehyde resin powder used for selective laser sintering and preparation and application thereof Download PDFInfo
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- CN106674552A CN106674552A CN201510751586.XA CN201510751586A CN106674552A CN 106674552 A CN106674552 A CN 106674552A CN 201510751586 A CN201510751586 A CN 201510751586A CN 106674552 A CN106674552 A CN 106674552A
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- acetal resin
- powder
- temperature
- weight
- selective laser
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 100
- 239000000843 powder Substances 0.000 title claims abstract description 81
- 238000000110 selective laser sintering Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 title abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 5
- 150000002576 ketones Chemical class 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 150000001408 amides Chemical class 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 80
- 239000011354 acetal resin Substances 0.000 claims description 80
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 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 group 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 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- -1 kelene hydro carbons Chemical class 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229940114926 stearate Drugs 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
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 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
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 102220042174 rs141655687 Human genes 0.000 claims description 2
- 102220076495 rs200649587 Human genes 0.000 claims description 2
- 102220043159 rs587780996 Human genes 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229940057977 zinc stearate Drugs 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229940078456 calcium stearate Drugs 0.000 claims 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000000149 argon plasma sintering Methods 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 14
- 239000000498 cooling water Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides polyformaldehyde resin powder used for selective laser sintering and a preparation and an application thereof. The method comprises the following steps: under heating temperature, dissolving polyformaldehyde resin in at least one of amides, cyclic ethers, ketones and chloralkanes to obtain a polyformaldehyde resin solution; cooling the obtained polyformaldehyde resin solution, precipitating the solid precipitate to obtain a solid-liquid mixture; adding an auxiliary agent in the obtained solid-liquid mixture, uniformly mixing the materials; performing solid-liquid separation, drying a solid to obtain the polyformaldehyde resin powder used for laser sintering; wherein the auxiliary agent comprises an antioxidant and/or a powder parting agent. The polyformaldehyde resin powder has the advantages of appropriate size, appropriate bulk density, uniform particle shape, uniform size distribution, good oxidation resistance and powder flowability, and is suitable for various molded products used for selective laser sintering. The invention provides the selective laser sintering method by taking polyformaldehyde resin powder as a raw material.
Description
Technical field
The present invention relates to technical field of polymer processing, and in particular to a kind of poly- first for selective laser sintering
Urea formaldehyde 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, is
At present most widely used and most market prospects technology in increases material manufacturing technology, presents in recent years fast development
Trend.SLS technologies are by computer 3D solid to be scanned first, are then shone by high intensity laser beam
The material powder spread on workbench or parts in advance optionally molten sintering layer by layer is penetrated,
Further realize the technology being successively molded.SLS technologies have the design of height flexible, can produce accurate mould
Type and prototype, can be molded the parts that can directly use with reliable structure, and with short production cycle,
Process is simple, is therefore particularly suited for the exploitation of new product.
The moulding material species that can be used in SLS technologies is relatively broad, including macromolecule, paraffin, metal, pottery
Porcelain and their composite.However, the performance of moulding material, proterties are again that SLS technologies sintering is successful
One key factor, it also directly affects the shaping speed of profiled member, precision, and physics, chemical property and
Its combination property.Although applicable moulding material species is various, SLS technologies can be directly applied at present
And successfully produce that scale error is little, surface is regular, the polymer powder powder stock of the moulded work that porosity is low is fresh
It is few.In prior art, the powder stock of SLS is generally prepared using comminuting method, such as deep cooling crush method, this
Particular device is not only needed, the particles of powdered ingredient surface for preparing is rougher, particle diameter not enough uniform, shape
Irregularly, it is unfavorable for the formation of sintered moulded body, and affects the performance of formed body.It is applied to SLS in the market
The polymer powder scarcity of raw material of technology, therefore the corresponding pressed powder raw material of various type of polymer urgently opens
Send out.
Polyformaldehyde (POM) is a kind of linear polymer obtained by oxymethylene polymerization, no side chain, high density,
Highly crystalline, water imbibition is little, dimensionally stable, and mechanical strength is most tough and tensile in thermoplastic resin, there is good thing
Reason, mechanically and chemically performance, especially with excellent crocking resistance, there is the title of " supersteel ", extensively application
In industrial circle, the POM pressed powders of SLS are developed, the products application demand of personalization can be met.
The content of the invention
Object of the present invention is to provide a kind of acetal resin powder suitable for selective laser sintering and
Its preparation method and application.The acetal resin powder provided according to the present invention has good non-oxidizability, good
Good powder flowbility, suitably sized size, suitable heap density, well-balanced particle profile and uniform
Particle diameter distribution, it is adaptable to which selective laser sintering is preparing various moulded works.
The invention provides a kind of preparation method of the acetal resin powder for selective laser sintering, described
Method is comprised the following steps：
A) at the heating temperature, acetal resin is dissolved in into amide-type, cyclic ethers class, ketone and kelene hydro carbons
In at least one organic solvent in, obtain acetal resin solution；
B) the acetal resin solution cooling for obtaining step a), separates out solids of sedimentation, obtains solid-liquid mixing
Thing；
C) auxiliary agent is added in the solidliquid mixture that step b) is obtained, is well mixed；
D) separation of solid and liquid, drying solid obtains being applied to the acetal resin powder of selective laser sintering；
Wherein, the auxiliary agent includes separator powder and/or antioxidant.
According to the present invention, in step a), the melt index of the acetal resin at 190 DEG C, 2.16kg
20-100g/10min, preferably 30～80g/10min are determined as under carrying capacity.Select such acetal resin, energy
Enough obtain more preferable selective laser sintering effect and sintered products.
Preferably, in step a), count by 100 parts by weight of the acetal resin, it is described organic molten
Agent is 600-1200 parts by weight, preferably 800-1000 parts by weight.
The amide-type is preferably C1-C8Acid amides, more preferably C2-C6Acid amides；And specifically, it is preferable to be
N,N-dimethylformamide and/or DMAC N,N' dimethyl acetamide.
The cyclic ethers class is preferably C2-C8Cyclic ethers, more preferably tetrahydrofuran and/or dioxane.
The ketone is preferably C3-C8Ketone, more preferably C3-C5Ketone；And specifically, it is preferable to be selected from acetone,
At least one in butanone and pentanone.
The kelene hydro carbons is C1-C8Chloralkane, more preferably C1-C5Chloralkane；Specifically,
In being preferably selected from dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloroethanes and tetrachloroethanes
It is at least one.
In a preferred embodiment, the organic solvent be preferably DMF and/or
DMAC N,N' dimethyl acetamide.
Although organic solvent deposit technology has been used for separating and purifying biochemical substances, especially protein, or
Person prepares crystal for precipitation.But, at present with regard to being prepared for selective laser using organic solvent precipitation method
The report of the resin material powder of sintering technology is also little.Especially not yet have been reported that and selected for preparing to be applied to
The laser sintered acetal resin powder of property.For organic solvent deposit technology, solvent species selected from most important.
For specific macromolecular material acetal resin, the present inventor passes through to be constantly trying to and exploration is ground
Study carefully, find using organic solvent as above, especially DMF and/or N, N- dimethyl
When acetamide dissolves simultaneously cryoprecipitation acetal resin as organic solvent, being suitably selected for property can be advantageously obtained
Laser sintered polyformaldehyde powder stock.
The present inventor is further had found by substantial amounts of experimental exploring, when using organic molten as mentioned above
Agent, such as acetone as acetal resin solvent when, acetal resin can be made with spherical and/or spherical
Proterties is separated out, and with 20-150 μm of particle diameter, surface is round and smooth, and good dispersion, Size Distribution is little, special
Shi Yongyu not Selective Laser Sintering.
When the consumption of organic solvent is in aforementioned range, pattern, dispersiveness preferably acetal resin is obtained in that
Powder.
, according to the invention it is preferred in step a), the heating-up temperature is 100-180 DEG C, preferably
110-150 DEG C, preferably 120-140 DEG C.
In a preferred embodiment, acetal resin solution is kept into for 30-180 minutes in heating-up temperature.
Preferably, step a) is heated under an inert gas, preferably nitrogen；The inert gas pressure
For 0.1-0.5Mpa, preferred 0.2-0.3Mpa.
, according to the invention it is preferred in step b), average rate of temperature fall is 0.1 DEG C/min-1 DEG C/min.
Preferably, acetal resin solution is cooled into cooling target temperature, and is kept in cooling target temperature
30-90 minutes；The cooling target temperature is preferably 10-30 DEG C, such as room temperature.
Preferably, step b) is carried out at autogenous pressures.
In the method that the present invention is provided, the temperature-fall period of acetal resin solution can at the uniform velocity lower the temperature, it is also possible to
Stage cooling.The present inventor has found preferred in some of the invention through substantial amounts of experimental exploring
In embodiment, in step b), acetal resin solution is cooled into one or more medium temperatures, and
Kept for 30-90 minutes in the medium temperature；The medium temperature is preferably 70-100 DEG C, preferably 80-90 DEG C.
Easy to understand, the medium temperature is referred between the heating-up temperature of step a) and the cooling target temperature of step b)
Temperature.Further, when medium temperature is, for example, any one temperature in 70-100 DEG C, step a)
In temperature should be more than the medium temperature.For example, it is in a specific embodiment, acetal resin is molten
Liquid from 130 DEG C of heating-up temperature be down to 90 DEG C when, in 90 DEG C of keeping temperatures 60 minutes；Or directly it is down to room temperature.
In other preferred embodiments, when acetal resin solution is down to 80-90 DEG C from heating-up temperature, insulation
30-90 minutes, it is obtained in that and preferably separate out effect.
By the heating cooling method invented, the powder particle for obtaining even particle size distribution is ensure that, thus it is special
The not laser sintered application of being suitably selected for property.
According to the present invention, in step c), the antioxidant is preferably antioxidant 1010 and/or irgasfos 168.
It is further preferred that counting by 100 parts by weight of acetal resin, the antioxidant 1010 consumption is 0.1～0.5
Parts by weight, preferably 0.2～0.4 parts by weight；Irgasfos 168 consumption is 0.1～0.5 parts by weight, preferably
For 0.2～0.4 parts by weight.
In a preferred embodiment, antioxidant by scope as defined above antioxidant 1010 and antioxidant
168 compounding compositions.
Acetal resin is the polymer formed by oxymethylene polymerization, due to the relation of its molecular structure, on methylene
Hydrogen atom easily affected by the stabilizing effect adjacent to oxygen atom and easily attacked by free radical, therefore heat endurance compared with
Difference, can degrade when being heated and discharge formaldehyde, cause plastic cracking, the preparation and use for acetal resin powder
It is all very unsuitable in selective laser sintering.In the method that the present invention is provided, poly- first is prevented using antioxidant
There is oxidation reaction in urea formaldehyde, the generation of this mechanism of degradation can be reduced, so as to improve obtained acetal resin
The heat resistance and service life of powder, it is adaptable to which selective laser sintering prepares the process of various product.
According to the present invention, in step c), the separator powder can be metallic soap, i.e., based on alkane one
The alkali metal or alkaline-earth metal of first carboxylic acid or dimeric dibasic acid, be preferably selected from odium stearate, potassium stearate, zinc stearate,
At least one in calcium stearate and lead stearate.According to the present invention, the separator powder can be nano oxygen
Compound or nano metal salt, be preferably selected from silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide,
At least one in calcium carbonate and barium sulfate nanoparticles.
In the present invention, count by 100 parts by weight of acetal resin, the separator powder consumption is 0.01-10
Parts by weight, preferably 0.1-5 parts by weight, preferably 0.5-1 parts by weight.
Can prevent from being bondd between polyformaldehyde powder particle using separator powder, so that affecting processability
Energy.On the other hand it is also possible to prevent the bonding of antioxidant so as to which being dispersed in acetal resin evenly is played
Antioxygenic property.Further, separator powder can also act synergistically with antioxidant, and especially its consumption is front
In the range of stating, it is obtained in that dispersiveness and good fluidity, is suitable for the acetal resin of selective laser sintering
Powder.
Present invention also offers the acetal resin for selective laser sintering prepared according to above method
Powder, the particle of the powder is spherical and/or spherical, and the particle size of particle is 20～150 μm, particle diameter
D10=41-73 μm, D50=51-105 μm, D90=68-132 μm of distribution.According to the poly- first that the present invention is provided
Urea formaldehyde powder is particularly suited for Selective Laser Sintering, and sintering success rate is high, the sintered products for obtaining with
Predetermined prod scale error is little, and section cavity is few.
Additionally, the present invention further provides a kind of selective laser sintering method, methods described is included by as above
Described method prepares acetal resin powder, using as sintered powder raw material.The choosing provided by the present invention
Selecting property laser sintering processes, can prepare with irregular figure, the well-balanced smooth, satisfactory mechanical property in surface
Polyoxymethylene molding product.
Provided by the present invention for the preparation method of the acetal resin powder of selective laser sintering, operating procedure
Simply, it is easily operated, by selecting suitable solvent, select under specific temperature and pressure, design is suitable
The gentle cooling method of liter, so as to obtain the polyformaldehyde that form, proterties etc. are particularly suitable for selective laser sintering
Toner raw material.Additionally, another advantage for projecting of the present invention is, by adding separator powder and resisting
Oxygen agent, can obtain that size is moderate, surface is round and smooth, dispersed and good fluidity, even particle size distribution,
Heap appropriate density, oxidation resistant acetal resin powder, when for Selective Laser Sintering, can be easily
Preparation scale error in ground is little, hole is few, profile is well-balanced, good mechanical property moulded work.Thus, the present invention is carried
A kind of acetal resin powder stock and its preparation side suitable for selective laser sintering of good performance is supplied
Method, only selective laser sintering does not provide new qualified raw materials for sintering, is also the processing of acetal resin
New direction is provided with application.
Description of the drawings
Fig. 1 is the SEM (SEM) of the according to embodiments of the present invention 1 acetal resin powder for providing
Figure.
Fig. 2 is the scanning electron microscope diagram of the powder of polyamide 12 for being commercially for selective laser sintering.Mesh
The front polyformaldehyde powder commercially still rarely having for selective laser sintering, here is enclosed in the market
The scanning electron microscope diagram of the powder of polyamide 12 for selective laser sintering for more generally circulating, uses
In with of the invention (Fig. 1) contrast.
Specific embodiment
The present invention will be described further by specific embodiment below, it should be appreciated that the scope of the present invention
It is not limited to this.
In the examples below that, using laser particle analyzer (Mastersizer 2000, Malvern companies of Britain)
Characterize the particle size and particle diameter distribution of obtained acetal resin powder.
Embodiment 1
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The acetone of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Then raise temperature to
130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.The solid-liquid for obtaining
The antioxidant 1010 of 0.25 weight portion and the irgasfos 168 of 0.25 weight portion, and 0.5 are added in mixture
After the calcium stearate of weight portion, it is centrifuged and obtains after being vacuum dried to be applied to the poly- of selective laser sintering
Formaldehyde resin powder.The particle size and particle diameter distribution of the acetal resin powder for being obtained the results are shown in Table 1.
Embodiment 2
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 65g/10min) and
The acetone of 800 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.3MPa；Then raise temperature to
140 DEG C, constant temperature 30 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
85 DEG C, constant temperature 60 minutes at this temperature；20 DEG C are down to the speed of 1.0 DEG C/min, and in 20 DEG C of holdings
60 minutes.The antioxidant 1010 of 0.25 weight portion and resisting for 0.25 weight portion are added in the solidliquid mixture for obtaining
After oxygen agent 168, and the zinc stearate of 1 weight portion, material is centrifuged and is fitted after being vacuum dried
For the acetal resin powder of selective laser sintering.The particle size of the acetal resin powder for being obtained and
Particle diameter distribution the results are shown in Table 1.
Embodiment 3
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 30g/10min) and
The acetone of 1200 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.1MPa；Then raise temperature to
130 DEG C, constant temperature 120 minutes at this temperature；Room temperature is down to the speed of 0.1 DEG C/min.The solid-liquid for obtaining is mixed
The antioxidant 1010 of 0.1 weight portion and the irgasfos 168 of 0.1 weight portion, and 0.75 weight are added in compound
Part nano silicon after, material is centrifuged and is obtained after be vacuum dried suitable for selective laser burning
The acetal resin powder of knot.The particle size and particle diameter distribution of the acetal resin powder for being obtained the results are shown in Table
1。
Embodiment 4
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 40g/10min) and
The acetone of 1200 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.1MPa；Then raise temperature to
120 DEG C, constant temperature 150 minutes at this temperature；Jing cooling waters are down to the speed of 0.5 DEG C/min after constant temperature terminates
85 DEG C, constant temperature 60 minutes at this temperature；Room temperature is down to the speed of 0.1 DEG C/min, 60 are kept at room temperature
Minute.The antioxidant 1010 of 0.3 weight portion and the antioxidant of 0.3 weight portion are added in the solidliquid mixture for obtaining
Behind 168, and the nano zine oxide of 0.9 weight portion, material is centrifuged and is suitable for after being vacuum dried
In the acetal resin powder of selective laser sintering.The particle size and grain of the acetal resin powder for being obtained
Footpath distribution results are shown in Table 1.
Embodiment 5
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 30g/10min) and
The N,N-dimethylformamide of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.3MPa；
140 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes；Constant temperature terminate after Jing cooling waters with 0.5 DEG C/min
Speed be down to 30 DEG C, and kept for 30 minutes at 30 DEG C.0.2 weight portion is added in the solidliquid mixture for obtaining
Antioxidant 1010 and 0.2 weight portion irgasfos 168, and after the nano-calcium carbonate of 0.6 weight portion, will
Material is centrifuged and obtains being applied to the acetal resin powder of selective laser sintering after being vacuum dried.Institute
The particle size and particle diameter distribution of the acetal resin powder of acquisition the results are shown in Table 1.
Embodiment 6
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 70g/10min) and
The N,N-dimethylformamide of 1200 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；
120 DEG C are then raised temperature to, at this temperature constant temperature 180 minutes；Constant temperature terminate after Jing cooling waters with 0.5 DEG C/min
Speed be down to 80 DEG C, constant temperature 90 minutes at this temperature；Room temperature is down to the speed of 0.2 DEG C/min.Obtain
Solidliquid mixture in add the antioxidant 1010 of 0.15 weight portion and the irgasfos 168 of 0.15 weight portion, with
And 0.8 weight portion odium stearate after, material is centrifuged and obtains after being vacuum dried being applied to selective
Laser sintered acetal resin powder.The particle size of the acetal resin powder for being obtained and particle diameter distribution are tied
Fruit is shown in Table 1.
Embodiment 7
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The dichloromethane of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Subsequently heat up
To 130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are dropped with the speed of 1.0 DEG C/min after constant temperature terminates
To 90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.What is obtained consolidates
The antioxidant 1010 of 0.25 weight portion and the irgasfos 168 of 0.25 weight portion, and 0.5 are added in liquid mixture
After the calcium stearate of weight portion, it is centrifuged and obtains after being vacuum dried to be applied to the poly- of selective laser sintering
Formaldehyde resin powder.The particle size and particle diameter distribution of the acetal resin powder for being obtained the results are shown in Table 1.
Embodiment 8
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The butanone of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Then raise temperature to
130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.The solid-liquid for obtaining
The antioxidant 1010 of 0.25 weight portion and the irgasfos 168 of 0.25 weight portion, and 0.5 are added in mixture
After the calcium stearate of weight portion, it is centrifuged and obtains after being vacuum dried to be applied to the poly- of selective laser sintering
Formaldehyde resin powder.The particle size and particle diameter distribution of the acetal resin powder for being obtained the results are shown in Table 1.
Table 1
| Particle size/μm | D10/μm | D50/μm | D90/μm | |
| Embodiment 1 | 55-150 | 73 | 105 | 132 |
| Embodiment 2 | 45-140 | 59 | 95 | 125 |
| Embodiment 3 | 30-94 | 47 | 57 | 78 |
| Embodiment 4 | 45-140 | 62 | 93 | 119 |
| Embodiment 5 | 20-90 | 41 | 51 | 68 |
| Embodiment 6 | 45-150 | 64 | 92 | 128 |
| Embodiment 7 | 49-140 | 65 | 90 | 125 |
| Embodiment 8 | 50-145 | 67 | 100 | 130 |
Comparative example 1
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The acetone of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Then raise temperature to
130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.The solid-liquid for obtaining
After the calcium stearate of 0.5 weight portion is added in mixture, it is centrifuged and obtains after being vacuum dried to be applied to choosing
The laser sintered acetal resin powder of selecting property.
Compared with Example 1, due to, without antioxidant, causing the polyformaldehyde power applications for obtaining in comparative example 1
It is heated when laser sintered degradable, obtained moulded work easily shrinks and subsides, it is impossible to preferably meet laser burning
The requirement of knot technique.
Comparative example 2
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The acetone of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Then raise temperature to
130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.The solid-liquid for obtaining
After the antioxidant 1010 of 0.25 weight portion and the irgasfos 168 of 0.25 weight portion are added in mixture, Jing centrifugations
Separate and obtain after being vacuum dried the acetal resin powder for being applied to selective laser sintering.
Compared with Example 1, due to, without interleaving agent, causing the polyformaldehyde powder for obtaining easy to stick in comparative example 2
Knot, mobility is poor, it is impossible to preferably meet the requirement of laser sintering process.
Comparative example 3
By the acetal resin of 100 weight portions ((190 DEG C, 2.16kg) of melt index is 50g/10min) and
The acetone of 1000 weight portions is placed in autoclave.High pure nitrogen is passed through to 0.2MPa；Then raise temperature to
130 DEG C, constant temperature 90 minutes at this temperature；Jing cooling waters are down to the speed of 1.0 DEG C/min after constant temperature terminates
90 DEG C, constant temperature 60 minutes at this temperature；Continuation is down to room temperature with the speed of 1.0 DEG C/min.The solid-liquid for obtaining
Mixture is centrifuged and obtains being applied to the acetal resin powder of selective laser sintering after being vacuum dried.
Compared with Example 1, due to, without antioxidant and interleaving agent, causing the polyformaldehyde for obtaining in comparative example 3
Power applications are heated degradable when laser sintered, and obtained moulded work easily shrinks and subsides, it is impossible to preferably full
The requirement of sufficient laser sintering process；And causing its easy bonding, mobility is poor, it is impossible to preferably meet laser burning
The requirement of knot technique.
Above example and comparative example illustrate that the acetal resin powder obtained according to the present invention has good resisting
Oxidisability, good powder flowbility, suitably sized size, suitable heap density, well-balanced particle profile
And uniform particle diameter distribution, it is adaptable to selective laser sintering prepares various moulded works.Further, pass through
The selective laser sintering method that the present invention is provided, can prepare with irregular figure, the well-balanced light in surface
Sliding, the polyoxymethylene molding product of satisfactory mechanical property.
Although the present invention is described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side, difference that the present invention is recorded
The each several part of specific embodiment and the various features enumerated can be combined or all or part of exchange.Above-mentioned
Each specific embodiment in, those with reference to another embodiment embodiment can suitably with its
Its embodiment combination, this is will be to understand by those skilled in the art.Additionally, those skilled in the art
It will be understood that, description above is only the mode of example, it is no intended to limit the present invention.
Claims (11)
1. a kind of preparation method of the acetal resin powder for selective laser sintering, methods described include with
Lower step：
A) at the heating temperature, acetal resin is dissolved in selected from amide-type, cyclic ethers class, ketone and kelene
In at least one organic solvent in hydro carbons, acetal resin solution is obtained；
B) the acetal resin solution cooling for obtaining step a), separates out solids of sedimentation, obtains solid-liquid mixing
Thing；
C) auxiliary agent is added in the solidliquid mixture that step b) is obtained, is well mixed；
D) separation of solid and liquid, drying solid obtains being applied to laser sintered acetal resin powder；
Wherein, the auxiliary agent includes separator powder and/or antioxidant.
2. method according to claim 1, it is characterised in that the melt index of the acetal resin exists
190 DEG C, 20-100g/10min, preferred 30-80g/10min are determined as under 2.16kg carrying capacity.
3. method according to claim 1 and 2, it is characterised in that with the acetal resin as 100
Parts by weight meter, the consumption of organic solvent is 600-1200 parts by weight, preferably 800-1000 weight portions
Number.
4. the method according to any one in claim 1-3, it is characterised in that
The amide-type is C1-C8Acid amides, is preferably selected from C2-C6Acid amides, preferably DMF
And/or DMAC N,N' dimethyl acetamide；
The cyclic ethers class is C2-C8Cyclic ethers, preferably tetrahydrofuran and/or dioxane；
The ketone is C3-C8Ketone, is preferably selected from C3-C5Ketone, in being preferably selected from acetone, butanone and pentanone
It is at least one；With
The kelene hydro carbons is C1-C8Chloralkane, is preferably selected from C1-C5Chloralkane, is preferably selected from two
At least one in chloromethanes, chloroform, tetrachloromethane, dichloroethanes, trichloroethanes and tetrachloroethanes.
5. the method according to any one in claim 1-4, it is characterised in that in step a),
The heating-up temperature is 100-180 DEG C, preferably 110-150 DEG C, more preferably 120-140 DEG C；It is preferred that
Acetal resin solution is kept into for 30-180 minutes in heating-up temperature.
6. the method according to any one in claim 1-5, it is characterised in that in step b),
Average rate of temperature fall is 0.1 DEG C/min-1 DEG C/min；Preferably, acetal resin solution is cooled into cooling mesh
Mark temperature, and kept for 30-90 minutes in cooling target temperature；It is preferred that the cooling target temperature is 10-30 DEG C.
7. the method according to any one in claim 1-6, it is characterised in that in step b),
Acetal resin solution is cooled into one or more medium temperatures, and is kept for 30-90 point in the medium temperature
Clock；The medium temperature is preferably 70-100 DEG C, preferably 80-90 DEG C.
8. the method according to any one in claim 1-7, it is characterised in that the antioxidant is selected from
Antioxidant 1010 and/or irgasfos 168；Count by 100 parts by weight of acetal resin, the antioxidant 1010
For consumption 0.1-0.5 parts by weight, preferably 0.2-0.4 parts by weight；Irgasfos 168 consumption is 0.1-0.5 weights
Amount number, preferably 0.2-0.4 parts by weight.
9. the method according to any one in claim 1-8, it is characterised in that the separator powder
Selected from based on the alkali metal or alkaline-earth metal of alkane monocarboxylic acid or dimeric dibasic acid, nano-oxide or nano metal salt
In at least one, be preferably selected from odium stearate, potassium stearate, zinc stearate, calcium stearate, lead stearate,
At least one in silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and barium sulfate；
Count by 100 parts by weight of acetal resin, the separator powder consumption is 0.01-10 parts by weight, excellent
Elect 0.1-5 parts by weight, more preferably 0.5-1 parts by weight as.
10. it is a kind of according to any one methods described in claim 1-9 prepare for selective laser
The acetal resin powder of sintering, the particle of the powder is spherical and/or spherical, and the particle size of particle is
20-150 μm, particle diameter distribution D10=41-73 μm, D50=51-105 μm, D90=68-132 μm.
A kind of 11. selective laser sintering methods, methods described is included by such as any one of claim 1-9
Described method prepares acetal resin powder, using as sintered powder raw material.
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| EP4092069A1 (en) * | 2021-05-20 | 2022-11-23 | Xerox Corporation | Polyoxymethylene microparticles and methods of production and use thereof |
| CN115678145A (en) * | 2022-09-29 | 2023-02-03 | 神华(北京)新材料科技有限公司 | High-fluidity powder material and preparation method and application thereof |
| CN115678145B (en) * | 2022-09-29 | 2024-02-27 | 神华(北京)新材料科技有限公司 | High-fluidity powder material, and preparation method and application thereof |
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Application publication date: 20170517 |