CN101623929B - Selective sintering of structurally modified polymers - Google Patents
Selective sintering of structurally modified polymers Download PDFInfo
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- CN101623929B CN101623929B CN200910159552.6A CN200910159552A CN101623929B CN 101623929 B CN101623929 B CN 101623929B CN 200910159552 A CN200910159552 A CN 200910159552A CN 101623929 B CN101623929 B CN 101623929B
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- polymer
- copolymer
- paek
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- phenylene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 243
- 238000005245 sintering Methods 0.000 title claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 159
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 128
- 125000003118 aryl group Chemical group 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 81
- 230000004048 modification Effects 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims abstract description 27
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 25
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 128
- 230000003252 repetitive effect Effects 0.000 claims description 50
- 229920002647 polyamide Polymers 0.000 claims description 45
- 239000004952 Polyamide Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 24
- 230000006872 improvement Effects 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- 229920000570 polyether Polymers 0.000 claims description 22
- -1 1,3-phenylene, 1,3-xylylene Chemical group 0.000 claims description 20
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 18
- 229920002530 polyetherether ketone Polymers 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000004957 naphthylene group Chemical group 0.000 claims description 14
- 125000001174 sulfone group Chemical group 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 13
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 8
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 claims description 4
- 229920000359 diblock copolymer Polymers 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 230000002349 favourable effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
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- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920001643 poly(ether ketone) Polymers 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000004662 dithiols Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QJZBYEVIOFWCCS-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1C(c(cc1)ccc1C(c(cc1)ccc1OC(C)(C)C)=O)=O Chemical compound CC(C)(C)c(cc1)ccc1C(c(cc1)ccc1C(c(cc1)ccc1OC(C)(C)C)=O)=O QJZBYEVIOFWCCS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 229920006153 PA4T Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000010603 microCT Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002699 waste material Substances 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08J3/28—Treatment by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material
- B29K2096/02—Graft polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
Abstract
A three-dimensional object is manufactured by selective sintering by means of electromagnetic radiation, wherein the powder comprises a polymer or copolymer having at least one of the following structural characteristics: (i) at least one branching group in the backbone chain of the polymer or copolymer, provided that in case of the use of polyaryletherketones (PAEK) the branching group is an aromatic structural unit in the backbone chain of the polymer or copolymer; (ii) modification of at least one end group of the backbone chain of the polymer or copolymer; (iii) at least one bulky group within the backbone chain of the polymer of copolymer, provided that in case of the use of polyaryletherketones (PAEK) the bulky group is not selected from the group consisting of phenylene, biphenylene, naphthalene and CH2 - or isopropylidene-linked aromatics; (iv) at least one aromatic group non-linearly linking the backbone chain.
Description
The field of the invention
The present invention relates to the method utilizing electromagnetic radiation to be manufactured three-dimensional body from powder by selective sintering method, wherein this powder comprises polymer or copolymer.In addition, the present invention relates to the three-dimensional body manufactured by the method, utilize the method to manufacture the device of three-dimensional body, and preselected polymer powder purposes in the method.
Such as know from DE 44 10 046, the method utilizing electromagnetic radiation to make three-dimensional body by selective sintering legal system can utilize electromagnetic radiation source to carry out with laminated form.In these class methods, three-dimensional body is layer by applying powder and on the position corresponding with the cross section of object, by the selective solidification of powder, these layers is bonded to one another and manufactures with laminated form.
The description of background technology
Fig. 1 exemplarily shows laser sintered equipment, utilizes it to carry out the method manufacturing three-dimensional body with laminated form.Can clearly be seen that from Fig. 1, equipment comprises container 1.This container opens wide at top and is used in bottom support that the support member 4 of the object 3 that will be formed limits.Working face 6 is determined by the top edge 2 sidewall of container (or by) of container.Object is positioned at the top side of support member 4 and is formed from the building material of the powder type of the electromagnetic radiation curable of multiple layers, and wherein these layers are parallel to the top side of support member 4.Therefore, it is movable that the sidewall that namely support member is parallel to container 1 in vertical direction comes via height adjusting apparatus.Immediately, the position of support member 4 can regulate relative to working face 6.
On container 1 or say more accurately a little on working face 6, provide the equipment of applying 10 by the dusty material 11 paint support surface 5 that will solidify or on the layer of prior cured.Further, the radiation device presenting laser instrument 7 form launching directional beam 8 is arranged on working face 6.This light beam 8 is as directed in revolving mirror as this working face 6 of deflected beam 8 ' directive by deflecting apparatus 9.Control unit 40 allows to control this support member 4, applies equipment 10 and deflecting apparatus 9.Parts 1-6,10 and 11 are positioned within machine frame 100.
In the manufacture of three-dimensional body 3, dusty material 11 to be applied on the layer of support member 4 or prior cured with laminated form and to utilize laser beam 8 ' to solidify on the position corresponding with object of each powder bed.After each selective solidification of coating, this support member reduce by the thickness of powder bed that applies subsequently.
Compared with system as above, the many improvement utilizing electromagnetic radiation to be made the method and apparatus of three-dimensional body by selective sintering legal system exist all, and they also can use.Such as, substitute and use laser and/or light beam, other system of selective output electromagnetic radiation can be used, as mask exposure system etc.
But carry out in the prior method of selective sintering in the electromagnetic radiation by polymer powder, the mechanical performance not giving manufactured object is enough noted.
Object of the present invention
Therefore, the object of this invention is to provide and carry out selective sintering to manufacture the improvement of a kind of method of three-dimensional body by the electromagnetic radiation of polymer powder, this causes manufactured object to have the mechanical performance of improvement.
General introduction of the present invention
Summarize in the following of the present invention various in, favorable characteristics and preferred embodiment-separately separately or combine-for realizing object of the present invention:
(1) utilize electromagnetic radiation to be manufactured the method for three-dimensional body from powder by selective sintering method, wherein this powder comprises polymer or the copolymer of the having structure characteristic with at least one:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group (bulky group) in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), this bulky group is not selected from phenylene, biphenylene, naphthylene and CH
2-or the aromatic hydrocarbon of isopropylidene-connection;
(iv) at least one aromatic group of non-linearly connecting framework chain.
(2) according to the method for (1) item, the successive layers of the object formed from curable dusty material is wherein needed to solidify in the position corresponding with the cross section of object subsequently.
(3) according to the method for (1) or (2) item, electromagnetic radiation is provided by laser in the method.
(4) can the method for according to appointing in every above, it be included in sintering step after pre-determining and/or the cooling step of control.
(5) according to the method for (4) item, it comprises with 0.01-10 DEG C/min, preferably 0.1-5 DEG C/min and the more preferably cooldown rate of 1-5 DEG C/min, by the object after the completion of object from the T than polymer contained in the powder or copolymer
mlow 1-50 DEG C, preferably 1-30 DEG C and the more preferably temperature of 1-10 DEG C are cooled to the T of polymer contained by powder or copolymer
gstep, wherein a T
mbe included in fusing point and the T of polymer in powder or copolymer
git is the glass transition temperature of this polymer or copolymer.
(6) according to any one method in project above, wherein powder comprises fusing point T
mat 100 DEG C-450 DEG C, preferably 150 DEG C-400 DEG C and the polymer more preferably within the scope of 250 DEG C-400 DEG C or copolymer.
(7) according to any one method in project above, wherein powder comprises glass transition temperature T
gat 50 DEG C-300 DEG C, preferably 100 DEG C-300 DEG C and the polymer more preferably within the scope of 130 DEG C-250 DEG C or copolymer.
(8) according to any one method in project above, wherein polymer or copolymer have at least 10,000, more preferably the equal M of number of 15,000-200,000 and especially 15,000-100,000
nor at least 20,000, and more preferably 30,000-500,000 weight average M
wespecially the weight average M of 30,000-200,000
w.
(9) according to any one method in project above, wherein polymer or copolymer have 10-10, and 000, the more preferably polymerization degree n of 20-5000 and especially 50-1000.
(10) according to any one method in project above, wherein polymer or copolymer in skeletal chain, preferably in the repetitive of skeletal chain containing at least one aromatic group.
(11) according to any one method in project above, wherein according to improvement (iv), the non-linear connection aromatic group of at least one is included in the repetitive of skeletal chain.
(12) according to the method for project (11), wherein according to improvement (iv), non-linear connection aromatic group is independently selected from 1,2-and 1,3-phenylene, 1,3-xylylene, 2,4 '-and 3,4 '-biphenylene, and 2,3-and 2,7-naphthylene.
(13) according to the method for project (11) or (12), wherein according to improvement (iv), aromatic group that polymer or copolymer in skeletal chain, preferably add containing at least one different from non-linear connection aromatic group in the repetitive of skeletal chain, linearly connected and/or at least one branched groups.
(14) according to any one method in project above, wherein this aromatic group is selected from monocycle that is unsubstituted or that replace or polycyclic aromatic hydrocarbon independently of one another.
(15) according to the method for project (13) or (14), wherein according to improvement (iv), the aromatic group of linearly connected is selected from Isosorbide-5-Nitrae-phenylene independently of one another, 4,4 '-biphenylene, 4,4 '-isopropylidenediphenylene, 4,4 '-diphenyl sulfone, Isosorbide-5-Nitrae-, 1,5-, 2,6-naphthylene, 4,4 "-p-sub-terphenyl base (terphenylene) and 2,2-pair-(4-phenylene)-propane.
(16) according to any one method in project above, wherein according to improvement (i), branched groups has the aliphatic hydrocarbon of at least one substituting group or a side chain, aromatic hydrocarbon or heteroaromatic hydrocarbon, for the situation using PAEK (PAEK), branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer.
(17) according to the method for project (16), wherein according to improvement (i), this side chain is selected from C independently of one another
1-C
6the alkyl of nonbranched or branching, chain or annular or alkoxyl and aryl.
(18) according to the method for project (16) or (17), wherein methyl is selected from independently of one another, isopropyl, the tert-butyl group or phenyl according to improvement (i) this side chain.
(19) according to any one method in project above, wherein according to improvement (ii), the end group of skeletal chain by end alkyl, alkoxyl, ester group and/or the modification of aryl institute.
(20) according to any one method in project above, wherein according to improvement (iii), bulky group is aromatics or nonaromatic, and for using the situation of PAEK (PAEK), this bulky group is not selected from phenylene, biphenylene, naphthylene and CH
2-or the aromatic hydrocarbon of isopropylidene-connection.
(21) according to the method for project (20), wherein according to improvement (iii), this bulky group is polycyclic aromatic or nonaromatic.
(22) according to the method for project (20) or (21), wherein according to improvement (iii), this bulky group is selected from phenylene, naphthalene, anthracene, biphenyl, fluorenes, terphenyl, decahydronaphthalene or norcamphane.
(23) according to any one method in project above, wherein use the mixture of at least two kinds of different polymer or copolymer, at least one in wherein blending (being total to) polymers compositions has at least one in the middle of the architectural characteristic mentioned in 1.
(24) according to any one method in project above, wherein polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES), polyester, polyethers, polyolefin, polystyrene, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise at least one above-mentioned polymer block copolymer based on formed.
(25) according to any one method in project above, wherein polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES) or comprise at least one above-mentioned polymer block copolymer based on formed.
(26) according to the method for project (24) or (25), wherein block copolymer is preferably PAEK (PAEK)/polyether sulphone (PAES)-diblock copolymer or PAEK/PAES/PAEK-triblock copolymer.
(27) according to any one method in project above, wherein polymer is with polyether-ether-ketone (PEEK), PEKK (PEKK), polyether-ketone (PEK), polyether ether ketone ketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), polyarylether ether ether ketone (PEEEK) or comprise the PAEK (PAEK) formed based on the copolymer of the above-mentioned polymer of at least one.
(28) according to the method for project (27), wherein PAEK (PAEK) is formed based on PEKK (PEKK) polymer or copolymer.
(29) according to any one method in project above, the polymer wherein based on PAEK (PAEK) or copolymer have 0.05-1.0kN*s/m
2, preferred 0.15-0.6kN*s/m
2especially 0.2-0.45kN*s/m
2melt viscosity.
(30) according to any one method in project (24)-(29), wherein PAEK (PAEK) polymer or copolymer have preferred 10-1,000, more preferably 20-500, and the polymerization degree n of especially 40-250.
(31) according to any one method in project (27)-(30), wherein PEKK (PEKK) polymer or copolymer comprise, in the skeletal chain of polymer, preferably in the repetitive of skeletal chain, 1,4-phenylene as linearly connected aromatic group and 1,3-phenylene as non-linear connection aromatic group.
(32) according to any one method in project (27)-(31), wherein comprise separately at least one 1, the repetitive of 4-phenylene-unit with comprise one 1 separately, the ratio of the repetitive of 3-phenylene-unit is 90/10-10/90, preferred 70/30-10/90, more preferably 60/40-10/90.
(33) utilize the three-dimensional body that electromagnetic radiation is obtained by the selective sintering method of the polymer of powder type, copolymer or blend polymer, wherein there is for the polymer of this powder or copolymer the having structure characteristic of at least one:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or the aromatic hydrocarbon of isopropylidene-connection;
(iv) at least one aromatic group of non-linearly connecting framework chain.
(34) according to the three-dimensional body of project (33), wherein polymer or copolymer defined according in 6-32 item.
(35) utilize the electromagnetic radiation of powder to be manufactured the device of three-dimensional body from this powder by selective sintering method, wherein this device comprises Temperature-controlled appliance, and the latter is mounted the predetermined cooling down operation being set in object after object manufacture is completed.
(36) according to the device of project (35), the cooldown rate wherein set by Temperature-controlled appliance depends on the type of polymer comprised in the powder, copolymer or blend polymer.
(37) according to the device of project (35) or (36), wherein Temperature-controlled appliance sets according to the predefined type of polymer, copolymer or blend polymer.
(38) manufacturing system, it comprises: according to any one device in the item of (35)-(37), and the powder comprising at least one polymer or copolymer defined in the item of (6)-(32).
(39) purposes of polymer powder in the process utilizing selective electromagnetic radiation sintering process manufacture three-dimensional body, wherein polymer is selected from polymer or the copolymer of the having structure characteristic with at least one in advance:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or the aromatic hydrocarbon of isopropylidene-connection;
(iv) at least one aromatic group of non-linearly connecting framework chain.
(40) according to the purposes of (39) item, wherein polymer or copolymer defined according in the item of (6)-(32).
Find surprisingly, when adopting polymer or the copolymer of structurally special modification in selective sintering process, the obvious improvement of some very favorable mechanical performance is obtained in manufactured three-dimensional body, these performances include but not limited to high stiffness, high compressive strength, high impact strength, high ultimate tensile strength and bending strength and high elongation at break and high heat deflection temperature, on the other hand, contrary characteristic such as good chemical resistance and low post crystallization still balance well simultaneously.In addition, find surprisingly, separately by special process conditions or by observing cooldown rate after sintering, ensure that above-mentioned mechanical performance larger improvement and and contrary characteristic between well balanced.In addition, can realize the suitable degree of crystallinity of setting and the comprehensively significantly improved of low porosity in manufactured three-dimensional body, this contributes to the further improvement of above-mentioned performance.When modified polyether ketone or poly (aryl ether ketone) copolymer or polyamide polymer or polyamide copolymer are used as the polymeric material of polymer powder separately, advantage of the present invention can reach especially.The intended overall of the various characteristics realized by the present invention is mainly owing to the following fact: the polymer of structurally special modification and copolymer allow the setting of the degree of crystallinity of a favourable scope in manufactured three-dimensional body and three-dimensional body has low porosity simultaneously.In addition, advantage of the present invention also can be used for composite, and wherein crystallinity value is relevant with the polymer substrate of composite.Except comprising the matrix of respective polymer, copolymer or blend polymer, this type of composite also comprises one or more fillers and/or additive.
For general polymer, the final degree of crystallinity in obtained object is 80% or less, preferably 50% or less, and more preferably 5-70%, even more preferably 15-50% and especially 15-35%.Especially for such as PAEK (PAEK), the final degree of crystallinity in obtained object is 5-45%, preferred 10-40%, more preferably 15-35%, even more preferably 15-30%, and especially 20-25%.Especially for such as polyamide (PA), the final degree of crystallinity in obtained object is 10-50%, preferred 15-40%, more preferably 15-35% and especially 20-30%.The porosity of general polymerization thing lower than 10%, preferably lower than 5%, more preferably less than 3% with especially lower than 2%.
Traditional polymer process technology as the pressure processing involving polymer resembles the preferred alternative hereto of such as injection moulding, can carry out with laminated form (layer-wise) in additive process (additive process) according to method of the present invention, wherein need the successive layers of the object formed from curable dusty material to be solidified by electromagnetic radiation on the position corresponding with the cross section of object subsequently.
The summary of accompanying drawing
Fig. 1 exemplarily shows the laser sintered equipment that the laminated form for three-dimensional body manufactures.
The description of preferred embodiment
The present invention describes in more detail with reference now to further preferred and more favourable embodiment and embodiment, but these provide just to illustrational object and should not be construed and limit the scope of the invention.
When polymer powder materials comprises the following condition in these of being selected from at least one, when the polymer of optional tool combination with these conditions or copolymer: (i) be at least one branched groups in skeletal chain, (ii) modification of end group, (iii) at least one aromatic group of at least one bulky group and (iv) non-linearly connecting framework chain, this can cause the remarkable improvement of some very favorable mechanical performance, these performances comprise high stiffness, high compressive strength, high impact strength, high ultimate tensile strength and flexural strength and high elongation at break and high thermal distoftion, on the other hand simultaneously, contrary performance such as good chemical resistance and the low post-shrinkage ratio caused by post crystallization still balance well.In addition, the minimizing of the porosity of manufactured object becomes possibility due to the improvement of the mechanical performance of manufactured object in addition.
The object utilizing the electromagnetic radiation comprising the powder of at least one polymer to be manufactured by selective sintering method typically has the crystallinity value more much higher than the degree of crystallinity being resembled the object that such as injection moulding manufactures by traditional polymer processing techniques, namely, manufacture the method for three-dimensional body by selective sintering method from powder utilizing the electromagnetic radiation comprising the powder of at least one polymer, that such as shown in FIG type method, the degree of crystallinity of manufactured object is tended to become higher, if do not use structurally-modified polymer of the present invention or copolymer.Specifically, in the method for laminated form structure, the general fusing point T used than polymer
mlow about 1-50 DEG C, preferred 1-30 DEG C, even more preferably 1-20 DEG C and the most preferably high powder bed temperature of 1-10 DEG C.This object is typically exposed to compared with high processing temperature considerable time and the cool time that experience is very long usually.In order to prevent or farthest reduce the curling of in construction process object, processing temperature should keep the fusing point close to polymer contained in the powder, to guarantee good connection between successive layers and farthest to reduce the formation of the hole caused by the inappropriate fusing of powder particle.Therefore, in whole construction process, the temperature of powder bed is kept above the crystallization temperature Tc of polymer.The object formed itself can be exposed to the temperature higher than Tc for a long time.At the end of construction process, when whole heating sources of sintering machine are closed, because the atural beat of environment loses, start the cooling procedure running through Tc of object.Because the low heat conductivity of polymer powder and large powder bed, this may need cost a few hours by several days,-depend on used polymer powder and processing conditions, namely pre-determine that suitable cooldown rate-this may further increase the crystallization of final polymeric object in cooling procedure.Do not have suitable control, the post crystallization of even laser sintered polymeric object also can occur.Therefore, not according to controlled cooling model step of the present invention, in manufactured object, higher and partly high degree of crystallinity is obtained.And then do not have suitable limiting crystal degree, the related mechanical properties of object may be impaired.
On the other hand, in selective sintering method according to the present invention, the height that degree of crystallinity in manufactured object can advantageously be conditioned still enough, guarantee the high chemical resistance for manufactured object simultaneously, at the post-shrinkage ratio that the temperature higher than Tg bends down, or the positive impact of high stiffness.Therefore, the excellent balance of properties can be realized by the present invention.
When the degree of crystallinity of the material from polymer powder materials manufacture suitably limits and is preferably adjusted in specific scope, the obvious improvement that some very favorable mechanical performance resembles hot strength, Young's modulus and elongation at break can be realized.The effective especially and preferred measure taked in order to the degree of crystallinity limiting manufactured object is: the 1) polymeric material of preselected suitable type, 2) architectural characteristic and/or the modification of the polymer that preselected powder comprises is noted, and/or 3) note cooling step that is predefined after the sintering process of object terminates and/or that control.
Therefore, according to the preferred embodiments of the invention, the cooling step pre-determining and/or control preferably is applied in the object after the completion of object after the sintering.The cooling step pre-determined and/or control can pass through predetermined Slow cooling, may be slower than nature (passive) cooling, or by active cooling to provide cooling fast to realize.Because the condition of the cooling step pre-determined and/or control depends primarily on type and the specification of used polymer, copolymer or blend polymer, useful the imposing a condition of this cooling step can be tested by experiment, precondition is that the final degree of crystallinity in manufactured object is controlled, and makes manufactured object have required mechanical property.
But the cooldown rate after the completion of object also can have influence on the curling of object and therefore have influence on the dimensional stability of object.Find surprisingly, cooldown rate can pre-determine and make three-dimensional body not only have the degree of crystallinity of reduction to provide above-mentioned favourable mechanical performance, and has high dimensional stability, and namely it is not curling.
The polymeric material of suitable type can be selected from: PAEK (PAEK), polyether sulphone (PAES), polyamide, polyester, polyethers, polyolefin, polystyrene, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides and comprise the copolymer of above-mentioned polymer of at least one, wherein this selection but be not limited to above-mentioned polymer and copolymer.Such as, suitable PAEK polymer and copolymer are preferably selected from: polyether-ether-ketone (PEEK), PEKK (PEKK), polyether-ketone (PEK), polyether ether ketone ketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), polyarylether ether ether ketone (PEEEK) and comprise the copolymer of above-mentioned polymer of at least one.Suitable polyamide polymer or copolymer can be selected from by polyamide PA6T/6I, poly hexamethylene adipamide sub-meta-xylene base diamines (poly-m-xylylenadipamide) (PA MXD6), polyamide 6/6T, polyamide elastane body image polyether block amide is as PEBAX
t mshaped material, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 612, polyamide 610, polyamide 1010, polyamide 1212, the group that polyamide PA6T/66, PA4T/46 form with the copolymer of the above-mentioned polymer comprising at least one.Suitable polyester polymers or copolymer can be selected from the group be made up of the copolymer of polyalkylene terephthalates (such as PET, PBT) and they and isophthalic acid and/or 1,4-CHDM.Suitable polyolefin polymer or copolymer can be selected from the group be made up of polyethylene and polypropylene.Suitable poly styrene polymer or copolymer can be selected from the group be made up of syndyotactic and isotactic polystyrene.The respective architectural characteristic defined in the following claims can according to suitable method and mode, and structure changes, and selection of the suitable ingredients of (being total to) polymer etc. is considered.
Be particularly preferred for having structure characteristic and/or the modification according to the polymer in selective sintering method of the present invention or copolymer with at least one:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or the aromatic hydrocarbon of isopropylidene-connection;
(iv) at least one aromatic group of non-linearly connecting framework chain.
This structurally-modified (i)-(iv) makes an explanation below.
For architectural characteristic (i) " branched groups ", group G is understood to refer to, except the key of the various piece (A of skeletal chain and part B) of the skeletal chain of connection polymer shown below,
, also there is at least one side chain and substituting group S (respectively).Advantageously, G is aliphatic hydrocarbon, aromatic hydrocarbon or heteroaromatic hydrocarbon.This side chain or substituting group " S " affect the activity of polymer chain in the melt respectively and therefore, it is possible to affect the final degree of crystallinity of manufactured object aptly.Preferably, this substituting group is selected from independently of one another by C
1-C
6the group of the nonbranched or straight chain of branching or the alkyl of annular or alkoxyl and aryl composition, wherein methyl, isopropyl, the tert-butyl group or phenyl are particularly preferred.In addition, side chain or substituting group S are preferred, they allow respectively the further derivatization of obtained polymer or copolymer-optionally after going protection-, the synthesis of such as graft copolymer.The above exemplary citing of branched groups only show a kind of branched groups.But, more branched groups can be had to be present in polymer, especially when branched groups is the repetitive of polymer a part of.This construction unit (G-S) also can be above shown in the A of skeletal chain and/or the single of part B or various ingredients.When using PAEK (PAEK), branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
Refer to for architectural characteristic (ii) " modification of at least one end group of the skeletal chain of polymer or copolymer ", as follows, one or both ends X and Y of polymer backbone chains is by end group R
1and/or R
2derivatization,
(X)
nskeletal chain-(Y) of-polymer
m→ (R
1)
nskeletal chain-(the R of-polymer
2)
m
Wherein n, m are 0 or integer independently of one another, preferably 1, and be 0 when wherein both n, m are different.Represented by n, m, also has the multiple modification of end group.Relevant in the present embodiment, therefore respective unmodified end group X and Y also can stimulate undesirable excessive crystallization as seed crystal.Therefore, at least one in end group X and Y of polymer or copolymer can derivatization, to disturb crystallization and the degree of crystallinity of the manufactured object of in this way restriction.Preferably, this end group R
1and R
2independently selected from alkyl, alkoxyl, ester group and/or aryl.Such as, R
1and R
2be selected from independently of one another by branching or nonbranched C
1-C
6alkyl, preferable methyl, isopropyl or the tert-butyl group; The nonbranched C of Zhi Huacheng
1-C
6alkoxyl, preferred methoxyl group, isopropoxy, tert-butoxy; Replace or unsubstituted C
1-C
6aliphatic (acid) ester group, preferable methyl ester, ethyl ester, isopropyl esters or tertiary butyl ester; Replace or unsubstituted aromatic ester group, preferred benzoate group and replacement or unsubstituted aryl, preferred phenyl, naphthyl, the group of anthryl composition.This end group also can be selected, and makes them preferably higher than polymer T
mtemperature under cause chain extension by chemical reaction each other, such as polycondensation reaction, parent's electricity or nucleophilic substitution, or coupling reaction.This so cause the final degree of crystallinity in object because increase mole and decline.
For architectural characteristic (iii) " bulky group ", refer to that such as cycloalkyl resembles cyclohexyl or how ring-like cycloalkyl as decahydronaphthalene or norbornane, wherein can contain hetero atom in their ring structure.Other example of bulky group is that aromatic hydrocarbon resembles phenylene or condensed polycyclic hydrocarbon or heteroaromatic hydrocarbon, such as naphthalene or anthracene (residue), fluorenes and fluorene derivative (residue), or polynuclear aromatic hydrocarbon resembles biphenylene or sub-terphenyl base.This bulky group represents the rigidity clavate segment in polymer chain, therefore, it is possible to disturb crystallization and result in the lower final degree of crystallinity in manufactured object.The type of polymer or copolymer is depended in the selection of bulky group.Although such as aliphatic polymer as a phenylene-unit for poly situation can represent bulky group already, bulky group is not considered to for phenylene for the situation of the PAEK of definition containing phenylene-unit.When using PAEK (PAEK), for the embodiment according to architectural characteristic (iii), this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH
2-or isopropylidene-connection aromatic hydrocarbon composition group.
As for architectural characteristic (iv) " aromatic group non-linearly connected ", aromatic group refers to that each several part of its connecting framework chain is located with making these part non-linear relative orientations, that is, the angle between each several part of skeletal chain is different from 180 °.
As for the introducing of the aromatic group non-linearly connected in the skeletal chain of polymer, final degree of crystallinity in manufactured object can reduce in a controlled fashion, accordingly, favourable mechanical performance can be obtained and resemble Young's modulus, hot strength and elongation at break.In addition, the fusing point of polymer can decline because of the introducing of the aromatic group of non-linear connection, makes it in particularly advantageous temperature range, and glass transition temperature can set and makes manufactured object have particularly advantageous thermal distoftion temperature.
The aromatic group non-linearly connected is such as 1,3-phenylene and 1,2-phenylene, because the A of polymer backbone chains and part B link together with the angle of 120 ° and 60 ° by respectively, as shown below:
Other preferred non-linear aromatic group is such as 1,3-xylylene, 2,4 ' and 3, and 4 '-biphenylene and 2,3-and 2,7-naphthylene.
With non-linearly linking group is contrary, the aromatic group connected linearly is with the various piece of the angle connecting framework chain of 180 °.Such as, Isosorbide-5-Nitrae-phenylene represents the aromatic group connected linearly, because the A of the polymer backbone chains described schematically and part B are connected with the angle of 180 °, as shown below.
The group of the linearly connected be made up of condensed aromatic groups can the various piece of connecting framework chain linearly in two different ways, and it is such as illustrated by naphthalene, but is also suitable for other condensed-nuclei aromatics such as anthracene or phenanthrene.Such as, the naphthalene of Isosorbide-5-Nitrae-naphthylene form can connect A and the part B of polymer backbone chains with the angle of 180 °.Additionally, naphthalene also can connect with the form of 1,5-naphthylene or 2,6-naphthylene linearly, and A and the part B of the skeletal chain wherein described in a schematic way are arranged in parallel with each other.
1, the 5-naphthylene as linearly connected unit:
2, the 6-naphthylenes as linearly connected unit:
Respectively non-linear connection with linearly connected with the above exemplary diagram of aromatic group only show one separately non-linearly with the aromatic group be connected linearly.But, manyly non-linearly to may reside in polymer with the group be connected linearly separately, if the group especially non-linearly or linearly connected is the component of the repetitive of polymer.
According to architectural characteristic (iv), non-linearly connect with aromatic group be possible with the combination of the aromatic group be connected linearly.
In addition, the molecular weight of the suitable setting of polymer contained in the powder can impel the remarkable decline of degree of crystallinity in manufactured object, this so that cause the remarkable improvement of some very favorable mechanical performance in manufactured object.Therefore, molecular weight M
n(mean value) is preferably set at least 10,000, and more preferably 15,000-200,000 and especially 15,000-100,000, or M
w(mean value) is preferably set at least 20,000, and more preferably 30,000-500,000, and especially 30,000-200,000.
Above the similar explanation described in molecular weight is also applicable to the melt viscosity of polymer or copolymer.The melt viscosity relevant to the molecular weight of polymer or copolymer is as follows: the molecular weight of polymer or copolymer is higher, and its melt viscosity is higher.Therefore, the preferred melt viscosity of such as general PAEK and their copolymer is at 0.05-1.0kN*s/m
2, preferred 0.15-0.6kN*s/m
2especially 0.2-0.45kN*s/m
2in scope.Melt viscosity can according to the introduction of US patent 2006/0251878 A1, at 400 DEG C and 1000s in capillary viscometer
-1shear rate under measure.
This polymer or copolymer can with the component blending in mixture (blend) forming alloy, wherein use the blend of at least two kinds of different polymer or copolymer.In such blends, the final degree of crystallinity of the object manufactured by least one component preferably in blend reduces.
In order to desired result, degree of crystallinity especially in manufactured object and its mechanical performance, exceed architectural characteristic (i) included in polymer or copolymer and the general condition of (iii), have following restriction for PAEK (PAEK):
For feature (i): branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer, and
For feature (iii): bulky group is not selected from by phenylene, biphenylene, naphthylene and CH
2-or isopropylidene-connection aromatic hydrocarbon composition group.
For the polymer of other type, especially polyamide (PA), polyester, polyethers, polyolefin, polystyrene, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise the copolymer of the above-mentioned polymer of at least one, the restrictive condition provided for PAEK is inapplicable.
Hereinafter, some important structural behaviours of polymer or copolymer material or modification to be illustrated description by the PAEK polymer and copolymer being suitable for preselected (this preselected be applicable to utilize the selective sintering process of electromagnetic radiation).It is evident that for person skilled in the art, the structural behaviour of the following stated or modification can similarly for polymer or the copolymers of other type.
The general formula below provided show for manufacture laser sintered object the general structure of preferred PAEK or PAES polymer and copolymer, wherein further describe to obtain low degree of crystallinity below, separately or the preferred structure combined unique:
Ar
1, Ar
2and Ar
3monocycle or the polycyclic aromatic hydrocarbon of the unsubstituted or replacement connected linearly or non-linearly, wherein with Rf
1, Rf
2and/or Rf
3for H independently, substituting group can optionally be selected from:
Rf
1, Rf
2, Rf
3be selected from independently of one another by C
1-C
6straight chain, branching or the alkyl of ring-type and alkoxyl, and the group of aryl composition, preferred Me, i-Pr, t-Bu, Ph are (for unsubstituted Ar
1, Ar
2and Ar
3, Rf
1, Rf
2, Rf
3=H), wherein each Ar
1, Ar
2and Ar
3one or more substituent R f can be had separately
1, Rf
2, Rf
3,
X=O and/or S
Y=CO and/or SO
2
Z=SO
2, CO, O and/or S
A is greater than 0, preferably lower than 12, and the more preferably rudimentary integer of 1-6 and especially 1-3,
B is greater than 0, and preferably lower than 12, more preferably the rudimentary integer of 1-6 and especially 1-3,
C is 0 or rudimentary integer, preferably lower than 12, and more preferably 1-6 and especially 1-3,
N represents the degree of polymerization.
In above-mentioned general formula, index a, b and c are illustrated respectively in the quantity of respective unit in the repetitive of polymer or the repetitive of copolymer, wherein one or more unit of identical type, such as with the unit that index a represents, dissimilar unit can be positioned at, such as with the unit that index b and/or c represent, between.In repetitive, the position of respective unit can draw from the abbreviation of PAEK derivative.
The above general formula of PAEK or PAES polymer or copolymer carrys out clear interpretation by by means of example below PAEK polymer according to the present invention.Therefore, in use according in an embodiment of PAEK of the present invention, Ar
1unsubstituted 4,4 "-p-sub-terphenyl base, X=O and a=1, Ar
2be unsubstituted Isosorbide-5-Nitrae-phenylene, Y is O and b=1 and Ar
3be unsubstituted Isosorbide-5-Nitrae-phenylene, Z is CO and c=1, and wherein structural formula represents this PAEK below
, wherein n represents the degree of polymerization.
In PAEK polymer or copolymer, except traditional Isosorbide-5-Nitrae phenylene, huger group is as being selected from by biphenylene, naphthylene and CH
2-or isopropylidene-connection aromatic hydrocarbon composition group in those should be selected, as p-sub-terphenyl base.
Following two example PEKK with PEKEKK of PAEK polymer are the examples of the PAEK polymer with the aromatic group be connected linearly.Such as, therefore, for PEKK, Ar
1be unsubstituted Isosorbide-5-Nitrae-phenylene, X is O and a=1, Ar
2be unsubstituted Isosorbide-5-Nitrae-phenylene, Y is CO and b=2 and c=0, and wherein following structural represents PEKK
Wherein n represents the degree of polymerization.In another example PEKEKK, Ar
1be unsubstituted Isosorbide-5-Nitrae-phenylene, X is O and a=2, Ar
2be unsubstituted Isosorbide-5-Nitrae-phenylene, Y is CO and b=3 and c=0, and wherein following structural represents PEKEKK
, wherein n represents the degree of polymerization.
Following example shows the PAEK polymer adopted according to the present invention, namely has the PEKK copolymer of the unit non-linearly connected.This PEKK copolymer has 2 kinds of different repetitives (repetitive A and B see in following structural formula).
Repetitive A:
Repetitive B:
In repetitive A, Ar
1be unsubstituted Isosorbide-5-Nitrae-phenylene, X is O and a=1, Ar
2be unsubstituted Isosorbide-5-Nitrae-phenylene, Y is CO, b=2 and c=0.In repetitive B, Ar
1be Isosorbide-5-Nitrae-phenylene that end is substituted, X is O and a=1, Ar
2be unsubstituted 1,3-phenylene, Y is CO and b=1 and Ar
3be Isosorbide-5-Nitrae-phenylene, Z is CO and c is 1.Depend on synthesis, repetitive A and B strictly can replace in the skeletal chain of copolymer, arrange random or block.The polymerization degree n of this PEKK copolymer represents n
1and n
2summation.
Find surprisingly in the selective sintering of above-mentioned PEKK copolymer, the final degree of crystallinity of manufactured object is lower, and the content of 1,3-phenylene-unit is higher (embodiment 1 being compared with embodiment 2).Find in addition, the fusing point of copolymer can reduce by improving the content of 1,3-phenylene-unit in PEKK copolymer.This reduction of fusing point is the advantage for processing at laser sintered Program.Therefore, it is possible to the lower temperature of Choice and process chamber, this allow that the sintering process of Energy Efficient.Therefore, the Isosorbide-5-Nitrae in repetitive A-phenylene-unit Ar
2with 1,3-phenylene-unit Ar in repetitive B
2ratio be preferably 90/10-10/90, more preferably 70/30-10/90 and especially 60/40-10/90.This type of PEKK copolymer can such as by diphenyl ether and as having 1, the terephthalic acid (TPA) of the monomer of 4-phenylene-unit and paraphthaloyl chloride (respectively) and replacing as the M-phthalic acid of monomer and parent's electricity aromatics of m-phthaloyl chloride (respectively) with 1,3-phenylene-unit obtains.
In addition, the ratio between the quantity and the quantity of ether or sulfide group of ketone group Y is preferably 1: 4 to 4: 1.Within the scope of this, the final degree of crystallinity in manufactured object can reduce significantly.
Aromatic hydrocarbon Ar
1, Ar
2and Ar
3requisite space larger, aromatic hydrocarbon is more as the rigidity clavate segment, and the final degree of crystallinity of manufactured object is lower.Because of than preferably, for the aromatic group connected linearly, this aromatic hydrocarbon radical Ar
1, Ar
2and Ar
3respectively with independently selected from by Isosorbide-5-Nitrae-phenylene, 4,4 '-biphenylene, 4,4 '-isopropylidenediphenylene, 4,4 '-diphenyl sulfone, 1,4-, 1,5-and 2,6-naphthylene, 4,4 " the sub-terphenyl base of-p-and 2,2-two-group of (4-phenylene)-propane composition; and for the aromatic group non-linearly connected, they are respectively with independently selected from by 1,2-and 1; 3-phenylene; 1,3-xylylene, 2; 4 '-and 3; group of 4 '-biphenylene and 2,3-and 2,7-naphthylene composition.
When PAEK, branched groups can by having substituent R f
1, Rf
2, Rf
3aromatic hydrocarbon Ar
1, Ar
2and Ar
3there is provided, wherein whether it is linear or nonlinear all irrelevant with the connecting key in aromatic hydrocarbon in this case.
Customize this polymer make the low-crystallinity in manufactured object be in selective sintering process after other possibility of realizing be the use of suitable copolymerizable thing.For PAEK, except above-mentioned PEKK copolymer, the copolymer of it and polyether sulphone (PAES) is preferred, especially preferably PAEK (PAEK)/polyether sulphone (PAES)-diblock copolymer or PAEK/PAES/PAEK-triblock copolymer, more preferably polyether-ketone (PEK)/polyether sulfone (PES)-diblock copolymer or PEK/PES/PEK-triblock copolymer.Have been found that the degree of crystallinity of manufactured object is lower, the amount of polyether sulphone component is higher.Therefore, the ratio of sulfuryl group's quantity of Z and the quantity of ketone groups Y is preferably between 50: 50 and 10: 90.Within this ratio ranges, the glass transition temperature (Tg) of polymeric material and fusing point (T
m) can regulate, make the selective sintering legal system be suitable for by employing electromagnetic radiation make processable polymer in the device of three-dimensional body.In order to provide suitable processing temperature for selective sintering method, this PEK/PES copolymer preferably has the fusion temperature T of Tg and 300-430 DEG C higher than 180 DEG C
m.
The end group of the skeletal chain of polymer or copolymer depend on for the synthesis of monomer type and depend on the type of polymerisation.Hereinafter, show two kinds of dissimilar PAEK synthetic routes, obtain the dissimilar PAEK with different end group.
PAEK can synthesize by two kinds of approach usually, namely replaces (Knut Fridell-Krafft-acidylate) or the replacement of nucleophilicity aromatics by electrophilic aromatic.Such as, in the nucleophilic synthesis of PAEK, Isosorbide-5-Nitrae-bis-hydroxy benzenes and 4,4 '-dihalogenated benzophenone component polymerization:
xHO-Ph-OH+(y+1)Hal-Ph-CO-Ph-Hal→
Hal-Ph-CO-Ph-[O-Ph-O]x[Ph-CO-Ph]y-Hal
, wherein Hal is the quantity that F, Cl, Br and x and y represent the monomer be incorporated in polymer.
Result, PAEK skeletal chain in above PEEK example is passable, not in the either end of skeletal chain or in one end (not shown) or two ends (showing) of skeletal chain, stopped by the residual halogens group after polymerisation, optimum is stopped by fluorine, is optionally alternatively stopped by chlorine or bromine.This is equally applicable to the synthesis of PAEK or polyether sulfone (PAES) copolymer, and wherein this dihalogenated ketone unit can partly be substituted by dihalogenated aromatic sulfones.The two hydroxy component of this aromatics can similarly partially or even wholly be substituted by dithiol component.
Such as, the end of the halogen substiuted of polymer can by carrying out derivatization by the cessation reaction of phenol:
2Ph-OH+Hal-Ph-CO-Ph-[O-Ph-O]x[Ph-CO-Ph]y-Hal→
Ph-O-Ph-CO-Ph-[O-Ph-O]x[Ph-CO-Ph]y-O-Ph
Preferably, the Hal in above general formula is F.
This is equally applicable to the synthesis of PAEK-or polyether sulfone (PAES) copolymer, and wherein this dihalogenated ketone cell mesh ground is substituted by dihalogenated aromatic sulfones unit.The two hydroxy component of aromatics can similarly partially or even wholly be substituted by dithiol component.
For the situation of being synthesized PAEK polymer or copolymer by electrophilic aromatic substitution reaction, diacyl aromatic hydrocarbons (diacylaromates) such as aromatic diacid or preferred aromatic dicarboxylic acid chloride or aromatic dianhydride are polymerized with two aromatic oxide or thioether component.Such as, for PEKK, this may obtain, and not in the either end of skeletal chain or in one end (not shown) or two ends (showing) of skeletal chain, has PEKK polymer or the copolymer of phenyl:
xR
AOC-Ph-COR
A+(y+1)Ph-O-Ph→
Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-H
, wherein R
athe quantity that Cl or-OH and x and y represent the monomer be incorporated in polymer.
Additionally, the synthetic method via using the single monomer route of such as aromatics list acyl chlorides to carry out can be adopted.
Such as, the phenyl in polymer ends can by carrying out derivatization by the cessation reaction of chlorobenzoyl chloride:
2Ph-COCl+Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-H→
Ph-CO-Ph-O-Ph-[OC-Ph-CO]x[Ph-O-Ph]y-OC-Ph
No matter select nucleophilic or aromatics substitution reaction, in order to the crystallization of the polymer that slows down, end group preferably can be substituted, such as, make PAEK polymer have general formula below:
R
T-U-[PAEK]-U-R
T
, wherein U is the structure division connected, such as NH, O, CO, CO-O-, SO, singly-bound ,-(CH
2)
k, wherein k is 1-6, etc.; And left hand and right hand configurations part R
tcan be identical or different building stones, this structure division R usually
tidentical.
Preferably, R
tbe selected from aliphatic that is unsubstituted or that replace or aromatic hydrocarbon residues.U can be formed by the direct reaction of the end with polymer or copolymer, and the hydroxy compounds of such as simple function can form O as U, or it can be used as and stops the substituting group of reagent and be introduced into, and the such as HO-Ph-COO-tert-butyl group can form COO as U.
In addition, if in order to suitably regulate the degree of crystallinity of manufactured three-dimensional body need improve crystalline rate, then have halogenation end group PAEK can by ionic end groups resemble such as phenates as NaOPhSO
3na or NaOPhCOPhOPhSO
3na stopped.The phenates follow-up acidifying of such as HCl causes formation-SO
3h end group, it demonstrates nucleation (nucleation) effect reduced a little.
In addition, hereinafter-again exemplary-present with PA polymer and copolymer citing, describe other important architectural characteristic or the modification of polymer or copolymer material, they are suitable for preselected, and this is preselected is applicable to the selective sintering method utilizing electromagnetic radiation.Be apparent that for person skilled in the art, the architectural characteristic of the following stated or modification can equally for the polymer of other type.
The general formula below provided show for manufacture laser sintered object the preferred PA polymer of partially aromatic and the general structure of copolymer, the structure wherein further described below to obtain required for low degree of crystallinity is unique:
K, L=unsubstituted or replace C
2-C
20straight chain or cyclic alkyl,
Ar
4and Ar
5monocycle or the polycyclic aromatic hydrocarbon of the unsubstituted or replacement connected linearly or non-linearly, wherein with Rf
4, Rf
5, Rf
6and/or Rf
7for H independently, substituting group can optionally be selected from:
Rf
4, Rf
5, Rf
6, Rf
7be selected from independently of one another by C
1-C
6the group of the alkyl of straight chain, branching or ring-type and alkoxyl and aryl composition, is preferably selected from Me, i-Pr, t-Bu, Ph, wherein K, L, Ar
4and Ar
5in each there is one or more substituent R f separately
4, Rf
5, Rf
6, Rf
7(for unsubstituted K, L, Ar
4and Ar
5, then Rf
4, Rf
5, Rf
6, Rf
7=H),
T, U, V, W=-NH-CO-or-CO-NH-,
D be greater than 0 and preferably lower than 12 rudimentary integer, more preferably 1-6 and especially 1-3,
E, f and g are 0 or rudimentary integer, preferably lower than 12, and more preferably 1-6 and especially 1-3,
N represents the degree of polymerization.
In above general formula, index d, e, f and g represent the quantity of the respective repetitive of polymer and the respective repetitive of copolymer respectively, wherein one or more unit of identical type, such as with the unit that index d represents, the unit of another type can be positioned at, such as with the unit that exponent e, f and/or g represent, between.The following Examples of polyamide polymer used according to the invention will illustrate the above general formula of polyamide polymer.
PA6-3-T polyamide polymer used according to the invention has following repetitive:
Repetitive A:
Repetitive B:
In repetitive A, K is by Rf
4=methyl on 2-position dibasic and on 4-position mono-substituted n-hexane chain, T is-NH-CO-and d=1, e=0, Ar
4be unsubstituted Isosorbide-5-Nitrae-phenylene, V is-CO-NH-and f=1 and g=O.Because have 2 kinds of possibilities for the diamines replaced and terephthaldehyde's acid reaction, this will obtain the second repetitive B.In repetitive B, K is by Rf
4=methyl on 2-position dibasic and on 4-position mono-substituted n-hexane chain, T is-NH-CO-and d=1, e=0, Ar
4be unsubstituted Isosorbide-5-Nitrae-phenylene, V is-CO-NH-and f=1 and g=0.
Polyamide polymer PA 6T/6I used according to the invention and following two kinds of examples of PA MXD6 are the examples of the polyamide polymer with the aromatic group be non-linearly connected.
This polyamide PA 6T/6I copolymer has 2 kinds of different repetitives (repetitive A and B see in following structural formula).
Repetitive A:
Repetitive B:
In repetitive A, K is unsubstituted n-hexane chain, and T is-NH-CO-and d=1, e=0, Ar
4be unsubstituted Isosorbide-5-Nitrae-phenylene, V is-CO-NH-and f=1 and g=0.In repetitive B, K is unsubstituted n-hexane chain, and T is-NH-CO-and d=1, e=0, Ar
4be unsubstituted 1,3-phenylene, V is-CO-NH-and f=1 and g=0.The polymerization degree n of this PA copolymer represents n
1and n
2summation.
Following example shows other polyamide adopted according to the present invention, in skeletal chain, namely have the poly-meta-xylylene adipamide (polyamide MXD6) of the unit non-linearly connected.According to above general formula, be unsubstituted normal butane chain for polyamide MXD6, K, T is-CO-NH-and d=1, e=0, Ar
4be unsubstituted 1,3-xylylene, V is-NH-CO-and f=1 and g=0, and wherein following structural represents MXD6
, wherein n represents the degree of polymerization.
When polyamide, branched groups can by aliphatic residue K and L and/or by one or more substituent R f
4, Rf
5, Rf
6and Rf
7the aromatic hydrocarbon Ar replaced
4and Ar
5there is provided.
When polyamide, bulky group is selected from aromatics or nonaromatic.Especially, the construction unit needs be selected from the group be made up of phenylene, naphthalene, anthracene, biphenyl, fluorenes, terphenyl, decahydronaphthalene or norcamphane take in.
In remaining polymer, similar consideration is equally applicable to for the bulky group given by polyamide.
For PAEK polymer and copolymer and the architectural characteristic explained for PA (being total to) polymer can be equally applicable to other, the exemplary polymer mentioned or copolymer material already.Those skilled in the art will recognize that, can carry out structurally-modified accordingly, and effect is reduced in the degree of crystallinity in produced three-dimensional body.
In addition, this powder can be composite powder, and it also comprises one or more filler and/or additive except comprising the matrix of respective polymer, copolymer or blend.Filler can be used to the mechanical performance improving manufactured object further.Such as, carbon fiber, glass fibre, Kevlar fabric, CNT, or filler, this filler preferably has low length-width ratio (bead, aloxite, etc.) or mineral filler such as Titanium Di Oxide can be incorporated in the powder comprising at least one polymer or copolymer.In addition, improve the processing aid of the machinability of powder, such as free-flow agents is as those (such as AerosilR974 of Aerosil series, Aerosil R812, Aerosil 200), or other functional additive is as heat stabilizer, oxidation stabilizers, coloring pigment (carbon black, graphite, etc.) can use.
Can infer from investigation result of the present invention, the having structure characteristic of polymer or copolymer or modification ensure that low-crystallinity in manufactured object and are therefore particularly preferred when the polymer of particular type or copolymer carry out preselected, such as at PAEK (PAEK), polyether sulphone (PAES), polyamide, polyester, polyethers, polyolefin, polystyrene, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides and comprise at least one above-mentioned polymer copolymer in the middle of carry out (preselected):
A) there is the having structure characteristic of at least one and/or the polymer of modification or the preselected of copolymer:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) at least one end group of the skeletal chain of this polymer of modification or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or isopropylidene-connection aromatic hydrocarbon composition group;
(iv) at least one aromatic group of non-linearly connecting framework chain,
B) higher molecular weight M is used
nor M
wor certain melt viscosity,
C) long chain length or the high degree of polymerization is used,
D) undertaken mixing by the blending of at least two kinds of different polymer or copolymer or blended.
The following example is only used for illustrating the present invention, in any case they should not be considered to limit the scope of the invention.Embodiment and modification or their other equivalent become clearly to those skilled in the art in the art in possession of this overall disclosure.
Embodiment
The density of manufactured three-dimensional body is according to ISO 1183, and Kern 770-60 balance is measured, and wherein said balance has Satorius density gauge YDK 01.The porosity of object can according to density measurement, when the degree of crystallinity of the solid density of 100% crystalline polymer, the solid density of amorphous polymer and manufactured polymeric object is known.Degree of crystallinity in manufactured object can be measured by dynamic differential calorimetry (DCC or DSC) according to DIN53765.
Additionally, this degree of crystallinity can measure via wide-angle x-ray scattering (WAXS) mensuration.This program is that person skilled in the art is known.If the theoretical density of polymer is not known, then porosity also can be measured by micro-computed tomography (micro-computerthomography).Suitable equipment is such as the μ-CT40 supplied by SCANCO Medical AG, Br ü ttisellen, Switzerland.This program is that person skilled in the art is known.
The following example only illustrates and should not be considered to restricted meaning.
Reference example
From the powder that the unmodified PEEK of the structure of the average particle size distribution with 48 μm (from Victrex Plc company, Thornton Cleveleys, Lancashire FY5 4QD, Great Britain is purchased) manufactures, wherein this PEEK polymer has M
n=23,000 and M
wthe molecular weight of=65,000 and 0.15kN*s/m
2melt viscosity, heat-treat at higher than the temperature of glass transition temperature in an oven.
There is 0.45g/cm
3the PEEK powder of bulk density process on the laser sintering machine of P700 type, this sintering machine has been improved by EOS Corp. so that high temperature application.The temperature of process cavity is 335 DEG C.
After laser sintered process completes, cooldown rate is controlled by the rear heating between 335 DEG C and the Tg (145 DEG C) of PEEK.This cooldown rate shows the maximum average value of 0.3 DEG C/min.
Manufactured three-dimensional part has following performance:
Density=1.316g/cm
3
Degree of crystallinity (by DSC)=52%
Porosity (being calculated by density/degree of crystallinity)=1.4%
Tensile strength test (AST
md638, Type I):
Young's modulus=4500MPa
Hot strength=44MPa
Elongation at break=1.04%
Embodiment 1 (according to the present invention)
The powder can produced from the structurally-modified PAEK with following structural formula
, this powder has the average particle size distribution of < 100 μm, heat-treats in an oven in the temperature higher than glass transition temperature.
PAEK powder is processed on the laser sintering machine of P700 type, and this sintering machine has been improved by EOS Corp. so that high temperature application.The temperature of process cavity is such as low than the fusing point of this PAEK powder 10 DEG C.
After laser sintered process completes, cooldown rate is controlled by the rear heating between the temperature and the Tg of PAEK of process cavity, makes cooldown rate show the maximum average value of 0.3 DEG C/min.
Embodiment 2 (according to the present invention)
The powder can produced from the structurally-modified PEEK with following structural formula
, this powder has the average particle size distribution of 50 μm, and wherein this PEEK polymer has M
n=32,000 and M
wthe molecular weight of=65,000, heat-treats in an oven at higher than the temperature of glass transition temperature.
PEEK powder is processed on the laser sintering machine of P700 type, and this sintering machine has been improved by EOS Corp. so that high temperature application.The temperature of process cavity is such as 335 DEG C.
At laser after knot process completes, cooldown rate is controlled by the rear heating between 335 DEG C and the Tg (about 145 DEG C) of PEEK, makes cooldown rate show the maximum average value of 0.3 DEG C/min.
Embodiment 3 (according to the present invention)
The powder can produced from the polyamide PA6-3-T with following structural formula
Repetitive A:
Repetitive B:
, this powder has the average particle size distribution of < 100 μm, heat-treats in an oven in the temperature higher than glass transition temperature.
Polyamide powder is processed on the laser sintering machine of P700 type, and this sintering machine has been improved by EOS Corp. so that high temperature application.The temperature of process cavity is such as low than the fusing point of this polyamide 5 DEG C.
After laser sintered process completes, cooldown rate is controlled by the rear heating between the temperature and the Tg of polyamide of process cavity, makes cooldown rate show the maximum average value of 0.3 DEG C/min.
Embodiment 4 (according to the present invention)
The powder can produced from the structurally-modified polythene PE-LLD (linea low density) with following structural formula
R=butyl, hexyl or octyl group
N, m=integer, makes to there is a kind of ratio that every 1000 carbon atoms have 15-30 short chain branch
, it can have the average particle size distribution of < 150 μm.
PE-LLD powder is processed on the laser winder of the P390 type of EOS Corp..The temperature of process cavity is such as low than the fusing point of this PE-LLD powder 5 DEG C.
After laser sintered process completes, the cooldown rate being in the process cavity of 40 DEG C is controlled, and makes cooldown rate show the maximum average value of 0.2 DEG C/min.
Embodiment 5 (according to the present invention)
The powder can produced from the structurally-modified polythene PE-HD (high density) with following structural formula
R=methyl
N, m=integer, make to there is a kind of ratio that every 1000 carbon atoms have 15-30 short chain branch, it can have the average particle size distribution of < 150 μm.
PE-HD powder is processed on the laser winder of the P390 type of EOS Corp..The temperature of process cavity is such as low than the fusing point of this PE-HD powder 5 DEG C.
After laser sintered process completes, the cooldown rate being in the process cavity of 40 DEG C is controlled, and makes cooldown rate show the maximum average value of 0.2 DEG C/min.
Embodiment 6 (according to the present invention)
Repetitive respectively containing at least one Isosorbide-5-Nitrae-phenylene-unit is 80: 20 with the ratio of the repetitive respectively containing at least one 1,3-phenylene-unit, and fusing point is 367 DEG C and particle mean size d
50the heat treatment PEKK powder (PEKK-C type, from OPM company, Enfield, CT, USA are purchased) of=55 μm is processed on the laser sintering machine being improved the P700 type being suitable for high temperature application by EOS Corp..The temperature of process cavity is 343 DEG C.This cooldown rate display maximum average value of 0.3K/ minute.
These laser sintered parts on average have following performance:
Density: 1.246g/cm
3
Hot strength (ISO 527-2):
Young's modulus: 4200MPa
Hot strength: 39MPa
Elongation at break: 1.0%
Embodiment 7 (according to the present invention)
Repetitive respectively containing at least one Isosorbide-5-Nitrae-phenylene-unit is 60: 40 with the ratio of the repetitive respectively containing at least one 1,3-phenylene-unit, and fusing point is 297 DEG C and particle mean size d
50the heat treatment PEKK powder (PEKK-SP type, from OPM company, Enfield, CT, USA are purchased) of=60 μm is processed on the laser sintering machine being improved the P700 type being suitable for high temperature application by EOS Corp..The temperature of process cavity is 286 DEG C.Average cooldown rate between 286-250 DEG C is higher than 0.3K/ minute.Between 250 DEG C and Tg, average cooldown rate is become homeless by natural heat waste and is determined.
These laser sintered parts on average have following performance:
Density: 1.285g/cm
3
Hot strength (ISO 527-2):
Young's modulus: 3900MPa
Hot strength: 69MPa
Elongation at break: 1.9%.
Claims (34)
1. utilize electromagnetic radiation to be manufactured the method for three-dimensional body from powder by selective sintering method, wherein this powder comprises polymer or the copolymer of the having structure characteristic with at least one:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or isopropylidene-connection aromatic hydrocarbon composition group;
(iv) at least one aromatic group of non-linearly connecting framework chain,
Wherein said polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES), polyethers, polyolefin, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise at least one above-mentioned polymer block copolymer based on formed, and
Wherein this powder comprises the polymer being selected from following characteristic in these or copolymer with at least one:
Fusing point T within the scope of 100 DEG C-450 DEG C
m;
Glass transition temperature T within the scope of 50-300 DEG C
g;
The equal M of number of at least 10,000
nor the weight average M of at least 20,000
w;
With
10-10, the polymerization degree n of 000.
2. method according to claim 1, wherein needs the successive layers of the object formed from curable dusty material to solidify in the position corresponding with the cross section of object subsequently; And/or electromagnetic radiation is provided by laser in the method.
3. method according to claim 1, it be included in sintering step after pre-determine and/or control cooling step.
4. method according to claim 3, wherein cooling step is used to the object after the completion of object, requires with the cooldown rate of 0.01-10 DEG C/min from the T than polymer contained in the powder or copolymer
mthe temperature of low 1-50 DEG C is cooled to polymer contained in the powder or the T of copolymer
g, wherein T
mfusing point and the T of polymer contained in the powder or copolymer
git is the glass transition temperature of this polymer or copolymer.
5. according to any one method in claim 1-4, wherein polymer or copolymer contain at least one aromatic group, and what the latter had an at least one is selected from following characteristic in these:
Aromatic group is in the repetitive of skeletal chain; With
This aromatic group is selected from monocycle that is unsubstituted or that replace or polycyclic aromatic hydrocarbon independently of one another.
6. method according to claim 5, wherein this aromatic group is selected from by Isosorbide-5-Nitrae-phenylene independently of one another, and 4,4 '-biphenylene, 4,4 '-isopropylidenediphenylene, 4,4 '-diphenyl sulfone, 1,4-, 1,5-, 2,6-naphthylenes, 4,4 " group of the sub-terphenyl base composition of-p-.
7., according to any one method in claim 1-4, what wherein have an at least one according to the aromatic group of modification (iv) non-linear connection is selected from following characteristic in these:
The aromatic group of the non-linear connection of at least one is included in the repetitive of skeletal chain; With
Polymer or copolymer in skeletal chain containing at least one other, linearly connected the aromatic group different from the aromatic group non-linearly connected and/or at least one branched groups.
8. method according to claim 7, the aromatic group of wherein this non-linear connection is selected from 1,2-and 1,3-phenylene, 1,3-xylylene, and 2,4 '-and 3,4 '-biphenylene, and 2,3-and 2,7-naphthylene.
9. method according to claim 7, wherein polymer or copolymer in the repetitive of skeletal chain containing at least one other, linearly connected the aromatic group different from the aromatic group non-linearly connected and/or at least one branched groups.
10. method according to claim 7, wherein this aromatic group that is other, linearly connected is selected from by Isosorbide-5-Nitrae-phenylene independently of one another, 4,4 '-biphenylene, 4,4 '-isopropylidenediphenylene, 4,4 '-diphenyl sulfone, Isosorbide-5-Nitrae-, 1,5-, 2,6-naphthylene, 4,4 " group of the sub-terphenyl base of-p-and 2,2-pair-(4-phenylene)-propane composition.
11. methods according to claim 9, wherein this aromatic group that is other, linearly connected is selected from by Isosorbide-5-Nitrae-phenylene independently of one another, 4,4 '-biphenylene, 4,4 '-isopropylidenediphenylene, 4,4,-diphenyl sulfone, Isosorbide-5-Nitrae-, 1,5-, 2,6-naphthylenes, 4, the group of the sub-terphenyl base of 4-p-and 2,2-pair-(4-phenylene)-propane composition.
12. according to any one method in claim 1-4, wherein according to improvement (i), branched groups has the aliphatic hydrocarbon of at least one substituting group or a side chain, aromatic hydrocarbon or heteroaromatic hydrocarbon, for the situation using PAEK (PAEK), branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer.
13. methods according to claim 12, wherein this side chain is selected from independently of one another by C
1-C
6the group of the chain of nonbranched or branching or cyclic alkyl or alkoxyl and aryl composition.
14. methods according to claim 12, wherein this side chain selects the group that free methyl, isopropyl, the tert-butyl group or phenyl form independently of one another.
15. according to any one method in claim 1-4, wherein according to improvement (ii), the end group of skeletal chain by end alkyl, alkoxyl, ester group and/or the modification of aryl institute.
16. according to any one method in claim 1-4, and wherein according to improvement (iii), bulky group is aromatics or nonaromatic, and for using the situation of PAEK (PAEK), this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH
2-or isopropylidene-connection aromatic hydrocarbon composition group.
17. methods according to claim 16, wherein this bulky group is polycyclic aromatic or nonaromatic.
18. methods according to claim 16, wherein this bulky group is selected from phenylene, naphthalene, anthryl, biphenyl, fluorenes, terphenyl, decahydronaphthalene or norcamphane.
19. according to any one method in claim 1-4, wherein polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES) or comprise at least one above-mentioned polymer block copolymer based on formed.
20. methods according to claim 19, wherein this block copolymer is PAEK (PAEK)/polyether sulphone (PAES)-diblock copolymer or PAEK/PAES/PAEK-triblock copolymer.
21. according to any one method in claim 1-4, wherein polymer is with polyether-ether-ketone (PEEK), PEKK (PEKK), polyether-ketone (PEK), polyether ether ketone ketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), polyarylether ether ether ketone (PEEEK) or comprise the PAEK (PAEK) formed based on the copolymer of the above-mentioned polymer of at least one.
22. methods according to claim 21, the polymer wherein based on PAEK (PAEK) or copolymer have 0.05-1.0kN*s/m
2melt viscosity and/or 10-1, the polymerization degree n of 000.
23. methods according to claim 21, wherein PEKK (PEKK) polymer or copolymer comprise 1 in the skeletal chain of this polymer, 4-phenylene is as the aromatic group of linearly connected and 1, the 3-phenylene aromatic group as non-linear connection.
24. methods according to claim 21, wherein PEKK (PEKK) polymer or copolymer comprise 1 at the repetitive of the skeletal chain of this polymer, 4-phenylene is as the aromatic group of linearly connected and 1, the 3-phenylene aromatic group as non-linear connection.
25. methods according to claim 21, the repetitive wherein comprising at least one Isosorbide-5-Nitrae-phenylene-unit is separately 90/10-10/90 with the ratio of the repetitive comprising 1, a 3-phenylene-unit separately.
26. methods according to claim 21, the repetitive wherein comprising at least one Isosorbide-5-Nitrae-phenylene-unit is separately 70/30-10/90 with the ratio of the repetitive comprising 1, a 3-phenylene-unit separately.
27. methods according to claim 21, the repetitive wherein comprising at least one Isosorbide-5-Nitrae-phenylene-unit is separately 60/40-10/90 with the ratio of the repetitive comprising 1, a 3-phenylene-unit separately.
28. three-dimensional bodies utilizing electromagnetic radiation to be obtained by the selective sintering method of the polymer of powder type, copolymer or blend polymer, wherein have the having structure characteristic of at least one for the polymer of this powder or copolymer:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or isopropylidene-connection aromatic hydrocarbon composition group;
(iv) at least one aromatic group of non-linearly connecting framework chain,
Wherein said polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES), polyethers, polyolefin, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise at least one above-mentioned polymer block copolymer based on formed, and
Wherein this powder comprises the polymer being selected from following characteristic in these or copolymer with at least one:
Fusing point T within the scope of 100 DEG C-450 DEG C
m;
Glass transition temperature T within the scope of 50-300 DEG C
g;
The equal M of number of at least 10,000
nor the weight average M of at least 20,000
w;
With
10-10, the polymerization degree n of 000.
29. three-dimensional bodies according to claim 28, wherein polymer or copolymer defined according in claim 4-27.
30. utilize the electromagnetic radiation of powder to be manufactured the device of three-dimensional body from this powder by selective sintering method, and wherein this device comprises Temperature-controlled appliance, and the latter is mounted the predetermined cooling down operation being set in object after object manufacture is completed,
Wherein this powder comprises polymer or the copolymer of the having structure characteristic with at least one:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or isopropylidene-connection aromatic hydrocarbon composition group;
(iv) at least one aromatic group of non-linearly connecting framework chain,
Wherein said polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES), polyethers, polyolefin, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise at least one above-mentioned polymer block copolymer based on formed, and
Wherein this powder comprises the polymer being selected from following characteristic in these or copolymer with at least one:
Fusing point T within the scope of 100 DEG C-450 DEG C
m;
Glass transition temperature T within the scope of 50-300 DEG C
g;
The equal M of number of at least 10,000
nor the weight average M of at least 20,000
w;
With
10-10, the polymerization degree n of 000.
31. devices according to claim 30, the cooldown rate wherein set by Temperature-controlled appliance depends on the type of polymer comprised in the powder, copolymer or blend polymer; And/or
Wherein Temperature-controlled appliance sets according to the predefined type of polymer, copolymer or blend polymer.
32. manufacturing systems, it comprises: according to device and the powder being included at least one polymer or the copolymer defined in claim 4-28 of claim 30 or 31.
The purposes of 33. polymer powders in the process utilizing selective electromagnetic radiation sintering process manufacture three-dimensional body, wherein polymer is selected from polymer or the copolymer of the having structure characteristic with at least one in advance:
(i) at least one branched groups in the skeletal chain of polymer or copolymer, precondition is when using PAEK (PAEK), and branched groups is the aromatic structure unit in the skeletal chain of polymer or copolymer;
(ii) modification of at least one end group of the skeletal chain of polymer or copolymer;
(iii) at least one bulky group in the skeletal chain of polymer or copolymer, precondition is that this bulky group is not selected from by phenylene, biphenylene, naphthylene and CH when using PAEK (PAEK)
2-or isopropylidene-connection aromatic hydrocarbon composition group;
(iv) at least one aromatic group of non-linearly connecting framework chain,
Wherein said polymer or copolymer are with polyamide (PA), PAEK (PAEK), polyether sulphone (PAES), polyethers, polyolefin, polyphenylene sulfide, polyvinylidene fluoride, polyphenylene oxide, polyimides or comprise at least one above-mentioned polymer block copolymer based on formed, and
Wherein this powder comprises the polymer being selected from following characteristic in these or copolymer with at least one:
Fusing point T within the scope of 100 DEG C-450 DEG C
m;
Glass transition temperature T within the scope of 50-300 DEG C
g;
The equal M of number of at least 10,000
nor the weight average M of at least 20,000
w;
With
10-10, the polymerization degree n of 000.
34. according to the purposes of claim 33, and wherein polymer or copolymer defined according in claim 4-27.
Priority Applications (1)
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| CN201410850625.7A CN104647764B (en) | 2008-05-20 | 2009-05-19 | The selective sintering of structurally modified polymers |
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| DE102008024281.0 | 2008-05-20 | ||
| DE102008024288.8 | 2008-05-20 | ||
| DE102008024288A DE102008024288A1 (en) | 2008-05-20 | 2008-05-20 | Preparing a three-dimensional object from a powder, comprising polymer or copolymer containing an aromatic group that non-linearly links to the main chain, comprises selective sintering of the powder by electromagnetic radiation |
| DE102008024281A DE102008024281A1 (en) | 2008-05-20 | 2008-05-20 | Producing a three-dimensional object by selectively sintering a polymer powder comprises using a polymer that has a branching group in the main chain, has a modified terminal group and/or has a bulky group in the main chain |
| US18896208P | 2008-08-14 | 2008-08-14 | |
| US18898708P | 2008-08-14 | 2008-08-14 | |
| US61/188,962 | 2008-08-14 | ||
| US61/188,987 | 2008-08-14 |
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| DE102012207609A1 (en) * | 2012-05-08 | 2013-11-14 | Evonik Industries Ag | METHOD FOR THE LAYERED MANUFACTURE OF THREE-DIMENSIONAL OBJECTS |
| DE102012212587A1 (en) * | 2012-07-18 | 2014-01-23 | Eos Gmbh Electro Optical Systems | Apparatus and method for layering a three-dimensional object |
| EP2994500B1 (en) * | 2013-05-08 | 2017-01-04 | Solvay Specialty Polymers USA, LLC. | Polyarylene ether sulfone (paes) compositions |
| KR101872628B1 (en) * | 2014-01-16 | 2018-06-28 | 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. | Generating a three-dimensional object |
| KR20170046759A (en) * | 2014-09-30 | 2017-05-02 | 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. | Cooling times for three-dimensional objects |
| CN105583399A (en) * | 2014-10-20 | 2016-05-18 | 优克材料科技股份有限公司 | Three-dimensional printing device and three-dimensional printing method for patterned amorphous structure |
| US9987051B2 (en) | 2015-01-27 | 2018-06-05 | K2M, Inc. | Interbody spacer |
| US10028841B2 (en) | 2015-01-27 | 2018-07-24 | K2M, Inc. | Interbody spacer |
| WO2017027784A1 (en) | 2015-08-13 | 2017-02-16 | Corning Incorporated | Method and system for printing 3d objects |
| US20200009785A1 (en) * | 2017-02-06 | 2020-01-09 | Solvay Specialty Polymers Usa, Llc | Method for manufacturing a three-dimensional object using paek and paes |
| JP7466267B2 (en) | 2017-05-25 | 2024-04-12 | ストライカー・ユーロピアン・オペレイションズ・ホールディングス・リミテッド・ライアビリティ・カンパニー | Fusion cage with integrated fixation and insertion features |
| US11006981B2 (en) | 2017-07-07 | 2021-05-18 | K2M, Inc. | Surgical implant and methods of additive manufacturing |
| AU2018327353B2 (en) | 2017-09-08 | 2024-12-12 | Xtant Medical Holdings, Inc. | Intervertebral implants, instruments, and methods |
| DE102018219303A1 (en) | 2018-11-12 | 2020-05-14 | Eos Gmbh Electro Optical Systems | Warp-optimized plastic powder |
| DE102018219302A1 (en) | 2018-11-12 | 2020-05-14 | Eos Gmbh Electro Optical Systems | Selective sintering of polymer-based building materials |
| DE102019212298A1 (en) | 2019-08-16 | 2021-02-18 | Eos Gmbh Electro Optical Systems | Selective sintering of polymer-based composite materials |
| FR3109848B1 (en) * | 2020-04-30 | 2022-12-16 | Arkema France | Insulated conductor suitable for use in a winding, branch winding and corresponding manufacturing processes. |
| DE102022134796A1 (en) * | 2022-12-23 | 2024-07-04 | Eos Gmbh Electro Optical Systems | Additive manufacturing processes |
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| CN1155258A (en) * | 1994-09-16 | 1997-07-23 | Eos有限公司 | Process for producing three-dimensional object |
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| DE4410046C2 (en) | 1994-03-23 | 2000-11-30 | Eos Electro Optical Syst | Method and material for producing a three-dimensional object by sintering |
| GB0322598D0 (en) | 2003-09-26 | 2003-10-29 | Victrex Mfg Ltd | Polymeric material |
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