US20220091504A1 - Blocking groups for light polymerizable resins useful in additive manufacturing - Google Patents
Blocking groups for light polymerizable resins useful in additive manufacturing Download PDFInfo
- Publication number
- US20220091504A1 US20220091504A1 US17/457,481 US202117457481A US2022091504A1 US 20220091504 A1 US20220091504 A1 US 20220091504A1 US 202117457481 A US202117457481 A US 202117457481A US 2022091504 A1 US2022091504 A1 US 2022091504A1
- Authority
- US
- United States
- Prior art keywords
- blocked
- composition
- polymerizable
- blocking group
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 230000000903 blocking effect Effects 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 title claims description 37
- 239000011347 resin Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 239000000654 additive Substances 0.000 title claims description 19
- 230000000996 additive effect Effects 0.000 title claims description 18
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000000470 constituent Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 18
- -1 styrenics Chemical class 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000004814 polyurethane Substances 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 229920002396 Polyurea Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 8
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
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- 125000000962 organic group Chemical group 0.000 claims description 7
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
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- 150000001298 alcohols Chemical class 0.000 claims description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- 150000003852 triazoles Chemical class 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
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- 239000002243 precursor Substances 0.000 claims description 2
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 2
- 238000009472 formulation Methods 0.000 description 39
- 239000002245 particle Substances 0.000 description 23
- 239000003085 diluting agent Substances 0.000 description 17
- 0 BC(=O)C[2*]CC(=O)CCC(=O)C[2*]CC(C)=O.BC(=O)N[2*]NC(C)=O.COC.CSC.C[1*]NC.N#CO*N=C=O.N#CO[2*]CC(=O)CCC(=O)C[2*]N=C=O.N#CO[2*]N=C=O.[H]B.[H]CC[H] Chemical compound BC(=O)C[2*]CC(=O)CCC(=O)C[2*]CC(C)=O.BC(=O)N[2*]NC(C)=O.COC.CSC.C[1*]NC.N#CO*N=C=O.N#CO[2*]CC(=O)CCC(=O)C[2*]N=C=O.N#CO[2*]N=C=O.[H]B.[H]CC[H] 0.000 description 15
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 13
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 230000009977 dual effect Effects 0.000 description 10
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- 230000009477 glass transition Effects 0.000 description 10
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 9
- 229940119545 isobornyl methacrylate Drugs 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 8
- 239000002981 blocking agent Substances 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
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- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 2
- LHYWXEOPBCZURX-UHFFFAOYSA-N C=C(C)C(=O)OCCN(C(C)C)C(C)(C)C Chemical compound C=C(C)C(=O)OCCN(C(C)C)C(C)(C)C LHYWXEOPBCZURX-UHFFFAOYSA-N 0.000 description 2
- MFIASDRONYBUHF-UHFFFAOYSA-N CC(C)C1CCC(CC2CCC(C(C)C)CC2)CC1.CC(C)CC1(C)CC(C(C)C)CC(C)(C)C1.CC(C)CC1(C)CC(C(C)C)CC(C)(C)C1.CC(C)CCCCCCC(C)C Chemical compound CC(C)C1CCC(CC2CCC(C(C)C)CC2)CC1.CC(C)CC1(C)CC(C(C)C)CC(C)(C)C1.CC(C)CC1(C)CC(C(C)C)CC(C)(C)C1.CC(C)CCCCCCC(C)C MFIASDRONYBUHF-UHFFFAOYSA-N 0.000 description 2
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
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- 229910052797 bismuth Inorganic materials 0.000 description 2
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
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- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
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- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
Definitions
- the present invention concerns additive manufacturing in general, and particularly concerns dual cure resins useful in methods such as stereolithography and continuous liquid interface production (CLIP).
- CLIP continuous liquid interface production
- continuous liquid interface production or “CLIP”
- CLIP continuous liquid interface production
- Dual cure stereolithography resins in which the shape of an article is created by light polymerization in the additive manufacturing process, and the mechanical properties of the article are created in a second cure that typically follows (for example, by baking).
- Dual cure resins that provide for a range of mechanical properties in the final product are described in, for example, J. Rolland et al., U.S. Pat. Nos. 9,453,142 and 9,598,606, and US Patent Application Publication Nos. 2016/0136889 and 2016/0160077.
- ingredients that provide for a liquid resin that is readily processed by additive manufacturing to produce an intermediate “green” part may be detrimental to producing a reasonably strong “green” part.
- ingredients that might provide for a strong green part may be detrimental to the mechanical properties of the finished part after a second cure such as a baking step.
- J. Rolland et al. solve this problem by employing, in a dual cure resin, light polymerizable ingredients that help form the green object, but then degrade during the second (typically heat) cure to form a constituent that participates in the second cure (and hence contribute to the mechanical properties of the finished part).
- light polymerizable (“reactive”) blocking groups were used to block the otherwise reactive isocyanate (“NCO”) groups of a monomer or prepolymer to create a light polymerizable constituent (Scheme 1), which blocking groups subsequently degrade on heating to unmask the NCO group so that it can participate in a subsequent cure (e.g., upon baking) to produce a polyurethane or polyurea polymer in the finished object.
- H—B 1 represents a UV-reactive blocking agent
- B 1 represents a UV-reactive blocking group (such as an acrylate)
- R 2 represents an organic group
- the wavy line represents a polymeric organic group (as found in a prepolymer); and x is as given therein.
- the foregoing approach is in some cases limited to chemical systems which produce finished objects having a glass transition temperature (T g ) close to room temperature. Yet, for finished objects that are to be elastomeric, glass transition temperatures substantially less than room temperature are preferred. On the other hand, for finished objects that are to be more rigid, glass transition temperatures substantially above room temperature are preferred.
- the more UV-reactive blocking agent used can make it difficult to maximize the polyurethane/polyurea weight fraction in the final material. From the perspective of formulation, it is often desirable to have more polyurethane/polyurea fraction in the final material as the UV fraction may either be too brittle or too fragile depending on the T g . Therefore, there is a need for additional approaches in dual cure resins for additive manufacturing that complement those previously developed.
- a method of forming a three-dimensional object can be carried out by:
- the heat polymerizable second component comprising (i) a first blocked reactive constituent that is blocked with a volatile blocking group, and optionally but preferably (ii) a curative;
- the volatile blocking group comprises a ketoxime, amide, imide, imidazole, pyrazole, alcohol, or sterically-hindered amine blocking group.
- the first blocked reactive constituent comprises a blocked polyisocyanate.
- the first blocked reactive constituent comprises a ketoxime-blocked polyisocyanate.
- the curative comprises a polyol, a polyamine, a polyetheramine, or a combination thereof.
- the three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from the first component and the second component.
- the second component comprises precursors to a polyurethane, polyurea, or copolymer thereof; a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber.
- the first blocked reactive constituent is included in the polymerizable liquid in an amount of from 1, 2, 5 or 10 percent by weight, to 30, 40, or 50 percent by weight, or more.
- the polymerizable liquid further comprises at least one photoinitiator (e.g., in an amount of from 0.1 to 1 or 5 percent by weight), optionally at least one dye (e.g., in an amount of 0.001 or 0.01 to 1 or 5 percent by weight), and optionally at least one filler (e.g., in an amount of 0.01 or 0.1 to 20 or 50 percent by weight).
- at least one photoinitiator e.g., in an amount of from 0.1 to 1 or 5 percent by weight
- at least one dye e.g., in an amount of 0.001 or 0.01 to 1 or 5 percent by weight
- at least one filler e.g., in an amount of 0.01 or 0.1 to 20 or 50 percent by weight.
- the light polymerizable first component comprises a second blocked reactive constituent that is blocked with a light reactive blocking group; and the curing step (d) is carried out under conditions in which at least a portion of the solid polymer scaffold produced by light polymerization of the second reactive constituent degrades and forms a constituent that participates in the heat polymerizing.
- the second blocked reactive constituent comprises a blocked polyisocyanate having two or more ethylenically unsaturated end groups.
- the second blocked reactive constituent is included in the polymerizable liquid in an amount of from 1, 2, 5 or 10 percent by weight, to 30, 40, or 50 percent by weight, or more.
- the first blocked reactive constituent e.g., VBPU
- the second blocked reactive constituent e.g., ABPU
- the first blocked reactive constituent e.g., VBPU
- the second blocked reactive constituent e.g., ABPU
- the object is elastomeric and is comprised of a polymer having a glass transition temperature of no more than ⁇ 20 or 0° C.; or (ii) the object is rigid and is comprised of a polymer having a glass transition temperature of at least 50 or 70° C.
- a further aspect of the invention is a three-dimensional object produced by the method of any preceding claim (e.g., wherein the object includes a three-dimensional lattice).
- a further aspect of the invention is a polymerizable liquid composition as described above, and described further below.
- a further aspect is a prepolymer compound of formula I:
- B 1 is a reactive blocking group
- B 2 is a volatile blocking group
- R 1 and R 2 are independently selected from the group comprising an aliphatic, aromatic or mixed aliphatic and aromatic group
- X is O, S, or NR 3 , wherein R 3 is H or a straight chain or branched C 1 -C 10 alkyl group;
- Z is a polymeric organic group
- n is an integer in the range of from 1, 5, 10, 20 or 30 to 80, 100, or 150;
- n is an integer in the range of from 1, 5, 10 or 20 to 50, 70 or 100.
- a further aspect is a monomer compound of formula II:
- B 1 is a reactive blocking group
- B 2 is a volatile blocking group
- R 1 is an aliphatic, aromatic or mixed aliphatic and aromatic group.
- a further aspect of the invention is a polymerizable liquid composition containing a prepolymer and/or monomer compound as described above.
- thermosetting compositions containing ketoxime-blocked isocyanates but suggest their use only as coatings.
- FIG. 1 Dynamic Mechanical Analysis (DMA) curve of Formulation I compared to a non-MEKO containing formulation (Control A).
- Control A formulation is described in Table 2 below.
- DMA RSA-G2, Temperature ramp 5° C./min, 10 Hz.
- FIG. 2 DMA curve of Formulation II compared to a non-MEKO containing formulation (Control A).
- DMA RSA-G2, Temperature ramp 5° C./min, 10 Hz.
- FIG. 3 DMA data of Formulation III, prepared in like manner to that described in connection with FIGS. 1-2 above.
- ABPU refers to UV-curable, (meth)acrylate blocked, polyurethane/polyurea (i.e., reactive blocked polyurethane) such as described in U.S. Pat. Nos. 9,453,142 and 9,598,606 to Rolland et al.
- ABPUs are reactive blocked polyurethanes.
- a particular example of a suitable reactive (or UV-curable) blocking group is a tertiary amine-containing (meth)acrylate (e.g., t-butylaminoethyl methacrylate, t-BAEMA). Note, however, that t-BAEMA has a glass transition temperature of about room temperature, which is less preferred for the production of rigid or elastomeric objects, as discussed further below.
- VBPU refers to a volatile blocking group blocked, polyurethane/polyurea.
- Volatile blocking agents that may be used to carry out the present invention include, for example, ketoximes, amides, imides, imidazoles, pyrazoles, alcohols, and sterically-hindered amines, such as 2-butanone oxime (also called methyl ethyl ketoxime or “MEKO”), acetone oxime, cyclopentanone oxime, cyclohexanone oxime, ⁇ -caprolactam, N-methylacetamide, imidazole, succinimide, benzotriazole, N-hydroxyphthalimide, 1,2,4-triazole, 2-ethyl-1-hexanol, phenol, 3,5-dimethylpyrazole, 2,2,6,6-tetramethylpiperidine, and diisopropylamine (see, e.g., Scheme 2).
- 2-butanone oxime also called methyl ethyl ketoxime or “MEKO”
- MEKO methyl ethyl
- Volatile blocking group refers to a substituent produced by the covalent coupling of a volatile blocking agent as described above to the reactive group (particularly an isocyanate group) of a reactive compound (such as a diisocyanate monomer or prepolymer).
- Polyisocyanates useful in carrying out the present invention include, but are not limited to, 1,1′-methylenebis(4-isocyanatobenzene) (MDI), 2,4-diisocyanato-1-methylbenzene (TDI), methylene-bis(4-cyclohexylisocyanate) (H 12 MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), polymeric MDI, 1,4-phenylene diisocyanate (PPDI), and o-tolidine diisocyanate (TODI).
- the preferred diisocyanate is H 12 MDI, such as Desmodur W, supplied by Covestro AG. Additional examples include but are not limited to those given in U.S. Pat. No. 3,694,389 to Levy.
- Catalysts useful in carrying out the present invention to prepare VBPUs from prepolymers and volatile blocking groups include, but are not limited to, dibutyltin dilaurate, stannous octoate, and bismuth octoate.
- a preferred catalyst is the bismuth catalyst K-KAT 348, supplied by King Industries, Inc.
- Polyols, polyamines, and polythiols useful in carrying out the present invention are known.
- examples include, but are not limited to, poly(ethylene glycol), poly(propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol) (PTMO), hydroxy-terminated poly(dimethylsiloxane), polyester diol especially polycaprolactone (PCL) diol, PTMO-PCL copolymer diol (Capa 7201A from Perstorp), hydroxy-terminated polybutadiene, and polyetheramines (for example JEFFAMINE® from Huntsman Corporation).
- a preferred polyol, polyamine, and polythiol is PTMO, with an average M n between 500 to 3000 Da.
- Curatives useful for carrying out the present invention are known.
- examples include, but are not limited to polyols such as diols (such as ethylene glycol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, hydroquinone bis(2-hydroxyethyl) ether, 1,4-cyclohexanedimethanol), aliphatic, aromatic, and mixed aliphatic and aromatic, polyamines, such as diamines (for example, 4,4′-methylenedicyclohexanamine (PACM), 4,4′-methylenebis(2-methylcyclohexyl-amine) (MACM), ethylene diamine, isophorone diamine, diethyltoluenediamine), and polyetheramines (for example JEFFAMINE® from Huntsman Corporation).
- diols such as ethylene glycol, 1,3-propane diol, 1,4-butanediol, 1,6-hex
- Photoinitiators useful in the present invention include, but are not limited to, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), 2-isopropylthioxanthone and/or 4-isopropylthioxanthone (ITX), etc.
- UV-curable diluents for example monoacrylates, mono-methacrylates, polyacrylates, polymethacrylates, acrylamides, methacrylamides, etc.
- non-UV-curable diluents for example, plasticizers such as bis(2-ethylhexyl) phthalate, bis(2-propylheptyl) phthalate, diisononyl phthalate, tri-(2-ethylhexyl) trimellitate, bis(2-ethylhexyl) adipate, diisononyl adipate, dibutyl sebacate, diisobutyl maleate, etc.).
- solvents as used herein includes, for example, diethyl ether, tetrahydrofuran, ethyl acetate, benzene, toluene, N,N-dimethylformamide, propylene carbonate, dimethyl carbonate, etc.
- Soft segment and “hard segment” as used herein have their usual meaning in the polymer chemistry field. “Soft segment” refers to a typically high molecular weight chain that has a glass transition temperature less than room temperature, is generally amorphous or partially crystalline, and provides flexibility to the copolymer, and generally has a large number of degrees of freedom. “Hard segment” as used herein refers to a higher glass transition temperature, generally crystalline, rigid, generally oligomeric molecular weight segment that can provide mechanical integrity or strength to the segmented copolymer.
- VBPUs can be prepared in accordance with known procedures (see, e.g., U.S. Pat. No. 3,694,389 to Levy) or variations thereof that will be apparent to those skilled in the art based on the disclosure below.
- a first example synthesis of a VBPU is given in Scheme 3 below, where R 2 represents an organic group (e.g., an optionally substituted aliphatic, aromatic, or mixed aliphatic and aromatic, group), the wavy line represents a polymer of an organic group (as found in a prepolymer), H—B 2 represents a volatile blocking agent, B 2 represents a volatile blocking group, and x is as given below.
- R 2 represents an organic group (e.g., an optionally substituted aliphatic, aromatic, or mixed aliphatic and aromatic, group)
- the wavy line represents a polymer of an organic group (as found in a prepolymer)
- H—B 2 represents a volatile blocking agent
- B 2 represents a volatile blocking group
- x is as given below.
- the benefit of incorporating such groups is that it provides multiple methods of tuning final mechanical properties by controlling the polyurethane/polyurea and UV-network percentages, allowing the ability to control the resulting glass transition temperature (T g ) and mechanical properties.
- the volatile blocking group blocked polyurethane/polyurea (VBPU) prepolymer can be added to a UV-curable formulation, such as one containing an acrylate-blocked polyurethane (ABPU) as described in J. Rolland et al., U.S. Pat. Nos. 9,453,142 and 9,598,606.
- the VBPU can be synthesized separately or in conjunction with a UV-reactive prepolymer, as shown in Scheme 4.
- R 1 represents an optionally substituted aliphatic, aromatic, or mixed aliphatic and aromatic, group
- H—B 2 represents a volatile blocking agent
- B 2 represents a volatile blocking group
- each x is as given in Scheme 3, each y is as given therein, each R 1 and R 2 represents an independently selected, optionally substituted, aliphatic, aromatic, or mixed aliphatic and aromatic, group, B 2 represents a volatile blocking group; and the wavy line represents the polymeric repeat segment of a polyurethane or polyurea prepolymer.
- Scheme 6 shows a more specific example of general Scheme 3 above, and includes initially reacting a diisocyanate molecule, in the presence of catalyst, with a polyol, polyamine, or polythiol, or combination thereof. The remaining isocyanate (NCO) is then reacted with the volatile blocking group 2-butanone oxime (methyl ethyl ketoxime, or “MEKO”).
- R 2 and the wavy line are as given in connection with Scheme 3 above, and the equivalent ratio of diisocyanate to polyol/polyamine/polythiol can be from 6:1 to 1.5:1 and preferably from 2.4:1 to 2:1.
- Schemes 7-8 below show a more specific example of general Scheme 4 above, including reacting a diisocyanate molecule directly with the volatile blocking group at a molar ratio of 1:2. This can also be synthesized in the presence of other components, such as UV-curable diluents, non-UV-curable diluents (such as plasticizer), solvents, and/or ABPUs.
- other components such as UV-curable diluents, non-UV-curable diluents (such as plasticizer), solvents, and/or ABPUs.
- the VBPU can include the volatile blocking group and the UV-curable group on the same prepolymer, as shown in Scheme 9, where H—B 1 is a UV-curable blocking group and H—B 2 is a volatile blocking group.
- VBPUs as described above can be incorporated into any of a variety of different dual cure resins for additive manufacturing, including but not limited to those described in U.S. Pat. Nos. 9,453,142 and 9,598,606 to Rolland et al.
- such resins can comprise: (a) light-polymerizable monomers and/or prepolymers that can form an intermediate object (typically in the presence of a photocatalyst); and (b) heat (or microwave, RF energy)-polymerizable (or otherwise further polymerizable) monomers and/or prepolymers.
- these constituents may be supplemented with an organic diluent as described above, and discussed further below.
- Part A Light-polymerizable monomers and/or prepolymers. Sometimes also referred to as “Part A” of the resin, these are monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light. This resin can have a functionality of 2 or higher.
- a purpose of Part A is to “lock” the shape of the object being formed or create a scaffold for the one or more additional components (e.g., Part B).
- Part A is present at or above the minimum quantity needed to maintain the shape of the object being formed after the initial solidification during photolithography. In some embodiments, this amount corresponds to less than ten, twenty, or thirty percent by weight of the total resin (polymerizable liquid) composition.
- Suitable reactive end groups suitable for Part A constituents, monomers, or prepolymers include, but are not limited to: acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
- Part A solidifies a scaffold in which a second reactive resin component, termed “Part B,” can solidify during a second step, as discussed further below.
- Part B a second reactive resin component
- a light polymerizable component (a “Part A” component), once polymerized, may degrade during further curing (e.g., during heating or baking) to form a constituent for the further (e.g., heat) cure.
- a constituent for the further (e.g., heat) cure e.g., heat
- Part B e.g., remaining light-reactive blocking groups such as t-BAEMA
- remaining fragments of the light-polymerized scaffold may be deleterious to those final properties, particularly when hard and soft segment content are to be tuned to obtain a high or low T g product.
- inclusion of VBPUs as described herein, along with ABPUs can be particularly advantageous.
- Part B Heat-polymerizable monomers and/or prepolymers.
- these constituents may comprise, consist of or consist essentially of a mix of monomers and/or prepolymers that possess reactive end groups that participate in a second solidification reaction after the Part A solidification reaction.
- methods used to solidify Part B include, but are not limited to, contacting the object or scaffold to heat, water or water vapor, light at a different wavelength than that at which Part A is cured, catalysts, (with or without additional heat), evaporation of a solvent from the polymerizable liquid (e.g., using heat, vacuum, or a combination thereof), microwave irradiation, etc., including combinations thereof.
- heat curing of the “Part B” resins is preferred.
- Suitable reactive end group pairs suitable for Part B constituents, monomers or prepolymers include, but are not limited to: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate*/hydroxyl, isocyanate*/amine, isocyanate/carboxylic acid, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—H (hydro silylation), Si—Cl/hydroxyl, Si—Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide (also known as one embodiment of “Click Chemistry,” along with additional reactions including thiolene, Michael additions, Diels-Alder reactions, nucleophilic substitution reactions, etc.), al
- Part B components generally comprise at least a pair of compounds, reactive with one another (e.g., a polyisocyanate, and a polyamine).
- Photoinitiators included in the polymerizable liquid (resin) can be any suitable photoinitiator, including type I and type II photoinitiators and including commonly used UV photoinitiators, examples of which include but are not limited to such as acetophenones (diethoxyacetophenone for example), phosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (PPO), Irgacure 369, etc. See, e.g., U.S. Pat. No. 9,453,142 to Rolland et al.
- the liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated.
- the particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof.
- the particles can be nonconductive, semi-conductive, or conductive (including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic.
- the particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc.
- the particles can be of any suitable size (for example, ranging from 1 nm to 20 ⁇ m average diameter).
- the particles can comprise an active agent or detectable compound as described below, though these may also be provided dissolved or solubilized in the liquid resin as also discussed below.
- magnetic or paramagnetic particles or nanoparticles can be employed.
- the liquid resin can have additional ingredients solubilized therein, including pigments, dyes, diluents, active compounds or pharmaceutical compounds, detectable compounds (e.g., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated.
- additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
- polymerizable liquids for carrying out the present invention include a non-reactive pigment or dye that absorbs light, particularly UV light.
- Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxypenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g., Mayzo BLS1326) (e.g., included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight).
- organic ultraviolet light absorbers include, but are not limited to, those described in U.S. Pat. Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695,643, the disclosures of which are incorporated herein by reference.
- fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.) inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including combinations of all of the foregoing.
- Suitable fillers include tougheners, such as core-shell rubbers, as discussed below.
- Tougheners One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention. See generally US Patent Application Publication No. 20150215430.
- the toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns ( ⁇ m) in diameter.
- Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
- PES polyhedral oligomeric silsesquioxanes
- carbonaceous materials e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes
- ceramics and silicon carbides with or without surface modification or functionalization.
- Core-shell rubbers are particulate materials (particles) having a rubbery core. Such materials are known and described in, for example, US Patent Application Publication No. 20150184039, as well as US Patent Application Publication No. 20150240113, and U.S. Pat. Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere.
- the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)).
- the average particle size of the core-shell rubber nanoparticles is less than 500 nm, e.g., less than 300 nm, less than 200 nm, less than 100 nm, or even less than 50 nm.
- such particles are spherical, so the particle size is the diameter; however, if the particles are not spherical, the particle size is defined as the longest dimension of the particle.
- Suitable core-shell rubbers include, but are not limited to, those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
- Kaneka Kane Ace including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
- diluents for use in the present invention are preferably reactive organic diluents; that is, diluents that will degrade, isomerize, cross-react, or polymerize, with themselves or a light polymerizable component, during the additive manufacturing step.
- the diluent(s) are included in an amount sufficient to reduce the viscosity of the polymerizable liquid or resin (e.g., to not more than 15,000, 10,000, 6,000, 5,000, 4,000, or 3,000 centipoise at 25 degrees Centigrade).
- Suitable examples of diluents include, but are not limited to, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, and N-vinyl formamide, or a mixture if two or more thereof.
- the diluent may be included in the polymerizable liquid in any suitable amount, typically from 1, 5 or 10 percent by weight, up to about 30 or 40 percent by weight, or more.
- Prepolymer compounds that may be useful in the resins (polymerizable liquids) described herein include those of formula I:
- B 1 is a reactive blocking group (e.g., comprising acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups);
- a reactive blocking group e.g., comprising acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups
- B 2 is a volatile blocking group (e.g., comprising ketoximes, amides, imides, imidazoles, oximes, pyrazoles, alcohols, phenols, sterically-hindered amines, lactams, succinimides, triazoles, and phthalimides, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C 1 -C 10 alkyl group));
- a suitable group such as a straight chain or branched C 1 -C 10 alkyl group
- R 1 and R 2 are independently selected from the group comprising an aliphatic, aromatic or mixed aliphatic and aromatic group, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C 1 -C 10 alkyl group)
- X is O, S, or NR 3 , wherein R 3 is H or a straight chain or branched C 1 -C 10 alkyl group;
- Z is a polymeric organic group (e.g., (CH 2 ) 3 );
- n is an integer in the range of from 1, 5, 10 or 20 to 50, 70 or 100.
- Monomer compounds that may be useful in the resins described herein include those of formula II:
- B 1 is a reactive blocking group (e.g., comprising acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups);
- a reactive blocking group e.g., comprising acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups
- B 2 is a volatile blocking group (e.g., comprising ketoximes, amides, imides, imidazoles, oximes, pyrazoles, alcohols, phenols, sterically-hindered amines, lactams, succinimides, triazoles, and phthalimides, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C 1 -C 10 alkyl group)); and
- R 1 is an aliphatic, aromatic or mixed aliphatic and aromatic group (e.g., a straight chain or branched C 1 -C 15 alkyl or aromatic group), optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C 1 -C 10 alkyl group).
- a suitable group such as a straight chain or branched C 1 -C 10 alkyl group.
- such prepolymer and/or monomer compounds may be provided as a mixture along with compounds having termini with reactive blocking groups and/or compounds having termini with volatile blocking groups (see Scheme 10 above).
- prepolymer and/or monomer compounds may be provided as a resin composition, which composition may include a curative, and/or other resin components as further described above.
- Polymerizable liquids or resins as described herein are used to make three-dimensional objects in a first “light” cure (typically by additive manufacturing) which generates a “green” intermediate object, followed by a second heat cure of that intermediate object.
- first “light” cure typically by additive manufacturing
- second heat cure of that intermediate object
- Suitable techniques include bottom-up or top-down additive manufacturing, generally known as stereolithography.
- Such methods are known and described in, for example, U.S. Pat. No. 5,236,637 to Hull, U.S. Pat. Nos. 5,391,072 and 5,529,473 to Lawton, U.S. Pat. No. 7,438,846 to John, U.S. Pat. No. 7,892,474 to Shkolnik, U.S. Pat. No. 8,110,135 to El-Siblani, U.S. Patent Application Publication No. 2013/0292862 to Joyce, and US Patent Application Publication No. 2013/0295212 to Chen et al. The disclosures of these patents and applications are incorporated by reference herein in their entirety.
- the intermediate object is formed by continuous liquid interface production (CLIP).
- CLIP is known and described in, for example, PCT Application Nos. PCT/US2014/015486 (published as U.S. Pat. No. 9,211,678 on Dec. 15, 2015); PCT/US2014/015506 (also published as U.S. Pat. No. 9,205,601 on Dec. 8, 2015), PCT/US2014/015497 (also published as U.S. Pat. No 9,216,546 on Dec. 22, 2015), and in J. Tumbleston, D. Shirvanyants, N. Ermoshkin et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (published online 16 Mar. 2015). See also R.
- CLIP employs features of a bottom-up three-dimensional fabrication as described above, but the the irradiating and/or said advancing steps are carried out while also concurrently maintaining a stable or persistent liquid interface between the growing object and the build surface or window, such as by: (i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and (ii) continuously maintaining a gradient of polymerization zone (such as an active surface) between the dead zone and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the first component in partially cured form.
- a gradient of polymerization zone such as an active surface
- the optically transparent member comprises a semipermeable member (e.g., a fluoropolymer), and the continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through the optically transparent member, thereby creating a gradient of inhibitor in the dead zone and optionally in at least a portion of the gradient of polymerization zone.
- a semipermeable member e.g., a fluoropolymer
- Other approaches for carrying out CLIP that can be used in the present invention and potentially obviate the need for a semipermeable “window” or window structure include utilizing a liquid interface comprising an immiscible liquid (see L. Robeson et al., WO 2015/164234, published Oct.
- the intermediate three-dimensional object After the intermediate three-dimensional object is formed, it is optionally washed, optionally dried (e.g., air dried) and/or rinsed (in any sequence). It is then further cured, preferably by heating (although further curing may in some embodiments be concurrent with the first cure, or may be by different mechanisms such as contacting to water, as described in U.S. Pat. No. 9,453,142 to Rolland et al.).
- Heating may be active heating (e.g., in an oven, such as an electric, gas, solar oven or microwave oven, or combination thereof), or passive heating (e.g., at ambient (room) temperature). Active heating will generally be more rapid than passive heating and in some embodiments is preferred, but passive heating—such as simply maintaining the intermediate at ambient temperature for a sufficient time to effect further cure—is in some embodiments preferred.
- the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300° C. (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature).
- the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300° C. (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature).
- the intermediate may be heated in a stepwise manner at a first temperature of about 70° C. to about 150° C., and then at a second temperature of about 150° C. to 200 or 250° C., with the duration of each heating depending on the size, shape, and/or thickness of the intermediate.
- the intermediate may be cured by a ramped heating schedule, with the temperature ramped from ambient temperature through a temperature of 70 to 150° C., and up to a final (oven) temperature of 250 or 300° C., at a change in heating rate of 0.5° C. per minute, to 5° C. per minute. (See, e.g., U.S. Pat. No. 4,785,075).
- SR252 and SR313B were received from Sartomer (Arkema Group).
- K-KAT 348 and K-KAT XK-651 were received from King Industries, Inc.
- the photoinitiator for example, TPO
- TPO photoinitiator
- a diluent from a selected group of UV-curable or non-UV active compounds.
- additives such as particle fillers, dyes, pigment, UV-stabilizers, UV absorbers, and non-reactive oligomers
- the curative is added and mixed prior to the production of three-dimensional sample objects by additive manufacturing step, preferably by stereolithography and particularly by continuous liquid interface production (CLIP). UV-curing profiles were measured to obtain the additive production parameters.
- Printed parts were wiped or washed with an organic solvent and post-cured by heating or by microwave. The heating temperature can be from 60° C.
- the heating time can be from minutes to days, and preferably from 1 to 12 hours.
- the formulations may be described as the hard segment weight percent (HS %) and polyurethane/polyurea weight percent (PU %). The calculation for the HS % and PU % is shown below:
- T g glass transition temperature
- elastomeric material may choose to select low-T g diluents such as lauryl methacrylate (LMA) or plasticizers such as diisononyl adipate (DINA).
- LMA lauryl methacrylate
- DINA diisononyl adipate
- the following procedure describes the formulation process using VBPU1 in a formulation.
- the HS includes the diisocyanate (H 12 MDI) components of the VBPU and ABPUs and the curative (MACM).
- the formulation recipe is shown below:
- the ratio of the MEKO:H 12 MDI:PTMO (Mn ⁇ 2,000 Da) and t-BAEMA:H 12 MDI:PTMO (Mn ⁇ 2,000 Da) can be added at any varying ratios.
- Table 4 describes the recipe for a formulation containing the 37% HS and 57% PU illustrating this example:
- the photoinitiator TPO (0.99 g) was dissolved in IBOMA (34.74 g). The remaining ABPU1 (19.31 g), ABPU2 (21.03 g), VBPU1 (16.79 g), and hydroxyphenylbenzotriazole (0.21 g) were added to the TPO-IBOMA mixture. Afterwards, MACM (6.87 g) was added to the formulation and mixed. The UV curing profile of the resin was measured. Sample three-dimensional objects were produced on a Carbon M1 apparatus, cleaned and baked at 120° C. for 12 h. Results are given in FIG. 2 and Table 5.
- Table 6 describes the formulation for example 5 containing VBPU2.
- the formulation contains 37% HS and 57% PU.
- Sample three-dimensional objects produced as described above were examined for evidence of surface defects such as blisters, bubbles, pores, pits or “fish eyes,” caused by out-gassing of the volatile blocking agent regenerated during either the initial additive manufacturing step (as the light polymerization reaction is generally exothermic) or during the subsequent heat cure step. No substantial defect formation was observed.
- Table 8 describes the formulation for Example 8 containing VBPU3.
- the formulation contains 38.5% HS and 69% PU.
Abstract
Description
- This application is a divisional of U.S. patent application Ser. No. 16/615,446, filed Nov. 21, 2019, which is a 35 U.S.C. § 371 national phase application of International Application Serial No. PCT/US2018/036441, filed Jun. 7, 2018, which claims the benefit of U.S. provisional patent application Ser. No. 62/516,893, filed on Jun. 8, 2017, the disclosure of which is incorporated by reference herein in its entirety.
- The present invention concerns additive manufacturing in general, and particularly concerns dual cure resins useful in methods such as stereolithography and continuous liquid interface production (CLIP).
- In conventional additive manufacturing techniques (often referred to as “3D printing”), construction of a three-dimensional object is performed in a step-wise or layer-by-layer manner by sequentially exposing a light-polymerizable resin to patterned light. Generally referred to as “stereolithography,” numerous examples are known, including those described in U.S. Pat. No. 5,236,637 to Hull (see, e.g.,
FIGS. 3-4 ) and U.S. Pat. No. 7,892,474 to Shkolnik. Additional examples are given in U.S. Pat. Nos. 5,391,072 and 5,529,473 to Lawton, U.S. Pat. No. 7,438,846 to John, U.S. Pat. No. 8,110,135 to El-Siblani, and US Patent Application Publication Nos. 2013/0292862 to Joyce and 2013/0295212 to Chen et al. - Unfortunately, additive manufacturing techniques have generally been slow, and have long been known to produce parts with a limited range of mechanical properties, frequently rendering such products unsuitable for real world use beyond simple prototyping.
- More recently, techniques referred to as “continuous liquid interface production” (or “CLIP”) have been developed. These techniques enable the rapid production of three-dimensional objects, preferably in a layerless manner, by which the parts may have desirable structural and mechanical properties. See, e.g., J. DeSimone et al., U.S. Pat. Nos. 9,211,678; 9,205,601; and 9,216,546; J. Tumbleston, et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (published online Mar. 16, 2015), and R. Janusziewcz et al., Layerless fabrication with continuous liquid interface production, Proc. Natl. Acad. Sci. USA 113, 11703-11708 (Oct. 18, 2016).
- The speed, and other attributes, of CLIP opened the door to the development of “dual cure” stereolithography resins, in which the shape of an article is created by light polymerization in the additive manufacturing process, and the mechanical properties of the article are created in a second cure that typically follows (for example, by baking). Dual cure resins that provide for a range of mechanical properties in the final product are described in, for example, J. Rolland et al., U.S. Pat. Nos. 9,453,142 and 9,598,606, and US Patent Application Publication Nos. 2016/0136889 and 2016/0160077.
- The requirements imposed on a light polymerizable resin during the different steps of a dual cure additive manufacturing process can, however, compete with one another. For example, ingredients that provide for a liquid resin that is readily processed by additive manufacturing to produce an intermediate “green” part (e.g., low viscosity) may be detrimental to producing a reasonably strong “green” part. And ingredients that might provide for a strong green part may be detrimental to the mechanical properties of the finished part after a second cure such as a baking step.
- J. Rolland et al. (cited above) solve this problem by employing, in a dual cure resin, light polymerizable ingredients that help form the green object, but then degrade during the second (typically heat) cure to form a constituent that participates in the second cure (and hence contribute to the mechanical properties of the finished part). Specifically, light polymerizable (“reactive”) blocking groups were used to block the otherwise reactive isocyanate (“NCO”) groups of a monomer or prepolymer to create a light polymerizable constituent (Scheme 1), which blocking groups subsequently degrade on heating to unmask the NCO group so that it can participate in a subsequent cure (e.g., upon baking) to produce a polyurethane or polyurea polymer in the finished object.
- In Scheme 1 above, H—B1 represents a UV-reactive blocking agent, B1 represents a UV-reactive blocking group (such as an acrylate); R2 represents an organic group, the wavy line represents a polymeric organic group (as found in a prepolymer); and x is as given therein.
- While satisfactory for many uses, the foregoing approach is in some cases limited to chemical systems which produce finished objects having a glass transition temperature (Tg) close to room temperature. Yet, for finished objects that are to be elastomeric, glass transition temperatures substantially less than room temperature are preferred. On the other hand, for finished objects that are to be more rigid, glass transition temperatures substantially above room temperature are preferred. In addition, the more UV-reactive blocking agent used can make it difficult to maximize the polyurethane/polyurea weight fraction in the final material. From the perspective of formulation, it is often desirable to have more polyurethane/polyurea fraction in the final material as the UV fraction may either be too brittle or too fragile depending on the Tg. Therefore, there is a need for additional approaches in dual cure resins for additive manufacturing that complement those previously developed.
- A method of forming a three-dimensional object can be carried out by:
- (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween;
- (b) filling the build region with an (optionally but preferably non-aqueous) polymerizable liquid, the polymerizable liquid comprising a mixture of (i) a light polymerizable first component, and (ii) a heat polymerizable second component;
- the heat polymerizable second component comprising (i) a first blocked reactive constituent that is blocked with a volatile blocking group, and optionally but preferably (ii) a curative;
- (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier and the build surface away from one another to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, with the three-dimensional intermediate containing the first blocked reactive constituent in unpolymerized form; and then
- (d) heating the three-dimensional intermediate sufficiently to (i) cleave the volatile blocking group from the reactive constituent and (ii) polymerize the blocked reactive constituent with itself, and/or the curative, and with (iii) the volatile blocking group vaporizing out of the three-dimensional intermediate, to form the three-dimensional object. (note that (i) and (ii) may occur in any order, or concurrently).
- In some embodiments, the volatile blocking group comprises a ketoxime, amide, imide, imidazole, pyrazole, alcohol, or sterically-hindered amine blocking group.
- In some embodiments, the first blocked reactive constituent comprises a blocked polyisocyanate.
- In some embodiments, the first blocked reactive constituent comprises a ketoxime-blocked polyisocyanate.
- In some embodiments, the curative comprises a polyol, a polyamine, a polyetheramine, or a combination thereof.
- In some embodiments, the three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from the first component and the second component.
- In some embodiments, the second component comprises precursors to a polyurethane, polyurea, or copolymer thereof; a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber.
- In some embodiments, the first blocked reactive constituent is included in the polymerizable liquid in an amount of from 1, 2, 5 or 10 percent by weight, to 30, 40, or 50 percent by weight, or more.
- In some embodiments, the polymerizable liquid further comprises at least one photoinitiator (e.g., in an amount of from 0.1 to 1 or 5 percent by weight), optionally at least one dye (e.g., in an amount of 0.001 or 0.01 to 1 or 5 percent by weight), and optionally at least one filler (e.g., in an amount of 0.01 or 0.1 to 20 or 50 percent by weight).
- In some embodiments: the light polymerizable first component comprises a second blocked reactive constituent that is blocked with a light reactive blocking group; and the curing step (d) is carried out under conditions in which at least a portion of the solid polymer scaffold produced by light polymerization of the second reactive constituent degrades and forms a constituent that participates in the heat polymerizing.
- In some embodiments, the second blocked reactive constituent comprises a blocked polyisocyanate having two or more ethylenically unsaturated end groups.
- In some embodiments, the second blocked reactive constituent is included in the polymerizable liquid in an amount of from 1, 2, 5 or 10 percent by weight, to 30, 40, or 50 percent by weight, or more.
- In some embodiments, the first blocked reactive constituent (e.g., VBPU) and the second blocked reactive constituent (e.g., ABPU), are included together in the polymerizable liquid in a weight ratio of from 1:5, 1:10 or 1:20, to 5:1, 10:1 or 20:1.
- In some embodiments: (i) the object is elastomeric and is comprised of a polymer having a glass transition temperature of no more than −20 or 0° C.; or (ii) the object is rigid and is comprised of a polymer having a glass transition temperature of at least 50 or 70° C.
- A further aspect of the invention is a three-dimensional object produced by the method of any preceding claim (e.g., wherein the object includes a three-dimensional lattice).
- A further aspect of the invention is a polymerizable liquid composition as described above, and described further below.
- A further aspect is a prepolymer compound of formula I:
- wherein:
- B1 is a reactive blocking group;
- B2 is a volatile blocking group;
- R1 and R2 are independently selected from the group comprising an aliphatic, aromatic or mixed aliphatic and aromatic group;
- X is O, S, or NR3, wherein R3 is H or a straight chain or branched C1-C10alkyl group;
- Z is a polymeric organic group;
- n is an integer in the range of from 1, 5, 10, 20 or 30 to 80, 100, or 150; and
- m is an integer in the range of from 1, 5, 10 or 20 to 50, 70 or 100.
- A further aspect is a monomer compound of formula II:
- wherein:
- B1 is a reactive blocking group;
- B2 is a volatile blocking group; and
- R1 is an aliphatic, aromatic or mixed aliphatic and aromatic group.
- A further aspect of the invention is a polymerizable liquid composition containing a prepolymer and/or monomer compound as described above.
- U.S. Pat. No. 3,694,389 to Levy describes thermosetting compositions containing ketoxime-blocked isocyanates, but suggest their use only as coatings.
- The foregoing and other objects and aspects of the present invention are explained in greater detail in the drawings herein and the specification set forth below. The disclosures of all United States patent references cited herein are to be incorporated herein by reference.
-
FIG. 1 : Dynamic Mechanical Analysis (DMA) curve of Formulation I compared to a non-MEKO containing formulation (Control A). Control A formulation is described in Table 2 below. DMA: RSA-G2, Temperature ramp 5° C./min, 10 Hz. -
FIG. 2 : DMA curve of Formulation II compared to a non-MEKO containing formulation (Control A). DMA: RSA-G2, Temperature ramp 5° C./min, 10 Hz. -
FIG. 3 : DMA data of Formulation III, prepared in like manner to that described in connection withFIGS. 1-2 above. - The present invention is now described more fully hereinafter with reference to the accompanying examples, in which embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art, as well as specific examples thereof.
- As used herein, the term “and/or” includes any and all possible combinations or one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”).
- “ABPU” as used herein refers to UV-curable, (meth)acrylate blocked, polyurethane/polyurea (i.e., reactive blocked polyurethane) such as described in U.S. Pat. Nos. 9,453,142 and 9,598,606 to Rolland et al. ABPUs are reactive blocked polyurethanes. A particular example of a suitable reactive (or UV-curable) blocking group is a tertiary amine-containing (meth)acrylate (e.g., t-butylaminoethyl methacrylate, t-BAEMA). Note, however, that t-BAEMA has a glass transition temperature of about room temperature, which is less preferred for the production of rigid or elastomeric objects, as discussed further below.
- “VBPU” as used herein refers to a volatile blocking group blocked, polyurethane/polyurea.
- Volatile blocking agents that may be used to carry out the present invention include, for example, ketoximes, amides, imides, imidazoles, pyrazoles, alcohols, and sterically-hindered amines, such as 2-butanone oxime (also called methyl ethyl ketoxime or “MEKO”), acetone oxime, cyclopentanone oxime, cyclohexanone oxime, ε-caprolactam, N-methylacetamide, imidazole, succinimide, benzotriazole, N-hydroxyphthalimide, 1,2,4-triazole, 2-ethyl-1-hexanol, phenol, 3,5-dimethylpyrazole, 2,2,6,6-tetramethylpiperidine, and diisopropylamine (see, e.g., Scheme 2).
- “Volatile blocking group” as used herein refers to a substituent produced by the covalent coupling of a volatile blocking agent as described above to the reactive group (particularly an isocyanate group) of a reactive compound (such as a diisocyanate monomer or prepolymer).
- Polyisocyanates (including diisocyanates) useful in carrying out the present invention include, but are not limited to, 1,1′-methylenebis(4-isocyanatobenzene) (MDI), 2,4-diisocyanato-1-methylbenzene (TDI), methylene-bis(4-cyclohexylisocyanate) (H12MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), polymeric MDI, 1,4-phenylene diisocyanate (PPDI), and o-tolidine diisocyanate (TODI). The preferred diisocyanate is H12MDI, such as Desmodur W, supplied by Covestro AG. Additional examples include but are not limited to those given in U.S. Pat. No. 3,694,389 to Levy.
- Catalysts useful in carrying out the present invention to prepare VBPUs from prepolymers and volatile blocking groups include, but are not limited to, dibutyltin dilaurate, stannous octoate, and bismuth octoate. A preferred catalyst is the bismuth catalyst K-KAT 348, supplied by King Industries, Inc.
- Polyols, polyamines, and polythiols useful in carrying out the present invention (e.g., for preparation of prepolymers as a resin constituent) are known. Examples include, but are not limited to, poly(ethylene glycol), poly(propylene glycol), poly(trimethylene glycol), poly(tetramethylene glycol) (PTMO), hydroxy-terminated poly(dimethylsiloxane), polyester diol especially polycaprolactone (PCL) diol, PTMO-PCL copolymer diol (Capa 7201A from Perstorp), hydroxy-terminated polybutadiene, and polyetheramines (for example JEFFAMINE® from Huntsman Corporation). A preferred polyol, polyamine, and polythiol is PTMO, with an average Mn between 500 to 3000 Da.
- Curatives useful for carrying out the present invention (e.g., for reacting with prepolymers after formation of an intermediate object) are known. Examples include, but are not limited to polyols such as diols (such as ethylene glycol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, hydroquinone bis(2-hydroxyethyl) ether, 1,4-cyclohexanedimethanol), aliphatic, aromatic, and mixed aliphatic and aromatic, polyamines, such as diamines (for example, 4,4′-methylenedicyclohexanamine (PACM), 4,4′-methylenebis(2-methylcyclohexyl-amine) (MACM), ethylene diamine, isophorone diamine, diethyltoluenediamine), and polyetheramines (for example JEFFAMINE® from Huntsman Corporation).
- Photoinitiators useful in the present invention include, but are not limited to, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), 2-isopropylthioxanthone and/or 4-isopropylthioxanthone (ITX), etc.
- “Diluents” as used herein includes both UV-curable diluents (for example monoacrylates, mono-methacrylates, polyacrylates, polymethacrylates, acrylamides, methacrylamides, etc.), and non-UV-curable diluents (for example, plasticizers such as bis(2-ethylhexyl) phthalate, bis(2-propylheptyl) phthalate, diisononyl phthalate, tri-(2-ethylhexyl) trimellitate, bis(2-ethylhexyl) adipate, diisononyl adipate, dibutyl sebacate, diisobutyl maleate, etc.).
- “Solvents” as used herein includes, for example, diethyl ether, tetrahydrofuran, ethyl acetate, benzene, toluene, N,N-dimethylformamide, propylene carbonate, dimethyl carbonate, etc.
- “Soft segment” and “hard segment” as used herein have their usual meaning in the polymer chemistry field. “Soft segment” refers to a typically high molecular weight chain that has a glass transition temperature less than room temperature, is generally amorphous or partially crystalline, and provides flexibility to the copolymer, and generally has a large number of degrees of freedom. “Hard segment” as used herein refers to a higher glass transition temperature, generally crystalline, rigid, generally oligomeric molecular weight segment that can provide mechanical integrity or strength to the segmented copolymer.
- VBPUs can be prepared in accordance with known procedures (see, e.g., U.S. Pat. No. 3,694,389 to Levy) or variations thereof that will be apparent to those skilled in the art based on the disclosure below.
- A first example synthesis of a VBPU is given in Scheme 3 below, where R2 represents an organic group (e.g., an optionally substituted aliphatic, aromatic, or mixed aliphatic and aromatic, group), the wavy line represents a polymer of an organic group (as found in a prepolymer), H—B2 represents a volatile blocking agent, B2 represents a volatile blocking group, and x is as given below.
- In some embodiments, the benefit of incorporating such groups is that it provides multiple methods of tuning final mechanical properties by controlling the polyurethane/polyurea and UV-network percentages, allowing the ability to control the resulting glass transition temperature (Tg) and mechanical properties. As shown in Scheme 3, the volatile blocking group blocked polyurethane/polyurea (VBPU) prepolymer can be added to a UV-curable formulation, such as one containing an acrylate-blocked polyurethane (ABPU) as described in J. Rolland et al., U.S. Pat. Nos. 9,453,142 and 9,598,606.
- In the alternative, the VBPU can be synthesized separately or in conjunction with a UV-reactive prepolymer, as shown in Scheme 4.
- In Scheme 4, R1 represents an optionally substituted aliphatic, aromatic, or mixed aliphatic and aromatic, group, H—B2 represents a volatile blocking agent, and B2 represents a volatile blocking group.
- As shown in Scheme 5, once a green intermediate object is produced from a dual cure resin containing a VBPU, the VBPU in the object is then reacted with a curative (H-y-R2-y-H in Scheme 5) to produce higher molecular weight polyurethane/polyurea in the final object, to aid in producing the desired mechanical properties in that object.
- In Scheme 5 above, each x is as given in Scheme 3, each y is as given therein, each R1 and R2 represents an independently selected, optionally substituted, aliphatic, aromatic, or mixed aliphatic and aromatic, group, B2 represents a volatile blocking group; and the wavy line represents the polymeric repeat segment of a polyurethane or polyurea prepolymer.
- Scheme 6 shows a more specific example of general Scheme 3 above, and includes initially reacting a diisocyanate molecule, in the presence of catalyst, with a polyol, polyamine, or polythiol, or combination thereof. The remaining isocyanate (NCO) is then reacted with the volatile blocking group 2-butanone oxime (methyl ethyl ketoxime, or “MEKO”).
- In Scheme 6, R2 and the wavy line are as given in connection with Scheme 3 above, and the equivalent ratio of diisocyanate to polyol/polyamine/polythiol can be from 6:1 to 1.5:1 and preferably from 2.4:1 to 2:1.
- Schemes 7-8 below show a more specific example of general Scheme 4 above, including reacting a diisocyanate molecule directly with the volatile blocking group at a molar ratio of 1:2. This can also be synthesized in the presence of other components, such as UV-curable diluents, non-UV-curable diluents (such as plasticizer), solvents, and/or ABPUs.
- In another alternative, the VBPU can include the volatile blocking group and the UV-curable group on the same prepolymer, as shown in Scheme 9, where H—B1 is a UV-curable blocking group and H—B2 is a volatile blocking group.
- More specifically, an exemplary synthesis to such a structure along with an ABPU is shown in Scheme 10, where the UV-curable blocking group is t-BAEMA and the volatile blocking group is 3,5-dimethylpyrazole (DMP), along with H12MDI diisocyanate and PTMO.
- VBPUs as described above (or other “Part B” reactive constituents as described below, blocked with a volatile reactive group as described above) can be incorporated into any of a variety of different dual cure resins for additive manufacturing, including but not limited to those described in U.S. Pat. Nos. 9,453,142 and 9,598,606 to Rolland et al.
- In general, such resins can comprise: (a) light-polymerizable monomers and/or prepolymers that can form an intermediate object (typically in the presence of a photocatalyst); and (b) heat (or microwave, RF energy)-polymerizable (or otherwise further polymerizable) monomers and/or prepolymers. As noted above, in the present invention these constituents may be supplemented with an organic diluent as described above, and discussed further below.
- A. Light-polymerizable monomers and/or prepolymers. Sometimes also referred to as “Part A” of the resin, these are monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light. This resin can have a functionality of 2 or higher. A purpose of Part A is to “lock” the shape of the object being formed or create a scaffold for the one or more additional components (e.g., Part B). Importantly, Part A is present at or above the minimum quantity needed to maintain the shape of the object being formed after the initial solidification during photolithography. In some embodiments, this amount corresponds to less than ten, twenty, or thirty percent by weight of the total resin (polymerizable liquid) composition.
- Examples of suitable reactive end groups suitable for Part A constituents, monomers, or prepolymers include, but are not limited to: acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
- An aspect of the solidification of Part A is that it provides a scaffold in which a second reactive resin component, termed “Part B,” can solidify during a second step, as discussed further below.
- Note that, in some embodiments, a light polymerizable component (a “Part A” component), once polymerized, may degrade during further curing (e.g., during heating or baking) to form a constituent for the further (e.g., heat) cure. Thus, it is converted, in part, to a “Part B” component, though other portions (e.g., remaining light-reactive blocking groups such as t-BAEMA), may not participate in the further cure, and hence make little or no contribution to the mechanical properties of the final product. Indeed, such remaining fragments of the light-polymerized scaffold may be deleterious to those final properties, particularly when hard and soft segment content are to be tuned to obtain a high or low Tg product. For applications such as these, inclusion of VBPUs as described herein, along with ABPUs, can be particularly advantageous.
- B. Heat-polymerizable monomers and/or prepolymers. Sometimes also referred to as “Part B”, these constituents may comprise, consist of or consist essentially of a mix of monomers and/or prepolymers that possess reactive end groups that participate in a second solidification reaction after the Part A solidification reaction. In general, for dual cure resins, examples of methods used to solidify Part B include, but are not limited to, contacting the object or scaffold to heat, water or water vapor, light at a different wavelength than that at which Part A is cured, catalysts, (with or without additional heat), evaporation of a solvent from the polymerizable liquid (e.g., using heat, vacuum, or a combination thereof), microwave irradiation, etc., including combinations thereof. In this case, heat curing of the “Part B” resins is preferred.
- Examples of suitable reactive end group pairs suitable for Part B constituents, monomers or prepolymers include, but are not limited to: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate*/hydroxyl, isocyanate*/amine, isocyanate/carboxylic acid, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—H (hydro silylation), Si—Cl/hydroxyl, Si—Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide (also known as one embodiment of “Click Chemistry,” along with additional reactions including thiolene, Michael additions, Diels-Alder reactions, nucleophilic substitution reactions, etc.), alkene/Sulfur (polybutadiene vulcanization), alkene/peroxide, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate*/water (polyurethane foams), Si—OH/hydroxyl, Si—OH/water, Si—OH/Si—H (tin catalyzed silicone), Si—OH/Si—OH (tin catalyzed silicone), perfluorovinyl (coupling to form perfluorocyclobutane), etc., where *isocyanates include protected isocyanates (e.g. oximes)), diene/dienophiles for Diels-Alder reactions, olefin metathesis polymerization, olefin polymerization using Ziegler-Natta catalysis, ring-opening polymerization (including ring-opening olefin metathesis polymerization, lactams, lactones, siloxanes, epoxides, cyclic ethers, imines, cyclic acetals, etc.), etc. As will be noted from the above, the “Part B” components generally comprise at least a pair of compounds, reactive with one another (e.g., a polyisocyanate, and a polyamine).
- C. Additional resin ingredients. Photoinitiators included in the polymerizable liquid (resin) can be any suitable photoinitiator, including type I and type II photoinitiators and including commonly used UV photoinitiators, examples of which include but are not limited to such as acetophenones (diethoxyacetophenone for example), phosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (PPO), Irgacure 369, etc. See, e.g., U.S. Pat. No. 9,453,142 to Rolland et al.
- The liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated. The particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof. The particles can be nonconductive, semi-conductive, or conductive (including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic. The particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc. The particles can be of any suitable size (for example, ranging from 1 nm to 20 μm average diameter).
- The particles can comprise an active agent or detectable compound as described below, though these may also be provided dissolved or solubilized in the liquid resin as also discussed below. For example, magnetic or paramagnetic particles or nanoparticles can be employed.
- The liquid resin can have additional ingredients solubilized therein, including pigments, dyes, diluents, active compounds or pharmaceutical compounds, detectable compounds (e.g., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated. Examples of such additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
- Dyes/non-reactive light absorbers. In some embodiments, polymerizable liquids for carrying out the present invention include a non-reactive pigment or dye that absorbs light, particularly UV light. Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxypenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g., Mayzo BLS1326) (e.g., included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight). Examples of suitable organic ultraviolet light absorbers include, but are not limited to, those described in U.S. Pat. Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695,643, the disclosures of which are incorporated herein by reference.
- Fillers. Any suitable filler may be used in connection with the present invention, depending on the properties desired in the part or object to be made. Thus, fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.) inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including combinations of all of the foregoing. Suitable fillers include tougheners, such as core-shell rubbers, as discussed below.
- Tougheners. One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention. See generally US Patent Application Publication No. 20150215430. The toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns (μm) in diameter. Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
- Core-shell rubbers. Core-shell rubbers are particulate materials (particles) having a rubbery core. Such materials are known and described in, for example, US Patent Application Publication No. 20150184039, as well as US Patent Application Publication No. 20150240113, and U.S. Pat. Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere. In some embodiments, the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)). Generally, the average particle size of the core-shell rubber nanoparticles is less than 500 nm, e.g., less than 300 nm, less than 200 nm, less than 100 nm, or even less than 50 nm. Typically, such particles are spherical, so the particle size is the diameter; however, if the particles are not spherical, the particle size is defined as the longest dimension of the particle. Suitable core-shell rubbers include, but are not limited to, those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
- Organic diluents. In some embodiments, diluents for use in the present invention are preferably reactive organic diluents; that is, diluents that will degrade, isomerize, cross-react, or polymerize, with themselves or a light polymerizable component, during the additive manufacturing step. In general, the diluent(s) are included in an amount sufficient to reduce the viscosity of the polymerizable liquid or resin (e.g., to not more than 15,000, 10,000, 6,000, 5,000, 4,000, or 3,000 centipoise at 25 degrees Centigrade). Suitable examples of diluents include, but are not limited to, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, and N-vinyl formamide, or a mixture if two or more thereof. The diluent may be included in the polymerizable liquid in any suitable amount, typically from 1, 5 or 10 percent by weight, up to about 30 or 40 percent by weight, or more.
- Prepolymer compounds that may be useful in the resins (polymerizable liquids) described herein include those of formula I:
- wherein:
- B1 is a reactive blocking group (e.g., comprising acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups);
- B2 is a volatile blocking group (e.g., comprising ketoximes, amides, imides, imidazoles, oximes, pyrazoles, alcohols, phenols, sterically-hindered amines, lactams, succinimides, triazoles, and phthalimides, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C1-C10alkyl group));
- R1 and R2 are independently selected from the group comprising an aliphatic, aromatic or mixed aliphatic and aromatic group, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C1-C10alkyl group)
- X is O, S, or NR3, wherein R3 is H or a straight chain or branched C1-C10alkyl group;
- Z is a polymeric organic group (e.g., (CH2)3);
- n is an integer in the range of from 1, 5, 10, 20 or 30 to 80, 100, or 150 (for example, PO3G with a MW of 2400 g/mol would have n=41 and PO3G with MW of 3000 g/mol would have n=51. Poly(propylene glycol) 4000 g/mol would have n=103); and
- m is an integer in the range of from 1, 5, 10 or 20 to 50, 70 or 100.
- Monomer compounds that may be useful in the resins described herein include those of formula II:
- wherein:
- B1 is a reactive blocking group (e.g., comprising acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and ethylenically unsaturated end groups);
- B2 is a volatile blocking group (e.g., comprising ketoximes, amides, imides, imidazoles, oximes, pyrazoles, alcohols, phenols, sterically-hindered amines, lactams, succinimides, triazoles, and phthalimides, optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C1-C10alkyl group)); and
- R1 is an aliphatic, aromatic or mixed aliphatic and aromatic group (e.g., a straight chain or branched C1-C15alkyl or aromatic group), optionally substituted (e.g., substituted 1, 2, 3 or 4 or more times with a suitable group, such as a straight chain or branched C1-C10alkyl group).
- As a non-limiting example, such prepolymer and/or monomer compounds may be provided as a mixture along with compounds having termini with reactive blocking groups and/or compounds having termini with volatile blocking groups (see Scheme 10 above).
- In some embodiments, prepolymer and/or monomer compounds may be provided as a resin composition, which composition may include a curative, and/or other resin components as further described above.
- Polymerizable liquids or resins as described herein are used to make three-dimensional objects in a first “light” cure (typically by additive manufacturing) which generates a “green” intermediate object, followed by a second heat cure of that intermediate object.
- Techniques for additive manufacturing are known. Suitable techniques include bottom-up or top-down additive manufacturing, generally known as stereolithography. Such methods are known and described in, for example, U.S. Pat. No. 5,236,637 to Hull, U.S. Pat. Nos. 5,391,072 and 5,529,473 to Lawton, U.S. Pat. No. 7,438,846 to John, U.S. Pat. No. 7,892,474 to Shkolnik, U.S. Pat. No. 8,110,135 to El-Siblani, U.S. Patent Application Publication No. 2013/0292862 to Joyce, and US Patent Application Publication No. 2013/0295212 to Chen et al. The disclosures of these patents and applications are incorporated by reference herein in their entirety.
- In some embodiments, the intermediate object is formed by continuous liquid interface production (CLIP). CLIP is known and described in, for example, PCT Application Nos. PCT/US2014/015486 (published as U.S. Pat. No. 9,211,678 on Dec. 15, 2015); PCT/US2014/015506 (also published as U.S. Pat. No. 9,205,601 on Dec. 8, 2015), PCT/US2014/015497 (also published as U.S. Pat. No 9,216,546 on Dec. 22, 2015), and in J. Tumbleston, D. Shirvanyants, N. Ermoshkin et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (published online 16 Mar. 2015). See also R. Janusziewcz et al., Layerless fabrication with continuous liquid interface production, Proc. Natl. Acad. Sci. USA 113, 11703-11708 (Oct. 18, 2016). In some embodiments, CLIP employs features of a bottom-up three-dimensional fabrication as described above, but the the irradiating and/or said advancing steps are carried out while also concurrently maintaining a stable or persistent liquid interface between the growing object and the build surface or window, such as by: (i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and (ii) continuously maintaining a gradient of polymerization zone (such as an active surface) between the dead zone and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the first component in partially cured form. In some embodiments of CLIP, the optically transparent member comprises a semipermeable member (e.g., a fluoropolymer), and the continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through the optically transparent member, thereby creating a gradient of inhibitor in the dead zone and optionally in at least a portion of the gradient of polymerization zone. Other approaches for carrying out CLIP that can be used in the present invention and potentially obviate the need for a semipermeable “window” or window structure include utilizing a liquid interface comprising an immiscible liquid (see L. Robeson et al., WO 2015/164234, published Oct. 29, 2015), generating oxygen as an inhibitor by electrolysis (see I Craven et al., WO 2016/133759, published Aug. 25, 2016), and incorporating magnetically positionable particles to which the photoactivator is coupled into the polymerizable liquid (see J. Rolland, WO 2016/145182, published Sep. 15, 2016).
- After the intermediate three-dimensional object is formed, it is optionally washed, optionally dried (e.g., air dried) and/or rinsed (in any sequence). It is then further cured, preferably by heating (although further curing may in some embodiments be concurrent with the first cure, or may be by different mechanisms such as contacting to water, as described in U.S. Pat. No. 9,453,142 to Rolland et al.).
- Heating may be active heating (e.g., in an oven, such as an electric, gas, solar oven or microwave oven, or combination thereof), or passive heating (e.g., at ambient (room) temperature). Active heating will generally be more rapid than passive heating and in some embodiments is preferred, but passive heating—such as simply maintaining the intermediate at ambient temperature for a sufficient time to effect further cure—is in some embodiments preferred.
- In some embodiments, the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300° C. (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature). In some embodiments, the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300° C. (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature).
- For example, the intermediate may be heated in a stepwise manner at a first temperature of about 70° C. to about 150° C., and then at a second temperature of about 150° C. to 200 or 250° C., with the duration of each heating depending on the size, shape, and/or thickness of the intermediate. In another embodiment, the intermediate may be cured by a ramped heating schedule, with the temperature ramped from ambient temperature through a temperature of 70 to 150° C., and up to a final (oven) temperature of 250 or 300° C., at a change in heating rate of 0.5° C. per minute, to 5° C. per minute. (See, e.g., U.S. Pat. No. 4,785,075).
- The present invention is explained in greater detail in the following examples. Abbreviations used below are given in the detailed description above. SR252 and SR313B were received from Sartomer (Arkema Group). K-KAT 348 and K-KAT XK-651 were received from King Industries, Inc.
- In a reactor was added Desmodur W (263.18 g) and K-KAT 348 (0.447 g). The mixture was heated to 70° C. and PTMO with an average Mn ˜2,000 (854.70 g) was added dropwise over 3 hours. After one additional hour of stirring, the temperature was decreased to 50° C. MEKO (100.52 g) was added dropwise over 3 hours while maintaining the temperature at 50° C. and stirred for an additional 12 hours. The reaction was complete when NCO content was <0.1%. VBPU1 was colorless, transparent, and had a viscosity of 304,000 cP at 25.0° C.
- In a reactor containing an ABPU (1128.81 g, comprised of H12MDI:PTMO (Mn ˜2,000 Da):t-BAEMA with a molar ratio of 2.2-1.0-2.4) at 50° C. was added Desmodur W (44.03 g). After stirring for 3 hours, MEKO (29.28 g) was added dropwise over 1 hour and stirred at 50° C. for 18 hours. The reaction was complete when NCO content was <0.1%. VBPU2 was colorless, transparent, and had a viscosity of 420,000 cP at 25.0° C.
- In brief overview, the photoinitiator (for example, TPO) was dissolved in a diluent from a selected group of UV-curable or non-UV active compounds. To this solution was added the remaining components ABPU, VBPU, and additives (such as particle fillers, dyes, pigment, UV-stabilizers, UV absorbers, and non-reactive oligomers) excluding the curative. The curative is added and mixed prior to the production of three-dimensional sample objects by additive manufacturing step, preferably by stereolithography and particularly by continuous liquid interface production (CLIP). UV-curing profiles were measured to obtain the additive production parameters. Printed parts were wiped or washed with an organic solvent and post-cured by heating or by microwave. The heating temperature can be from 60° C. to 250° C. and preferably from 80° C. to 140° C. The heating time can be from minutes to days, and preferably from 1 to 12 hours. The formulations may be described as the hard segment weight percent (HS %) and polyurethane/polyurea weight percent (PU %). The calculation for the HS % and PU % is shown below:
-
- Therefore, in rigid systems, it is desirable to formulate systems with high glass transition temperature (Tg) monomers such as isobornyl methacrylate (IBOMA). In contrast, elastomeric material may choose to select low-Tg diluents such as lauryl methacrylate (LMA) or plasticizers such as diisononyl adipate (DINA).
- The following procedure describes the formulation process using VBPU1 in a formulation. The HS includes the diisocyanate (H12MDI) components of the VBPU and ABPUs and the curative (MACM). The formulation recipe is shown below:
-
TABLE 1 Formulation I Component Amount (g) VBPU1 15.11 ABPU1* 38.61 ABPU2* 30.78 IBOMA 48.63 4,4′-Methylenebis(2- 10.01 methylcyclohexylamine) (MACM) hydroxyphenylbenzotriazoles 0.41 TPO 1.44 *synthesized as shown in Scheme 1, and analogously to the VBPU 1 shown in Example 1, where ABPU1 is comprised of t-BAEMA:H12MDI:PTMO (Mn~2,000 Da) with a molar ratio of 2.7:2.35:1.0 and ABPU2 is comprised of t-BAEMA:H12MDI:PTMO (Mn~1,000 Da) with a molar ratio of 2.4:2.2:1.0. -
TABLE 2 Formulation of Control A Component Amount (g) ABPU1 38.61 ABPU2 21.55 IBOMA 31.51 4,4′-Methylenebis(2- 7.04 methylcyclohexylamine) (MACM) hydroxyphenylbenzotriazoles 0.21 TPO 0.99
The photoinitiator TPO (1.44 g) was dissolved in IBOMA (48.63 g). The remaining ABPU1 (38.61 g), ABPU2 (30.78 g), VBPU1 (15.11 g), and hydroxyphenylbenzotriazole (0.41 g) were added to the TPO-IBOMA mixture. Afterwards, MACM (10.01 g) was added to the formulation and mixed. The UV curing profile of the resin was measured. Sample three dimensional objects were produced on a Carbon M1 apparatus, cleaned and baked at 120° C. for 12 h. Results are given inFIG. 1 and in Table 3. - The ratio of the MEKO:H12MDI:PTMO (Mn ˜2,000 Da) and t-BAEMA:H12MDI:PTMO (Mn ˜2,000 Da) can be added at any varying ratios. Table 4 describes the recipe for a formulation containing the 37% HS and 57% PU illustrating this example:
-
TABLE 4 Formulation II Component Amount (g) VBPU1 16.79 ABPU1 19.31 ABPU2 21.03 IBOMA 34.74 MACM 6.87 hydroxyphenylbenzotriazoles 0.21 TPO 0.99 - The photoinitiator TPO (0.99 g) was dissolved in IBOMA (34.74 g). The remaining ABPU1 (19.31 g), ABPU2 (21.03 g), VBPU1 (16.79 g), and hydroxyphenylbenzotriazole (0.21 g) were added to the TPO-IBOMA mixture. Afterwards, MACM (6.87 g) was added to the formulation and mixed. The UV curing profile of the resin was measured. Sample three-dimensional objects were produced on a Carbon M1 apparatus, cleaned and baked at 120° C. for 12 h. Results are given in
FIG. 2 and Table 5. - Table 6 describes the formulation for example 5 containing VBPU2. The formulation contains 37% HS and 57% PU.
-
TABLE 6 Formulation III Component Amount (g) VBPU2 48.19 ABPU2 9.59 IBOMA 33.68 TPO 0.99 hydroxyphenylbenzotriazoles 0.21 MACM 7.25
The photoinitiator TPO (0.99 g) was dissolved in IBOMA (33.68 g). The remaining ABPU2 (9.59 g), VBPU2 (48.19 g), and hydroxyphenylbenzotriazole (0.21 g) were added to the TPO-IBOMA mixture. Afterwards, MACM (7.25 g) was added to the formulation and mixed. The UV curing profile of the resin was measured. Sample three-dimensional objects were produced on a Carbon, Inc. M1 apparatus, wiped clean, and then baked at 120° C. for 12 h. Results are given inFIG. 3 and Table 7. - Sample three-dimensional objects produced as described above were examined for evidence of surface defects such as blisters, bubbles, pores, pits or “fish eyes,” caused by out-gassing of the volatile blocking agent regenerated during either the initial additive manufacturing step (as the light polymerization reaction is generally exothermic) or during the subsequent heat cure step. No substantial defect formation was observed.
- In a reactor was added Desmodur W (580.50 g), SR313B (145.70 g), and K-KAT XK-651 (0.83 g). The mixture was heated to 70° C. and PTMO with an average Mn ˜2,000 (1489.50 g) was added dropwise over 2 hours. After 5 additional minutes of stirring, 3,5-dimethylpyrazole (133.24 g) was added in one portion. After stirring for 1 hour, the mixture temperature was decreased to 50° C. and 4-methoxyphenol (0.988 g) was added. t-BAEMA (288.04 g) was added over 2 hours and stirred for 16 hours. SR252 (654.19 g) was then added and the mixture was stirred for 90 minutes. The reaction was complete when NCO content was <0.1%. VBPU3 was colorless and transparent when collected with a viscosity of 20,600 cP at 25.0° C.
- Table 8 describes the formulation for Example 8 containing VBPU3. The formulation contains 38.5% HS and 69% PU.
-
TABLE 8 Formulation IV Component Amount (g) VBPU3 90.38 TPO 0.66 Wikoff White 0.56 MACM 9.63 - The photoinitiator TPO (0.66 g) and wikoff white pigment (0.56 g) was dissolved in VBPU3 (90.38 g). Afterwards, MACM (9.63 g) was added to the formulation and mixed. The UV curing profile of the resin was measured. Sample three-dimensional objects were produced on a Carbon, Inc. M1 apparatus, wiped clean, and then baked at 120° C. for 12 h. Results are given in Table 9.
- The foregoing is illustrative of the present invention, and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein.
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