Digitally-controlled three-dimensional printing of polymerizable materials
a technology of polymerizable materials and digital control, applied in printing, inks, manufacturing tools, etc., can solve the problems of narrowing the choice of materials and chemical reactions that can be utilized in this technology
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example 1
Polyamide-Forming Materials
[0451]Materials:
[0452]A caprolactam monomer and a catalyst for anionic ring opening polymerization (ROP), were obtained from Bruggerman, in accordance with a monomer and a catalyst used for preparing NYRIM® products.
[0453]The monomer and catalysts were mixed to form composition A (an exemplary first composition according to some embodiments of the present invention).
[0454]A caprolactam activator used for preparing NYRIM® products, was also obtained from Bruggerman. The caprolactam activator is 1,3-Benzenedicarbonyl dichloride, polymer with 2-methyloxirane polymer with oxirane ether with 1,2,3-propanetriol (3:1), caprolactam-terminated; otherwise referred to as Polyoxypropylene-polyoxyethylene-block copolymer isophthalic acid biscaprolactam ester; CAS No. 718612-97-6; C20H24N2O4·[C3H8O3·3(C3H6O·C2H4O)x], the chemical structure of which is shown below:
wherein R is:
wherein k is approx. 23 and j is approx. 5.
[0455]The polymer has Mn of 10,485 Da; and Mw of 27,...
example 2
Polyamide-Forming Materials
[0462]Materials:
[0463]Table 3 below presents materials usable for forming polyamide materials while using a method as described herein.
TABLE 3Trade name / ChemicalCompoundFunctionCompositionSourceε-CLCurableAP-NYLON ® CaprolactamBruggemannmonomerKGε-CLECurableε-Caprolactone; Capa ™Perstorpmonomer / MonomerImpactmodifierC10CurableBRUGGOLEN ® C10BruggemannMonomer +(about 17-18% of NaCL inKGcatalystε-CL)C20CurableBruggolen ® C20PBruggemannMonomer +(about 80% of ε-CL blockedKGactivatorHDI in ε-CL)BruggolenTPActivatorBruggolen TP C-1312BruggemannC-1312(PPG / PEG based highKGmolecular weight ε-CLblocked isocyanatemacroactivator)LLCurableLaurolactamSigma-monomer(12-Aminododecanolactam,Aldrich98%)PDLCurableω-Pentadecalactone, ≧98%Sigma-monomerAldrichPEI FGImpactLupasol ® FGBASFmodifier / (polyethyleneimine, aboutamine800 g / mol, 99%)boosterPEI PR8515ImpactLupasol ® PR8515BASFmodifier / (polyethyleneimine, aboutamine2000 g / mol, 99%)boosterPEI WFImpactLupasol ® WFBASFmodifier / ...
example 3
Exemplary Process
[0488]Post-process treatment:
[0489]The present inventors have uncovered that following a 3D inkjet printing process of polyamide-forming compositions, the obtained cured material is not fully polymerized, and typically exhibits a relatively low HDT of about 40-50° C.
[0490]In order to achieve higher HDT values, thermal post process is required in order to complete the polymerization and obtain cured material featuring HDT of 150° C.
[0491]For example, the present inventors have successfully practiced a thermal post-process curing for 1 hour at 150° C.
[0492]In order to monitor polymerization completion, weight loss upon the post-process thermal treatment was measured. Weight of the cured material was measured prior to and following thermal post process.
[0493]A minimum weight loss during post-process (e.g., of about 1.5-2.5% by weight), is indicative of a successful printing and of obtaining a printed object with mechanical properties identical to those polymerized in m...
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