US 11,939,480 B2
Water dispersible sulfonated thermoplastic copolymer for use in additive manufacturing
William R. Priedeman, Jr., Long Lake, MN (US)
Assigned to Stratasys, Inc., Eden Prairie, MN (US)
Appl. No. 17/283,819
Filed by Stratasys, Inc., Eden Prairie, MN (US)
PCT Filed Oct. 10, 2019, PCT No. PCT/US2019/055694
§ 371(c)(1), (2) Date Apr. 8, 2021,
PCT Pub. No. WO2020/077127, PCT Pub. Date Apr. 16, 2020.
Claims priority of provisional application 62/743,997, filed on Oct. 10, 2018.
Prior Publication US 2021/0348010 A1, Nov. 11, 2021
Int. Cl. C09D 11/107 (2014.01); B29C 64/118 (2017.01); B29C 64/40 (2017.01); B29K 33/00 (2006.01); B29K 105/00 (2006.01); B33Y 10/00 (2015.01); B33Y 70/00 (2020.01); C09D 11/54 (2014.01)
CPC C09D 11/107 (2013.01) [B29C 64/40 (2017.08); B33Y 70/00 (2014.12); C09D 11/54 (2013.01); B29C 64/118 (2017.08); B29K 2033/12 (2013.01); B29K 2105/0085 (2013.01); B29K 2995/0062 (2013.01); B33Y 10/00 (2014.12)] 16 Claims
OG exemplary drawing
 
1. A method of additive manufacturing a soluble support structure to support a part printed from a thermoplastic build material, the method comprising:
extruding or depositing by electrophotography a water-dispersible sulfonated thermoplastic copolymer provided as a consumable feedstock, the water-dispersible sulfonated thermoplastic copolymer produced from a reaction product of a monomer A and a monomer B forming a primary carbon chain, wherein the monomer A contains a pendant functional group extending from the primary carbon chain and comprises an acid group or an anhydride group; and wherein the reaction product comprises at least 18 mol % of the monomer A, and wherein a sulfonate salt consisting of sodium sulfonate salt, ammonium sulfonate salt, or lithium sulfonate salt is reacted onto some or all of the pendant functional groups of the reaction product to produce the water-dispersible sulfonated thermoplastic copolymer containing at least 18 mol % of the sulfonated monomer A by one of the following reactions:
esterifying the acid group of the reaction product with a hydroxyl-functionalized sulfonate salt of the sulfonate salt,
amidizing the acid group of the reaction product with an amine sulfonate salt of the sulfonate salt, or
imidizing the anhydride group of the reaction product with the amine sulfonate salt of the sulfonate salt;
wherein the sulfonated monomer A in the water-dispersible sulfonated thermoplastic copolymer is at least 18 mol % but not more than 40 mol %, and the water-dispersible sulfonated thermoplastic copolymer has a glass transition temperature of at least 45° C., is melt-extrudable; and
separating the water-dispersible sulfonated thermoplastic copolymer from the part by subjecting the water-dispersible sulfonated thermoplastic copolymer to ambient temperature water without aid of any other solubility or dispersibility adjuvant.