# US 11,993,000 B2 · Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof

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- Number: US 11,993,000 B2
- Document ID: US11993000B2
- Status: Granted
- Kind: B2
- Application number: 17/321,696
- Filed: 2021-05-17
- Published: 2021-09-02
- Granted: 2024-05-28
- Earliest claimed: 2014-01-17
- Assignees: Lubrizol Advanced Materials, Inc.
- Applicants: Lubrizol Advanced Materials, Inc.
- Inventors: John M. Cox; Joseph J. Vontorcik, Jr.; Edward W. Ault
- Web page: https://patentgrep.com/patent/US11993000B2

## CPC

- B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM]
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/112: using individual droplets, e.g. from jetting heads
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 50/02: for controlling or regulating additive manufacturing processes
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C08J 5/00: Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00)
- C08L 75/06: from polyesters
- C08L 75/08: from polyethers
- B29K 2075/00: Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material
- B29L 2031/753: {Medical equipment; Accessories therefor (bloodbags, medical bags B29L2031/7148; artificial eyes B29L2011/0008)}
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08J 2375/06: from polyesters
- C08J 2375/08: from polyethers
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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
- B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES

## Abstract

The present invention relates to systems and methods for solid freeform fabrication, especially fused deposition modeling, as well as various articles made using the same, where the systems and methods utilize certain thermoplastic polyurethanes which are particularly suited for such processing. The useful thermoplastic polyurethanes are derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component where the resulting thermoplastic polyurethane has a crystallization temperature above 80° C. and retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

## Claims

### Claim 1

A method of fabricating a three-dimensional object, comprising the step of: operating a system for solid freeform fabrication of a three-dimensional object;
wherein said system comprises a solid freeform fabrication apparatus that deposits a semi-continuous flow or filament of building materials in a controlled manner;
so as to form the three-dimensional object;
wherein said building materials comprise a thermoplastic polyurethane derived from (a) a polyisocyanate component, (b) a polyol component, and (c) a chain extender component, wherein the mole ratio of the chain extender to the polyol is greater than 1.5;
wherein the resulting thermoplastic polyurethane has a crystallization temperature above 80° C.; and
wherein the resulting thermoplastic polyurethane retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

### Claim 2 (depends on 1)

The method of claim 1, wherein said solid freeform fabrication apparatus comprises (a) a plurality of dispensing heads; (b) a building material supply apparatus configured to supply a plurality of building materials to said fabrication apparatus; and (c) a control unit configured for controlling said fabrication apparatus and said building material supply apparatus, based on an operation mode selected from a plurality of predetermined operation modes.

### Claim 3 (depends on 1)

The method of claim 1, wherein said solid freeform fabrication apparatus comprises a fused deposition modeling apparatus.

### Claim 4 (depends on 1)

The method of claim 1, wherein the polyol has a number average molecular weight of at least 900.

### Claim 5 (depends on 1)

The method of claim 1, wherein the polyisocyanate component comprises an aromatic diisocyanate.

### Claim 6 (depends on 1)

The method of claim 1, wherein the polyisocyanate component comprises 4,4′-methylenebis(phenyl isocyanate).

### Claim 7 (depends on 1)

The method of claim 1, wherein the polyol component comprises a polyether polyol, a polyester polyol, or a combination thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the polyol component comprises poly(tetramethylene ether glycol), polybutylene adipate, or a combination thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the chain extender component comprises a linear alkylene diol.

### Claim 10 (depends on 1)

The method of claim 1, wherein the polyol component comprises poly(tetramethylene ether glycol).

### Claim 11 (depends on 1)

The method of claim 1, wherein the polyol component comprises polybutylene adipate.

### Claim 12 (depends on 1)

The method of claim 1, wherein the chain extender component comprises 1,4-butanediol.

### Claim 13 (depends on 1)

The method of claim 1, wherein the thermoplastic polyurethane further comprises one or more colorants, antioxidants (including phenolics, phosphites, thioesters, and/or amines), antiozonants, stabilizers, inert fillers, lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, hindered amines light stabilizers, benzotriazole UV absorber, heat stabilizers, stabilizers to prevent discoloration, dyes, pigments, inorganic and organic fillers, reinforcing agents, or any combinations thereof.