# US 2023/0101431 A1 · Three-dimensional printing device for printing polyurethane articles

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- Number: US 2023/0101431 A1
- Document ID: US20230101431A1
- Status: Published application
- Kind: A1
- Application number: 17/957,472
- Filed: 2022-09-30
- Published: 2023-03-30
- Earliest claimed: 2021-09-30
- Assignees: Evoco Limited
- Applicants: Evoco Limited
- Inventors: Jason James Robinson; Syed Muhammad Husainie; Adel Kakroodi
- Web page: https://patentgrep.com/patent/US20230101431A1

## CPC

- B29C 64/314: Preparation
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/209: Heads; Nozzles
- B29C 64/35: Cleaning
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 40/00: Auxiliary operations or equipment, e.g. for material handling
- B33Y 40/10: Pre-treatment
- B29K 2075/00: Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material
- 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
- 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

## Abstract

A 3D printing device includes: a travelling dispenser including: a mixing chamber, a nozzle, a first gear pump, and a second gear pump, each of the first gear pump, the second gear pump and nozzle being in respective fluid communication with the mixing chamber; a first polyurethane reagent supply in fluid communication with the first gear pump; and a second polyurethane reagent supply in fluid communication with the second gear pump. The first polyurethane reagent supply accommodates a polyol mixture, and the second polyurethane reagent supply accommodates a diisocyanate.

## Claims

### Claim 1

A 3D printing device comprising:
a travelling dispenser comprising:
a mixing chamber,
a nozzle,
a first gear pump, and
a second gear pump, each of the first gear pump, the second gear pump and nozzle being in respective fluid communication with the mixing chamber;
a first polyurethane reagent supply in fluid communication with the first gear pump, the first polyurethane reagent supply comprising a polyol mixture; and
a second polyurethane reagent supply in fluid communication with the second gear pump, the second polyurethane reagent supply comprising a diisocyanate.

### Claim 2 (depends on 1)

The 3D printing device of claim 1, wherein each gear pump comprises a drive gear and a pour pressure adjustment valve.

### Claim 3 (depends on 1)

The 3D printing device of claim 1, wherein the polyol mixture comprises a hydroxy terminated polymer, a catalyst, and a surfactant.

### Claim 4 (depends on 3)

The 3D printing device of claim 3, wherein the hydroxy terminated polymer comprises one or more of: polyethylene oxide, polypropylene oxide, polyethylene-propylene oxide, a polyester resin with hydroxyl end groups, and mixtures thereof.

### Claim 5 (depends on 3)

The 3D printing device of claim 3, wherein the polyol mixture further comprises one or more of: a chain extender, a blowing agent, a colorant, and a crosslinker.

### Claim 6 (depends on 1)

The 3D printing device of claim 1, wherein the diisocyanate comprises one or more of: hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4-diisocyanate, 1-methylcyclohexane 2,6-diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate, dicyclohexylmethane 2,2′-diisocyanate, aromatic diisocyanates, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, diphenylmethane 2,2′-diisocyanate, diphenylmethane 4,4′-diisocyanate, urethane-modified liquid diphenylmethane 4,4′-diisocyanate, urethane-modified liquid diphenylmethane 2,4′-diisocyanate, 4,4′-diisocyanato-1,2-diphenylethane, naphthylene 1,5-diisocyanate, corresponding isomers thereof, and mixtures thereof.

### Claim 7 (depends on 1)

The 3D printing device of claim 1, further comprising:
a cleaning solvent supply; and
a pressurized gas source, each of the cleaning solvent supply and the pressurized gas source being in respective fluid communication with the mixing chamber.

### Claim 8 (depends on 1)

The 3D printing device of claim 1, further comprising from 2 to 10 of the travelling dispensers arranged in an array.

### Claim 9

A method of 3D printing a polyurethane article comprising:
introducing, using a first gear pump, a first polyurethane reagent into a mixing chamber of a travelling dispenser, the first polyurethane reagent comprising a polyol mixture;
introducing, using a second gear pump, a second polyurethane reagent into the mixing chamber of the travelling dispenser, the second polyurethane reagent comprising a diisocyanate; and
operating a rotor housed in the mixing chamber to mix the first polyurethane reagent and the second polyurethane reagent in the mixing chamber to form a polyurethane reagent mixture and extrude the polyurethane reagent mixture out of a nozzle onto a substrate, the extruded polyurethane reagent mixture forming at least a portion of the polyurethane article.

### Claim 10 (depends on 9)

The method of claim 9, wherein the travelling dispenser is in communication with processing structure, and wherein the steps of introducing using the first gear pump, introducing using the second gear pump, and operating the rotor, are carried out in response to signals output by the processing structure.

### Claim 11 (depends on 9)

The method of claim 9, further comprising, during said operating, moving the travelling dispenser in one or more directions.

### Claim 12 (depends on 9)

The method of claim 9, wherein the polyol mixture comprises a hydroxy terminated polymer, a catalyst, and a surfactant.

### Claim 13 (depends on 12)

The method of claim 12, wherein the hydroxy terminated polymer comprises one or more of: polyethylene oxide, polypropylene oxide, polyethylene-propylene oxide, a polyester resin with hydroxyl end groups, and mixtures thereof.

### Claim 14 (depends on 12)

The method of claim 12, wherein the catalyst comprises one or more of: triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, bismuth neodecanoate), (bis-(2-dimethylaminoethyl)ether in dipropylene glycol), tin diacetate, tin dioctoate, tin dilaurate, the dialkyl tin salts of aliphatic carboxylic acids like dibutyltin diacetate, dibutyltin dilaurate, and mixtures thereof.

### Claim 15 (depends on 12)

The method of claim 12, wherein surfactant comprises one or more of: polyether-silicone oil sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl, sulfates polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy), and mixtures thereof.

### Claim 16 (depends on 12)

The method of claim 12, wherein the polyol mixture further comprises one or more of: a chain extender, a blowing agent, a colorant, and a crosslinker.

### Claim 17 (depends on 16)

The method of claim 16, wherein the crosslinker comprises one or more of: diethanolamine, glycerol, trimethylol propane, pentaerythritol, 1,2,4-butanetriol, thioglycolic acid, 2,6-dihydroxybenzoic acid, melamine, diglycolamine, 1,2,6-hexanetriol, glycerol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, triisopropanol amine, triethanol amine, tartaric acid, citric acid, malic acid, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride; trimethylolpropane, trimethylolethane; pentaerythritol, polyethertriols, tartaric acid, citric acid, malic acid, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, trimethylolpropane, trimethylolethane; pentaerythritol, polyethertriols, and mixtures thereof.

### Claim 18 (depends on 16)

The method of claim 16, wherein the chain extender comprises one or more of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-ethyl-2-butyl 1,3-propanediol; alkylene glycols, like ethylene glycol, propylene glycol, monoethylene glycol, diethylene glycol, monopropylene glycol, dipropylene glycol, and mixtures thereof.

### Claim 19 (depends on 9)

The method of claim 9, wherein the diisocyanate comprises one or more of: hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4-diisocyanate, 1-methylcyclohexane 2,6-diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate, dicyclohexylmethane 2,2′-diisocyanate, aromatic diisocyanates, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, diphenylmethane 2,2′-diisocyanate, diphenylmethane 4,4′-diisocyanate, urethane-modified liquid diphenylmethane 4,4′-diisocyanate, urethane-modified liquid diphenylmethane 2,4′-diisocyanate, 4,4′-diisocyanato-1,2-diphenylethane, naphthylene 1,5-diisocyanate, corresponding isomers thereof, and mixtures thereof.

### Claim 20 (depends on 9)

A polyurethane article formed using the method of claim 9.