Water-borne precursors for forming heterophasic anti-fouling, polymeric coatings having a fluorinated continuous phase with non-fluorinated domains

Patent metadata

Field	Value
Publication number	US-11098204-B2
Application number	US-202016746090-A
Country	US
Kind code	B2
Filing date	Jan 17, 2020
Priority date	Oct 9, 2018
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

An aqueous or water-borne precursor for forming an anti-fouling heterophasic thermoset polymeric coating is provided. The precursor includes a fluorine-containing polyol precursor having a functionality greater than about 2 that forms a branched fluorine-containing polymer component defining a continuous phase in the anti-fouling heterophasic thermoset polymeric coating. The precursor also includes a fluorine-free precursor that forms a fluorine-free component present as a plurality of domains each having an average size of greater than or equal about 100 nm to less than or equal about 5,000 nm defining a discrete phase within the continuous phase in the anti-fouling heterophasic thermoset polymeric coating. A crosslinking agent and water are also present. An emulsifier may also be included. Methods of making anti-fouling heterophasic thermoset polymeric coatings with such precursors are also provided.

First claim

What is claimed is:

1. A heterophasic thermoset polymeric coating comprising:
a continuous phase comprising a fluorine-containing polymer component formed from at least one fluorine-containing polyol precursor having a functionality of greater than 2; and
a discrete phase defining a plurality of domains comprising a fluorine-free component formed from a fluorine-free precursor, wherein the fluorine-free component is substantially immiscible with the fluorine-containing polymer component, each domain of the plurality of domains has an average size of greater than or equal to about 100 nm to less than or equal to about 5,000 nm within the continuous phase, and at least a portion of the fluorine-free component in the discrete phase is bonded together with a moiety selected from the group consisting of a nitrogen-containing moiety, an oxygen-containing moiety, an isocyanate-containing moiety, and a combination thereof, wherein the heterophasic thermoset polymeric coating is formed from an aqueous precursor comprising water, the fluorine-containing polyol precursor, and the fluorine-free precursor.

2. The heterophasic thermoset polymeric coating of claim 1 , wherein the fluorine-containing polyol precursor comprises a polyol fluoroacrylate or a polyol copolymer of polyvinylidene difluoride.

3. The heterophasic thermoset polymeric coating of claim 1 , wherein the heterophasic thermoset polymeric coating has an average light absorbency of about 5% to about 35% over a wavelength range of about 400 nm to about 800 nm.

4. The heterophasic thermoset polymer coating of claim 1 , wherein the fluorine-containing polymer component has an average molecular weight of greater than or equal to 10,000 g/mol to less than or equal to about 50,000 g/mol and the fluorine-free component has an average molecular weight of about 100 g/mol to about 15,000 g/mol.

5. The heterophasic thermoset polymer coating of claim 1 , wherein:
(i) the fluorine-containing polymer component comprises a fluoropolymer selected from the group consisting of a polyvinylidene fluoride, a polyfluoroacrylate, a polytetrafluoroethylene copolymer, a fluorinated polyol, a perfluorocarbon, a perfluoropolyether, a polyfluorosiloxane, a polytrifluoroethylene, and a combination thereof; and
(ii) the fluorine-free component is selected from the group consisting of a hygroscopic polymer, a hydrophobic polymer that is not lipophobic, an ionic hydrophilic precursor, an amphiphilic polymer, and a combination thereof, wherein:
(a) the hygroscopic polymer is selected from the group consisting of poly(acrylic acid), poly(alkene glycol) selected from the group consisting of poly(ethylene glycol), and a combination thereof, poly(2-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline), poly(2-ethyle-oxazoline), poly(vinylpyrolidone), a modified cellulose polymer selected from the group consisting of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and a combination thereof;
(b) the hydrophobic polymer is selected from the group consisting of a polyalkylene glycol selected from the group consisting of poly(propylene glycol), poly(tetramethylene glycol), a polybutadiene, a polycarbonate, a polycaprolactone, a polyacrylic polyol, and a combination thereof;
(c) the ionic hydrophilic precursor comprising a pendant carboxylate group, an amine group, a sulfate group, a phosphate group, and a combination thereof; and
(d) the amphiphilic polymer is selected from the group consisting of poloxamers, a polyethylene-block-poly(ethylene glycol) polymer, poly(ethylene glycol) and poly(propylene oxide) triblock polymer, polyethylene glycol (PEG)—polylactic acid (PLA) diblock polymer, polyethylene glycol (PEG)—poly(lactic-co-glycolic acid) (PLGA) diblock polymer, polyethylene glycol (PEG)—polycaprolactone (PCL) diblock polymer, polyethylene glycol (PEG)—polyethylene (PE) diblock polymer, and polyethylene glycol (PEG)—polystyrene (PS) diblock polymer, and a combination thereof.

6. The heterophasic thermoset polymer coating of claim 1 , wherein the fluorine-containing polyol precursor is a branched fluorine-containing polyol precursor that forms a branched fluorine-containing polymer component.

7. The heterophasic thermoset polymer coating of claim 1 , wherein the fluorine-containing polyol precursor comprises a polyol fluoroacrylate or a polyol copolymer of polyvinylidene difluoride.

8. The heterophasic thermoset polymer coating of claim 1 , wherein the fluorine-free component is present in the coating in an amount of greater than or equal to about 5% to less than or equal to about 90% by weight of the total heterophasic thermoset polymer coating.

9. The heterophasic thermoset polymer coating of claim 1 , further comprising a third polymer as a block.

10. A heterophasic thermoset polymeric coating comprising:
a continuous phase comprising a fluorine-containing polymer component formed from at least one fluorine-containing polyol precursor having a functionality of greater than 2 and having an average molecular weight of greater than or equal to 2,000 g/mol to less than or equal to about 50,000 g/mol; and
a discrete phase defining a plurality of domains comprising a fluorine-free component formed from a fluorine-free precursor, wherein the fluorine-free component is substantially immiscible with the fluorine-containing polymer component, each domain of the plurality of domains has an average size of greater than or equal to about 100 nm to less than or equal to about 5,000 nm within the continuous phase, the fluorine-free component having an average molecular weight of about 100 g/mol to about 15,000 g/mol, and at least a portion of the fluorine-free component in the discrete phase is bonded together with a moiety selected from the group consisting of a nitrogen-containing moiety, an oxygen-containing moiety, an isocyanate-containing moiety, and a combination thereof, wherein the heterophasic thermoset polymeric coating is formed from an aqueous precursor comprising water, the fluorine-containing polyol precursor, and the fluorine-free precursor.

11. The heterophasic thermoset polymeric coating of claim 10 , wherein the fluorine-containing polyol precursor comprises a polyol fluoroacrylate or a polyol copolymer of polyvinylidene difluoride.

12. The heterophasic thermoset polymeric coating of claim 10 , wherein the heterophasic thermoset polymeric coating has an average light absorbency of about 5% to about 35% over a wavelength range of about 400 nm to about 800 nm.

13. The heterophasic thermoset polymer coating of claim 10 , wherein the fluorine-free component has an average molecular weight of about 100 g/mol to about 4,000 g/mol.

14. The heterophasic thermoset polymer coating of claim 10 , wherein:
(i) the fluorine-containing polymer component comprises a fluoropolymer selected from the group consisting of a polyvinylidene fluoride, a polyfluoroacrylate, a polytetrafluoroethylene copolymer, a fluorinated polyol, a perfluorocarbon, a perfluoropolyether, a polyfluorosiloxane, a polytrifluoroethylene, and a combination thereof; and
(ii) the fluorine-free component is selected from the group consisting of a hygroscopic polymer, a hydrophobic polymer that is not lipophobic, an ionic hydrophilic precursor, an amphiphilic polymer, and a combination thereof, wherein:
(a) the hygroscopic polymer is selected from the group consisting of poly(acrylic acid), poly(alkene glycol) selected from the group consisting of poly(ethylene glycol), and a combination thereof, poly(2-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline), poly(2-ethyle-oxazoline

Assignees

• Gm Global Tech Operations Llc

Inventors

• Rodriguez April R
• Gross Adam F
• Dustin Ashley M
• Smith Anthony L
• Nowak Andrew P
• Drummey Kevin J

Classifications

• C09D5/00 Primary

  Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title

• C08G18/6541

  the low-molecular compounds being compounds of group C08G18/34 · CPC title

• C08G18/706

  the liquid medium being water · CPC title

• C08G18/4825

  Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title

• C08G18/6692

  with compounds of group C08G18/34 · CPC title