Segmented copolymer compositions and coatings incorporating these compositions

Patent metadata

Field	Value
Publication number	US-2016194574-A1
Application number	US-201514829640-A
Country	US
Kind code	A1
Filing date	Aug 19, 2015
Priority date	Mar 14, 2014
Publication date	Jul 7, 2016
Grant date	—

Abstract

Some variations provide a segmented copolymer composition comprising: fluoropolymer first soft segments that are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; polyester or polyether second soft segments that are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; isocyanate species possessing an isocyanate functionality of 2 or greater; and polyol or polyamine chain extenders or crosslinkers, wherein the molar ratio of the second soft segments to the first soft segments is less than 2.0. Exemplary segmented copolymers are disclosed. The segmented copolymer composition may be present in a low-friction, low-adhesion coating. Such a coating may be characterized by a coefficient of friction, measured at 90% relative humidity, less than 0.7. Such a coating may be characterized by an average kinetic delay of surface ice formation of at least 10 minutes at −10° C. These coatings are useful as bugphobic and icephobic coatings.

First claim

1 . A segmented copolymer composition comprising:
(a) one or more first soft segments selected from fluoropolymers having an average molecular weight from about 500 g/mol to about 10,000 g/mol, wherein said fluoropolymers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; (b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; (c) one or more isocyanate species, or a reacted form thereof, possessing an isocyanate functionality of 2 or greater; and (d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof, wherein the molar ratio of said second soft segments to said first soft segments is less than 2.0.

2 . The segmented copolymer composition of claim 1 , wherein said molar ratio of said second soft segments to said first soft segments is from about 0.1 to about 1.5.

3 . The segmented copolymer composition of claim 1 , wherein said fluoropolymers are selected from the group consisting of polyfluoroethers, perfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes, and combinations thereof.

4 . The segmented copolymer composition of claim 1 , wherein said fluoropolymers include a fluoropolymer having the structure:

wherein:
X=CH 2 —(CH 2 —CH 2 —O) p —OH wherein p=0 to 50;
m=1 to 100; and
n=1 to 100.

5 . The segmented copolymer composition of claim 1 , wherein said polyesters or polyethers are selected from the group consisting of poly(oxymethylene), poly(ethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), and combinations thereof.

6 . The segmented copolymer composition of claim 1 , wherein said isocyanate species is selected from the group consisting of 4,4′-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate, 4,4′-methylenebis(phenyl isocyanate), isophorone diisocyanate, and combinations or derivatives thereof.

7 . The segmented copolymer composition of claim 1 , wherein at least one polyol or polyamine chain extender or crosslinker of said one or more polyol or polyamine chain extenders or crosslinkers possesses a functionality of 2 or greater.

8 . The segmented copolymer composition of claim 7 , wherein said at least one polyol or polyamine chain extender or crosslinker is selected from the group consisting of 1,3-butanediol,1,4-butanediol, 1,3-propanediol, 1,2-ethanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanol amine, diethanol amine, methyldiethanolamine, phenyldiethanolamine, glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, pentaerythritol, ethylenediamine, 1,3-propanediamine, 1,4-buatendiamine, diethyltoluenediamine, dimethylthiotoluenediamine, isophoronediamine, diaminocyclohexane, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and homologues, derivatives, or combinations thereof.

9 . The segmented copolymer composition of claim 1 , wherein said composition contains, in a hard segment, said reacted form of said one or more isocyanate species, combined with said reacted form of said one or more polyol or polyamine chain extenders or crosslinkers.

10 . The segmented copolymer composition of claim 1 , wherein said hard segment is present in an amount from about 5 wt % to about 60 wt %, based on total weight of said composition.

11 . The segmented copolymer composition of claim 1 , wherein said segmented copolymer composition is present in a coating.

12 . The segmented copolymer composition of claim 11 , wherein said coating is characterized by a coefficient of friction, measured at 90% relative humidity, less than 0.7.

13 . The segmented copolymer composition of claim 11 , wherein said coating is characterized by an average kinetic delay of surface ice formation of at least 5 minutes at −10° C.

14 . A low-friction, low-adhesion material comprising:
a substantially continuous matrix containing a first component; a plurality of inclusions containing a second component, wherein said inclusions are dispersed within said matrix; wherein one of said first component or said second component is a low-surface-energy polymer having a surface energy between about 5 mJ/m 2 to about 50 mJ/m 2 , and the other of said first component or said second component is a hygroscopic material, and wherein said continuous matrix and said inclusions form a lubricating surface layer in the presence of humidity.

15 . The low-friction, low-adhesion material of claim 14 , wherein said surface energy of said low-surface-energy polymer is between about 10 mJ/m 2 to about 40 mJ/m 2 .

16 . The low-friction, low-adhesion material of claim 14 , wherein said low-surface-energy polymer is a fluoropolymer.

17 . The low-friction, low-adhesion material of claim 16 , wherein said fluoropolymer is selected from the group consisting of polyfluoroethers, perfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes, and combinations thereof.

18 . The low-friction, low-adhesion material of claim 14 , wherein said hygroscopic material is selected from the group consisting of poly(acrylic acid), poly(ethylene glycol), poly(2-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydrogels, PEG diacryalate, monoacrylate, and combinations thereof.

19 . The low-friction, low-adhesion material of claim 14 , wherein said low-surface-energy polymer and said hygroscopic material are covalently connected in a block copolymer.

20 . The low-friction, low-adhesion material of claim 19 , wherein said block copolymer is a segmented copolymer composition comprising:
(a) one or more first soft segments selected from fluoropolymers having an average molecular weight from about 500 g/mol to about 10,000 g/mol, wherein said fluoropolymers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; (b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated; (c) one or more isocyanate species, or a reacted form thereof, possessing an isocyanate functionality of 2 or greater; and (d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof, wherein the molar ratio of said second soft segments to said first soft segments is less than 2.0.

21 . The low-friction, low-adhesion material of claim 20 , wherein said molar ratio of said second soft segments to said first soft segments is from about 0.1 to about 1.5.

22 . The low-friction, low-adhesion material of claim 20 , wherein said fluoropolymers include a fluoropolymer having the structure:

wherein:
X=CH 2 —(CH 2 —CH 2 —O) p —OH wherein p=0 to 50;
m=1 to 100; and
n=1 to 100.

23 . The low-friction, low-adh

Assignees

• Hrl Lab Llc

Inventors

• Gross Adam F
• Nowak Andrew P

Classifications

• C08G81/025 Primary

  containing polyether sequences · CPC title

• C10M125/26

  Compounds containing silicon or boron, e.g. silica, sand · CPC title

• C10M2201/105

  Silica · CPC title

• C10M2213/0606

  used as base material · CPC title

• C10M107/38 Primary

  containing halogen · CPC title