Degradable, amorphous, fluorochemical acrylate polymers

Details Degradable, amorphous, fluorochemical acrylate polymers Degradable, amorphous, fluorochemical acrylate polymers

2001-08-16

2003-11-18

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C524S544000, C560S223000, C564S209000

Reexamination Certificate

active

06649719

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a novel class of degradable, amorphous fluorochemical acrylate monomers, oligomers, and/or polymers containing pendant branched fluoroalkyl groups that may exhibit low surface energy and improved environmental compatibility.
BACKGROUND OF THE INVENTION
In the art of repellent treatments for substrates, fluorochemicals have found extensive use for nearly half a century as low surface energy materials for imparting repellency to a variety of substrates. For an overview of fluorochemical repellents, see Mason Hayek, Waterproofing and Water/Oil Repellency, 24 Kirk-Othmer Encyclopedia Of Chemical Technology 448-455, 460-462, 3rd ed. (1979).
The treatment of fibrous substrates (e.g., carpets, fabrics, leather, nonwovens and paper) with fluorochemicals to render them repellent to water and oil-based stains and resistant to dry soil has been well documented in the art. Successfully treated with these fluorochemical repellents, such fibrous substrates resist the discoloration that results from normal staining and soiling and thus retain their original aesthetic appeal. A wide variety of such fluorochemical repellents are known and described in the art. Among them are the fluorochemical acrylate polymers disclosed in U.S. Pat. No. 3,341,497 (Sherman et al.) and U.S. Pat. No. 3,462,296 (Raynolds et al.), fluorochemical carbodiimides disclosed in U.S. Pat. No. 3,896,251 (Landucci), fluorochemical esters disclosed in U.S. Pat. No. 3,923,715 (Dettre), U.S. Pat. No. 4,029,585 (Dettre), and U.S. Pat. No. 4,264,484 (Patel) and fluorochemical urethanes and ureas disclosed in U.S. Pat. No. 3,398,182 (Guenthner et al.), U.S. Pat. No. 4,001,305 (Dear et al.), U.S. Pat. No. 4,792,354 (Matsuo et al.) and U.S. Pat. No. 5,410,073 (Kirchner). Commercial fluorochemical repellents of these various types are widely available and are sold, for example, under the SCOTCHGARD and TEFLON trademarks.
Also important is the treatment of hard surface substrates, such as masonry, stone and glass, with repellents to retard the discoloration of the masonry or stone from exposure to water- and oil-based stains and deterioration from spalling and efflorescence. Fluorochemical repellents for masonry and stone are known. U.S. Pat. No. 5,274,159 (Pellerite et al.) describes certain water-soluble or dispersible fluorocarbylalkoxysilane surfactants that may be cured onto a masonry surface. U.S. Pat. No. 6,037,429 (Linert et al.) discloses water-soluble treatments for masonry and stone containing fluorochemical polymers having pendent fluoroaliphatic, carboxyl, (poly)oxyalkylene and optional silyl groups.
In addition to being useful as repellents, fluorochemical polymers have found use as low refractive index coatings for glass optical fibers to help retain the light in the fiber. U.S. Pat No. 5,223,593 (McAllister et al.) describes optical fiber coatings made from homopolymers of 1,1-dihydroperfluorocyclohexylmethyl methacrylate.
Particularly useful as repellents are fluorochemicals containing long chain perfluoroalkyl moieties (i.e., C
6
F
13
— to C
12
F
25
—), as such moieties impart very low surface energy to the substrate surface and thus provide the treated substrate with excellent water and oil repellency. (See, for example, H. C. Fielding, “Organofluorine Compounds and Their Applications,” R. E. Banks, Ed., Society of Chemical Industry, p. 214 (1979).) Especially preferred from both cost and performance standpoints are fluorochemical repellents containing primarily straight-chain perfluorooctyl (C
8
F
17
—) moieties. It is thought, but not relied upon that such repellents (those containing perfluorooctyl moieties) impart a high degree of repellency to a treated substrate because the perfluoroalkyl groups align to form an ordered, low energy, liquid crystalline-like structure at the substrate surface. This liquid crystalline-like structure, is normally formed by heating the substrate treated with a polymer containing perfluorooctyl moieties, to an elevated temperature, e.g., from about 100° C. to about 150° C., to properly orient the perfluoroalkyl chains.
However, perfluorooctyl group-containing polymers can ultimately degrade to form functional perfluorooctyl-containing compounds. It has been reported that certain functional perfluorooctyl-containing compounds may tend to bio-accumulate in living organisms. This tendency has been cited as a potential concern with regard to some fluorochemical compounds. For example, see U.S. Pat. No. 5,688,884 (Baker et al.).
As a result, there is a desire for new fluorine-containing compounds that can effectively provide water- and oil-repellent properties and can be eliminated more effectively from the body (both the polymer/oligomer and its degradation products). One approach has been to replace the C
6
F
13
— to C
12
F
25
— perfluoroalkyl moieties in the compound with shorter chain analogues (i.e., C
3
-C
5
moieties). For example, U.S. patent application Ser. No. 09/803702 describes water- and oil-repellent urethane oligomers containing at least one pendant C
4
F
9
— repeatable unit and at least one C
4
F
9
— terminal group. Published World Patent Application WO 01/30873 describes fluorochemical sulfonamide polymeric surfactants having at least one pendant group containing a C
4
F
9
— or C
3
F
7
— moiety.
The acrylate monomer CF
3
CF
2
CF
2
OCF(CF
3
)CH(CF(CF
3
)
2
)(OC(O)CH═CH
2
) is known. Also known is the acrylate monomer CF
2
CF
2
CF
3
CH(CF
3
)C(O)CH═CH
2
and its polymers and copolymers. The diacrylate monomer CH
2
═CHC(O)OCH(CF(CF
3
)
2
)—(CF
2
)
8
—CH(CF(CF
3
)
2
)(OC(O)CH═CH
2
) and its preparation are disclosed in Published World Application WO 00/50517, as well as the conversion of the diacrylate monomer to a polymer by UV curing with a photoinitiator.
SUMMARY OF THE INVENTION
In one aspect, this invention relates to compounds comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure —O—CH(R
f
)(R
f
′), wherein R
f
is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and R
f
′ is a branched perfluoroalkyl group with three to five carbon atoms.
In another aspect, this invention relates to a method of treating a substrate to render it oil-and/or water-repellent comprising treating the substrate with a composition comprising a compound that comprises at least one acrylate monomer, said monomer comprising at least one pendant group of the structure —O—CH(R
f
)(R
f
′), wherein R
f
is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and R
f
′ is a branched perfluoroalkyl group with three to five carbon atoms.
In still another aspect, this invention relates to a method of reducing the surface tension of a liquid comprising adding to the liquid a compound comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure —O—CH(R
f
)(R
f
′), wherein R
f
is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and R
f
′ is a branched perfluoroalkyl group with three to five carbon atoms.
In yet another aspect, this invention relates to an article comprising a substrate treated with a composition comprising a compound comprising at least one acrylate monomer, said monomer comprising at least one pendant group of the structure —O—CH(R
f
)(R
f
′), wherein R
f
is a straight chain or branched perfluoroalkyl group with five or less carbon atoms, and R
f
′ is a branched perfluoroalkyl group with three to five carbon atoms.
In addition to exhibiting surface energies comparable to known fluorochemical compounds containing pendant straight-chain perfluorooctyl (C
8
F
17
—) or perfluorobutyl (C
4
F
9
—) groups, the compounds of this invention containing pendant —O—CH(R
f
)(R
f
′) groups offer two additional advantages. First, the compounds of this invention generally resist hydrolysis under application conditions, possibly due to steric effects caused by the branched flu

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