WO2008002509A2

WO2008002509A2 - Perfluoro styrene polymers and their use as surfactant and substrate treating reagents

Info

Publication number: WO2008002509A2
Application number: PCT/US2007/014671
Authority: WO
Inventors: Ji Guo; Joseph M. Desimone; Paul R. Resnick
Original assignee: The University Of North Carolina At Chapel Hill
Priority date: 2006-06-28
Filing date: 2007-06-25
Publication date: 2008-01-03
Also published as: WO2008002509A3

Abstract

The invention provides a polymer, useful as a surfactant and textile reagent, comprising: (a) monomeric units containing a lipophobic group, said monomeric units comprising a styrene having a fluoro or perfluoro group substituted thereon, (b) optionally but preferably, monomeric units containing an attachment group; and (c) optionally but preferably, monomeric units containing a hydrophobic group.

Description

Perfluoro Styrene Polymers and Their Use as Surfactant and Substrate Treating Reagents

Ji Guo, Joseph M. DeSimone, and Paul R. Resnick

Government Support

This invention was made with Government support under a grant from the NSF-STC. The US Government has certain rights to this invention.

Field of the Invention

The present invention concerns compounds, compositions and methods for treating substrates to impart lipophobic properties, hydrophobic properties, and/or stain resistance thereto.

Background of the Invention

Certain fluorinated acrylates and methacrylates, previously used in products for imparting stain resistance and/or water repellency to textiles, have been found to produce perfluorooctanoic acid (C-8) or perfluorooctanesulfonic acid (PFOS), which can bioaccumulate. Some of these materials have accordingly been either banned or voluntarily withdrawn from the market, and there is a need for alternatives thereto. The following references are noted herein:

J. Guo et al., Perfluoro alkyl (meth)acrylate polymers and their use as surfactant and substrate treating reagents, PCT Publication No. WO 2006/116222 (2 November 2006)(docket no. 5470-433WO);

R.F. Service, Safer alternative could replace widespread contaminant, Science 309, 1810 (16 Sept. 2005);

R.D. van de Grampel et al., The outermost atomic layer of thin films of fluorinated polymethacrylates, Langmuir 20, 6344-6351; M. Uffner and D. Holland, Fluoropolymer-carboxylated styrene-butadiene functional surface coating compositions, US Patent No. 3,792,128; and

A. Ahlbrecht, Perfluoroalkyl acrylate polymers and process of producing a latex thereof, US Patent No. 3,102,103. Smnmary of the Invention

The invention describes the novel polymers (including copolymers, terpolymers and tetrapolymers) and their use as surfactant and textile treating reagents. The polymers can be synthesized in carbon dioxide under high pressure. The fluorinated polymers and derivatives can be used for surfactant and textile reagents.

These novel materials and techniques exhibit several advantages over current systems: (1) The new polymers used for textile reagent have been obtained; (2) They address the environmental problem of degredation to perfluorooctanoic acid (C-8) or perfluorooctanesulfonic acid (PFOS) which can bioaccumulate. The novel materials have reduced bioaccumulation in the environment; and (3) We disclose a convenient way to synthesize the polymers using the carbon dioxide as the medium.

These novel polymers and their derivatives provide a wide application in textile field as water and oil repellents. Also these can be applied as novel aqueous or carbon dioxide surfactants. Thus, a first aspect of the present invention is a polymer comprising:

(a) monomelic units containing a lipophobic group, said monomelic units comprising a compound of Formula I:

wherein:

R_f is C3 to C6 fluoroalkyl optionally containing one or two heteroatoms selected from N and O; R², R³, R⁴ and R⁵ are each independently H or halo;

X is -O- or a covalent bond; and o and p are each 0 or 1 or 2; (b) optionally but preferably, monomelic units containing an attachment group; and

(c) optionally but preferably, monomelic units containing a hydrophobic group. A second aspect of the present invention is a composition comprising a polymer as described herein in a carrier {e.g., water, carbon dioxide, organic solvents, and combinations theeof).

A third aspect of the present invention is a method of treating a substrate such as a paper product or textile material, comprising; (a) applying a polymer as described herein to said substrate so that said compound is deposited thereon or impregnated therein; and (b) optionally but preferably, drying said substrate.

A further aspect of the present invention is a substrate such as a paper product or textile material comprising carrying, or having contacted thereto, a polymer as described herein (e.g., having a polymer as described herein deposited thereon or impregnated therein).

The foregoing and other objects and aspects of the present invention are explained in greater detail in the specification set forth below. The disclosures of all United States patent references cited herein are incorporated by reference herein in their entirety.

Detailed Description of the Preferred Embodiments "Halo" as used herein includes fluoro, chloro, bromo, and iodo. "Aryl" as used herein, refers to a monocyclic carbocyclic ring system or a bicyclic carbocyclic fused ring system having one or more aromatic rings. Representative examples of aryl include, azulenyl, indanyl, indenyl, naphthyl, phenyl, tetrahydronaphthyl, and the like. Aryl groups maybe unsubstituted or substituted 1, 2, 3, or 4 or more times with substituents such as halo (preferably fluoro), methyl, trifluoromethyl, etc.

Fluoroalkyl groups R_f of the present invention are preferably C2 to C6 fluoroalkyl, and more preferably C3 to C5 fluoroalkyl. The fluoroalkyl groups may be linear or branched. The fluoroalkyl groups are optionally but preferably perfluoroalkyl (that is, all hydrogens replaced by fluorine); where the fluoroalkyl groups are not perfluorinated then preferably only one or two hydrogens remain, and preferably the remaining hydrogens are not bonded to the terminal or end-chain carbon position (that is, the terminal carbon is preferably substituted by three fluro groups in the fluoroalkyl groups used herein). The fluoroalkyl groups may contain one or two heteroatoms selected from N and O, examples of which include but are not limited to: -R_f'-O-R_f ²; -R^-NRf²R_f ³; R_f ^l-O-Rf²-R_f ³-NR_f ⁴R_f ⁵ _J where R_f', R_f ²' R_f ³, R⁴, and Rf⁵are each independently fluoroalkyl or perfluoroalkyl (subject to the proviso that the total number of carbons in the fluoroalkyl group is as given above).

1. POLYMERS. As noted above, the present invention provides a polymer comprising, consisting of, or consisting essentially of:

(a) from 20 or 30 to 70 or 80 percent by weight of monomelic units (produced by polymerization of a corresponding monomer) containing a lipophobic group, said monomeric units comprising, consisting of or consisting essentially of a compound of a compound of Formula I:

wherein:

Rf is C3 to C6 fluoroalkyl optionally containing one or two heteroatoms selected from N and O;

R², R³, R⁴ and R⁵ are each independently H or halo; X is — O- or a covalent bond; and o and p are each 0 or 1 or 2; (b) optionally but preferably, from 1 or 2 to 5 or 10 percent by weight of monomelic units (produced by polymerization of a comonomer) containing an attachment group (epoxide, hydroxy, silane or amine group); and

(c) optionally but preferably, from 10 or 20 to 70 or 80 percent by weight of monomelic units (produced by polymerization of a comonomer) containing a hydrophobic group (e.g., a C10-C20 alkyl group).

The polymers may have any suitable molecular weight, for example, from 1,000 or 2,000 daltons up to 5,000 daltons, or in some embodiments up to 50,000 or 100,000 daltons or more. Any suitable comonomer (generally ethylenically unsaturated compounds) can be used as for the comonomer containing the hydrophobic group or the comonomer containing the attachment group, including but not limited to those described in US Patent No. 6,660,803. Thus examples of suitable comonomers are are compounds included in the following groups (a), (b) and (c). However, the ethylenically unsaturated compound is not limited to these examples, and may be basically an ethylenically unsaturated compound capable of copolymerizing with a (meth)acrylic acid.

Examples of the group (a) include ethylene, vinyl acetate, vinyl chloride, vinylidene halide, (meth)acrylic acid, (meth)acrylonitrile. styrene, alpha- methylstyrene, p-methylstyrene, (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, N,N- dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, hydroxypropyl- trimethylammonium chloride methacrylate, ethyltrimethylammonium chloride methacrylate, vinyl alkyl ether, alkyl vinyl ether halide, butadiene, isoprene, chloroprene, and maleie anhydride.

Examples of the group (b) include (meth)acrylates represented by the general formula (Formula 4): CH₂=CA¹COOA² (Formula 4)

[wherein A¹ represents a hydrogen atom or a methyl group, and A² represents an alkyl group represented by C_mH2m⁺l (m represents an integer of 1 to 30)]. Examples of the group (c) include compound represented by the formula 5:

manufactured by KYOEISHA CHEMICAL Co., LTD. under the trade name of LIGHT-ESTER G), compound represented by the formula 6:

(manufactured by KYOEISHA CHEMICAL Co., LTD. under the trade name of LIGHT-ESTER CL), compound represented by the formula 7:

CH₂= C COOCH₂CH₂CH₂Si(OCHs)₃

CH₃

(manufactured by DOW CORNING TORAY SILICONE CO., LTD. under the trade name of SZ6030), the compound represented by the formula 8:

the compound represented by the formula 9:

and compounds (sulfonic acid-containing monomers) represented by the formula 10:

wehere n=l to 20.

2. MONOMERS.

Monomers of the invention are, in general, compounds of Formula II:

wherein:

R_f is C3 to C6 fluoroalkyl optionally containing one or two heteroatoms selected from N and O;

R², R³, R⁴ and R⁵ are each independently H or halo;

X is -O- or a covalent bond; and o and p are each 0 or 1 or 2.

Such monomers can be made in accordance with known techniques or variations thereof that will be apparent to those skilled in the art based upon the disclosure herein. 3. COMPOSITIONS, METHODS OF USE AND PRODUCTS.

For convenient use, the polymers described above can be provided in a carrier to form a composition, with about 0.01 or 0.1 up to 20, 30, or 50 percent by weight of the composition being the polymer. Any suitable carrier can be employed, including carbon dioxide, organic solvents, and combinations theeof. Any suitable organic solvent can be used, including but not limited to alcohols, aromatic solvents, esters, ketones, aliphatic solvents, and combinations thereof (and more particularly acetone, hexane, cyclohexane, methanol, ethanol, ethyl acetate, toluene, acetone, methyl ethyl ketone, and mixtures thereof). The composition can be provided in any suitable form as desired for the particular end use by adjusting the carrier or carriers and how the ingredients are combined in accordance with known techniques, such forms including but not limited to solutions, dispersions, suspensions, emulsions and microemulsions (including water emulsions and dispersions).

In some embodiments where the composition is an emulsion or dispersion, the composition comprises dispersed particles comprising, consisting of or consisting essentially of a polymer of the invention, typically in an average particle size of 5, 10 or 20 to 400, 600 or 800 nm dispersed in an aqueous phase comprising, consisting of or consisting essentially of water, with the emulsion or dispersion having an amount of solids between 20 or 30 and 70 or 80 percent by weight. The compositions can be provided in dilute form, or in concentrated form for subsequent dilution if desired.

In use, a textile material can be treated by (a) applying a polymer as described above to the textile material so that said compound is deposited thereon (e.g., by meniscus coating such as dip coating, withdrawal coating, slot coating, and drainage coating processes, spraying, or any other suitable application technique, and then, optionally but preferably, (b) drying said textile material (e.g., by drying at ambient temperature or heating to an elevated temperature, e.g., heating for a time and to a temperature sufficient to "set" the polymer on the substrate by any suitable technique, including but not limited to those described in US Patent Nos. 6,855,175 and 6,572,703). Any suitable textile material can be treated, including but not limited to cotton, wool, silk, polyesters, polyamides and blends thereof. The textile material can be in any suitable form, including woven and nonwoven fabrics, as well as threads, yarns, etc. The textile material can be in the form of a garment or article of clothing (e.g., shirts, pants, skirts, ties, outerware such as coats and jackets), or the textile material can be formed into such a garment after treatement.

In addition to textile materials other organic and inorganic substrates, including but not limited to paper products (e.g., sheet paper, paperboard, cardboard, etc.), wood, polymers, metals, inorganic crystalline or semicrystalline materials such as quartz, glass or silicon dioxide, conductors, semiconductors, insulators, and composites thereof (incuding composites formed with textile materials), etc. can likewise be treated, coated with, or impregnated with compounds and compositions of the invention treated by the method of the invention. Treating can be carried out by any suitable technique including but not limited to those described in connection with textile materials above.

In the manufacture of paper products the treating or applying step can be carried out after the paper product is formed or during production of the paper product (e.g., by including the compounds or compositions into the pulp slurry before web formation, applying the compounds or compositions to a fibrous web before drying, applying the compounds or compositions to the fibrous web after drying, etc.). Paper products can be formed or shaped into useful articles such as cartons, boxes, containers or the like (particularly for food packaging to produce packages configured to contain, or containing, meat, ground meat, pizza, bread or other baked goods, etc.) comprising the paper product, in accordance with known techniques.

Wallpaper (or wallcoverings) and carpet (including either, or both, the front surface or the back surface of carpet) may also be coated by the method of the present invention, for example to apply a stain-resistant coating thereto. The thickness of the coating formed on the substrate after evaporation of any carrier composition will depend upon the particular coating component employed, the substrate employed, the coating method, the purpose of the process, etc., but can range between about five or ten Angstroms up to one or five millimeters or more.

The present invention as described above can be implemented in accordance with further features or elements, including but not limited to those described in US Patents Nos. 3,462,296; 3,282,905; and 3,491,169; US Patent Application No. 2004/0048974; and in Shean-Jeng Jong and Hong-Yue She, Taiwan Patent Application 583302 (assigned to Chung-Shan Institute of Science & Technology). The present invention is explained in greater detail in the following non- limiting examples.

Examples 1-3 CH₂=CHC₆H₄CH₂OCH₂Rf (where R_r = C₄F₉)

Synthesis of Monomer: Prepare a solution of potassium hydroxide(30g) in water (3OmL). Add this solution into a mixture of sokane (1,1,1,3,3 — pentafluorobutane) (30 mL), terbutylammonium hydrogensulfate and 3,3,4,4,5,5,6,6,6-Nonafluoro-l-petanol (30 mmol) with vigorous stirring. 4- vinylbenzyl chloride (30mmol) is added drop by drop into the mixture and the reaction is allowed to proceed at room temperature for 48 hours. The organic layer is then separated and extracted three times with brine solution. After drying with anhydrous magnesium sulfate, the solvent is evaporated and the residue product is purified by running through a silica gel. Synthesis of polymers: (1) in CO₂. Monomer, along with 0.5-1.0 wt% AIBN as the initiator, is placed into a 10 mL high pressure optical cell. The mixture is purged with argon for 15 to 30 minutes. The cell is sealed, the pressure is raised up to 4500 psi, and the temperature is raised up to 60 ⁰C. The polymerization is allowed to proceed for up to to 36 hours. Polymer is then isolated by dissolving in trifiuorotoluene, followed by precipitate in methanol.

2) In trifiuorotoluene. Monomer, along with 0.5-1.0 wt% AIBN as the initiator, is placed into a 100 mL round flask. The mixture is purged with argon for 15 to 30 minutes. The polymerization is allowed to proceed for 24 hours at 70 ⁰C. The polymer is then isolated by precipitate in methanol.

Examples 4-5

C₄F₉)

Synthsis of monomer: (1) Grignard reagent p-vinylphenylmagnesium chloride. A 250 mL three-neck flask is equiped with a sealed stirer unit, a reflux condenser and an addition funnel. 40 mmol magnesium, 10 mL of dry tetrahydrofuran and a small crystal of iodide is placed into the flask. The system is vacuumed and maintained under argon. The reactor is then heated to about 60 ⁰C. A solution of 20 mmol p- chlorostyrene in 50 mL of tetrahydrofuran is introduced dropwise over a period of 35 minutes at a rate to maintain gentle reflux. The reaction mixture is refluxed for 15 minutes and stirred for another 45 minutes without heating.

(2) The Grignard reagent is cooled in a dry ice/2-propanol bath under a nitrogen atmosphere. Copper (I) iodide (3.1 mmol) and 1-Iodo-1H,1H- nonafluoropentane mixture is added dropwise to the cooled solution. This is stirred at

-80 ⁰C for 30 minutes, slowly raised to reflux temperature over a 2-hour period, and then heated at reflux for 6 hours, Tetrahydrofuran is removed by rotary evaporation and the residue is poured into aqueous ammonium chloride solution (40OmL). The product is extracted with ether (3 x 10OmL), dried with anhydrous magnesium sulfate, and distilled under reduced pressure.

Synthesis of polymer: Polymer is synthesized from the monomer in like manner as described in Examples 2-3.

The foregoing is illustrative of the present invention, and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein.

Claims

THAT WHICH IS CLAIMED IS:

1. A polymer comprising:

wherein:

R², R³, R⁴ and R⁵ are each independently H or halo; X is — O- or a covalent bond; and o and p are each 0 or 1 or 2.

2. The polymer of claim 1, further comprising: (b) monomeric units containing an attachment group.

3. The polymer of claim 1-2, further comprising; (c) monomeric units containing a hydrophobic group.

4. The polymer of claim 3, wherein said hydrophobic group comprises an alkyl group.

5. The polymer of claim 2-4, wherein said attachment group comprises an epoxide, hydroxy, silane or amine group.

6. The polymer of claims 1-5, wherein said monomelic units containing a lipophobic group consists essentially of a compound of Formula I.

7. The polymer of claim 1-6, wherein R_f is C3 to C5 linear or branched perfluoroalkyl.

8. A composition comprising a polymer of claim 1-7 in a carrier, said carrier selected from the group consisting of water, carbon dioxide, organic solvents, and combinations theeof.

9. A composition of claim 8, wherein said organic solvent is selected from the group consisting of alcohols, aromatic solvents, esters, ketones, aliphatic solvents, and combinations thereof.

10. A composition of claim 8-9, wherein said organic solvent is selected from the group consisting of acetone, hexane, cyclohexane, methanol, ethanol, ethyl acetate, toluene, acetone, methyl ethyl ketone, and mixtures thereof.

11. A composition of claim 8-10, wherein said composition is a solution, dispersion, suspension, emulsion or microemulsion.

12. A method of treating a substrate, comprising

(a) applying a polymer of claim 1-7 to said substrate so that said compound is deposited thereon.

13. The method of claim 12, wherein said applying step is carried out by spraying or dip coating.

14. The method of claim 12-13, wherein said applying step is followed by the step of:

(b) drying said substrate.

15. The method of claim 12-14, wherein said substrate is a textile material is selected from the group consisting of cotton, wool, silk, polyesters, polyamides and blends thereof.

16. The method of claim 12-14, wherein said substrate is a textile material selected from the group consisting of woven and nonwoven textile materials.

17. A textile material produced by the method of claim 12-16.

18. A textile material having a polymer of claim 1-7 deposited thereon or impregnated therein.

19. A paper product produced by the method of claim 12-14.

20. A paper product having a polymer of claim 1-7 deposited thereon or impregnated therein.

21. A carpet produced by the method of claim 12-14.

22. A carpet having a polymer of claim 1-7 deposited thereon or impregnated therein.

23. A wallpaper produced by the method of claim 12-14.

24. A wallpaper having a polymer of claim 1-7 deposited thereon or impregnated therein.

25. A method of making a polymer of claim 1-15, comprising polymerizing a monomer of Formula II:

optionally in the presence of a comonomer, to produce said polymer of claim 1-15.

26. The method of claim 25, wherein said polymerizing step is carried out in carbon dioxide.