TRIPHOSPHONATE COMPOSITIONS, SELF-ASSEMBLED TRIPHOSPHONATE MONOLAYERS, PRODUCTS AND APPARATUS MADE FROM SUCH COMPOSITIONS AND MONOLAYERS, AND METHODS OF MAKING AND USING SUCH COMPOSITIONS, MONOLAYERS, PRODUCTS, AND APPARATUS

Abstract

Triphosphonate compositions, self-assembled triphosphonate monolayers, products and apparatus made thereof, and methods of making and using such compositions, monolayers, products, and apparatus.

Claims

1. A composition comprising a head having at least 3 phosphonate groups, a functional end group, a linker having a first end and a second end, with the head appended to the first end of the linker, and the functional end group appended to the second end of the linker.

2. The composition of claim 1, wherein the head group comprises exactly 3 phosphonate groups.

3. The composition of claim 1, wherein the linker comprises a number of carbons equal to any one of the following integers, or may comprises a number of carbons in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

4. The composition of claim 1, wherein the composition has the general formula of Formula I, Formula II, Formula III, or mixtures thereof, wherein: each R.sub.1 is independently an H, Li, Na, K, or an alkyl group having from 1 to 20 carbon atoms that is substituted or unsubstituted, linear or branched, or saturated or unsaturated; R.sub.2 is a single chemical bond, —O—, S—, or —NH—; each R.sub.3 independently comprises an alkyl group comprising up to 50 carbon atoms, in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; R.sub.4 is an alkyl group comprising up to 50 carbon atoms in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; and, each X is independently a single bond, —O—, or —S—.

5. The composition of claim 1, wherein R.sub.4 is —(CH.sub.2).sub.n—Y.sub.1—Z or —(CH.sub.2).sub.n—Y.sub.1—(CH.sub.2).sub.p—Y.sub.2—Z, and wherein n and p, are independently integers between 1 and 50 and may be the same or different, and wherein Y.sub.1 and Y.sub.2 are independently —O—, —S—, —NH—, —OCO—, —SCO—, —HNCO—, or —HNCO—CF(CF.sub.3)—, and wherein Z is H, R.sub.f, —(OCF.sub.2CF.sub.2).sub.n—OR.sub.f, —(OCF.sub.2CF(CF.sub.3)).sub.n—OR.sub.f, or —(OCF(CF.sub.3)CF.sub.2).sub.n—OR.sub.f, wherein R.sub.f comprises a perfluorinated alkyl having from 1 to 50 carbon atoms, that is linear or branched, saturated or unsaturated, or substituted or unsubstituted.

6. A product comprising a surface, wherein at least a portion of the surface comprises a composition comprising a head having at least 3 phosphonate groups, a functional end group, a linker having a first end and a second end, with the head positioned at the first end of the linker, and the functional end group appended to the second end of the linker.

7. The product of claim 6, wherein the head group comprises exactly 3 phosphonate groups.

8. The product of claim 6, wherein the linker comprises a number of carbons equal to any one of the following integers, or may comprises a number of carbons in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

9. The product of claim 6, wherein the composition has the general formula of Formula I, Formula II, Formula III, or mixtures thereof, wherein: each R.sub.1 is independently H, Li, Na, K, or an alkyl group having from 1 to 20 carbon atoms, that is substituted or unsubstituted, linear or branched, or saturated or unsaturated; R.sub.2 is a single chemical bond, O—, —S—, or —NH—; each R.sub.3 independently comprises an alkyl group comprising up to 50 carbon atoms, in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; R.sub.4 is an alkyl group comprising up to 50 carbon atoms which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; and, each X is independently a single bond, —O—, or —S—.

10. The product of claim 6, wherein R.sub.4 is —(CH.sub.2).sub.n—Y.sub.1—Z, or —(CH.sub.2).sub.n—Y.sub.1—(CH.sub.2).sub.p—Y.sub.2—Z, and wherein n and p, are independently integers between 1 and 50 and may be the same or different, and wherein Y.sub.1 and Y.sub.2 are independently a single chemical bond, —O—, S—, —NH—, —OCO—, —SCO—, —HNCO—, or —HNCO—CF(CF.sub.3)—, and wherein Z is H, R.sub.f, —(OCF.sub.2CF.sub.2).sub.n—OR.sub.f, —(OCF.sub.2CF(CF.sub.3)).sub.n—OR.sub.f, or —(OCF(CF.sub.3)CF.sub.2).sub.n—OR.sub.f, wherein R.sub.f comprises a perfluorinated alkyl having from 1 to 50 carbon atoms, that is linear or branched, saturated or unsaturated, or substituted or unsubstituted.

11. A machine comprising a surface, wherein at least a portion of the surface comprises a composition comprising a head having at least 3 phosphonate groups, a functional end group, a linker having a first end and a second end, with the head positioned at the first end of the linker, and the functional end group appended to the second end of the linker.

12. The machine of claim 12, wherein the head group comprises exactly 3 phosphonate groups.

13. The machine of claim 12, wherein the linker comprises a number of carbons equal to any one of the following integers, or may comprises a number of carbons in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

14. The machine of claim 12, wherein the composition has the general formula of Formula I, Formula II, Formula III, or mixtures thereof, wherein: each R.sub.1 is independently H, Li, Na, K, an alkyl group having from 1 to 20 carbon atoms, that is substituted or unsubstituted, linear or branched, or saturated or unsaturated; R.sub.2 is a single chemical bond, —O—, —S—, or —NH—; each R.sub.3 independently comprises an alkyl group comprising up to 50 carbon atoms, in which the alkyl group is linear or branched, substituted or unsubstituted, saturated or unsaturated; R.sub.4 is an alkyl group comprising up to 50 carbon atoms in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; and, each X is independently selected from a group consisting of a single bond, or —O—, or —S—.

15. The machine of claim 12, wherein R.sub.4 is —(CH.sub.2).sub.n—Y.sub.1—Z or —(CH.sub.2).sub.n—Y.sub.1—(CH.sub.2).sub.p—Y.sub.2—Z, and wherein n and p, are independently integers between 1 and 50 and may be the same or different, and wherein Y.sub.1 and Y.sub.2 are a single chemical bond, —O—, —S—, —NH—, —OCO—, —SCO—, —HNCO—, or —HNCO—CF(CF.sub.3)—, and wherein Z is H, R.sub.f, —(OCF.sub.2CF.sub.2).sub.n—OR.sub.f, —(OCF.sub.2CF(CF.sub.3)).sub.n—OR.sub.f, or —(OCF(CF.sub.3)CF.sub.2).sub.n—OR.sub.f, wherein R.sub.f comprises a perfluorinated alkyl having from 1 to 50 carbon atoms, that is linear or branched, saturated or unsaturated, and substituted or unsubstituted.

16. A method of treating a surface, comprising contacting the surface with a treating composition comprising a head having at least 3 phosphonate groups, a functional end group, a linker having a first end and a second end, with the head positioned at the first end of the linker, and the functional end group appended to the second end of the linker.

17. The method of claim 16, wherein the head group comprises 3 phosphonate groups.

18. The method of claim 16, wherein the linker comprises a number of carbons equal to any one of the following integers, or may comprises a number of carbons in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

19. The method of claim 16, wherein the composition has the general formula of Formula I, Formula II, Formula III, or mixtures thereof, wherein: each R.sub.1 is independently H, Li, Na, K, or an alkyl group having from 1 to 20 carbon atoms that is substituted or unsubstituted, linear or branched, or saturated or unsaturated; R.sub.2 is a single chemical bond, —O—, —S—, —NH—; each R.sub.3 independently comprises an alkyl group comprising up to 50 carbon atoms, in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; R.sub.4 is an alkyl group comprising up to 50 carbon atoms in which the alkyl group is linear or branched, substituted or unsubstituted, or saturated or unsaturated; and, each X is independently selected from a group consisting of a single bond, —O—, or —S—.

20. The method of claim 17, wherein R.sub.4 is —(CH.sub.2).sub.n—Y.sub.1—Z or —(CH.sub.2).sub.n—Y.sub.1—(CH.sub.2).sub.p—Y.sub.2—Z, and wherein n and p, are independently integers between 1 and 50 and may be the same or different, and wherein Y.sub.1 and Y.sub.2 are independently selected from the group consisting of a single chemical bond, —O—, —S—, —NH—, —OCO—, —SCO—, —HNCO—, or —HNCO—CF(CF.sub.3)—, and wherein Z is H, R.sub.f, —(OCF.sub.2CF.sub.2).sub.n—OR.sub.f, —(OCF.sub.2CF(CF.sub.3)).sub.n—OR.sub.f, or —(OCF(CF.sub.3)CF.sub.2).sub.n—OR.sub.f, wherein R.sub.f comprises a perfluorinated alkyl having from 1 to 50 carbon atoms, that is linear or branched, saturated or unsaturated, or substituted or unsubstituted.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The following drawings illustrate some of the many possible embodiments of this disclosure in order to provide a basic understanding of this disclosure. These drawings do not provide an extensive overview of all embodiments of this disclosure. These drawings are not intended to identify key or critical elements of the disclosure or to delineate or otherwise limit the scope of the claims. The following drawings merely present some concepts of the disclosure in a general form. Thus, for a detailed understanding of this disclosure, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements have been given like numerals.

[0055] FIG. 1 is a schematic showing one non-limiting embodiment of a reaction scheme suitable for use in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0056] It is to be understood that the following disclosure provides many different non-limiting embodiments, or examples, for implementing different features of various non-limiting embodiments. Specific examples of compositions are described below to simplify the disclosure and are not intended to limit the scope of the claims. These are, of course, merely examples and are not intended to be limiting of the scope of the claims. The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described.

[0057] The present invention provides for triphosphonate compositions, self-assembled triphosphonate monolayers, products and apparatus made thereof, and methods of making and using such compositions, monolayers, products, and apparatus.

[0058] The compositions of the present invention comprise a head having at least 3 phosphonate groups (usually a triphosphonate), a functional end group, a linker, with the head and end group affixed to and positioned at opposite ends of the linker.

[0059] Certain non-limiting embodiments of the triphosphonate compositions of the present invention may be represented by the following Formula I, Formula II, Formula III and/or mixtures thereof. Of course, the compositions of the present invention are not meant to be limited by the following Formulas I, II and III, but rather compositions of the present invention include all SAM precursors that comprise a head having at least 3 phosphonate groups, any functional end group, and any linker joining the head and end groups.

##STR00001##

[0060] For each Formula I, II and III: [0061] Each R.sub.1 can independently be selected from a group consisting of H, Li, Na, K, or substituted or unsubstituted, linear or branched, saturated or unsaturated, alkyl group having from 1 to 20 carbon atoms (it should be understood that any two R.sub.1's may be the same or different); [0062] R.sub.2 can be selected from a group consisting of a single chemical bond, or —O—, or —S—, or —NH—; R.sub.2 is preferably a single chemical bond; [0063] Each R.sub.3 can independently represent an alkyl group which may be linear or branched, substituted or unsubstituted, saturated or unsaturated and can have up to 50 carbon atoms. Preferably R.sub.3 can be an —(CH.sub.2).sub.m—, where for each R.sub.3, m is independently selected to be an integer from 1 to 50 (it should be understood that any two R.sub.3's may be the same or different); and/or, [0064] R.sub.4 can be an alkyl group which may be linear or branched, substituted or unsubstituted, saturated or unsaturated and can have up to 50 carbon atoms. [0065] OR [0066] R.sub.4 can also be is selected from a group which may consist of —(CH.sub.2).sub.n—Y.sub.1—Z or —(CH.sub.2).sub.n—Y.sub.1—(CH.sub.2).sub.p—Y.sub.2—Z, wherein n and p, are independently integers between 1 and 50 and may be the same or different, and wherein Y.sub.1 and Y.sub.2 are independently selected from a group consisting of a single chemical bond, or —O—, —S—, —NH—, —OCO—, —SCO—, —HNCO—, —HNCO—CF(CF.sub.3)— group; [0067] wherein Z can represent H or R.sub.f, or —(OCF.sub.2CF.sub.2).sub.n—OR.sub.f, or —(OCF.sub.2CF(CF.sub.3)).sub.n—OR.sub.f, or —(OCF(CF.sub.3)CF.sub.2).sub.n—OR.sub.f, wherein R.sub.f could be a perfluorinated alkyl, that may be linear or branched, saturated or unsaturated, substituted or unsubstituted, having from 1 to 50 carbon atoms. [0068] Each X can independently be selected from a group consisting of a single bond, or —O—, or —S— (it should be understood that any two X's may be the same or different).

[0069] In other non-limiting embodiments of the present invention, R.sub.1 comprises a linear alkyl. In even other non-limiting embodiments of the present invention, R.sub.1 comprises an unsubstituted linear alkyl. In even other non-limiting embodiments of the present invention, R.sub.1 comprises a substituted linear alkyl.

[0070] In other non-limiting embodiments of the present invention, R.sub.1 comprises a branched alkyl. In even other non-limiting embodiments of the present invention, R.sub.1 comprises an unsubstituted branched alkyl. In even other non-limiting embodiments of the present invention, R.sub.1 comprises a substituted branched alkyl.

[0071] It should be understood that the various R.sub.1's may be the same or different type of alkyls, and may be selected from the group of alkyl types consisting of branched alkyls, unsubstituted branched alkyls, substituted branched alkyls, linear alkyls, unsubstituted linear alkyls, and substituted linear alkyls, any of which may be saturated or unsaturated.

[0072] In other non-limiting embodiments of the present invention, R.sub.1 may comprise an alkyl group having more than 20 carbon atoms.

[0073] In even other non-limiting embodiments of the present invention, R.sub.1 may comprise an alkyl group having a number of carbon atoms equal to any one of the following numbers, or having a number of carbon atoms in the range from/to or between any two of the following numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0074] In even other non-limiting embodiments of the present invention, R.sub.1 may comprise an alkyl group having a number of carbon atoms equal to any one of the following numbers, or having a number of carbon atoms in the range from/to or between any two of the following numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0075] In even other non-limiting embodiments of the present invention, R.sub.1 may comprise an alkyl group having a number of carbon atoms equal to any one of the following numbers, or having a number of carbon atoms in the range from/to or between any two of the following numbers: 1, 2, 3, 4, and 5.

[0076] In other non-limiting embodiments of the present invention, R.sub.4 may comprise more than 50 carbon atoms, and n and/or p may be an integer greater than 50.

[0077] In even other non-limiting embodiments of the present invention, with respect to R.sub.4, n and p, may be the same or different, and each may be equal to any one of the following integers, or may be an integer in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30.

[0078] In even other non-limiting embodiments of the present invention, with respect to R.sub.4, n and p, may be the same or different, and each may be equal to any one of the following integers, or may be an integer in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0079] In even other non-limiting embodiments of the present invention, with respect to R.sub.4, n and p, may be the same or different, and each may be equal to any one of the following integers, or may be an integer in the range from/to or between any two of the following integers: 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0080] The compositions of the present invention are generally made by appending a trisphosphonic acid structure to one end of a linker chain as the “head” group (also termed an ‘anchor’ in some cases), and appending a desired functional group to the other end of the linker chain (as the end group, also termed as ‘tail’ in some cases).

[0081] Non-limiting examples of suitable acid structures having at least 3 phosphonic groups that are useful in the present invention include:

##STR00002##

[0082] Various functional end groups are well known in the SAM art, and any functional group suitable for the end application may be utilized in the present invention. Any particular SAM molecule may comprise one or more functional groups, and a collection of SAM molecules may comprise one or more functional groups distributed among one or more of the SAM molecules of the collection. Non-limiting examples of suitable end groups include those disclosed by Ulrike Kraft et al. in the Journal of Materials Chemistry, 2010, 20, 6414-6418, and by Michael Salinas, Interface Engineering with Self-assembled Monolayers for Organic Electronics, FAU University Press (2014), both of which are herein incorporated by reference for all that they teach and suggest. In various non-limiting embodiments of the present invention, end groups may be hydrophilic, hydrophobic, oleophilic, oleophobic, or any combinations of two or more of the foregoing.

[0083] The present invention provides for the modification of any substrates to which the head group may attach. Non-limiting examples of suitable substrates include those whose free surface comprises titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, tungsten, zirconium, steel, stainless steel, or alloys thereof or oxides, such as sapphire or ruby, silicon or germanium, optionally doped, or their oxides, or quartz, mica, glass, limestone, or subterranean formation.

[0084] According to methods of the present invention, the substrate surface is contacted with a covering liquid composition containing triphosphonate compounds to allow for the self-assembly of said triphosphonate compounds in a monolayer covering said surface.

[0085] It should be understood, that the triphosphonate composition can be liquid, gaseous or supercritical.

[0086] In those non-limiting embodiments in which the triphosphonate composition is liquid, the composition containing triphosphonate compounds may be an aqueous or organic composition. In some non-limiting embodiments, it should be understood, that the solvent of the liquid composition is selected so as to allow the solubilization of these triphosphonate compounds. In some non-limiting embodiments, the organic solvent may be selected from alcohols, aldehydes, ketones, ethers, alkanes, and mixtures thereof. Non-limiting examples of alcohols suitable for use as solvents include alcohols having from 1 to 6 carbon atoms, non-limiting examples of which include isopropanol, ethanol, and methanol. Non-limiting examples of the ketones suitable for use as solvents includes acetone. Non-limiting examples of ethers suitable for use as solvents includes diethyl ether or tetrahydrofuran. Non-limiting examples of alkanes includes alkanes having from 1 to 8 carbon atoms.

[0087] In some non-limiting embodiments, the triphosphonate composition may be gaseous, and applied to the surface to be treated in a vapor state.

[0088] In some non-limiting embodiments, the triphosphonate composition may be a “supercritical composition” meaning that the composition that is in a supercritical fluid state. As a non-limiting example, the solvent of such a supercritical composition may be supercritical carbon dioxide.

[0089] The composition of the present invention is advantageously utilized in the form of a solution, suspension, emulsion, of a supercritical fluid, an aerosol or a foam.

[0090] In some non-limiting embodiments, the method of contacting of the triphosphonate liquid composition to overlap with the substrate surface may be carried out by coating, dipping, flushing, spin coating, wiping, spraying, and/or contact applying, to name only a few non-limiting examples.

[0091] In some non-limiting embodiments, the contacting of the covering liquid composition with the substrate surface may be performed by dipping the substrate in an aqueous solution containing between 0.001 and 5% of triphosphonate composition, for a time comprised between 0.1 seconds and 3 hours at room temperature with or without stirring.

[0092] In those non-limiting embodiments in which the composition is gaseous or supercritical state, the contacting with the surface of the substrate may be carried out using a reactor whose pressure and temperature are controllable and which allows the injection of a gas.

[0093] After the step of contacting the substrate with the composition, the procedure is the removal of the composition, to remove the surface of the substrate the solvent and all the trisphosphonic solute that is not attached to the substrate during contacting. As non-limiting examples, the removal of the excess composition may be accomplished by rinsing, or mechanically by draining, centrifugation or evaporation.

[0094] The substrate may be further rinsed, in particular by immersion in a suitable solvent, in order to ensure complete removal of excess composition.

[0095] Once the deposition of the molecular layer of triphosphonate compounds is formed, the method of the present invention may include drying of the modified surface. Without being bound to this theory, it is assumed that drying of the triphosphonate layer formed on the substrate allows the formation of a bond, in some cases a covalent type bond between the triphosphonate molecules and free hydroxyl functions of the surface of the substrate. In practice, the drying of the substrate surface may be carried out by heating thereof to a temperature between 20° C. and 150° C., preferably at 20−50° C. for a time between 10 secs and 72 hours, preferably for about 10 secs to 1 hr. All these different successive steps may be repeated several times cyclically.

[0096] In the present context, “solvent” means a substance, preferably liquid, which has the property of dissolving or diluting other substances without chemically modifying them and without itself being modified.

[0097] In the present context, “fluorinated solvent” means a solvent or mixture of solvents at least one component of which is partially fluorinated or perfluorinated. In the present context, “non-flammable” or “non-inflammable” means a chemical that does not have a flash point or has a flash point above 60° C.

[0098] Preferably, the solvents of the invention include HFCs (hydrofluorocarbons), HFEs (hydrofluoroethers), HFOs (hydrofluoroolefins), PFPEs (perfluoropolyethers), aqueous or alcoholic solvents, aldehydes, ketones, ethers, alkanes, naphthas or a mixture thereof (cf. EP 2054165, WO 2013/167624, WO 2012/085130, all of which are herein incorporated by reference).

[0099] In general, the SAMs of the present invention find utility in a wide range of applications, including those applications in which SAMs are traditionally utilized, including for a range of applications, including consumer goods, industrial equipment, electronics, optics, medical and biotech.

[0100] For example, SAM's of the present invention find utility in repellency treatments to modify the repellency properties of a surface at the nanoscale level, including hydrophobic and oleophobic treatments, to create surfaces that are easy to clean, water resistant, oil resistant, and/or anti-smudge.

[0101] For example, SAMs of the present invention find utility in adhesion promotion, in all sorts of applications, including electronics and industrial applications.

[0102] For example, SAM's of the present invention find utility in the treatment of substrates, powders and particles, comprising a wide range of materials including metals, metal oxides, polymers and ceramics, and comprising a wide range of sizes all the way down to nanoparticles.

[0103] The SAM's of the present invention find utility in modifying all or part of the surfaces of equipment, such as but not limited to, level sensors, sucker rods, turbine meters, coriolis meters, magnetic flow meters, down hole pumps, check valves, valves, cables, drill bits, wire lines, and pigs, tuning forks, LACT units, separators, just to name a few. The present invention is useful for surfaces that come into contact with hydrocarbon liquids, including both crude oils and condensates, in which paraffins and/or asphaltenes are present or may become present and may deposit on any surface of such equipment. The present invention is useful for surfaces of equipment that may come into contact with other fluids like glycols and glycol-based compounds, drag reducing agents or other similar operating conditions where the surface of said equipment can be fouled by contaminants and/or deposits.

[0104] As a non-limiting example, the present invention may find utility when utilized with sucker rods. In the production of oil and gas, a sucker rod is a rod, typically made of steel and between 25 and 30 feet (7 to 9 meters) in length, and threaded at both ends, used to join together the surface and downhole components of a reciprocating piston pump installed in an oil well. The pump jack is the visible above-ground drive for the well pump and is connected to the downhole pump at the bottom of the well by a series of interconnected sucker rods that are extending through the cased or uncased wellbore. One problem encountered by sucker rods is the buildup of paraffin/asphaltenes on the surface of the sucker rod during operation in oil and gas wells. The buildup may occur to such an extent that the rod string can break under the added weight of the combined rod string and wax. In further method embodiments the present invention may be applied to one or more surfaces of the sucker rod to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0105] The present invention will also have utility with a wide variety of flow meters in which it is important to slow down and/or prevent buildup of paraffin/wax on any surface of the meter to maintain the integrity of the meter. The present invention is believed to be useful on the surfaces of at least the following flow meters: mechanical flow meters such as piston meter/rotary piston (for example, oval gear meter), gear meter (for example helical gear nutating disk meter), variable area meter, turbine flow meter, Woltman meter, single jet meter, paddle wheel meter, multiple jet meter, Pelton wheel and current meter; pressure-based meters such as venturi meter, orifice plate, Dall tube, pitot-tube, multi-hole pressure probe, cone meters and linear resistance meters; optical flow meters; open-channel flow measurement meters such as level to flow, area/velocity, dye testing and acoustic doppler velocimetry; thermal mass flow meters such as the MAF sensor; Vortex flow meters; electromagnetic, ultrasonic and coriolis flow meters such as magnetic flow meters, non-contact electromagnetic flow meters, ultrasonic flow meters (Doppler, transit time), and coriolis flow meters; and laser Doppler flow measurement meters.

[0106] As another non-limiting example, the present invention may also have utility with turbine meters. In general, a turbine flow meter (better described as an axial turbine) translates the mechanical action of the turbine rotating in the liquid flow around an axis into a user-readable rate of flow (gpm, lpm, etc.). The turbine tends to have all the flow traveling around it. The turbine wheel is set in the path of a fluid stream. The flowing fluid impinges on the turbine blades, imparting a force to the blade surface and setting the rotor in motion. When a steady rotation speed has been reached, the speed is proportional to fluid velocity. Optionally, there may be positioned upstream and/or downstream of the turbine wheel one or more fluid stabilizers to help stabilize the fluid flow prior to contact with the turbine meter and/or as the fluid flows away from the turbine meter. Turbine meters are carefully machined to straighten the flow of fluids and pass them through a turbine to measure the flow through the meter. When operating in an oil and gas environment, especially where paraffin/asphaltene are an issue, the surfaces of the stabilizers, turbine wheel and/or even tube in which they are positioned may become coated with such paraffin/asphaltene buildup. When these surfaces become irregular due to such buildup they then cease to function properly and give erroneous results. In extreme cases deposition on the straightening vanes, turbine blades or housing may lead to plugging of the meter. Thus, in further method embodiments the present invention may be applied to one or more surfaces of the turbine meter, including to one or more surfaces of the stabilizers, turbine wheel and/or even tube in which they are positioned, to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0107] Coriolis meters (also known as inertial or mass flow meters) are well known devices that measure mass flow rate of a fluid traveling through a tube. The mass flow rate is the mass of the fluid traveling past a fixed point per unit time. Coriolis meters generally comprise a set of parallel tubes in rotation or vibration, and an actuator which induces a vibration of the tubes. When the fluid to be measured is flowing, it is led through two parallel tubes that are designed to be counter-vibrating. The actual frequency of the vibration depends on the size of the mass flow meter, and commonly ranges from 80 to 1000 vibrations per second. When no fluid is flowing, the vibration of the two tubes is symmetrical. However, when there is mass flow, there is some twisting of the tubes. In those portions of the tube through which fluid flows away from the axis of rotation it must exert a force on the fluid to increase its angular momentum, so it is lagging behind the overall vibration. In other portions of the tube through which fluid is pushed back towards the axis of rotation it must exert a force on the fluid to decrease the fluid's angular momentum again, hence that arm leads the overall vibration. The inlet tube and the outlet tube vibrate with the same frequency as the overall vibration, but when there is mass flow the two vibrations are out of sync: the inlet arm is behind, the outlet arm is ahead. The two vibrations are shifted in phase with respect to each other, and the degree of phase-shift is a measure for the amount of mass that is flowing through the tubes. As might be guessed, flow of fluid though these tubes, is quite sensitive to any paraffin/asphaltene buildup which might occur, especially when the fluid is a crude oil. Specifically, paraffin and asphaltene buildup on the surfaces of measurement tubes will cause a change in the cross sectional area of the tube at the point of buildup, and will cause a change in the mass of the tube at the point of buildup, either of which will have a detrimental effect on any resulting measurement. Thus, in further method embodiments the present invention may be applied to one or more surfaces of the Coriolis meter in contact with the flowing fluid (i.e., the interior surfaces of the tubes), to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0108] Magnetic flow meters, often called “mag meter”s or “electromag”s, use a magnetic field applied to the metering tube, which results in a potential difference proportional to the flow velocity perpendicular to the flux lines. The potential difference is sensed by electrodes aligned perpendicular to the flow and the applied magnetic field. The physical principle at work is Faraday's law of electromagnetic induction. The magnetic flow meter requires a conducting fluid and a nonconducting pipe liner. The electrodes must not corrode in contact with the process fluid; some magnetic flowmeters have auxiliary transducers installed to clean the electrodes in place. The applied magnetic field is pulsed, which allows the flowmeter to cancel out the effect of stray voltage in the piping system. Because the magnetic flow meters measure the electromagnetic flux across the whole diameter of the measuring tube, they can be subject to asphaltene and asphaltene deposits that reduce the diameter and interfere with the proper operation of the meter. Thus, in further method embodiments the present invention may be applied to one or more surfaces of the magnetic flow meter in contact with the flowing fluid (i.e., the electrode and/or the interior of the flow tube), to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0109] Downhole pumps, both reciprocating as well as rotational both suffer from wax and asphaltene deposition. On reciprocating pumps, the ball and seat assemblies can be fouled preventing a good seal and disrupting pump operation. Rotating pumps rely on spinning stages to increase pressure and small changes in the stage shape can cause flow to be disrupted and efficiency to drop to a point the pump must be pulled and replaced. Thus, in further method embodiments the present invention may be applied to one or more surfaces of downhole pumps in contact with the pumped fluid to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0110] Check valves are used to control fluid by sealing at a specified pressure and only allowing flow when the pressure on the other side of the value exceeds the sealing pressure. The sealing pressure could come from well fluids, a spring, a control line, or other source of force. Check valves are often used as safety devices to allow flow to be relieved if a critical pressure is reached or to only allow flow if pressure is applied. In either case deposition on the internal components of the valve can either cause the valve to fail to open or fail to close which could shut in production or create a potentially hazardous situation due to over pressurizing a line or vessel. Thus, in further method embodiments the present invention may be applied to one or more surfaces of check valves in contact with fluid to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0111] Valves are used to control flow both for simple on and off control as well as to regulate flow rate. When the sealing surfaces are fouled with deposits, they no longer can function as designed. When valves can no longer properly control flow a variety of problems such as leaks, spills, fires, gas releases, or other hazards can occur. Thus, in further method embodiments the present invention may be applied to one or more surfaces of valves in contact with fluid to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0112] Cables are used to supply power to downhole equipment. Deposits can form on the outside of the cables. Weight can become a problem with unsupported cables which could lead to breakage. For cables that are strapped to pipe the deposition interferes with the strapping used to keep the cable attached to the pipe. This slows the process of removing the equipment from the well. Thus, in further method embodiments the present invention may be applied to one or more surfaces of cables in contact with fluid to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0113] Wirelines are used to clean wells, set tools, log wells, fish for broken tools or equipment and many other functions. Wirelines can pick up deposits that impede their ability to feed through guides, increase weight, foul centralizers, skates and other critical equipment needed for proper operation. Thus, in further method embodiments the present invention may be applied to one or more surfaces of wirelines in contact with fluid to slow down, discourage or even prevent such buildup, resulting in further apparatus and products of the present invention.

[0114] Non-limiting examples of commercial applicability of the present invention include petroleum production, petroleum pipelines, petroleum equipment (storage tanks and specialty vessels, etc.), and petroleum sensor and instrument manufacturing.

[0115] The SAMs of the present invention may also find utility in Electronics: Transistor devices like Organic Thin film transistors, Organic light-emitting diodes.

[0116] The SAMs of the present invention may also find utility in well treatments.

[0117] The SAMs of the present invention may also find utility in medical applications, such as but not limited to modification of biomaterials and biosensors. Further, from a biomedical point of view a wide variety of biomolecules and biomaterials involving proteins, peptides, DNA, carbohydrates, antibodies, and therapeutics, may be attached to the same of the SAMs of the present invention. Thus, the SAMs of the present invention may be utilized for implanting functional molecules on surfaces or to modify chemical-physical properties of themselves.

[0118] The SAMs of the present invention find utility with the attachment of therapeutic drugs to functional self-assembled monolayers (SAMs) after their assembly on a substrate (for example 316L SS) and can serve as a localized drug delivery system.

EXAMPLES

[0119] The following prophetic reaction scheme and prophetic examples are provided merely as an illustration of one non-limiting embodiment of the present invention and does not in any way limit the scope of the claims.

[0120] Referring now to FIG. 1, there is shown a schematic representation of Reaction Scheme 100, a non-limiting example of a reaction scheme suitable for use in the present invention:

Example 1: Preparation of Intermediate 1

[0121] ##STR00003##

[0122] The preparation of compounds suitable for use as Intermediate 1 in this prophetic reaction scheme are well known. In this prophetic example, 3-Bromo-2,2-bis(bromomethyl)propanol (3.25 g, 0.01 mol) may be dissolved in DMF (20 mL), followed by the addition of trimethyl phosphite (4.96 g, 4.72 mL). The resulting solution is then heated at 80° C. for 12 h under inert atmosphere. The solvent is then as removed in vacuum and upon standing the desired product 1 is obtained as a light yellow solid (ca. 4.12 g, ca. 100% yield). See, Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981, 81, 415-430.

Example 2: Preparation of Intermediate 3

[0123] ##STR00004##

[0124] The preparation of compounds suitable for use as Intermediate 3 are well known. In general, Intermediate 1 (4.12 g, 0.01 mol) and N-Boc-6-amino-1-hexanoic acid 2 (2.53 g, 0.011 mol) are mixed with a catalytic amount of 4-(dimethylamino)pyridine (0.03 g) and dissolved in anhydrous CH.sub.2Cl.sub.2 (40 mL), followed by the addition of N,N′-dicyclohexylcarbodiimide (DCC, 2.27 g, 0.011 mol). See, Hassner, A.; Alexanian, V. Tetrahedron Lett. 1978, 19, 4475. The solution is stirred at rt for 12 h and subsequently filtered to removed insoluble urea by-product. The filtrate is concentrated to an oil, and then further purified with silica gel flash chromatography (SiO.sub.2, eluent CH.sub.2Cl.sub.2, 3% MeOH/CH.sub.2Cl.sub.2). Upon standing, the desired product 3 (5.75 g, 92%) will be obtained as a white solid.

Example 3: Preparation of Product 4

[0125] ##STR00005##

[0126] Intermediate 3 (5.75 g, 0.0092 mol) is dissolved in anhydrous CH.sub.2Cl.sub.2 (20 mL), followed by the addition of 3M HCl in EtOAc solution (0.0184 mol, 6.15 mL). See, Stahl, G. L.; Walter, R.; Smith, C. W. J. Org. Chem. 1978, 43, 2285. The mixture is then stirred at ambient temperature for 16 h before the solvent is removed under vacuum. The viscous residue may be re-dissolved in CH.sub.2Cl.sub.2 (40 mL). Triethylamine (Et.sub.3N, 1.92 mL, 0.0138 mol), perfluorooctanoic acid (PFOA, 4.97 g, 0.012 mol) and DCC (2.12 g, 0.012 mol) are added to the solution in sequence. The mixture is then stirred under inert atmosphere for 12 h. After the insoluble urea by-product was filtered off, the clear filtrate is concentrated to afford a light-yellow oil, which was further purified with silica gel flash chromatography (SiO.sub.2, eluent CH.sub.2Cl.sub.2, 3% MeOH/CH.sub.2Cl.sub.2). The purified oil is further dissolved in acetone (100 mL). Following addition of NaI (13.8 g, 0.092 mol), the mixture is then refluxed for 24 h under inert atmosphere. The solvent is removed under vacuum and the residue is washed thoroughly with DI water to yield 4 (ca. 9.0 g). (Delfino, J. M.; Stankovic, C. J.; Schreiber, S. L.; Richards, F. M. Tetrahedron Lett. 1987, 28, 2323.)

[0127] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present disclosure to its fullest extent. The embodiments described herein are to be construed as illustrative and not as constraining the remainder of the disclosure in any way whatsoever. While the embodiments have been shown and described, many variations and modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the present disclosure as set forth herein. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims, including all equivalents of the subject matter of the claims.

[0128] The foregoing outlines several embodiments with numerous features so that those skilled in the art may better understand the aspects of the disclosure. Those skilled in the art should appreciate that they may readily use the disclosure as a basis for designing or modifying other processes and compositions for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the disclosure, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the disclosure. The scope of the invention should be determined only by the language of the claims that follow. The term “comprising” within the claims is intended to mean “including at least” such that the recited listing of elements in a claim are an open group. The terms “a,” “an,” and other singular terms are intended to include the plural forms thereof unless specifically excluded.

[0129] All materials described, cited and/or referenced herein, including patents, patent publications, books, journals, articles, websites/pages, and any other publications, are incorporated by reference for all that they disclose or teach.