Process for preparing reaction product comprising quaternary ammonium salt

Abstract

Disclosed is a method for preparing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt. Compositions comprising such reaction products and methods of utilizing such compositions are also disclosed.

Description

[0001] The disclosed technology relates to a method for preparing a reaction product comprising a quaternary ammonium salt. Also disclosed are compositions comprising such reaction products, methods utilizing such compositions, uses of such compositions in fuel compositions and / or lubricating compositions, methods of using such fuel compositions and / or lubricating compositions, and / or uses of such fuel compositions and / or lubricating compositions.

[0002] Deposit formation in diesel fuel injector nozzles is often problematic, resulting in incomplete diesel combustion and therefore power loss and / or misfires. Traditionally, polyisobutylene succinimide detergents have been used to inhibit injector fouling, but these materials have shown poor efficacy in modern engines. A class of compounds based on quaternized polyisobutylene succinimides has been shown to provide improved detergency performance in both conventional and modern diesel engines.

[0003] It has been discovered that quaternary ammonium salts prepared from hydrocarbyl-substituted acylating agents result in quaternary ammonium salts that provide demulsification properties when blended into a fuel. It has now been discovered that utilizing a free radical functionalized PIBSA product (as defined and described herein) to produce a reaction product comprising a quaternary ammonium salt can provide an alternative (and potentially superior) quaternary ammonium salt for use as a deposit control additive in fuels.

[0004] The subject matter disclosed herein provides a method for preparing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt.

[0005] The following implementations of the present subject matter are contemplated:

[0006] 1. A method for preparing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt.

[0007] 2. The method of embodiment 1, wherein the nitrogen-containing compound has: (a) a nitrogen atom capable of reacting with the free radical functionalized PIBSA product to form an imide; and (b) at least one quaternizable amino group.

[0008] 3. The method according to embodiment 1 or embodiment 2, wherein the quaternizing agent is suitable for converting the quaternizable amino group into a quaternary nitrogen group.

[0009] 4. The method of any one of embodiments 1 to 3, wherein the quaternizing agent comprises at least one of an alkyl sulfonate, a dialkyl sulfate, an alkyl halide, a sultone, an alkyl phosphate, a borate, an alkyl nitrite, an alkyl nitrate, a dialkyl carbonate, an alkyl alkanoate, a hydrocarbyl substituted carbonate, or a hydrocarbyl epoxide.

[0010] 5. The method of any one of embodiments 1 to 4, wherein the quaternizing agent comprises a hydrocarbyl epoxide in combination with an acid.

[0011] 6. The method of any one of embodiments 1 to 5, wherein the free radical functionalized PIBSA product is the product of a process comprising the steps of: reacting polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150° C. to 225° C. to produce the product; wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

[0012] 7. The process of embodiment 6, wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the process.

[0013] 8. The method of embodiment 6, wherein the ethylenically unsaturated acylating agent is combined with the free radical initiator for addition to the polyisobutylene after the polyisobutylene is brought to the reaction temperature.

[0014] 9. The method of any one of embodiments 6 to 8, wherein the free radical functionalized PIBSA product comprises less than 15 wt.% of material comprising two or more polyisobutylene units linked by one or more acylating agent units.

[0015] 10. The method according to any one of embodiments 6 to 9, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

[0016] 11. The method of any one of embodiments 6 to 10, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

[0017] 12. The method according to embodiment 11, wherein the organic peroxide initiator comprises diglutaroyl, dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di(tert-butyl)peroxide, tert-butyl hydroperoxide, 3,4-dimethyl-3,4-diphenyl-hexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-3,5,5-trimethyl-hexanoate, di(2,4-dichlorobenzoyl)peroxide, di(2-methylbenzoyl)peroxide, or di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0018] 13. The method of any one of embodiments 6 to 12, wherein the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, or methylenemalonic anhydride.

[0019] 14. The method according to any one of embodiments 6 to 13, wherein the free radical functionalized PIBSA product comprises at least one compound of the following general formula I:

[0020]

[0021] Among them: Each R 1 independently represents –(CH2)–(C(CH2))–(CH3); H; or absent; wherein when R 1 When not present, a dotted double bond represents a double bond, and when R 1 When present, a dashed double bond represents a single bond; each m is independently an integer from 1 to 52; and each n is independently 0, 1 or 2.

[0022] 15. The method according to any one of embodiments 6 to 14, wherein the free radical functionalized PIBSA product comprises at least 30 mol% of the at least one compound of formula I.

[0023] 16. The method of any one of embodiments 6 to 15, wherein the free radical functionalized PIBSA product comprises less than 40 wt% unreacted polyisobutylene.

[0024] 17. A composition comprising the reaction product of the method according to any one of embodiments 1 to 16.

[0025] 18. A fuel composition comprising a fuel and the composition according to embodiment 17.

[0026] 19. A lubricating composition comprising an oil of lubricating viscosity and the composition of embodiment 17.

[0027] 20. A method of improving the dehydration properties of a fuel composition, the method comprising incorporating the composition according to embodiment 17 into the fuel composition.

[0028] 21. A method of reducing and / or preventing injector deposits in an engine, the method comprising supplying the fuel composition according to embodiment 18 to a fuel injector of the engine and operating the engine.

[0029] 22. A method of lubricating a crankcase of an engine, the method comprising supplying the lubricating composition according to embodiment 19 to the engine and operating the engine.

[0030] 23. Use of a fuel composition according to embodiment 18 for reducing and / or preventing internal deposits in an engine operated with said fuel composition.

[0031] 24. Use of the lubricating composition according to embodiment 19 for lubricating the crankcase of an engine.

[0032] Various features and embodiments of the present subject matter are described below by way of non-limiting illustration.

[0033] Unless otherwise noted, the amount of each chemical component described herein does not include any solvent or diluent oil which may be customarily present in the commercial material, i.e., on an active chemical basis. Unless otherwise noted, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0034] As used herein, the term "alkyl" refers to a group having a carbon atom directly connected to the rest of the molecule, wherein the group includes at least a carbon atom and a hydrogen atom. If the alkyl group contains more than one carbon atom, these carbons do not have to be connected to each other. For example, at least two carbons can be connected via a suitable element or group. In various embodiments, the term "alkyl" refers to a group having a carbon atom directly connected to the rest of the molecule, wherein the group is composed of carbon, hydrogen, and optionally one or more heteroatoms, provided that the heteroatom does not change the main hydrocarbon nature of the substituent. The heteroatom may be connected to at least two carbons in the alkyl group and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art, and include, for example, sulfur, nitrogen, oxygen, phosphorus, and silicon. When the alkyl group contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the alkyl group. Suitable non-hydrocarbon substituents are also apparent to those skilled in the art, and include, for example, halogen, hydroxyl, alkoxy, sulfhydryl, alkylthiol, nitro, nitroso, and sulfoxyl.

[0035] Thus, examples of hydrocarbon groups in the context of the present technology include: (i) hydrocarbon groups selected from aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl, cycloalkadienyl) and aromatic groups; (ii) substituted hydrocarbon groups selected from hydrocarbon groups defined in (i) substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halogen, hydroxyl, alkoxy, thiol, alkylthiol, nitro, nitroso and thioxy groups; and / or (iii) heteroatom-containing hydrocarbon groups selected from hydrocarbon groups defined in (i) containing one or more heteroatoms in a ring or chain, provided that no more than two heteroatoms are present per ten carbon atoms in the group, the heteroatoms being selected from sulfur, nitrogen, oxygen, phosphorus and silicon. Hydrocarbon groups containing heteroatoms may be substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In certain embodiments, the term "hydrocarbon group" refers to a group having a carbon atom directly attached to the rest of the molecule, wherein the group consists of carbon atoms and hydrogen atoms.

[0036] It is known that some of the materials described herein can interact in the final formulation so that the components of the final formulation may be different from those initially added. For example, metal ions (e.g., metal ions of detergents) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed when the compositions of the present subject matter are employed in their intended use, may not be easy to describe. However, all such adjustments and reaction products are included within the scope of the present subject matter; the present subject matter includes compositions prepared by mixing the components described herein.

[0037] As used herein, the indefinite article "a" / "an" is intended to mean one or more than one / one or more than one. As used herein, the phrase "at least one / at least one" means one or more than one / one or more than one of the following terms. Therefore, "a" / "an" and "at least one / at least one" can be used interchangeably. For example, "at least one of A, B or C" means that in alternative embodiments, only one of A, B or C may be included, and any mixture of two or more of A, B and C may be included.

[0038] As used herein, the term "substantially free" means that a component does not include any intentional addition of a material that the component is "substantially free of." For example, the component may include a material that the component is "substantially free of" to no more than impurity levels that may be the result of an incomplete chemical reaction and / or an unintentional / undesirable (but perhaps unavoidable) reaction product.

[0039] As used herein, the transitional term "comprising," which is synonymous with "comprising," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each use of "comprising" herein, it is intended that the term also encompasses the phrases "consisting essentially of" and "consisting of" as alternative embodiments, wherein "consisting of" excludes any element or step not specified, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0040] Reaction products containing quaternary ammonium salts

[0041] A method for preparing a reaction product is provided, the method comprising: reacting a free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt. The preparation of a reaction product comprising a quaternary ammonium salt generally results in a mixture of compounds comprising the quaternary ammonium salt, and the mixture may be difficult to define other than the process steps used to prepare the reaction product.

[0042] In certain embodiments, the quaternary ammonium salt consists essentially of an imide quaternary ammonium salt. In certain embodiments, the quaternary ammonium salt consists of an imide quaternary ammonium salt. In certain embodiments, the quaternary ammonium salt is substantially free of an amide quaternary ammonium salt. In certain embodiments, the reaction product is substantially free of an amide quaternary ammonium salt.

[0043] Embodiments of the present technology described herein can provide for the use of reaction products comprising quaternary ammonium salts for at least one of antiwear performance, friction modification (such as for improving fuel economy), detergent performance (such as deposit control and / or varnish control), or dispersancy (such as soot control, sludge control and / or corrosion control).

[0044] Free radical functionalized PIBSA products

[0045] Acylated polyisobutylenes, such as polyisobutylene succinic anhydride / acid ("PIBSA"), are useful as chemical intermediates in the preparation of a number of chemical compositions, such as reaction products comprising the quaternary ammonium salts described herein. As used herein, the terms "polyisobutylene succinic anhydride," "polyisobutylene succinic acid," "polyisobutylene succinic anhydride / acid," and / or "PIBSA" mean any molecule (or composition comprising such a molecule) comprising a polyisobutylene moiety bonded (directly or indirectly) to a succinic anhydride / acid unit.

[0046] In certain embodiments, a free radical functionalized polyisobutylene succinic anhydride / acid ("PIBSA") product is the product of a process comprising the steps of: reacting polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150°C to 225°C to produce a product; wherein the polyisobutylene is brought to the reaction temperature prior to the addition of the free radical initiator; and wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator. Thus, as used herein, the term "free radical functionalized PIBSA product" refers to the product of such a reaction, optionally including the embodiments described below. Thus, in addition to the intended and / or desired PIBSA product, the free radical functionalized PIBSA product may include other products of such a reaction, as would be understood by one of ordinary skill in the art.

[0047] In certain embodiments, the ethylenically unsaturated acylating agent may be combined with the polyisobutylene at the beginning of the process. In certain embodiments, the ethylenically unsaturated acylating agent may be combined with a free radical initiator to be added to the polyisobutylene after the polyisobutylene is brought to reaction temperature. In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting a polyisobutylene (such as high vinylidene polyisobutylene) with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product, wherein the polyisobutylene is brought to reaction temperature prior to adding the free radical initiator and the ethylenically unsaturated acylating agent.

[0048] As used herein, the term "high vinylidene polyisobutylene" means a compound comprising at least 55 (such as at least 60, at least 65, at least 70, at least 75, or at least 80) weight % α-methyl-vinylidene polyisobutylene. In certain embodiments, the high vinylidene polyisobutylene may comprise 55 to 80 weight % (such as 55 to 75 weight %, 55 to 70 weight %, 55 to 65 weight %, 55 to 60 weight %, 60 to 80 weight %, 60 to 75 weight %, 60 to 70 weight %, 60 to 65 weight %, 65 to 80 weight %, 65 to 75 weight %, 65 to 70 weight %, 70 to 80 weight %, 70 to 75 weight %, or 75 to 80 weight %) of α-methyl-vinylidene polyisobutylene. High vinylidene polyisobutylenes are well known, are known to be highly reactive relative to other polyisobutylenes, and are useful as chemical intermediates in many chemical synthesis processes.

[0049] In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting a polyisobutylene, such as a high vinylidene polyisobutylene, with a free radical initiator and an ethylenically unsaturated acylating agent in two or more additions at a temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product.

[0050] In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting polyisobutylene, such as high vinylidene polyisobutylene, with a free radical initiator and an ethylenically unsaturated acylating agent in two or more additions at a reaction temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product, wherein each of the two or more additions comprises at least 5 weight percent of the total amount of free radical initiator and / or at least 5 weight percent of the total amount of ethylenically unsaturated acylating agent to be reacted with the polyisobutylene.

[0051] In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting a polyisobutylene, such as a high vinylidene polyisobutylene, with a free radical initiator and an ethylenically unsaturated acylating agent in two or more additions at a reaction temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product, wherein each of the two or more additions is separated in time by at least two times the half-life of the free radical initiator.

[0052] In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting polyisobutylene, such as high vinylidene polyisobutylene, with a free radical initiator and an ethylenically unsaturated acylating agent in two or more additions at a reaction temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product; wherein each addition of the two or more additions comprises at least 5 weight percent of the total amount of free radical initiator and / or at least 5 weight percent of the total amount of ethylenically unsaturated acylating agent to be reacted with the polyisobutylene; and wherein each addition of the two or more additions is separated in time by at least two times the half-life of the free radical initiator.

[0053] In certain embodiments, a method for preparing a free radical functionalized PIBSA product may include reacting polyisobutylene (such as high vinylidene polyisobutylene) with a free radical initiator and an ethylenically unsaturated acylating agent at a temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product, wherein the polyisobutylene is brought to the reaction temperature in a continuous reactor prior to commencing continuous addition of the free radical initiator to the polyisobutylene in the continuous reactor; and wherein the ethylenically unsaturated acylating agent is added to the continuous reactor: (i) as a mixture with the polyisobutylene; (ii) as a mixture with the free radical initiator; and / or (iii) continuously and separately from the polyisobutylene or the free radical initiator.

[0054] Compared to known methods for preparing PIBSA, the methods described above for preparing free radical functionalized PIBSA products generally provide lighter colored products (e.g., no black specks / resins without filtration), the ability to obtain functionalities greater than 2, reduced energy consumption, reduced equipment maintenance, and / or reduced reaction times, as will become apparent in the detailed description and examples below. It is believed that these and / or other features of the free radical functionalized PIBSA products contribute to the benefits of the reaction products comprising the quaternary ammonium salts described herein.

[0055] In certain embodiments, the reaction temperature utilized in the methods described herein for preparing free radical functionalized PIBSA products is between 155°C and 225°C, 160°C and 225°C, 165°C and 225°C, 166°C and 225°C, 167°C and 225°C, 168°C and 225°C, 169°C and 225°C, 170°C and 225°C, 171°C and 225°C, 172°C and 225°C, 173°C and 225°C, 174°C and 225°C, 175°C and 225°C, 150°C and 220°C, 155°C and 220°C, 160°C and 220°C, 165°C and 220°C, 166°C and 220°C, 167°C and 220°C, 168°C and 220°C, 169°C and 225°C ℃ to 220℃、170℃ to 220℃、171℃ to 220℃、172℃ to 220℃、173℃ to 220℃、174℃ to 220℃、175℃ to 220℃、150℃ to 215℃、155℃ to 215℃、160℃ to 215℃、165℃ to 215℃、166℃ to 215℃、167℃ to 21 5℃、168℃ to 215℃、169℃ to 215℃、170℃ to 215℃、171℃ to 215℃、172℃ to 215℃、173℃ to 215℃、174℃ to 215℃、175℃ to 215℃、150℃ to 210℃、155℃ to 210℃、160℃ to 210℃、165℃ to 210℃、16 6℃ to 210℃, 167℃ to 210℃, 168℃ to 210℃, 169℃ to 210℃, 170℃ to 210℃, 171℃ to 210℃, 172℃ to 210℃, 173℃ to 210℃, 174℃ to 210℃, 175℃ to 210℃, 150℃ to 205℃, 155℃ to 205℃, 160℃ to 2 05℃、165℃~205℃、166℃~205℃、167℃~205℃、168℃~205℃、169℃~205℃、170℃~205℃、171℃~205℃、172℃~205℃、173℃~205℃、174℃~205℃、175℃~205℃、150℃~200℃、1 55℃ to 200℃、160℃ to 200℃、165℃ to 200℃、166℃ to 200℃、167℃ to 200℃、168℃ to 200℃、169℃ to 200℃、170℃ to 200℃、171℃ to 200℃、172℃ to 200℃、173℃ to 200℃、174℃ to 200℃、175℃ to 200℃、150℃ to 195℃、155℃ to 195℃、160℃ to 195℃、165℃ to 195℃、166℃ to 195℃、167℃ to 195℃、168℃ to 195℃、169℃ to 195℃、170℃ to 195℃、171℃ to 195℃、172℃ to 195℃、173℃ to 195℃、174°C to 195°C, 175°C to 195°C, 150°C to 190°C, 155°C to 190°C, 160°C to 190°C, 165°C to 190°C, 166°C to 190°C, 167°C to 190°C, 168°C to 190°C, 169°C to 190°C, 170°C to 190°C, 171°C to 190°C, 172°C to 190℃、173℃ to 190℃、174℃ to 190℃、175℃ to 190℃、150℃ to 185℃、155℃ to 185℃、160℃ to 185℃、165℃ to 185℃、166℃ to 185℃、167℃ to 185℃、168℃ to 185℃、169℃ to 185℃、170℃ to 185℃、 171°C to 185°C, 172°C to 185°C, 173°C to 185°C, 174°C to 185°C, 175°C to 185°C, 150°C to 180°C, 155°C to 180°C, 160°C to 180°C, 165°C to 180°C, 166°C to 180°C, 167°C to 180°C, 168°C to 180°C, 169°C to 180℃、170℃ to 180℃、171℃ to 180℃、172℃ to 180℃、173℃ to 180℃、174℃ to 180℃、175℃ to 180℃、150℃ to 175℃、155℃ to 175℃、160℃ to 175℃、165℃ to 175℃、166℃ to 175℃、167℃ to 175℃、 168℃ to 175℃, 169℃ to 175℃, 170℃ to 175℃, 171℃ to 175℃, 172℃ to 175℃, 173℃ to 175℃, 174℃ to 175℃, 150℃ to 174℃, 155℃ to 174℃, 160℃ to 174℃, 165℃ to 174℃, 166℃ to 174℃, 167℃ to 174°C、168°C to 174°C、169°C to 174°C、170°C to 174°C、171°C to 174°C、172°C to 174°C、173°C to 174°C、150°C to 173°C、155°C to 173°C、160°C to 173°C、165°C to 173°C、166°C to 173°C、167°C to 173°C、 168°C to 173°C, 169°C to 173°C, 170°C to 173°C, 171°C to 173°C, 172°C to 173°C, 150°C to 172°C, 155°C to 172°C, 160°C to 172°C, 165°C to 172°C, 166°C to 172°C, 167°C to 172°C, 168°C to 172°C, 169°C to 172°C、170°C to 172°C、171°C to 172°C、150°C to 171°C、155°C to 171°C、160°C to 171°C、165°C to 171°C、166°C to 171°C、167°C to 171°C、168°C to 171°C、169°C to 171°C、170°C to 171°C、150°C to 170°C、155°C to 170°C, 160°C to 170°C, 165°C to 170°C, 166°C to 170°C, 167°C to 170°C, 168°C to 170°C or 169°C to 170°C.

[0056] In certain embodiments, the total amount of free radical initiator added during the methods described herein for preparing free radical functionalized PIBSA products can be from 0.01 equivalents to 1 equivalent (such as from 0.01 equivalents to 0.9 equivalents, from 0.01 equivalents to 0.8 equivalents, from 0.01 equivalents to 0.7 equivalents, from 0.01 equivalents to 0.6 equivalents, from 0.01 equivalents to 0.5 equivalents, from 0.01 equivalents to 0.45 equivalents, from 0.01 equivalents to 0.4 equivalents, from 0.01 equivalents to 0.35 equivalents, from 0.01 equivalents to 0.3 equivalents, from 0.01 equivalents to 0.25 equivalents, from 0.01 equivalents to 0.2 equivalents, from 0.01 equivalents to 0.19 equivalents, from 0.01 equivalents to 0.18 equivalents), based on the amount of polyisobutylene being reacted. Equivalent, 0.01 equivalent to 0.17 equivalent, 0.01 equivalent to 0.16 equivalent, 0.01 equivalent to 0.15 equivalent, 0.01 equivalent to 0.14 equivalent, 0.01 equivalent to 0.13 equivalent, 0.01 equivalent to 0.12 equivalent, 0.01 equivalent to 0.11 equivalent, 0.01 equivalent to 0.1 equivalent, 0.02 equivalent to 0.9 equivalent amount, 0.02 equivalent to 0.8 equivalent, 0.02 equivalent to 0.7 equivalent, 0.02 equivalent to 0.6 equivalent, 0.02 equivalent to 0.5 equivalent, 0.02 equivalent to 0.45 equivalent, 0.02 equivalent to 0.4 equivalent, 0.02 equivalent to 0.35 equivalent, 0.02 equivalent to 0.3 equivalent, 0.02 equivalent to 0.25 equivalent, 0.0 2 equivalents to 0.2 equivalents, 0.02 equivalents to 0.19 equivalents, 0.02 equivalents to 0.18 equivalents, 0.02 equivalents to 0.17 equivalents, 0.02 equivalents to 0.16 equivalents, 0.02 equivalents to 0.15 equivalents, 0.02 equivalents to 0.14 equivalents, 0.02 equivalents to 0.13 equivalents, 0.02 equivalents to 0.12 equivalents, 0.0 2 equivalents to 0.11 equivalents, 0.02 equivalents to 0.1 equivalents, 0.03 equivalents to 0.9 equivalents, 0.03 equivalents to 0.8 equivalents, 0.03 equivalents to 0.7 equivalents, 0.03 equivalents to 0.6 equivalents, 0.03 equivalents to 0.5 equivalents, 0.03 equivalents to 0.45 equivalents, 0.03 equivalents to 0.4 equivalents, 0.03 equivalents to 0. 35 equivalents, 0.03 equivalents to 0.3 equivalents, 0.03 equivalents to 0.25 equivalents, 0.03 equivalents to 0.2 equivalents, 0.03 equivalents to 0.19 equivalents, 0.03 equivalents to 0.18 equivalents, 0.03 equivalents to 0.17 equivalents, 0.03 equivalents to 0.16 equivalents, 0.03 equivalents to 0.15 equivalents, 0.03 equivalents to 0.1 4 equivalents, 0.03 equivalents to 0.13 equivalents, 0.03 equivalents to 0.12 equivalents, 0.03 equivalents to 0.11 equivalents, 0.03 equivalents to 0.1 equivalents, 0.04 equivalents to 0.9 equivalents, 0.04 equivalents to 0.8 equivalents, 0.04 equivalents to 0.7 equivalents, 0.04 equivalents to 0.6 equivalents, 0.04 equivalents to 0.5 equivalents, 0.0.4 equivalent to 0.45 equivalent, 0.04 equivalent to 0.4 equivalent, 0.04 equivalent to 0.35 equivalent, 0.04 equivalent to 0.3 equivalent, 0.04 equivalent to 0.25 equivalent, 0.04 equivalent to 0.2 equivalent, 0.04 equivalent to 0.19 equivalent, 0.04 equivalent to 0.18 equivalent, 0.04 equivalent to 0.17 equivalent, 0.0 4 equivalents to 0.16 equivalents, 0.04 equivalents to 0.15 equivalents, 0.04 equivalents to 0.14 equivalents, 0.04 equivalents to 0.13 equivalents, 0.04 equivalents to 0.12 equivalents, 0.04 equivalents to 0.11 equivalents, 0.04 equivalents to 0.1 equivalents, 0.05 equivalents to 0.9 equivalents, 0.05 equivalents to 0.8 equivalents, 0.05 equivalents to 0. 0.05 equivalents to 0.7 equivalents, 0.05 equivalents to 0.6 equivalents, 0.05 equivalents to 0.5 equivalents, 0.05 equivalents to 0.45 equivalents, 0.05 equivalents to 0.4 equivalents, 0.05 equivalents to 0.35 equivalents, 0.05 equivalents to 0.3 equivalents, 0.05 equivalents to 0.25 equivalents, 0.05 equivalents to 0.2 equivalents, 0.05 equivalents to 0.1 9 equivalents, 0.05 equivalents to 0.18 equivalents, 0.05 equivalents to 0.17 equivalents, 0.05 equivalents to 0.16 equivalents, 0.05 equivalents to 0.15 equivalents, 0.05 equivalents to 0.14 equivalents, 0.05 equivalents to 0.13 equivalents, 0.05 equivalents to 0.12 equivalents, 0.05 equivalents to 0.11 equivalents, 0.05 equivalents to 0. 1 equivalent, 0.06 equivalent to 0.9 equivalent, 0.06 equivalent to 0.8 equivalent, 0.06 equivalent to 0.7 equivalent, 0.06 equivalent to 0.6 equivalent, 0.06 equivalent to 0.5 equivalent, 0.06 equivalent to 0.45 equivalent, 0.06 equivalent to 0.4 equivalent, 0.06 equivalent to 0.35 equivalent, 0.06 equivalent to 0.3 equivalent, 0. 0.06 equivalent to 0.25 equivalent, 0.06 equivalent to 0.2 equivalent, 0.06 equivalent to 0.19 equivalent, 0.06 equivalent to 0.18 equivalent, 0.06 equivalent to 0.17 equivalent, 0.06 equivalent to 0.16 equivalent, 0.06 equivalent to 0.15 equivalent, 0.06 equivalent to 0.14 equivalent, 0.06 equivalent to 0.13 equivalent, 0. 0.06 equivalent to 0.12 equivalent, 0.06 equivalent to 0.11 equivalent, 0.06 equivalent to 0.1 equivalent, 0.07 equivalent to 0.9 equivalent, 0.07 equivalent to 0.8 equivalent, 0.07 equivalent to 0.7 equivalent, 0.07 equivalent to 0.6 equivalent, 0.07 equivalent to 0.5 equivalent, 0.07 equivalent to 0.45 equivalent, 0.07 equivalent to 0.4 equivalent, 0.07 equivalent to 0.35 equivalent, 0.07 equivalent to 0.3 equivalent, 0.07 equivalent to 0.25 equivalent, 0.07 equivalent to 0.2 equivalent, 0.07 equivalent to 0.19 equivalent, 0.07 equivalent to 0.18 equivalent, 0.07 equivalent to 0.17 equivalent, 0.07 equivalent to 0.16 equivalent, 0.07 equivalent to 0.15 equivalents, 0.07 equivalents to 0.14 equivalents, 0.07 equivalents to 0.13 equivalents, 0.07 equivalents to 0.12 equivalents, 0.07 equivalents to 0.11 equivalents, 0.07 equivalents to 0.1 equivalents, 0.08 equivalents to 0.9 equivalents, 0.08 equivalents to 0.8 equivalents, 0.08 equivalents to 0.7 equivalents, 0.08 equivalents to 0.6 equivalents, 0.08 equivalents to 0.5 equivalents, 0.08 equivalents to 0.45 equivalents, 0.08 equivalents to 0.4 equivalents, 0.08 equivalents to 0.35 equivalents, 0.08 equivalents to 0.3 equivalents, 0.08 equivalents to 0.25 equivalents, 0.08 equivalents to 0.2 equivalents, 0.08 equivalents to 0. 0.08 equiv to 0.19 equiv, 0.08 equiv to 0.18 equiv, 0.08 equiv to 0.17 equiv, 0.08 equiv to 0.16 equiv, 0.08 equiv to 0.15 equiv, 0.08 equiv to 0.14 equiv, 0.08 equiv to 0.13 equiv, 0.08 equiv to 0.12 equiv, 0.08 equiv to 0.11 equiv, 0.08 equiv to 0.1 equiv, 0.09 equiv to 0.9 equiv, 0.09 equiv to 0.8 equiv, 0.09 equiv to 0.7 equiv, 0.09 equiv to 0.6 equiv, 0.09 equiv to 0.5 equiv, 0.09 equiv to 0.45 equiv, 0.09 equiv to 0.4 0.09 equivalents to 0.15 equivalents, 0.09 equivalents to 0.16 equivalents, 0.09 equivalents to 0.17 equivalents, 0.09 equivalents to 0.18 equivalents, 0.09 equivalents to 0.19 equivalents, 0.09 equivalents to 0.18 equivalents, 0.09 equivalents to 0.19 equivalents, 0.09 equivalents to 0.19 equivalents, 0.09 equivalents to 0.18 equivalents, 0.09 equivalents to 0.18 equivalents, 0.09 equivalents to 0.19 equivalents, 0.09 equivalents to 0.11 equivalents, 0.09 equivalents to 0.15 equivalents, 0.09 equivalents to 0.15 equivalents, 0.09 equivalents to 0.16 ... 0.1 equiv to 0.7 equiv, 0.1 equiv to 0.6 equiv, 0.1 equiv to 0.5 equiv, 0.1 equiv to 0.45 equiv, 0.1 equiv to 0.4 equiv, 0.1 equiv to 0.35 equiv, 0.1 equiv to 0.3 equiv, 0.1 equiv to 0.25 equiv, 0.1 equiv to 0.2 equiv, 0.1 equiv to 0.19 equiv, 0.1 equiv to 0.18 equiv, 0.1 equiv to 0.17 equiv, 0.1 equiv to 0.16 equiv, 0.1 equiv to 0.15 equiv, 0.1 equiv to 0.14 equiv, 0.1 equiv to 0.13 equiv, 0.1 equiv to 0.12 equiv, or 0.1 equiv to 0.11 equiv).

[0057] In certain embodiments, the total amount of ethylenically unsaturated acylating agent added during the methods described herein for preparing a free radical functionalized PIBSA product can be from 0.5 equivalents to 3 equivalents (such as from 0.5 equivalents to 2.9 equivalents, 0.5 equivalents to 2.8 equivalents, 0.5 equivalents to 2.7 equivalents, 0.5 equivalents to 2.6 equivalents, 0.5 equivalents to 2.5 equivalents, 0.5 equivalents to 2.4 equivalents, 0.5 equivalents to 2.3 equivalents, 0.5 equivalents to 2.4 equivalents, 0.5 equivalents to 2.3 equivalents, 0.5 equivalents to 2.2 equivalents, 0.5 equivalents to 2.1 equivalents, 0.5 equivalents to 2 equivalents, 0.5 equivalents to 1.9 equivalents, 0.5 equivalents to 1.8 ... 0.5 equivalents to 1.7 equivalents, 0.5 equivalents to 1.6 equivalents, 0.5 equivalents to 1.5 equivalents, 0.5 equivalents to 1.4 equivalents, 0.5 equivalents to 1.3 equivalents, 0.5 equivalents to 1.2 equivalents, 0.5 equivalents to 1.1 equivalents, 0.5 equivalents to 1 equivalent, 0.6 equivalents to 3 equivalents, 0.6 equivalents to 2.9 equivalents, 0.6 equivalents to 2.8 equivalents, 0.6 equivalents to 2.7 equivalents, 0.6 equivalents to 2.6 equivalents, 0.6 equivalents to 2.5 equivalents, 0.6 equivalents to 2.4 equivalents, 0.6 equivalents to 2.3 equivalents, 0.6 equivalents to 2.4 equivalents, 0.6 equivalents to 2.3 equivalents, 0.6 equivalents to 2.2 equivalents, 0.6 equivalents to 2.1 equivalents, 0.6 equivalents to 2 equivalents, 0.6 equivalents to 1 .9 equivalents, 0.6 equivalents to 1.8 equivalents, 0.6 equivalents to 1.7 equivalents, 0.6 equivalents to 1.6 equivalents, 0.6 equivalents to 1.5 equivalents, 0.6 equivalents to 1.4 equivalents, 0.6 equivalents to 1.3 equivalents, 0.6 equivalents to 1.2 equivalents, 0.6 equivalents to 1.1 equivalents, 0.6 equivalents to 1 equivalent, 0.7 equivalents to 3 equivalents, 0.7 equivalents 0.7 equivalents to 2.9 equivalents, 0.7 equivalents to 2.8 equivalents, 0.7 equivalents to 2.7 equivalents, 0.7 equivalents to 2.6 equivalents, 0.7 equivalents to 2.5 equivalents, 0.7 equivalents to 2.4 equivalents, 0.7 equivalents to 2.3 equivalents, 0.7 equivalents to 2.4 equivalents, 0.7 equivalents to 2.3 equivalents, 0.7 equivalents to 2.2 equivalents, 0.7 equivalents to 2.1 equivalent, 0.7 equivalent to 2 equivalents, 0.7 equivalent to 1.9 equivalents, 0.7 equivalent to 1.8 equivalents, 0.7 equivalent to 1.7 equivalents, 0.7 equivalent to 1.6 equivalents, 0.7 equivalent to 1.5 equivalents, 0.7 equivalent to 1.4 equivalents, 0.7 equivalent to 1.3 equivalents, 0.7 equivalent to 1.2 equivalents, 0.7 equivalent to 1.1 equivalents, 0.7 equivalent to 1. to 1 equivalent, 0.8 equivalent to 3 equivalents, 0.8 equivalent to 2.9 equivalents, 0.8 equivalent to 2.8 equivalents, 0.8 equivalent to 2.7 equivalents, 0.8 equivalent to 2.6 equivalents, 0.8 equivalent to 2.5 equivalents, 0.8 equivalent to 2.4 equivalents, 0.8 equivalent to 2.3 equivalents, 0.8 equivalent to 2.4 equivalents, 0.8 equivalent to 2.3 equivalents, 0.8 equivalents to 2.2 equivalents, 0.8 equivalents to 2.1 equivalents, 0.8 equivalents to 2 equivalents, 0.8 equivalents to 1.9 equivalents, 0.8 equivalents to 1.8 equivalents, 0.8 equivalents to 1.7 equivalents, 0.8 equivalents to 1.6 equivalents, 0.8 equivalents to 1.5 equivalents, 0.8 equivalents to 1.4 equivalents, 0.8 equivalents to 1.3 equivalents, 0.8 equivalents to 1.2 equivalent, 0.8 equivalent to 1.1 equivalent, 0.8 equivalent to 1 equivalent, 0.9 equivalent to 3 equivalent, 0.9 equivalent to 2.9 equivalent, 0.9 equivalent to 2.8 equivalent, 0.9 equivalent to 2.7 equivalent, 0.9 equivalent to 2.6 equivalent, 0.9 equivalent to 2.5 equivalent, 0.9 equivalent to 2.4 equivalent, 0.9 equivalent to 2.3 equivalent, 0.9 equivalent to 2.2 equivalents, 0.9 equivalents to 2.1 equivalents, 0.9 equivalents to 2 equivalents, 0.9 equivalents to 1.9 equivalents, 0.9 equivalents to 1.8 equivalents, 0.9 equivalents to 1.7 equivalents, 0.9 equivalents to 1.6 equivalents, 0.9 equivalents to 1.5 equivalents, 0.9 equivalents to 1.4 equivalents, 0.9 equivalents to 1.3 equivalents, 0.9 equivalents to 1.2 equivalents, 0. .9 equivalents to 1.1 equivalents, 0.9 equivalents to 1 equivalent, 1 equivalent to 3 equivalents, 1 equivalent to 2.9 equivalents, 1 equivalent to 2.8 equivalents, 1 equivalent to 2.7 equivalents, 1 equivalent to 2.6 equivalents, 1 equivalent to 2.5 equivalents, 1 equivalent to 2.4 equivalents, 1 equivalent to 2.3 equivalents, 1 equivalent to 2.2 equivalents, 1 equivalent to 2.1 equivalents, 1 equivalent to 2 equivalents , 1 equivalent to 1.9 equivalents, 1 equivalent to 1.8 equivalents, 1 equivalent to 1.7 equivalents, 1 equivalent to 1.6 equivalents, 1 equivalent to 1.5 equivalents, 1 equivalent to 1.4 equivalents, 1 equivalent to 1.3 equivalents, 1 equivalent to 1.2 equivalents, 1 equivalent to 1.1 equivalents, 1.1 equivalents to 3 equivalents, 1.1 equivalents to 2.9 equivalents, 1.1 equivalents to 2.8 equivalents , 1.1 equivalents to 2.7 equivalents, 1.1 equivalents to 2.6 equivalents, 1.1 equivalents to 2.5 equivalents, 1.1 equivalents to 2.4 equivalents, 1.1 equivalents to 2.3 equivalents, 1.1 equivalents to 2.2 equivalents, 1.1 equivalents to 2.1 equivalents, 1.1 equivalents to 2 equivalents, 1.1 equivalents to 1.9 equivalents, 1.1 equivalents to 1.8 equivalents, 1.1 equivalents to 1.7 equivalents, 1.1 equivalents to 1.6 equivalents, 1.1 equivalents to 1.5 equivalents, 1.1 equivalents to 1.4 equivalents, 1.1 equivalents to 1.3 equivalents, 1.1 equivalents to 1.2 equivalents, 1.2 equivalents to 3 equivalents, 1.2 equivalents to 2.9 equivalents, 1.2 equivalents to 2.8 equivalents, 1.2 equivalents to 2.7 equivalents, 1.2 equivalents to 2.6 equivalents, 1 .2 equivalents to 2.5 equivalents, 1.2 equivalents to 2.4 equivalents, 1.2 equivalents to 2.3 equivalents, 1.2 equivalents to 2.2 equivalents, 1.2 equivalents to 2.1 equivalents, 1.2 equivalents to 2 equivalents, 1.2 equivalents to 1.9 equivalents, 1.2 equivalents to 1.8 equivalents, 1.2 equivalents to 1.7 equivalents, 1.2 equivalents to 1.6 equivalents, 1.2 equivalents to 1.5 equivalents, 1.2 equivalents to 1.4 equivalents, 1.2 equivalents to 1.3 equivalents, 1.3 equivalents to 3 equivalents, 1.3 equivalents to 2.9 equivalents, 1.3 equivalents to 2.8 equivalents, 1.3 equivalents to 2.7 equivalents, 1.3 equivalents to 2.6 equivalents, 1.3 equivalents to 2.5 equivalents, 1.3 equivalents to 2.4 equivalents, 1.3 equivalents to 2.3 equivalents, 1. 3 equivalents to 2.2 equivalents, 1.3 equivalents to 2.1 equivalents, 1.3 equivalents to 2 equivalents, 1.3 equivalents to 1.9 equivalents, 1.3 equivalents to 1.8 equivalents, 1.3 equivalents to 1.7 equivalents, 1.3 equivalents to 1.6 equivalents, 1.3 equivalents to 1.5 equivalents, 1.3 equivalents to 1.4 equivalents, 1.4 equivalents to 3 equivalents, 1.4 equivalents to 2.9 equivalents , 1.4 equivalents to 2.8 equivalents, 1.4 equivalents to 2.7 equivalents, 1.4 equivalents to 2.6 equivalents, 1.4 equivalents to 2.5 equivalents, 1.4 equivalents to 2.4 equivalents, 1.4 equivalents to 2.3 equivalents, 1.4 equivalents to 2.2 equivalents, 1.4 equivalents to 2.1 equivalents, 1.4 equivalents to 2 equivalents, 1.4 equivalents to 1.9 equivalents, 1.4 equivalents to 1.8 equivalents, 1.4 equivalents to 1.7 equivalents, 1.4 equivalents to 1.6 equivalents, 1.4 equivalents to 1.5 equivalents, 1.5 equivalents to 3 equivalents, 1.5 equivalents to 2.9 equivalents, 1.5 equivalents to 2.8 equivalents, 1.5 equivalents to 2.7 equivalents, 1.5 equivalents to 2.6 equivalents, 1.5 equivalents to 2.5 equivalents, 1.5 equivalents to 2.4 equivalents, 1 .5 equivalents to 2.3 equivalents, 1.5 equivalents to 2.2 equivalents, 1.5 equivalents to 2.1 equivalents, 1.5 equivalents to 2 equivalents, 1.5 equivalents to 1.9 equivalents, 1.5 equivalents to 1.8 equivalents, 1.5 equivalents to 1.7 equivalents, 1.5 equivalents to 1.6 equivalents, 1.6 equivalents to 3 equivalents, 1.6 equivalents to 2.9 equivalents, 1.6 equivalents to 2.8 equivalents, 1.6 equivalents to 2.7 equivalents, 1.6 equivalents to 2.6 equivalents, 1.6 equivalents to 2.5 equivalents, 1.6 equivalents to 2.4 equivalents, 1.6 equivalents to 2.3 equivalents, 1.6 equivalents to 2.2 equivalents, 1.6 equivalents to 2.1 equivalents, 1.6 equivalents to 2 equivalents, 1.6 equivalents to 1.9 equivalents, 1.6 equivalents to 1.8 equivalents, 1.6 equivalents to 2. 1.7 equivalents to 1.7 equivalents, 1.7 equivalents to 3 equivalents, 1.7 equivalents to 2.9 equivalents, 1.7 equivalents to 2.8 equivalents, 1.7 equivalents to 2.7 equivalents, 1.7 equivalents to 2.6 equivalents, 1.7 equivalents to 2.5 equivalents, 1.7 equivalents to 2.4 equivalents, 1.7 equivalents to 2.3 equivalents, 1.7 equivalents to 2.2 equivalents, 1.7 equivalents to 2.1 equivalents , 1.7 equivalents to 2 equivalents, 1.7 equivalents to 1.9 equivalents, 1.7 equivalents to 1.8 equivalents, 1.8 equivalents to 3 equivalents, 1.8 equivalents to 2.9 equivalents, 1.8 equivalents to 2.8 equivalents, 1.8 equivalents to 2.7 equivalents, 1.8 equivalents to 2.6 equivalents, 1.8 equivalents to 2.5 equivalents, 1.8 equivalents to 2.4 equivalents, 1.8 equivalents to 2.3 equivalents, 1.8 equivalents to 2.2 equivalents, 1.8 equivalents to 2.1 equivalents, 1.8 equivalents to 2 equivalents, 1.8 equivalents to 1.9 equivalents, 1.9 equivalents to 3 equivalents, 1.9 equivalents to 2.9 equivalents, 1.9 equivalents to 2.8 equivalents, 1.9 equivalents to 2.7 equivalents, 1.9 equivalents to 2.6 equivalents, 1.9 equivalents to 2.5 equivalents, 1.9 equivalents to 2.4 equivalents, 1.9 equivalents to 2.3 equivalents, 1.9 equivalents to 2.2 equivalents, 1.9 equivalents to 2.1 equivalents, 1.9 2 equivalents to 2 equivalents, 2 equivalents to 3 equivalents, 2 equivalents to 2.9 equivalents, 2 equivalents to 2.8 equivalents, 2 equivalents to 2.7 equivalents, 2 equivalents to 2.6 equivalents, 2 equivalents to 2.5 equivalents, 2 equivalents to 2.4 equivalents, 2 equivalents to 2.3 equivalents, 2 equivalents to 2.2 equivalents, 2 equivalents to 2.1 equivalents, 2.1 equivalents to 3 equivalents, 2.1 equivalents to 2.9 equivalents, 2.1 equivalents to 2.8 equivalents, 2.1 equivalents to 2.7 equivalents, 2.1 equivalents to 2.6 equivalents, 2.1 equivalents to 2.5 Equivalent, 2.1 equivalents to 2.4 equivalents, 2.1 equivalents to 2.3 equivalents, 2.1 equivalents to 2.2 equivalents, 2.2 equivalents to 3 equivalents, 2.2 equivalents to 2.9 equivalents, 2.2 equivalents to 2.8 equivalents, 2.2 equivalents to 2.7 equivalents, 2.2 equivalents to 2.6 equivalents, 2.2 equivalents to 2.5 equivalents, 2.2 equivalents to 2.4 equivalents, 2.2 equivalents to 2.3 equivalents, 2.3 equivalents to 3 equivalents, 2.3 equivalents to 2.9 equivalents, 2.3 equivalents to 2.8 equivalents, 2.3 equivalents to 2.7 equivalents, 2.3 equivalents to 2.6 equivalents, 2.3 equivalents to 2.5 equivalents, 2.3 equivalents to 2.4 equivalents, 2.4 equivalents to 3 equivalents, 2.4 equivalents to 2.9 equivalents, 2.4 equivalents to 2.8 equivalents, 2.4 equivalents to 2.7 equivalents, 2.4 equivalents to 2.6 equivalents, 2.4 equivalents to 2.5 equivalents, 2.5 equivalents to 3 equivalents, 2.5 equivalents to 2.9 equivalents, 2.5 equivalents to 2.8 equivalents, 2.5 equivalents to 2.7 equivalents, or 2.5 equivalents to 2.6 equivalents).

[0058] In certain embodiments, the free radical functionalized PIBSA product comprises less than 15 wt %, such as less than 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 wt % of material comprising two or more polyisobutylene units linked by one or more acylating agent units. In certain embodiments, the free radical functionalized PIBSA product is substantially free of material comprising two or more polyisobutylene units linked by one or more acylating agent units. In certain embodiments, the free radical functionalized PIBSA product comprises from 0 wt %, such as greater than 0 wt %, to 15 wt %, such as 14 wt %, 13 wt %, 12 wt %, 11 wt %, 10 wt %, 9 wt %, 8 wt %, 7 wt %, 6 wt %, 5 wt %, 4.5 wt %, 4 wt %, 3.5 wt %, 3 wt %, 2.5 wt %, 2 wt %, 1.9 wt %, 1.8 wt %, 1.7 wt %, 1.6 wt %, 1.5 wt %, 1.4 wt %, 1.3 wt %, 1.2 wt %, 1.1 wt %, 1 wt %, 0.9 wt %, 0.8 wt %, 0.7 wt %, 0.6 wt %, 0.5 wt %, 0.4 wt %, 0.3 wt %, 0.2 wt %, or 0.1 wt % of material comprising two or more polyisobutylene units linked by one or more acylating agent units. In certain embodiments, the free radical functionalized PIBSA product comprises 0 wt % to 15 wt % (such as 0 wt % to 14 wt %, 0 wt % to 13 wt %, 0 wt % to 12 wt %, 0 wt % to 11 wt %, 0 wt % to 10 wt %, 0 wt % to 9 wt %, 0 wt % to 8 wt %, 0 wt % to 7 wt %, 0 wt % to 6 wt %, 0 wt % to 5 wt %, 0 wt % to 4.5 wt %, 0 wt % to 4 wt %, 0 wt % to 5 wt %. % to 3.5 wt %, 0 wt % to 3 wt %, 0 wt % to 2.5 wt %, 0 wt % to 2 wt %, 0 wt % to 1.9 wt %, 0 wt % to 1.8 wt %, 0 wt % to 1.7 wt %, 0 wt % to 1.6 wt %, 0 wt % to 1.5 wt %, 0 wt % to 1.4 wt %, 0 wt % to 1.3 wt %, 0 wt % to 1.2 wt %, 0 wt % to 1.1 wt %, 0 wt % to 1 wt %, 0 wt % to 0.9 wt %, 0 wt % to 0.8 wt %, 0 wt % to 0.7 wt %, 0 wt % to 0.6 wt %, 0 wt % to 0.5 wt %, 0 wt % to 0.4 wt %, 0 wt % to 0.3 wt %, 0 wt % to 0.2 wt %, 0 wt % to 0.1 wt %, greater than 0 wt % to 15 wt %, greater than 0 wt % to 14 wt %, greater than 0 wt % to 13 wt %, greater than 0 wt % to 12 wt %, greater than 0 wt % to 11 wt %, greater than 0 wt % to 10 wt %, greater than 0 wt % to 9 wt %, greater than 0 wt % to 8 wt %, greater than 0 wt % to 7 wt %, greater than 0 wt % to 6 wt %, greater than 0 wt % to 5 wt %, greater than 0 wt % to 4.5 wt %. %, greater than 0 wt % to 4 wt %, greater than 0 wt % to 3.5 wt %, greater than 0 wt % to 3 wt %, greater than 0 wt % to 2.5 wt %, greater than 0 wt % to 2 wt %, greater than 0 wt % to 1.9 wt %, greater than 0 wt % to 1.8 wt %, greater than 0 wt % to 1.7 wt %, greater than 0 wt % to 1.6 wt %, greater than 0 wt % to 1.5 wt %, greater than 0 wt % to 1.4 wt %, greater than 0 wt % to 1.3 wt %, greater than 0 wt % to 1.2 wt %, greater than 0 wt % to 1.1 wt %, greater than 0 wt % to 1 wt %, greater than 0 wt % to 0.9 wt %, greater than 0 wt % to 0.8 wt %, greater than 0 wt % to 0.7 wt %, greater than 0 % to 0.6 wt%, greater than 0 wt% to 0.5 wt%, greater than 0 wt% to 0.4 wt%, greater than 0 wt% to 0.3 wt%, greater than 0 wt% to 0.2 wt%, greater than 0 wt% to 0.1 wt%, 0.1 wt% to 15 wt%, 0.1 wt% to 14 wt%, 0.1 wt% to 13 wt%, 0.1 wt% to 12 wt%, 0.1 wt% to 11 wt%, 0.1 wt% to 10 wt%, 0.1 wt% to 9 wt%, 0.1 wt% to 8 wt%, 0.1 wt% to 7 wt%, 0.1 wt% to 6 wt%, 0.1 wt% to 5 wt%, 0.1 wt% to 4.5 wt%, 0.1 wt% to 4 wt%, 0.1 wt% to 5 wt%. % to 3.5 wt %, 0.1 wt % to 3 wt %, 0.1 wt % to 2.5 wt %, 0.1 wt % to 2 wt %, 0.1 wt % to 1.9 wt %, 0.1 wt % to 1.8 wt %, 0.1 wt % to 1.7 wt %, 0.1 wt % to 1.6 wt %, 0.1 wt % to 1.5 wt %, 0.1 wt % to 1.4 wt %, 0.1 wt % to 1.3 wt %, 0.1 wt % to 1.2 wt %, 0.1 wt % to 1.1 wt %, 0.1 wt % to 1 wt %, 0.1 wt % to 0.9 wt %, 0.1 wt % to 0.8 wt %, 0.1 wt % to 0.7 wt %, 0.1 wt % to 0.6 wt %, 0.1 wt % to 0.5 wt %, 0.1 wt % to 0.4 wt %, 0.1 wt % to 0.3 wt %, 0.1 wt % to 0.2 wt %, 0.2 wt % to 15 wt %, 0.2 wt % to 14 wt %, 0.2 wt % to 13 wt %, 0.2 wt % to 12 wt %, 0.2 wt % to 11 wt %, 0.2 wt % to 10 wt %, 0.2 wt % to 9 wt %, 0.2 wt % to 8 wt %, 0.2 wt % to 7 wt %, 0.2 wt % to 6 wt %, 0.2 wt % to 5 wt %, 0.2 wt % to 4.5 wt %, 0.2 wt % to 4 wt %, 0.2 wt % to 3.5 wt %, 0.2 wt % to 3 wt %, 0.2 wt % to 2.5 % by weight, 0.2 wt % to 2 wt %, 0.2 wt % to 1.9 wt %, 0.2 wt % to 1.8 wt %, 0.2 wt % to 1.7 wt %, 0.2 wt % to 1.6 wt %, 0.2 wt % to 1.5 wt %, 0.2 wt % to 1.4 wt %, 0.2 wt % to 1.3 wt %, 0.2 wt % to 1.2 wt %, 0.2 wt % to 1.1 wt %, 0.2 wt % to 1 wt %, 0.2 wt % to 0.9 wt %, 0.2 wt % to 0.8 wt %, 0.2 wt % to 0.7 wt %, 0.2 wt % to 0.6 wt %, 0.2 wt % to 0.5 wt %, 0.2 wt % to 0.4 wt %, 0.2 wt % to 0.3 %, 0.3 wt % to 15 wt %, 0.3 wt % to 14 wt %, 0.3 wt % to 13 wt %, 0.3 wt % to 12 wt %, 0.3 wt % to 11 wt %, 0.3 wt % to 10 wt %, 0.3 wt % to 9 wt %, 0.3 wt % to 8 wt %, 0.3 wt % to 7 wt %, 0.3 wt % to 6 wt %, 0.3 wt % to 5 wt %, 0.3 wt % to 4.5 wt %, 0.3 wt % to 4 wt %, 0.3 wt % to 3.5 wt %, 0.3 wt % to 3 wt %, 0.3 wt % to 2.5 wt %, 0.3 wt % to 2 wt %, 0.3 wt % to 1.9 wt %, 0.3 wt % to 1.8 wt %, 0.3 wt % to 1.7 wt %, 0.3 wt % to 1.6 wt %, 0.3 wt % to 1.5 wt %, 0.3 wt % to 1.4 wt %, 0.3 wt % to 1.3 wt %, 0.3 wt % to 1.2 wt %, 0.3 wt % to 1.1 wt %, 0.3 wt % to 1 wt %, 0.3 wt % to 0.9 wt %, 0.3 wt % to 0.8 wt %, 0.3 wt % to 0.7 wt %, 0.3 wt % to 0.6 wt %, 0.3 wt % to 0.5 wt %, 0.3 wt % to 0.4 wt %, 0.4 wt % to 15 wt %, 0.4 wt % to 14 wt %, 0.4 wt % to 13 wt %, 0.4 wt % to 12 wt %, 0.4 wt % to 11 wt %, 0.4 wt % to 10 wt %, 0.4 wt % to 9 wt %, 0.4 wt % to 8 wt %, 0.4 wt % to 7 wt %, 0.4 wt % to 6 wt %, 0.4 wt % to 5 wt %, 0.4 wt % to 4.5 wt %, 0.4 wt % to 4 wt %, 0.4 wt % to 3.5 wt %, 0.4 wt % to 3 wt %, 0.4 wt % to 2.5 wt %, 0.4 wt % to 2 wt %, 0.4 wt % to 1.9 wt %, 0.4 wt % to 1.8 wt %, 0.4 wt % to 1.7 wt %, 0.4 wt % to 1.6 wt %, 0.4 wt % to 1.5 wt %, 0.4 wt % to 1.4 wt %, 0.4 % to 1.3 wt%, 0.4 wt% to 1.2 wt%, 0.4 wt% to 1.1 wt%, 0.4 wt% to 1 wt%, 0.4 wt% to 0.9 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.7 wt%, 0.4 wt% to 0.6 wt%, 0.4 wt% to 0.5 wt%, 0.5 wt% to 15 wt%, 0.5 wt% to 14 wt%, 0.5 wt% to 13 wt%, 0.5 wt% to 12 wt%, 0.5 wt% to 11 wt%, 0.5 wt% to 10 wt%, 0.5 wt% to 9 wt%, 0.5 wt% to 8 wt%, 0.5 wt% to 7 wt%, 0.5 wt% to 6 wt%, 0.5 % to 5 wt%, 0.5 wt% to 4.5 wt%, 0.5 wt% to 4 wt%, 0.5 wt% to 3.5 wt%, 0.5 wt% to 3 wt%, 0.5 wt% to 2.5 wt%, 0.5 wt% to 2 wt%, 0.5 wt% to 1.9 wt%, 0.5 wt% to 1.8 wt%, 0.5 wt% to 1.7 wt%, 0.5 wt% to 1.6 wt%, 0.5 wt% to 1.5 wt%, 0.5 wt% to 1.4 wt%, 0.5 wt% to 1.3 wt%, 0.5 wt% to 1.2 wt%, 0.5 wt% to 1.1 wt%, 0.5 wt% to 1 wt%, 0.5 wt% to 0.9 wt%, 0.5 wt% to 0.8 %, 0.5 wt % to 0.7 wt %, 0.5 wt % to 0.6 wt %, 0.6 wt % to 15 wt %, 0.6 wt % to 14 wt %, 0.6 wt % to 13 wt %, 0.6 wt % to 12 wt %, 0.6 wt % to 11 wt %, 0.6 wt % to 10 wt %, 0.6 wt % to 9 wt %, 0.6 wt % to 8 wt %, 0.6 wt % to 7 wt %, 0.6 wt % to 6 wt %, 0.6 wt % to 5 wt %, 0.6 wt % to 4.5 wt %, 0.6 wt % to 4 wt %, 0.6 wt % to 3.5 wt %, 0.6 wt % to 3 wt %, 0.6 wt % to 2.5 wt %, 0.6 wt % to 2 wt %, 0.% to 1.9 wt %, 0.6 wt % to 1.8 wt %, 0.6 wt % to 1.7 wt %, 0.6 wt % to 1.6 wt %, 0.6 wt % to 1.5 wt %, 0.6 wt % to 1.4 wt %, 0.6 wt % to 1.3 wt %, 0.6 wt % to 1.2 wt %, 0.6 wt % to 1.1 wt %, 0.6 wt % to 1 wt %, 0.6 wt % to 0.9 wt %, 0.6 wt % to 0.8 wt %, 0.6 wt % to 0.7 wt %, 0.7 wt % to 15 wt %, 0.7 wt % to 14 wt %, 0.7 wt % to 13 wt %, 0.7 wt % to 12 wt %, 0.7 wt % to 11 wt %, 0.7 wt % to 1 % to 10 wt %, 0.7 wt % to 9 wt %, 0.7 wt % to 8 wt %, 0.7 wt % to 7 wt %, 0.7 wt % to 6 wt %, 0.7 wt % to 5 wt %, 0.7 wt % to 4.5 wt %, 0.7 wt % to 4 wt %, 0.7 wt % to 3.5 wt %, 0.7 wt % to 3 wt %, 0.7 wt % to 2.5 wt %, 0.7 wt % to 2 wt %, 0.7 wt % to 1.9 wt %, 0.7 wt % to 1.8 wt %, 0.7 wt % to 1.7 wt %, 0.7 wt % to 1.6 wt %, 0.7 wt % to 1.5 wt %, 0.7 wt % to 1.4 wt %, 0.7 wt % to 1.3 wt %, 0.7 wt % to 1.9 wt %, % to 1.2 wt %, 0.7 wt % to 1.1 wt %, 0.7 wt % to 1 wt %, 0.7 wt % to 0.9 wt %, 0.7 wt % to 0.8 wt %, 0.8 wt % to 15 wt %, 0.8 wt % to 14 wt %, 0.8 wt % to 13 wt %, 0.8 wt % to 12 wt %, 0.8 wt % to 11 wt %, 0.8 wt % to 10 wt %, 0.8 wt % to 9 wt %, 0.8 wt % to 8 wt %, 0.8 wt % to 7 wt %, 0.8 wt % to 6 wt %, 0.8 wt % to 5 wt %, 0.8 wt % to 4.5 wt %, 0.8 wt % to 4.5 wt %, 0.8 wt % to 3.5 wt %, 0.8 wt % to 3 %, 0.8 wt % to 2.5 wt %, 0.8 wt % to 2 wt %, 0.8 wt % to 1.9 wt %, 0.8 wt % to 1.8 wt %, 0.8 wt % to 1.7 wt %, 0.8 wt % to 1.6 wt %, 0.8 wt % to 1.5 wt %, 0.8 wt % to 1.4 wt %, 0.8 wt % to 1.3 wt %, 0.8 wt % to 1.2 wt %, 0.8 wt % to 1.1 wt %, 0.8 wt % to 1 wt %, 0.8 wt % to 0.9 wt %, 0.9 wt % to 15 wt %, 0.9 wt % to 14 wt %, 0.9 wt % to 13 wt %, 0.9 wt % to 12 wt %, 0.9 wt % to 11 wt %, 0.9 wt % to 10 wt %, 0.9 wt % to 9 wt %, 0.9 wt % to 8 wt %, 0.9 wt % to 7 wt %, 0.9 wt % to 6 wt %, 0.9 wt % to 5 wt %, 0.9 wt % to 4.5 wt %, 0.9 wt % to 4 wt %, 0.9 wt % to 3.5 wt %, 0.9 wt % to 3 wt %, 0.9 wt % to 2.5 wt %, 0.9 wt % to 2 wt %, 0.9 wt % to 1.9 wt %, 0.9 wt % to 1.8 wt %, 0.9 wt % to 1.7 wt %, 0.9 wt % to 1.6 wt %, 0.9 wt % to 1.5 wt %, 0.9 wt % to 1.4 wt %, 0.9 wt % to 1.3 wt %, 0.9 wt % to 1.5 wt %, 9 wt % to 1.2 wt %, 0.9 wt % to 1.1 wt %, 0.9 wt % to 1 wt %, 1 wt % to 15 wt %, 1 wt % to 14 wt %, 1 wt % to 13 wt %, 1 wt % to 12 wt %, 1 wt % to 11 wt %, 1 wt % to 10 wt %, 1 wt % to 9 wt %, 1 wt % to 8 wt %, 1 wt % to 7 wt %, 1 wt % to 6 wt %, 1 wt % to 5 wt %, 1 wt % to 4.5 wt %, 1 wt % to 4 wt %, 1 wt % to 3.5 wt %, 1 wt % to 3 wt %, 1 wt % to 2.5 wt %, 1 wt % to 2 wt %, 1 wt % to 1.9 wt %, 1 wt % to 1.8 wt %, 1 wt % to 1.7 wt %, 1 wt % to 1.6 wt %, 1 wt % to 1.5 wt %, 1 wt % to 1.4 wt %, 1 wt % to 1.3 wt %, 1 wt % to 1.2 wt %, 1 wt % to 1.1 wt %, 1.1 wt % to 15 wt %, 1.1 wt % to 14 wt %, 1.1 wt % to 13 wt %, 1.1 wt % to 12 wt %, 1.1 wt % to 11 wt %, 1.1 wt % to 10 wt %, 1.1 wt % to 9 wt %, 1.1 wt % to 8 wt %, 1.1 wt % to 7 wt %, 1.1 wt % to 6 wt %, 1.1 wt % to 5 wt %, 1.1 wt % to 4.5 wt %, 1.1 wt % to 4 wt %, 1.1 wt % % to 15 wt %, 1.2 wt % to 14 wt %, 1.2 wt % to 13 wt %, 1.2 wt % to 12 wt %, 1.2 wt % to 11 wt %, 1.2 wt % to 10 wt %, 1.2 wt % to 9 wt %, 1.1 wt % to 15 wt %, 1.1 wt % to 16 wt %, 1.1 wt % to 17 wt %, 1.1 wt % to 18 wt %, 1.1 wt % to 19 wt %, 1.2 wt % to 20 wt %, 1.2 wt % to 21 wt %, 1.2 wt % to 22 wt %, 1.2 wt % to 23 wt %, 1.2 wt % to 24 wt %, 1.2 wt % to 25 wt %, 1.2 wt % to 26 wt %, 1.2 wt % to 27 wt %, 1.2 wt % to 28 wt %, 1.2 wt % to 29 wt %, 1.2% to 1.2 wt %, 1.2 wt % to 8 wt %, 1.2 wt % to 7 wt %, 1.2 wt % to 6 wt %, 1.2 wt % to 5 wt %, 1.2 wt % to 4.5 wt %, 1.2 wt % to 4 wt %, 1.2 wt % to 3.5 wt %, 1.2 wt % to 3 wt %, 1.2 wt % to 2.5 wt %, 1.2 wt % to 2 wt %, 1.2 wt % to 1.9 wt %, 1.2 wt % to 1.8 wt %, 1.2 wt % to 1.7 wt %, 1.2 wt % to 1.6 wt %, 1.2 wt % to 1.5 wt %, 1.2 wt % to 1.4 wt %, 1.2 wt % to 1.3 wt %, 1.3 wt % to 15 wt %, 1.3 wt % to 14 wt %, 1.2 wt % to 15 wt %, 1.2 wt % to 16 wt %, 1.2 wt % to 17 wt %, 1.2 wt % to 18 wt %, 1.2 wt % to 19 wt %. 3 wt % to 13 wt %, 1.3 wt % to 12 wt %, 1.3 wt % to 11 wt %, 1.3 wt % to 10 wt %, 1.3 wt % to 9 wt %, 1.3 wt % to 8 wt %, 1.3 wt % to 7 wt %, 1.3 wt % to 6 wt %, 1.3 wt % to 5 wt %, 1.3 wt % to 4.5 wt %, 1.3 wt % to 4 wt %, 1.3 wt % to 3.5 wt %, 1.3 wt % to 3 wt %, 1.3 wt % to 2.5 wt %, 1.3 wt % to 2 wt %, 1.3 wt % to 1.9 wt %, 1.3 wt % to 1.8 wt %, 1.3 wt % to 1.7 wt %, 1.3 wt % to 1.6 wt %, 1.3 wt % % to 1.5 wt %, 1.3 wt % to 1.4 wt %, 1.4 wt % to 15 wt %, 1.4 wt % to 14 wt %, 1.4 wt % to 13 wt %, 1.4 wt % to 12 wt %, 1.4 wt % to 11 wt %, 1.4 wt % to 10 wt %, 1.4 wt % to 9 wt %, 1.4 wt % to 8 wt %, 1.4 wt % to 7 wt %, 1.4 wt % to 6 wt %, 1.4 wt % to 5 wt %, 1.4 wt % to 4.5 wt %, 1.4 wt % to 4 wt %, 1.4 wt % to 3.5 wt %, 1.4 wt % to 3 wt %, 1.4 wt % to 2.5 wt %, 1.4 wt % to 2 wt %, 1.4 wt % to 1.9 wt %. %, 1.4 wt % to 1.8 wt %, 1.4 wt % to 1.7 wt %, 1.4 wt % to 1.6 wt %, 1.4 wt % to 1.5 wt %, 1.5 wt % to 15 wt %, 1.5 wt % to 14 wt %, 1.5 wt % to 13 wt %, 1.5 wt % to 12 wt %, 1.5 wt % to 11 wt %, 1.5 wt % to 10 wt %, 1.5 wt % to 9 wt %, 1.5 wt % to 8 wt %, 1.5 wt % to 7 wt %, 1.5 wt % to 6 wt %, 1.5 wt % to 5 wt %, 1.5 wt % to 4.5 wt %, 1.5 wt % to 4.5 wt %, 1.5 wt % to 3 ...% to 15 wt %, 1.6 wt % to 14 wt %, 1.6 wt % to 13 wt %, 1.6 wt % to 12 wt %, 1.6 wt % to 11 wt %, 1.6 wt % to 10 wt %, 1.6 wt % to 9 wt %, 1.6 wt % to 8 wt %, 1.6 wt % to 7 wt %, 1.6 wt % to 6 wt %, 1.6 wt % to 5 wt %, 1.6 wt % to 4.5 wt %, 1.6 wt % to 4.5 wt %, 1.6 wt % to 5.5 wt %, 1.6 wt % to 6.5 wt %, % to 3.5 wt %, 1.6 wt % to 3 wt %, 1.6 wt % to 2.5 wt %, 1.6 wt % to 2 wt %, 1.6 wt % to 1.9 wt %, 1.6 wt % to 1.8 wt %, 1.6 wt % to 1.7 wt %, 1.7 wt % to 15 wt %, 1.7 wt % to 14 wt %, 1.7 wt % to 13 wt %, 1.7 wt % to 12 wt %, 1.7 wt % to 11 wt %, 1.7 wt % to 10 wt %, 1.7 wt % to 9 wt %, 1.7 wt % to 8 wt %, 1.7 wt % to 7 wt %, 1.7 wt % to 6 wt %, 1.7 wt % to 5 wt %, 1.7 wt % to 4.5 wt %, 1.7 wt % % to 4 wt %, 1.7 wt % to 3.5 wt %, 1.7 wt % to 3 wt %, 1.7 wt % to 2.5 wt %, 1.7 wt % to 2 wt %, 1.7 wt % to 1.9 wt %, 1.7 wt % to 1.8 wt %, 1.8 wt % to 15 wt %, 1.8 wt % to 14 wt %, 1.8 wt % to 13 wt %, 1.8 wt % to 12 wt %, 1.8 wt % to 11 wt %, 1.8 wt % to 10 wt %, 1.8 wt % to 9 wt %, 1.8 wt % to 8 wt %, 1.8 wt % to 7 wt %, 1.8 wt % to 6 wt %, 1.8 wt % to 5 wt %, 1.8 wt % to 4.5 wt %, 1.8 wt % to 4. %, 1.8 wt% to 3.5 wt%, 1.8 wt% to 3 wt%, 1.8 wt% to 2.5 wt%, 1.8 wt% to 2 wt%, 1.8 wt% to 1.9 wt%, 1.9 wt% to 15 wt%, 1.9 wt% to 14 wt%, 1.9 wt% to 13 wt%, 1.9 wt% to 12 wt%, 1.9 wt% to 11 wt%, 1.9 wt% to 10 wt%, 1.9 wt% to 9 wt%, 1.9 wt% to 8 wt%, 1.9 wt% to 7 wt%, 1.9 wt% to 6 wt%, 1.9 wt% to 5 wt%, 1.9 wt% to 4.5 wt%, 1.9 wt% to 4 wt%, 1.9 wt% to 3.5 wt%, 1.9 wt% to 4.5 wt%, 1.9 wt% to 3.5 wt%, 1.9 wt% to 5.9 wt % to 3 wt %, 1.9 wt % to 2.5 wt %, 1.9 wt % to 2 wt %, 2 wt % to 15 wt %, 2 wt % to 14 wt %, 2 wt % to 13 wt %, 2 wt % to 12 wt %, 2 wt % to 11 wt %, 2 wt % to 10 wt %, 2 wt % to 9 wt %, 2 wt % to 8 wt %, 2 wt % to 7 wt %, 2 wt % to 6 wt %, 2 wt % to 5 wt %, 2 wt % to 4.5 wt %, 2 wt % to 4 wt %, 2 wt % to 3.5 wt %, 2 wt % to 3 wt %, 2 wt % to 2.5 wt %, 2.5 wt % to 15 wt %, 2.5 wt % to 14 wt %, 2.5 wt % to 1 3 wt %, 2.5 wt % to 12 wt %, 2.5 wt % to 11 wt %, 2.5 wt % to 10 wt %, 2.5 wt % to 9 wt %, 2.5 wt % to 8 wt %, 2.5 wt % to 7 wt %, 2.5 wt % to 6 wt %, 2.5 wt % to 5 wt %, 2.5 wt % to 4.5 wt %, 2.5 wt % to 4 wt %, 2.5 wt % to 3.5 wt %, 2.5 wt % to 3 wt %, 3 wt % to 15 wt %, 3 wt % to 14 wt %, 3 wt % to 13 wt %, 3 wt % to 12 wt %, 3 wt % to 11 wt %, 3 wt % to 10 wt %, 3 wt % to 9 wt %, 3 wt % to 8 wt %, 3 wt % to 7 wt %, 3 wt % to 6 wt %, 3 wt % to 5 wt %, 3 wt % to 4.5 wt %, 3 wt % to 4 wt %, 3 wt % to 3.5 wt %, 3.5 wt % to 15 wt %, 3.5 wt % to 14 wt %, 3.5 wt % to 13 wt %, 3.5 wt % to 12 wt %, 3.5 wt % to 11 wt %, 3.5 wt % to 10 wt %, 3.5 wt % to 9 wt %, 3.5 wt % to 8 wt %, 3.5 wt % to 7 wt %, 3.5 wt % to 6 wt %, 3.5 wt % to 5 wt %, 3.5 wt % to 4.5 wt %, 3.5 wt % to 4.5 wt %, 4 wt % to 15 wt %, 4 wt % to 14 wt %, % to 14 wt %, 4 wt % to 13 wt %, 4 wt % to 12 wt %, 4 wt % to 11 wt %, 4 wt % to 10 wt %, 4 wt % to 9 wt %, 4 wt % to 8 wt %, 4 wt % to 7 wt %, 4 wt % to 6 wt %, 4 wt % to 5 wt %, 4 wt % to 4.5 wt %, 4.5 wt to 15 wt %, 4.5 wt to 14 wt %, 4.5 wt to 13 wt %, 4.5 wt to 12 wt %, 4.5 wt to 11 wt %, 4.5 wt to 10 wt %, 4.5 wt to 9 wt %, 4.5 wt to 8 wt %, 4.5 wt to 7 wt %, 4.5 wt to 6 wt %, 4.5 wt % to 5 wt %, 5 wt % to 15 wt %, 5 wt % to 14 wt %, 5 wt % to 13 wt %, 5 wt % to 12 wt %, 5 wt % to 11 wt %, 5 wt % to 10 wt %, 5 wt % to 9 wt %, 5 wt % to 8 wt %, 5 wt % to 7 wt %, 5 wt % to 6 wt %, 6 wt % to 15 wt %, 6 wt % to 14 wt %, 6 wt % to 13 wt %, 6 wt % to 12 wt %, 6 wt % to 13 wt %, 6 wt % to 12 wt %, 6 wt % to 14 wt %, % to 11 wt %, 6 wt % to 10 wt %, 6 wt % to 9 wt %, 6 wt % to 8 wt %, 6 wt % to 7 wt %, 7 wt % to 15 wt %, 7 wt % to 14 wt %, 7 wt % to 13 wt %, 7 wt % to 12 wt %, 7 wt % to 11 wt %, 7 wt % to 10 wt %, 7 wt % to 9 wt %, 7 wt % to 8 wt %, 8 wt % to 15 wt %, 8 wt % to 14 wt %, 8 wt % to 13 %, 8 wt % to 12 wt %, 8 wt % to 11 wt %, 8 wt % to 10 wt %, 8 wt % to 9 wt %, 9 wt % to 15 wt %, 9 wt % to 14 wt %, 9 wt % to 13 wt %, 9 wt % to 12 wt %, 9 wt % to 11 wt %, 9 wt % to 10 wt %, 10 wt % to 15 wt %, 10 wt % to 14 wt %, 10 wt % to 13 wt %, 10 wt % to 12 wt %, 10 % to 11 wt%, 11 wt% to 15 wt%, 11 wt% to 14 wt%, 11 wt% to 13 wt%, 11 wt% to 12 wt%, 12 wt% to 15 wt%, 12 wt% to 14 wt%, 12 wt% to 13 wt%, 13 wt% to 15 wt%, 13 wt% to 14 wt%, or 14 wt% to 15 wt%) of a material comprising two or more polyisobutylene units linked by one or more acylating agent units.

[0059] In certain embodiments, polyisobutylene comprises an average of at least 4 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 9 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 8 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 3 to 7 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 6 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 5 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 3 to 4 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 12 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 4 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 9 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 8 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 7 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 6 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 4 to 5 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 16 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 5 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 9 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 8 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 7 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 5 to 6 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 18 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 6 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 9 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 8 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 6 to 7 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 18 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 7 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 9 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 7 to 8 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 16 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 8 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 8 to 9 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 9 to 12 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 9 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 10 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 55 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 12 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 12 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 51 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 14 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 14 to 16 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 42 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 16 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 16 to 18 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 30 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 18 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 18 to 20 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 20 to 22 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 54 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 22 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 22 to 24 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 40 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 24 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 28 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 24 to 26 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 26 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 53 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 28 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 32 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 28 to 30 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 30 to 32 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 32 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 36 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 32 to 34 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 34 to 36 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 36 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 36 to 38 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 38 to 40 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 53 isobutylene monomer units per molecule.In certain embodiments, polyisobutylene comprises an average of 40 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 48 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 46 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 44 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 40 to 42 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 42 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 42 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 42 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 44 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 54 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 46 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 46 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 48 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 48 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 48 to 50 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 55 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 54 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 53 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 52 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 50 to 51 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 51 to 56 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 51 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 52 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 53 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 53 to 55 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 53 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 54 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 54 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 55 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 51, 52, 53, 54, 55 or 56 isobutylene monomer units per molecule.

[0060] In certain embodiments, the free radical initiator can be any suitable free radical initiator, and can include an organic peroxide initiator or a peracid initiator.

[0061] In certain embodiments, the organic peroxide initiator comprises diglutaryl, dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di(tert-butyl) peroxide, tert-butyl hydroperoxide, 3,4-dimethyl-3,4-diphenyl-hexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-3,5,5-trimethyl-tert-butyl hexanoate, di(2,4-dichlorobenzoyl) peroxide, di(2-methylbenzoyl) peroxide, or di(4-tert-butylcyclohexyl) peroxydicarbonate. The half-lives of these and other free radical initiators are widely available in the relevant scientific literature.

[0062] In certain embodiments, the ethylenically unsaturated acylating agent comprises at least one monoethylenically unsaturated C3-C 28 Monocarboxylic acid or its ester or at least one C4-C 28 A dicarboxylic acid, an anhydride or an ester thereof.

[0063] In certain embodiments, the ethylenically unsaturated acylating agent may comprise one or more compounds falling within the following general formula:

[0064]

[0065] Wherein X and X' are the same or different, provided that at least one of X and X' is a group that can react to esterify an alcohol, form an amide or amine salt with ammonia or an amine, form a metal salt with a reactive metal or a substantially reactive metal compound and additionally act as an acylating agent. In certain embodiments, X and / or X' is -OH, -O-hydrocarbyl, OM+, where M+ represents one equivalent of a metal, an ammonium or amine cation, -NH2, -Cl, -Br, and / or X and X' together can be -O- to form an anhydride. In certain embodiments, X and X' are such that both carboxyl functional groups can enter into an acylation reaction. Suitable reactants include: maleic anhydride; monophenylmaleic anhydride; monomethylmaleic anhydride, dimethylmaleic anhydride, monochloromaleic anhydride, monobromomaleic anhydride, monofluoromaleic anhydride, dichloromaleic anhydride and difluoromaleic anhydride; N-phenylmaleimide and other substituted maleimides, isomaleimides; fumaric acid, maleic acid, alkyl hydrogen maleates and alkyl hydrogen fumarate esters, dialkyl fumarate esters and dialkyl maleate esters, fumaronilic acid and maleanic acid; and maleonitrile and fumaronitrile.

[0066] In certain embodiments, the monoethylenically unsaturated dicarboxylic acid or anhydride having 3 to 28 carbon atoms may be selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride and mixtures of these with each other.

[0067] In certain embodiments, the monoethylenically unsaturated C3-C 28 - The monocarboxylic acid may be selected from the group consisting of acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, crotonic acid, allyl acetic acid and vinyl acetic acid. Another group of suitable monomers is monoethylenically unsaturated C3-C 10 C1-C 40 Alkyl esters such as ethyl acrylate, butyl acrylate, 2-ethyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate and esters of mixtures of industrial alcohols having 14 to 28 carbon atoms, ethyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octadecyl methacrylate, monobutyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate, monooctadecyl maleate and disoctadecyl maleate.

[0068] In certain embodiments, the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, or methylenemalonic anhydride.

[0069] In certain embodiments, the free radical functionalized PIBSA product comprises at least one compound of the following Formula I:

[0070]

[0071] Among them: Each R 1 independently represents –(CH2)–(C(CH2))–(CH3); H; or absent; wherein when R 1 When not present, a dotted double bond represents a double bond, and when R 1 When present, a dashed double bond represents a single bond; each m is independently an integer from 1 to 52; and each n is independently 0, 1 or 2.

[0072] In certain embodiments, each m is independently 1 to 53, 1 to 52, 1 to 51, 1 to 50, 1 to 49, 1 to 48, 1 to 46, 1 to 44, 1 to 42, 1 to 40, 1 to 38, 1 to 36, 1 to 34, 1 to 32, 1 to 30, 1 to 28, 1 to 26, 1 to 24, 1 to 22, 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 54, 2 to 53, 2 to 52, 2 to 51, 2 to 50, 2 to 49, 2 to 48, 2 to 46, 2 to 44, 2 to 42, 2 to 40, 2 to 38, 2 to 36, 2 to 34, 2 to 32, 2 to 30, 2 to 28, 2 to 26, 2 to 24, 2 to 22, 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 54, 3 to 53, 3 to 52, 3 to 51, 3 to 50, 3 to 49, 3 to 48, 3 to 46, 3 to 44, 3 to 42, 3 to 40, 3 to 38, 3 to 36, 3 to 34, 3 to 32, 3 to 30, 3 to 28, 3 to 26, 3 to 24, 3 to 22, 3 to 20, 3 to 18, 3 to 16, 3 to 14, 3 to 12, 3 to 10, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 54, 4 to 53, 4 to 52, 4 to 51, 4 to 50, 4 to 49,4 to 48,4 to 46,4 to 44,4 to 42,4 to 40,4 to 38,4 to 36,4 to 34,4 to 32,4 to 30,4 to 28,4 to 26,4 to 24,4 to 22,4 to 20,4 to 18,4 to 16,4 to 14,4 to 12,4 to 10,4 to 8,4 to 7,4 to 6,4 to 5,5 to 54, 5 to 53, 5 to 52, 5 to 51, 5 to 50, 5 to 49, 5 to 48, 5 to 46, 5 to 44, 5 to 42, 5 to 40, 5 to 38, 5 to 36, 5 to 34, 5 to 32, 5 to 30, 5 to 28, 5 to 26, 5 to 24, 5 to 22, 5 to 20, 5 to 18, 5 to 16, 5 to 14, 5 to 12, 5 to 10, 5 to 8, 5 to 7, 5 to 6, 6 to 54, 6 to 53, 6 to 52, 6 to 51, 6 to 50, 6 to 49, 6 to 48, 6 to 46, 6 to 44, 6 to 42, 6 to 40, 6 to 38, 6 to 36, 6 to 34, 6 to 32, 6 to 30, 6 to 28, 6 to 26, 6 to 24, 6 to 22, 6 to 20, 6 to 18, 6 to 1 6, 6 to 14, 6 to 12, 6 to 10, 6 to 8, 6 to 7, 7 to 54, 7 to 53, 7 to 52, 7 to 51, 7 to 50, 7 to 49, 7 to 48, 7 to 46, 7 to 44, 7 to 42, 7 to 40, 7 to 38, 7 to 36, 7 to 34, 7 to 32, 7 to 30, 7 to 28, 7 to 26, 7 to 24, 7 to 22,7 to 20, 7 to 18, 7 to 16, 7 to 14, 7 to 12, 7 to 10, 7 to 8, 8 to 54, 8 to 53, 8 to 52, 8 to 51, 8 to 50, 8 to 49, 8 to 48, 8 to 46, 8 to 44, 8 to 42, 8 to 40, 8 to 38, 8 to 36, 8 to 34, 8 to 32, 8 to 30, 8 to 28, 8 to 26, 8 to 24, 8 to 22, 8 to 20, 8 to 18, 8 to 16, 8 to 14, 8 to 12, 8 to 10, 10 to 54, 10 to 53, 10 to 52, 10 to 51, 10 to 50, 10 to 49, 10 to 48, 10 to 46, 10 to 44, 10 to 42, 10 to 40, 10 to 38, 10 to 36, 10 to 34, 1 0 to 32, 10 to 30, 10 to 28, 10 to 26, 10 to 24, 10 to 22, 10 to 20, 10 to 18, 10 to 16, 10 to 14, 10 to 12, 12 to 54, 12 to 53, 12 to 52, 12 to 51, 12 to 50, 12 to 49, 12 to 48, 12 to 46, 12 to 44, 12 to 42, 12 to 40, 12 to 38, 12 to 36, 12 to 34, 12 to 32, 12 to 30, 12 to 28, 12 to 26, 12 to 24, 12 to 22, 12 to 20, 12 to 18, 12 to 16, 12 to 14, 14 to 54, 14 to 53, 14 to 52, 14 to 51, 14 to 50, 14 to 49, 14 to 48 , 14 to 46, 14 to 44, 14 to 42, 14 to 40, 14 to 38, 14 to 36, 14 to 34, 14 to 32, 14 to 30, 14 to 28, 14 to 26, 14 to 24, 14 to 22, 14 to 20, 14 to 18, 14 to 16, 16 to 54, 16 to 53, 16 to 52, 16 to 51, 16 to 50, 16 to 49, 16 to 48, 16 to 46, 16 to 44, 16 to 42, 16 to 40, 16 to 38, 16 to 36, 16 to 34, 16 to 32, 16 to 30, 16 to 28, 16 to 26, 16 to 24, 16 to 22, 16 to 20, 16 to 18, 18 to 54, 18 to 53, 18 to 52, 18 to 51, 18 to 50, 18 to 49, 18 to 48, 18 to 46, 18 to 44, 18 to 42, 18 to 40, 18 to 38, 18 to 36, 18 to 34, 18 to 32, 18 to 30, 18 to 28, 18 to 26, 18 to 24, 18 to 22, 18 to 20, 20 to 54, 20 to 53, 20 to 52, 2 0 to 51, 20 to 50, 20 to 49, 20 to 48, 20 to 46, 20 to 44, 20 to 42, 20 to 40, 20 to 38, 20 to 36, 20 to 34, 20 to 32, 20 to 30, 20 to 28, 20 to 26, 20 to 24, 20 to 22, 22 to 54, 22 to 53, 22 to 52, 22 to 51,22 to 50, 22 to 49, 22 to 48, 22 to 46, 22 to 44, 22 to 42, 22 to 40, 22 to 38, 22 to 36, 22 to 34, 22 to 32, 22 to 30, 22 to 28, 22 to 26, 22 to 24, 24 to 54, 24 to 53, 24 to 52, 24 to 51, 24 to 50, 24 to 4 9, 24 to 48, 24 to 46, 24 to 44, 24 to 42, 24 to 40, 24 to 38, 24 to 36, 24 to 34, 24 to 32, 24 to 30, 24 to 28, 24 to 26, 26 to 54, 26 to 53, 26 to 52, 26 to 51, 26 to 50, 26 to 49, 26 to 48, 26 to 46, 26 to 44, 26 to 42, 26 to 40, 26 to 38, 26 to 36, 26 to 34, 26 to 32, 26 to 30, 26 to 28, 28 to 54, 28 to 53, 28 to 52, 28 to 51, 28 to 50, 28 to 49, 28 to 48, 28 to 46, 28 to 44, 28 to 42, 28 to 40, 28 to 38, 2 8 to 36, 28 to 34, 28 to 32, 28 to 30, 30 to 54, 30 to 53, 30 to 52, 30 to 51, 30 to 50, 30 to 49, 30 to 48, 30 to 46, 30 to 44, 30 to 42, 30 to 40, 30 to 38, 30 to 36, 30 to 34, 30 to 32, 32 to 54, 32 to 53, 32 to 52, 32 to 51, 32 to 50, 32 to 49, 32 to 48, 32 to 46, 32 to 44, 32 to 42, 32 to 40, 32 to 38, 32 to 36, 32 to 34, 34 to 54, 34 to 53, 34 to 52, 34 to 51, 34 to 50, 34 to 49, 34 to 48, 34 to 46, 34 to 4 4, 34 to 42, 34 to 40, 34 to 38, 34 to 36, 36 to 54, 36 to 53, 36 to 52, 36 to 51, 36 to 50, 36 to 49, 36 to 48, 36 to 46, 36 to 44, 36 to 42, 36 to 40, 36 to 38, 38 to 54, 38 to 53, 38 to 52, 38 to 51, 38 to 50, 38 to 49, 38 to 48, 38 to 46, 38 to 44, 38 to 42, 38 to 40, 40 to 54, 40 to 53, 40 to 52, 40 to 51, 40 to 50, 40 to 49, 40 to 48, 40 to 46, 40 to 44, 40 to 42, 42 to 54, 42 to 53, 42 to 52, 42 to 51, 4 2 to 50, 42 to 49, 42 to 48, 42 to 46, 42 to 44, 44 to 54, 44 to 53, 44 to 52, 44 to 51, 44 to 50, 44 to 49, 44 to 48, 44 to 46, 46 to 54, 46 to 53, 46 to 52, 46 to 51, 46 to 50, 46 to 49, 46 to 48, 48 to 54,48 to 53, 48 to 52, 48 to 51, 48 to 50, 48 to 49, 49 to 54, 49 to 53, 49 to 52, 49 to 51, 49 to 50, 50 to 54, 50 to 53, 50 to 52, 50 to 51, 51 to 54, 51 to 53, 51 to 52, 51 to 51, 52 to 54, 52 to 53, or 53 to 54. In certain embodiments, each m is independently 1, 2, 3, 4, 5, 6, 7, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 49, 50, 51, 52, 53, or 54.

[0073] In certain embodiments, the free radical functionalized PIBSA product comprises at least 30 mol % (such as at least 35 mol %, 40 mol %, 45 mol %, 50 mol %, 55 mol %, 60 mol %, 65 mol %, 70 mol %, 75 mol %, 80 mol %, 85 mol %, 90 mol %, 95 mol % or 99 mol %) of at least one compound of Formula I. In certain embodiments, the free radical functionalized PIBSA product comprises 30 mol% to 100 mol% (such as 35 mol% to 100 mol%, 40 mol% to 100 mol%, 45 mol% to 100 mol%, 50 mol% to 100 mol%, 55 mol% to 100 mol%, 60 mol% to 100 mol%, 65 mol% to 100 mol%, 70 mol% to 100 mol%, 75 mol% to 100 mol%, 80 mol% to 100 mol%, 85 mol% to 100 mol%, 90 mol% to 100 mol%, 95 mol% to 100 mol%, 10 ... % to 99mol%, 75mol% to 99mol%, 80mol% to 99mol%, 85mol% to 99mol%, 90mol% to 99mol%, 95mol% to 100mol%, 99mol% to 100mol%, 30mol% to 99mol%, 35mol% to 99mol%, 40mol% to 99mol%, 45mol% to 99mol%, 50mol% to 99mol%, 55mol% to 99mol%, 60mol% to 99mol%, 65mol% to 99mol%, 70mol% to 99mol%, 75mol% to 99mol%, 80mol% to 99mol%, 85mol% to 99mol%, % to 95mol%, 90mol% to 99mol%, 95mol% to 99mol%, 30mol% to 95mol%, 35mol% to 95mol%, 40mol% to 95mol%, 45mol% to 95mol%, 50mol% to 95mol%, 55mol% to 95mol%, 60mol% to 95mol%, 65mol% to 95mol%, 70mol% to 95mol%, 75mol% to 95mol%, 80mol% to 95mol%, 85mol% to 95mol%, 90mol% to 95mol%, % to 90mol%, 30mol% to 90mol%, 35mol% to 90mol%, 40mol% to 90mol%, 45mol% to 90mol%, 50mol% to 90mol%, 55mol% to 90mol%, 60mol% to 90mol%, 65mol% to 90mol%, 70mol% to 90mol%, 75mol% to 90mol%, 80mol% to 90mol%, 85mol% to 90mol%, 30mol% to 85mol%, 35mol% to 85mol%, 40mol% to 85mol%,45 mol% to 85 mol%, 50 mol% to 85 mol%, 55 mol% to 85 mol%, 60 mol% to 85 mol%, 65 mol% to 85 mol%, 70 mol% to 85 mol%, 75 mol% to 85 mol%, 80 mol% to 85 mol%, 30 mol% to 80 mol%, 35 mol% to 80 mol%, 40 mol% to 80 mol%, 45 mol% to 80 mol%, 50 mol% to 80 mol%, 55 mol% to 80 mol%, 60 mol% to 80 mol%, 65 mol% to 80 mol% %, 70 mol% to 80 mol%, 75 mol% to 80 mol%, 30 mol% to 75 mol%, 35 mol% to 75 mol%, 40 mol% to 75 mol%, 45 mol% to 75 mol%, 50 mol% to 75 mol%, 55 mol% to 75 mol%, 60 mol% to 75 mol%, 65 mol% to 75 mol%, 70 mol% to 75 mol%, 30 mol% to 70 mol%, 35 mol% to 70 mol%, 40 mol% to 70 mol%, 45 mol% to 70 mol%, 50 mol% to 70 mol% %, 55 mol% to 70 mol%, 60 mol% to 70 mol%, 65 mol% to 70 mol%, 30 mol% to 65 mol%, 35 mol% to 65 mol%, 40 mol% to 65 mol%, 45 mol% to 65 mol%, 50 mol% to 65 mol%, 55 mol% to 65 mol%, 60 mol% to 65 mol%, 30 mol% to 60 mol%, 35 mol% to 60 mol%, 40 mol% to 60 mol%, 45 mol% to 60 mol%, 50 mol% to 60 mol%, 55 mol% to 60 mol% %, 30 mol% to 55 mol%, 35 mol% to 55 mol%, 40 mol% to 55 mol%, 45 mol% to 55 mol%, 50 mol% to 55 mol%, 30 mol% to 50 mol%, 35 mol% to 50 mol%, 40 mol% to 50 mol%, 45 mol% to 50 mol%, 30 mol% to 45 mol%, 35 mol% to 45 mol%, 40 mol% to 45 mol%, 30 mol% to 40 mol%, 35 mol% to 40 mol% or 30 mol% to 35 mol%) of at least one compound of Formula I. 、

[0074] In certain embodiments, the free radical functionalized PIBSA product comprises less than 40 wt %, such as less than 35 wt %, 30 wt %, 25 wt %, 20 wt %, 15 wt %, 14 wt %, 13 wt %, 12 wt %, 11 wt %, 10 wt %, 9 wt %, 8 wt %, 7 wt %, 6 wt %, 5 wt %, 4 wt %, 3 wt %, 2 wt %, or 1 wt % of unreacted polyisobutylene. In certain embodiments, the free radical functionalized PIBSA product comprises from 0 wt % to 40 wt % (such as from 0 wt % to 35 wt %, from 0 wt % to 30 wt %, from 0 wt % to 25 wt %, from 0 wt % to 20 wt %, from 0 wt % to 15 wt %, from 0 wt % to 14 wt %, from 0 wt % to 13 wt %, from 0 wt % to 12 wt %, from 0 wt % to 11 wt %, from 0 wt % to 10 wt %, from 0 wt % to 9 wt %, from 0 wt % to 8 wt %, from 0 wt % to 7 wt %, from 0 wt % to 6 wt %, from 0 wt % to 5 wt %, from 0 wt % to 4 wt %, from 0 wt % to % to 3 wt %, 0 wt % to 2 wt %, 0 wt % to 1 wt %, greater than 0 wt % to 40 wt %, greater than 0 wt % to 35 wt %, greater than 0 wt % to 30 wt %, greater than 0 wt % to 25 wt %, greater than 0 wt % to 20 wt %, greater than 0 wt % to 15 wt %, greater than 0 wt % to 14 wt %, greater than 0 wt % to 13 wt %, greater than 0 wt % to 12 wt %, greater than 0 wt % to 11 wt %, greater than 0 wt % to 10 wt %, greater than 0 wt % to 9 wt %, greater than 0 wt % to 8 wt %, greater than 0 wt % to 7 wt %, greater than 0 wt % to % to 6 wt %, greater than 0 wt % to 5 wt %, greater than 0 wt % to 4 wt %, greater than 0 wt % to 3 wt %, greater than 0 wt % to 2 wt %, greater than 0 wt % to 1 wt %, greater than 0 wt % to 35 wt %, 1 wt % to 40 wt %, 1 wt % to 35 wt %, 1 wt % to 30 wt %, 1 wt % to 25 wt %, 1 wt % to 20 wt %, 1 wt % to 15 wt %, 1 wt % to 14 wt %, 1 wt % to 13 wt %, 1 wt % to 12 wt %, 1 wt % to 11 wt %, 1 wt % to 10 wt %, 1 wt % to 9 wt %, 1 wt % to 8 wt %, 1 wt % to 7 wt %, 1 wt % to 6 wt %, 1 wt % to 5 wt %, 1 wt % to 4 wt %, 1 wt % to 3 wt %, 1 wt % to 2 wt %, 2 wt % to 40 wt %, 2 wt % to 35 wt %, 2 wt % to 30 wt %, 2 wt % to 25 wt %, 2 wt % to 20 wt %, 2 wt % to 15 wt %, 2 wt % to 14 wt %, 2 wt % to 13 wt %, 2 wt % to 12 wt %, 2 wt % to 11 wt %, 2 wt % to 10 wt %, 2 wt % to 9 wt %, 2 wt % to 8 wt %,2% to 7% by weight, 2% to 6% by weight, 2% to 5% by weight, 2% to 4% by weight, 2% to 3% by weight, 3% to 40% by weight, 3% to 35% by weight, 3% to 30% by weight, 3% to 25% by weight, 3% to 20% by weight, 3% to 15% by weight, 3% to 14% by weight, 3% to 13% by weight, 3% to 12% by weight, 3% to 11% by weight, 3% to 10% by weight, 3% to 9% by weight, 3% to 8% by weight, 3% to 7% by weight, 3% to 6% by weight, 3% to 5% by weight, 3% to 4% by weight, 4% to 40% by weight, 4% to 35% by weight %, 4 to 30 wt %, 4 to 25 wt %, 4 to 20 wt %, 4 to 15 wt %, 4 to 14 wt %, 4 to 13 wt %, 4 to 12 wt %, 4 to 11 wt %, 4 to 10 wt %, 4 to 9 wt %, 4 to 8 wt %, 4 to 7 wt %, 4 to 6 wt %, 4 to 5 wt %, 5 to 40 wt %, 5 to 35 wt %, 5 to 30 wt %, 5 to 25 wt %, 5 to 20 wt %, 5 to 15 wt %, 5 to 14 wt %, 5 to 13 wt %, 5 to 12 wt %, %, 5 wt % to 11 wt %, 5 wt % to 10 wt %, 5 wt % to 9 wt %, 5 wt % to 8 wt %, 5 wt % to 7 wt %, 5 wt % to 6 wt %, 6 wt % to 40 wt %, 6 wt % to 35 wt %, 6 wt % to 30 wt %, 6 wt % to 25 wt %, 6 wt % to 20 wt %, 6 wt % to 15 wt %, 6 wt % to 14 wt %, 6 wt % to 13 wt %, 6 wt % to 12 wt %, 6 wt % to 11 wt %, 6 wt % to 10 wt %, 6 wt % to 9 wt %, 6 wt % to 8 wt %, 6 wt % to 7 wt %, 7 wt % to 40 wt %, 7 wt % to 35 wt %, 7 wt % to 30 wt %, % to 25% by weight, 7% to 20% by weight, 7% to 15% by weight, 7% to 14% by weight, 7% to 13% by weight, 7% to 12% by weight, 7% to 11% by weight, 7% to 10% by weight, 7% to 9% by weight, 7% to 8% by weight, 8% to 40% by weight, 8% to 35% by weight, 8% to 30% by weight, 8% to 25% by weight, 8% to 20% by weight, 8% to 15% by weight, 8% to 14% by weight, 8% to 13% by weight, 8% to 12% by weight, 8% to 11% by weight, 8% to 10% by weight, 8% to 9% by weight, 9% to 40% by weight,9 wt % to 35 wt %, 9 wt % to 30 wt %, 9 wt % to 25 wt %, 9 wt % to 20 wt %, 9 wt % to 15 wt %, 9 wt % to 14 wt %, 9 wt % to 13 wt %, 9 wt % to 12 wt %, 9 wt % to 11 wt %, 9 wt % to 10 wt %, 10 wt % to 40 wt %, 10 wt % to 35 wt %, 10 wt % to 30 wt %, 10 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 15 wt %, 10 wt % to 14 wt %, 10 wt % to 13 wt %, 10 wt % to 12 wt %, 10 wt % to 11 wt %, 11 wt % to 40 wt %, 11 wt % to 35 wt %, 11 wt % to 30 wt %, 11 wt % to 25 wt %, 11 wt % to 20 wt %, 11 wt % to 15 wt %, 11 wt % to 14 wt %, 11 wt % to 13 wt %, 11 wt % to 12 wt %, 12 wt % to 40 wt %, 12 wt % to 35 wt %, 12 wt % to 30 wt %, 12 wt % to 25 wt %, 12 wt % to % to 20 wt%, 12 wt% to 15 wt%, 12 wt% to 14 wt%, 12 wt% to 13 wt%, 13 wt% to 40 wt%, 13 wt% to 35 wt%, 13 wt% to 30 wt%, 13 wt% to 25 wt%, 13 wt% to 20 wt%, 13 wt% to 15 wt%, 13 wt% to 14 wt%, 14 wt% to 40 wt%, 14 wt% to 35 wt%, 14 wt% to 30 wt%, 14 wt% to 25 wt%, 14 wt% to 20 wt%, 14 wt% to % to 30 wt %, 15 wt % to 25 wt %, 15 wt % to 20 wt %, 20 wt % to 40 wt %, 20 wt % to 35 wt %, 20 wt % to 30 wt %, 20 wt % to 25 wt %, 25 wt % to 40 wt %, 25 wt % to 35 wt %, 25 wt % to 30 wt %, 30 wt % to 40 wt %, 30 wt % to 35 wt %, or 35 wt % to 40 wt %) of unreacted polyisobutylene.

[0075] Also provided are embodiments of the above-described method for preparing a free radical functionalized PIBSA product, wherein the method comprises reacting polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent in two or more additions at a reaction temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product. In certain embodiments, the free radical initiator and the ethylenically unsaturated acylating agent are added in two to ten additions, such as two to nine, two to eight, two to seven, two to six, two to five, two to four, two to three, or three additions.

[0076] In certain embodiments, each of the two or more additions independently comprises at least 5 wt % (such as at least 10 wt %, 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, or 50 wt %) of the total amount of free radical initiator to be reacted with the polyisobutylene and / or at least 5 wt % (such as at least 10 wt %, 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, or 50 wt %) of the total amount of ethylenically unsaturated acylating agent to be reacted. In certain embodiments, each of the two or more additions independently constitutes up to 95 wt % (such as up to 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10 wt %) of the total amount of free radical initiator to be reacted with the polyisobutylene and / or up to 95 wt % (such as up to 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10 wt %) of the total amount of ethylenically unsaturated acylating agent. In certain embodiments, each of the two or more additions independently comprises 5% to 95% by weight (such as 5% to 90% by weight, 5% to 85% by weight, 5% to 80% by weight, 5% to 75% by weight, 5% to 70% by weight, 5% to 65% by weight, 5% to 60% by weight, 5% to 55% by weight, 5% to 50% by weight, 5% to 45% by weight, 5% to 40% by weight, 5% to 35% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 15% by weight, 5% to 10% by weight, 10% to 95% by weight, 10% to 90% by weight, 10% to 55% by weight, % to 85 wt %, 10 wt % to 80 wt %, 10 wt % to 75 wt %, 10 wt % to 70 wt %, 10 wt % to 65 wt %, 10 wt % to 60 wt %, 10 wt % to 55 wt %, 10 wt % to 50 wt %, 10 wt % to 45 wt %, 10 wt % to 40 wt %, 10 wt % to 35 wt %, 10 wt % to 30 wt %, 10 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 15 wt %, 15 wt % to 95 wt %, 15 wt % to 90 wt %, 15 wt % to 85 wt %, 15 wt % to 80 wt %, 15 wt % to 75 wt %, 15 wt % to 70 wt %, 15 wt % to 65 wt %,% to 60 wt%, 15 wt% to 55 wt%, 15 wt% to 50 wt%, 15 wt% to 45 wt%, 15 wt% to 40 wt%, 15 wt% to 35 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, 15 wt% to 20 wt%, 20 wt% to 95 wt%, 20 wt% to 90 wt%, 20 wt% to 85 wt%, 20 wt% to 80 wt%, 20 wt% to 75 wt%, 20 wt% to 70 wt%, 20 wt% to 65 wt%, 20 wt% to 60 wt%, 20 wt% to 55 wt%, 20 wt% to 50 wt%, 20 wt% to 45 wt%, 20 wt% to 40 wt% %, 20 wt % to 35 wt %, 20 wt % to 30 wt %, 20 wt % to 25 wt %, 25 wt % to 95 wt %, 25 wt % to 90 wt %, 25 wt % to 85 wt %, 25 wt % to 80 wt %, 25 wt % to 75 wt %, 25 wt % to 70 wt %, 25 wt % to 65 wt %, 25 wt % to 60 wt %, 25 wt % to 55 wt %, 25 wt % to 50 wt %, 25 wt % to 45 wt %, 25 wt % to 40 wt %, 25 wt % to 35 wt %, 25 wt % to 30 wt %, 30 wt % to 95 wt %, 30 wt % to 90 wt %, 30 wt % to 85 wt %, 30 wt % to %, 30% to 75% by weight, 30% to 70% by weight, 30% to 65% by weight, 30% to 60% by weight, 30% to 55% by weight, 30% to 50% by weight, 30% to 45% by weight, 30% to 40% by weight, 30% to 35% by weight, 35% to 95% by weight, 35% to 90% by weight, 35% to 85% by weight, 35% to 80% by weight, 35% to 75% by weight, 35% to 70% by weight, 35% to 65% by weight, 35% to 60% by weight, 35% to 55% by weight, 35% to 50% by weight, 35% to 45% by weight, 35% to 35% by weight % to 40% by weight, 40% to 95% by weight, 40% to 90% by weight, 40% to 85% by weight, 40% to 80% by weight, 40% to 75% by weight, 40% to 70% by weight, 40% to 65% by weight, 40% to 60% by weight, 40% to 55% by weight, 40% to 50% by weight, 40% to 45% by weight, 45% to 95% by weight, 45% to 90% by weight, 45% to 85% by weight, 45% to 80% by weight, 45% to 75% by weight, 45% to 70% by weight, 45% to 65% by weight, 45% to 60% by weight, 45% to 45% by weight,% to 85 wt %, 50 wt % to 80 wt %, 50 wt % to 75 wt %, 50 wt % to 70 wt %, 50 wt % to 65 wt %, 50 wt % to 60 wt % or 50 wt % to 55 wt % and / or a total amount of free radical initiators of 5 wt % to 95 wt %, such as 5 wt % to 90 wt %, 5 wt % to 85 wt %, 50 wt % to 80 wt %, 50 wt % to 75 wt %, 50 wt % to 70 wt %, 50 wt % to 65 wt %, 50 wt % to 60 wt %, or 50 wt % to 55 wt % % to 45% by weight, 5% to 40% by weight, 5% to 35% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 15% by weight, 5% to 10% by weight, 10% to 95% by weight, 10% to 90% by weight, 10% to 85% by weight, 10% to 80% by weight, 10% to 75% by weight, 10% to 70% by weight, 10% to 65% by weight, 10% to 60% by weight, 10% to 55% by weight, 10% to 50% by weight, 10% to 45% by weight, 10% to 40% by weight, 10% to 35% by weight, 10% to 3 %, 15 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 15 wt %, 15 wt % to 95 wt %, 15 wt % to 90 wt %, 15 wt % to 85 wt %, 15 wt % to 80 wt %, 15 wt % to 75 wt %, 15 wt % to 70 wt %, 15 wt % to 65 wt %, 15 wt % to 60 wt %, 15 wt % to 55 wt %, 15 wt % to 50 wt %, 15 wt % to 45 wt %, 15 wt % to 40 wt %, 15 wt % to 35 wt %, 15 wt % to 30 wt %, 15 wt % to 25 wt %, 15 wt % to 20 wt %, 20 wt % to 95 wt %, 20 wt % to % to 90 wt%, 20 wt% to 85 wt%, 20 wt% to 80 wt%, 20 wt% to 75 wt%, 20 wt% to 70 wt%, 20 wt% to 65 wt%, 20 wt% to 60 wt%, 20 wt% to 55 wt%, 20 wt% to 50 wt%, 20 wt% to 45 wt%, 20 wt% to 40 wt%, 20 wt% to 35 wt%, 20 wt% to 30 wt%, 20 wt% to 25 wt%, 25 wt% to 95 wt%, 25 wt% to 90 wt%, 25 wt% to 85 wt%, 25 wt% to 80 wt%, 25 wt% to 75 wt%, 25 wt% to 70 wt%, 25 wt% to 65 wt%,25% to 60% by weight, 25% to 55% by weight, 25% to 50% by weight, 25% to 45% by weight, 25% to 40% by weight, 25% to 35% by weight, 25% to 30% by weight, 30% to 95% by weight, 30% to 90% by weight, 30% to 85% by weight, 30% to 80% by weight, 30% to 75% by weight, 30% to 70% by weight, 30% to 65% by weight, 30% to 60% by weight, 30% to 55% by weight %, 30% to 50% by weight, 30% to 45% by weight, 30% to 40% by weight, 30% to 35% by weight, 35% to 95% by weight, 35% to 90% by weight, 35% to 85% by weight, 35% to 80% by weight, 35% to 75% by weight, 35% to 70% by weight, 35% to 65% by weight, 35% to 60% by weight, 35% to 55% by weight, 35% to 50% by weight, 35% to 45% by weight, 35% to 40% by weight %, 40% to 95% by weight, 40% to 90% by weight, 40% to 85% by weight, 40% to 80% by weight, 40% to 75% by weight, 40% to 70% by weight, 40% to 65% by weight, 40% to 60% by weight, 40% to 55% by weight, 40% to 50% by weight, 40% to 45% by weight, 45% to 95% by weight, 45% to 90% by weight, 45% to 85% by weight, 45% to 80% by weight, 45% to 75% by weight %, 45 wt % to 70 wt %, 45 wt % to 65 wt %, 45 wt % to 60 wt %, 45 wt % to 45 wt %, 45 wt % to 50 wt %, 50 wt % to 95 wt %, 50 wt % to 90 wt %, 50 wt % to 85 wt %, 50 wt % to 80 wt %, 50 wt % to 75 wt %, 50 wt % to 70 wt %, 50 wt % to 65 wt %, 50 wt % to 60 wt %, or 50 wt % to 55 wt %) of the total amount of ethylenically unsaturated acylating agent to react with the polyisobutylene.

[0077] In certain embodiments, at least two of the two or more additions are separated in time by at least a half-life of the free radical initiator. In certain embodiments, at least two of the two or more additions are separated in time by at least 1.1 times (such as at least 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, 3 times, 3.1 times, 3.2 times, 3.3 times, 3.4 times, 3.5 times, 3.6 times, 3.7 times, 3.8 times, 3.9 times, 4 times, 4.2 times, 4.4 times, 4.6 times, 4.8 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 9.5 times, or 10 times) the half-life of the free radical initiator. In certain embodiments, each of the two or more additions is separated in time by 1 to 10 times the half-life of the free radical initiator (such as 1.1 to 10 times, 1.2 to 10 times, 1.3 to 10 times, 1.4 to 10 times, 1.5 to 10 times, 1.6 to 10 times, 1.7 to 10 times, 1.8 to 10 times, 1.9 to 10 times, 2 to 10 times, 2.1 to 10 times, 2.2 to 10 times, 2.3 to 10 times, 2.4 to 10 times, 2.5 to 10 times, 2.6 to 10 times, 2.7 to 10 times, 2.8 to 10 times, 2.9 to 10 times, 3 to 10 times, 4 to 10 times, 5 to 10 times, 6 to 10 times, 7 to 10 times, 8 to 10 times, 9 to 10 times, 10 to 11 times, 11 to 12 times, 12 to 13 times, 13 to 14 times, 14 to 15 times, 15 to 16 times, 16 to 17 times, 17 to 18 times, 18 to 19 times, 19 to 20 times, 20 to 21 times, 2.5 times to 10 times, 2.6 times to 10 times, 2.7 times to 10 times, 2.8 times to 10 times, 2.9 times to 10 times, 3 times to 10 times, 3.1 times to 10 times, 3.2 times to 10 times, 3.3 times to 10 times, 3.4 times to 10 times, 3.5 times to 10 times, 3.6 times to 10 times, 3.7 times to 10 times, 3.8 times to 10 times, 3.9 times to 10 times, 4 times to 10 times, 4.2 times to 10 times, 4.4 times to 10 times, 4.6 times to 10 times, 4.8 times to 10 times times, 5 times to 10 times, 5.5 times to 10 times, 6 times to 10 times, 6.5 times to 10 times, 7 times to 10 times, 7.5 times to 10 times, 8 times to 10 times, 8.5 times to 10 times, 9 times to 10 times, 9.5 times to 10 times, 1 times to 9.5 times, 1.1 times to 9.5 times, 1.2 times to 9.5 times, 1.3 times to 9.5 times, 1.4 times to 9.5 times, 1.5 times to 9.5 times, 1.6 times to 9.5 times, 1.7 times to 9.5 times, 1.8 times to 9.5 times, 1.9 times to 9.5 times, 2 times to 9.5 times, 2.1 times to 9.5 times, 2.2 times to 9.5 times, 2.3 times to 9.5 times, 2.4 times to 9.5 times, 2.5 times to 9.5 times, 2.6 times to 9.5 times, 2.7 times to 9.5 times, 2.8 times to 9.5 times, 2.9 times to 9.5 times, 3 times to 9.5 times, 3.1 times to 9.5 times, 3.2 times to 9.5 times, 3.3 times to 9.5 times, 3.4 times to 9.5 times, 3.5 times to 9.5 times, 3.6 times to 9.5 times, 3.7 times to 9.5 times, 3.8 times to 9.5 times, 3.9 times to 9.5 times, 4 times to 9.5 times, 4.2 times to 9.5 times, 4.4 times to 9.5 times, 4.6 times to 9.5 times, 4.8 times to 9.5 times, 5 times to 9.5 times, 5.5 times to 9.5 times, 6 times to 9.5 times, 6.5 times to 9.5 times, 7 times to 9.5 times, 7.5 times to 9.5 times, 8 times to 9.5 times, 8.5 times to 9.5 times, 9 times to 9.5 times, 1 times to 9 times, 1.1 times to 9 times, 1.2 times to 9 times, 1.3 times to 9 times, 1.4 times to 9 times, 1.5 times to 9 times, 1.6 times to 9 times, 1.7 times to 9 times, 1.8 times to 9 times, 1.9 times to 9 times, 2 times to 9 times, 2.1 times to 9 times, 2 .2 times to 9 times, 2.3 times to 9 times, 2.4 times to 9 times, 2.5 times to 9 times, 2.6 times to 9 times, 2.7 times to 9 times, 2.8 times to 9 times, 2.9 times to 9 times, 3 times to 9 times, 3.1 times to 9 times, 3.2 times to 9 times, 3.3 times to 9 times, 3.4 times to 9 times, 3.5 times to 9 times, 3.6 times to 9 times, 3.7 times to 9 times, 3.8 times to 9 times, 3.9 times to 9 times, 4 times to 9 times, 4.2 times to 9 times, 4.4 times to 9 times, 4.6 times to 9 times, 4.8 times to 9 times, 5 times to 9 times, 5.5 times to 9 times, 6 times to 9 times, 6.5 times to 9 times, 7 times to 9 times, 7.5 times to 9 times, 8 times to 9 times, 8.5 times to 9 times, 1 times to 8.5 times, 1.1 times to 8. 5 times, 1.2 times to 8.5 times, 1.3 times to 8.5 times, 1.4 times to 8.5 times, 1.5 times to 8.5 times, 1.6 times to 8.5 times, 1.7 times to 8.5 times, 1.8 times to 8.5 times, 1.9 times to 8.5 times, 2 times to 8.5 times, 2.1 times to 8.5 times, 2.2 times to 8.5 times, 2.3 times to 8.5 times, 2.4 times to 8.5 times, 2.5 times to 8.5 times, 2.6 times to 8.5 times, 2.7 times to 8.5 times, 2.8 times to 8.5 times, 2.9 times to 8.5 times, 3 times to 8.5 times, 3.1 times to 8.5 times, 3.2 times to 8.5 times, 3.3 times to 8.5 times, 3.4 times to 8.5 times, 3.5 times to 8.5 times, 3.6 times to 8.5 times, 3.7 to 8.5 times, 3.8 to 8.5 times, 3.9 to 8.5 times, 4 to 8.5 times, 4.2 to 8.5 times, 4.4 to 8.5 times, 4.6 to 8.5 times, 4.8 to 8.5 times, 5 to 8.5 times, 5.5 to 8.5 times, 6 to 8.5 times, 6.5 to 8.5 times, 7 to 8.5 times, 7.5 times to 8.5 times, 8 times to 8.5 times, 1 times to 8 times, 1.1 times to 8 times, 1.2 times to 8 times, 1.3 times to 8 times, 1.4 times to 8 times, 1.5 times to 8 times, 1.6 times to 8 times, 1.7 times to 8 times, 1.8 times to 8 times, 1.9 times to 8 times, 2 times to 8 times, 2.1 times to 8 times, 2.2 times to 8 times, 2.3 times to 8 times, 2.4 times to 8 times, 2.5 times to 8 times, 2.6 times to 8 times, 2.7 times to 8 times, 2.8 times to 8 times, 2.9 times to 8 times, 3 times to 8 times, 3.1 times to 8 times, 3.2 times to 8 times, 3.3 times to 8 times, 3.4 times to 8 times, 3.5 times to 8 times, 3.6 times to 8 times, 3.7 times to 8 times, 3.8 times to 8 times, 3.9 times to 8 times, 4 times to 8 times, 4.2 times to 8 times, 4.4 times to 8 times, 4.6 times to 8 times, 4.8 times to 8 times, 5 times to 8 times, 5.5 times to 8 times, 6 times to 8 times, 6.5 times to 8 times, 7 times to 8 times, 7.5 times to 8 times, 1 times to 7.5 times, 1.1 times to 7.5 times, 1.2 times to 7.5 times, 1.3 times to 7.5 times, 1.4 times to 7. 5 times, 1.5 times to 7.5 times, 1.6 times to 7.5 times, 1.7 times to 7.5 times, 1.8 times to 7.5 times, 1.9 times to 7.5 times, 2 times to 7.5 times, 2.1 times to 7.5 times, 2.2 times to 7.5 times, 2.3 times to 7.5 times, 2.4 times to 7.5 times, 2.5 times to 7.5 times, 2.6 times to 7.5 times, 2.7 times to 7.5 times, 2.8 times to 7.5 times, 2.9 times to 7.5 times, 3 times to 7.5 times, 3.1 times to 7.5 times, 3.2 times to 7.5 times, 3.3 times to 7.5 times, 3.4 times to 7.5 times, 3.5 times to 7.5 times, 3.6 times to 7.5 times, 3.7 times to 7.5 times, 3.8 times to 7.5 times, 3.9 times to 7.5 times, 4 times to 7.5 times, 4.2 times to 7.5 times, 4.4 times to 7.5 times, 4.6 times to 7.5 times, 4.8 times to 7.5 times, 5 times to 7.5 times, 5.5 times to 7.5 times, 6 times to 7.5 times, 6.5 times to 7.5 times, 7 times to 7.5 times, 1 times to 7 times, 1.1 times to 7 times, 1.2 times to 7 times, 1.3 times to 7 times, 1.4 times to 7 times, 1.5 times to 7 times, 1.6 times to 7 times, 1.7 times to 7 times, 1.8 times to 7 times, 1.9 times to 7 times, 2 times to 7 times, 2.1 times to 7 times, 2.2 times to 7 times, 2.3 times to 7 times, 2.4 times to 7 times, 2.5 times to 7 times, 2.6 times to 7 times, 2.7 times to 7 times, 2.8 times to 7 times, 2.9 times to 7 times, 3 times to 7 times, 3.1 times to 7 times, 3.2 times to 7 times, 3.3 times to 7 times, 3.4 times to 7 times, 3.5 times to 7 times, 3.6 times to 7 times, 3.7 times to 7 times, 3.8 times to 7 times, 3.9 times to 7 times, 4 times to 7 times, 4.2 times to 7 times, 4.4 times to 7 times, 4.6 times to 7 times, 4.8 times to 7 times, 5 times to 7 times, 5.5 times to 7 times, 6 times to 7 times, 6.5 times to 7 times, 1 times to 6.5 times, 1.1 times to 6.5 times, 1.2 times to 6.5 times, 1.3 times to 6.5 times, 1.4 times to 6.5 times, 1.5 times to 6.5 times, 1.6 times to 6.5 times, 1.7 times to 6.5 times, 1.8 times to 6.5 times, 1.9 times to 6.5 times, 2 times to 6.5 times, 2.1 to 6.5 times, 2.2 to 6.5 times, 2.3 to 6.5 times, 2.4 to 6.5 times, 2.5 to 6.5 times, 2.6 to 6.5 times, 2.7 to 6.5 times, 2.8 to 6.5 times, 2.9 to 6.5 times, 3 to 6.5 times, 3.1 to 6.5 times, 3.2 to 6.5 times, 3.3 to 6.5 times, 3.4 times to 6.5 times, 3.5 times to 6.5 times, 3.6 times to 6.5 times, 3.7 times to 6.5 times, 3.8 times to 6.5 times, 3.9 times to 6.5 times, 4 times to 6.5 times, 4.2 times to 6.5 times, 4.4 times to 6.5 times, 4.6 times to 6.5 times, 4.8 times to 6.5 times, 5 times to 6.5 times, 5.5 times to 6. 5 times, 6 times to 6.5 times, 1 times to 6 times, 1.1 times to 6 times, 1.2 times to 6 times, 1.3 times to 6 times, 1.4 times to 6 times, 1.5 times to 6 times, 1.6 times to 6 times, 1.7 times to 6 times, 1.8 times to 6 times, 1.9 times to 6 times, 2 times to 6 times, 2.1 times to 6 times, 2.2 times to 6 times, 2.3 times to 6 times, 2.4 times to 6 times, 2.5 to 6 times, 2.6 to 6 times, 2.7 to 6 times, 2.8 to 6 times, 2.9 to 6 times, 3 to 6 times, 3.1 to 6 times, 3.2 to 6 times, 3.3 to 6 times, 3.4 to 6 times, 3.5 to 6 times, 3.6 to 6 times, 3.7 to 6 times, 3.8 to 6 times, 3.9 to 6 times, 4 to 6 times , 4.2 to 6 times, 4.4 to 6 times, 4.6 to 6 times, 4.8 to 6 times, 5 to 6 times, 5.5 to 6 times, 1 to 5.5 times, 1.1 to 5.5 times, 1.2 to 5.5 times, 1.3 to 5.5 times, 1.4 to 5.5 times, 1.5 to 5.5 times, 1.6 to 5.5 times, 1.7 to 5.5 times , 1.8 to 5.5 times, 1.9 to 5.5 times, 2 to 5.5 times, 2.1 to 5.5 times, 2.2 to 5.5 times, 2.3 to 5.5 times, 2.4 to 5.5 times, 2.5 to 5.5 times, 2.6 to 5.5 times, 2.7 to 5.5 times, 2.8 to 5.5 times, 2.9 to 5.5 times, 3 to 5.5 times, 3.1 times to 5.5 times, 3.2 times to 5.5 times, 3.3 times to 5.5 times, 3.4 times to 5.5 times, 3.5 times to 5.5 times, 3.6 times to 5.5 times, 3.7 times to 5.5 times, 3.8 times to 5.5 times, 3.9 times to 5.5 times, 4 times to 5.5 times, 4.2 times to 5.5 times, 4.4 times to 5.5 times, 4.6 times to 5.5 times, 4.8 times to 5.5 times, 5 times to 5.5 times, 1 times to 5 times, 1.1 times to 5 times, 1.2 times to 5 times, 1.3 times to 5 times, 1.4 times to 5 times, 1.5 times to 5 times, 1.6 times to 5 times, 1.7 times to 5 times, 1.8 times to 5 times, 1.9 times to 5 times, 2 times to 5 times, 2.1 times to 5 times, 2.2 times to 5 times, 2.3 times to 5 times, 2.4 times to 5 times, 2.5 times to 5 times, 2.6 times to 5 times, 2.7 times to 5 times, 2.8 times to 5 times, 2.9 times to 5 times, 3 times to 5 times, 3.1 times to 5 times, 3.2 times to 5 times, 3.3 times to 5 times, 3.4 times to 5 times, 3.5 times to 5 times, 3.6 times to 5 times, 3.7 times to 5 times, 3.8 times to 5 times, 3.9 to 5 times, 4 to 5 times, 4.2 to 5 times, 4.4 to 5 times, 4.6 to 5 times, 4.8 to 5 times, 1 to 4.8 times, 1.1 to 4.8 times, 1.2 to 4.8 times, 1.3 to 4.8 times, 1.4 to 4.8 times, 1.5 to 4.8 times, 1.6 to 4.8 times, 1.7 to 4.8 times, 1 .8 times to 4.8 times, 1.9 times to 4.8 times, 2 times to 4.8 times, 2.1 times to 4.8 times, 2.2 times to 4.8 times, 2.3 times to 4.8 times, 2.4 times to 4.8 times, 2.5 times to 4.8 times, 2.6 times to 4.8 times, 2.7 times to 4.8 times, 2.8 times to 4.8 times, 2.9 times to 4.8 times, 3 times to 4.8 times, 3.1 times to 4.8 times, 3.2 times to 4.8 times, 3.3 times to 4.8 times, 3.4 times to 4.8 times, 3.5 times to 4.8 times, 3.6 times to 4.8 times, 3.7 times to 4.8 times, 3.8 times to 4.8 times, 3.9 times to 4.8 times, 4 times to 4.8 times, 4.2 times to 4.8 times, 4.4 times to 4.8 times, 4.6 times to 4.8 times. 8 times, 1. to 4.6 times, 1.1 to 4.6 times, 1.2 to 4.6 times, 1.3 to 4.6 times, 1.4 to 4.6 times, 1.5 to 4.6 times, 1.6 to 4.6 times, 1.7 to 4.6 times, 1.8 to 4.6 times, 1.9 to 4.6 times, 2 to 4.6 times, 2.1 to 4.6 times, 2.2 times to 4.6 times, 2.3 times to 4.6 times, 2.4 times to 4.6 times, 2.5 times to 4.6 times, 2.6 times to 4.6 times, 2.7 times to 4.6 times, 2.8 times to 4.6 times, 2.9 times to 4.6 times, 3 times to 4.6 times, 3.1 times to 4.6 times, 3.2 times to 4.6 times, 3.3 times to 4.6 times, 3.4 times to 4.6 times, 3 .5 times to 4.6 times, 3.6 times to 4.6 times, 3.7 times to 4.6 times, 3.8 times to 4.6 times, 3.9 times to 4.6 times, 4 times to 4.6 times, 4.2 times to 4.6 times, 4.4 times to 4.6 times, 1 times to 4.4 times, 1.1 times to 4.4 times, 1.2 times to 4.4 times, 1.3 times to 4.4 times, 1.4 times to 4.4 times, 1.5 times to 4.4 times, 1.6 times to 4.4 times, 1.7 times to 4.4 times, 1.8 times to 4.4 times, 1.9 times to 4.4 times, 2 times to 4.4 times, 2.1 times to 4.4 times, 2.2 times to 4.4 times, 2.3 times to 4.4 times, 2.4 times to 4.4 times, 2.5 times to 4.4 times, 2.6 times to 4.4 times, 2.7 times to 4.4 times.4 times, 2.8 times to 4.4 times, 2.9 times to 4.4 times, 3 times to 4.4 times, 3.1 times to 4.4 times, 3.2 times to 4.4 times, 3.3 times to 4.4 times, 3.4 times to 4.4 times, 3.5 times to 4.4 times, 3.6 times to 4.4 times, 3.7 times to 4.4 times, 3.8 times to 4.4 times, 3.9 times to 4.4 times, 4 times to 4.4 times, 4.2 times to 4.4 times, 1 times to 4.2 times, 1.1 times to 4.2 times, 1.2 times to 4.2 times, 1.3 times to 4.2 times, 1.4 times to 4.2 times, 1.5 times to 4.2 times, 1.6 times to 4.2 times, 1.7 times to 4.2 times, 1.8 times to 4.2 times, 1.9 times to 4.2 times, 2 times to 4.2 times, 2.1 times to 4.2 times, 2.2 times to 4.2 times, 2.3 times to 4.2 times, 2.4 times to 4.2 times, 2.5 times to 4.2 times, 2.6 times to 4.2 times, 2.7 times to 4.2 times, 2.8 times to 4.2 times, 2.9 times to 4.2 times, 3 times to 4.2 times, 3.1 times to 4.2 times, 3.2 times to 4.2 times, 3.3 times to 4.2 times, 3 .4 times to 4.2 times, 3.5 times to 4.2 times, 3.6 times to 4.2 times, 3.7 times to 4.2 times, 3.8 times to 4.2 times, 3.9 times to 4.2 times, 4 times to 4.2 times, 1 times to 4 times, 1.1 times to 4 times, 1.2 times to 4 times, 1.3 times to 4 times, 1.4 times to 4 times, 1.5 times to 4 times, 1.6 times to 4 times, 1.7 times to 4 times, 1.8 times to 4 times, 1.9 times to 4 times, 2 times to 4 times, 2.1 times to 4 times, 2.2 times to 4 times, 2.3 times to 4 times, 2.4 times to 4 times, 2.5 times to 4 times, 2.6 times to 4 times, 2.7 times to 4 times, 2.8 times to 4 times, 2.9 times to 4 times, 3 times to 4 times, 3.1 times to 4 times, 3.2 times to 4 times, 3.3 times to 4 times, 3.4 times to 4 times, 3.5 times to 4 times, 3.6 times to 4 times, 3.7 times to 4 times, 3.8 times to 4 times, 3.9 times to 4 times, 1 times to 3.9 times, 1.1 times to 3.9 times, 1.2 times to 3.9 times, 1.3 times to 3.9 times, 1.4 times to 3.9 times, 1.5 times to 3.9 times, 1.6 times to 3.9 times, 1.7 times to 3 .9 times, 1.8 times to 3.9 times, 1.9 times to 3.9 times, 2 times to 3.9 times, 2.1 times to 3.9 times, 2.2 times to 3.9 times, 2.3 times to 3.9 times, 2.4 times to 3.9 times, 2.5 times to 3.9 times, 2.6 times to 3.9 times, 2.7 times to 3.9 times, 2.8 times to 3.9 times, 2.9 times to 3.9 times, 3 times to 3.9 times, 3.1 times to 3.9 times, 3.2 times to 3.9 times, 3.3 times to 3.9 times, 3.4 times to 3.9 times, 3.5 times to 3.9 times, 3.6 times to 3.9 times, 3.7 times to 3.9 times, 3.8 times to 3.9 times, 1 times to 3.8 times, 1.1 times to 3.8 times, 1.2 times to 3.8 times, 1.3 times to 3.8 times, 1.4 times to 3.8 times, 1.5 times to 3.8 times, 1.6 times to 3.8 times, 1.7 times to 3.8 times, 1.8 times to 3.8 times, 1.9 times to 3.8 times, 2 times to 3.8 times, 2.1 times to 3.8 times, 2.2 times to 3.8 times, 2.3 times to 3.8 times, 2.4 times to 3.8 times, 2.5 times to 3.8 times, 2.6 times to 3.8 times , 2.7 to 3.8 times, 2.8 to 3.8 times, 2.9 to 3.8 times, 3 to 3.8 times, 3.1 to 3.8 times, 3.2 to 3.8 times, 3.3 to 3.8 times, 3.4 to 3.8 times, 3.5 to 3.8 times, 3.6 to 3.8 times, 3.7 to 3.8 times, 1 to 3.7 times, 1.1 to 3.7 times, 1.2 times to 3.7 times, 1.3 times to 3.7 times, 1.4 times to 3.7 times, 1.5 times to 3.7 times, 1.6 times to 3.7 times, 1.7 times to 3.7 times, 1.8 times to 3.7 times, 1.9 times to 3.7 times, 2 times to 3.7 times, 2.1 times to 3.7 times, 2.2 times to 3.7 times, 2.3 times to 3.7 times, 2.4 times to 3.7 times, 2.5 times to 3.7 times, 2.6 times to 3.7 times, 2.7 times to 3.7 times, 2.8 times to 3.7 times, 2.9 times to 3.7 times, 3 times to 3.7 times, 3.1 times to 3.7 times, 3.2 times to 3.7 times, 3.3 times to 3.7 times, 3.4 times to 3.7 times, 3.5 times to 3.7 times, 3.6 times to 3.7 times, 1 times to 3.6 times, 1.1 times to 3.6 times, 1.2 times to 3.6 times, 1.3 times to 3.6 times, 1.4 times to 3.6 times, 1.5 times to 3.6 times, 1.6 times to 3.6 times, 1.7 times to 3.6 times, 1.8 times to 3.6 times, 1.9 times to 3.6 times, 2 times to 3.6 times, 2.1 times to 3.6 times, 2.2 times to 3.6 times, 2 .3 times to 3.6 times, 2.4 times to 3.6 times, 2.5 times to 3.6 times, 2.6 times to 3.6 times, 2.7 times to 3.6 times, 2.8 times to 3.6 times, 2.9 times to 3.6 times, 3 times to 3.6 times, 3.1 times to 3.6 times, 3.2 times to 3.6 times, 3.3 times to 3.6 times, 3.4 times to 3.6 times, 3.5 times to 3.6 times, 1 to 3.5 times, 1.1 to 3.5 times, 1.2 to 3.5 times, 1.3 to 3.5 times, 1.4 to 3.5 times, 1.5 to 3.5 times, 1.6 to 3.5 times, 1.7 to 3.5 times, 1.8 to 3.5 times, 1.9 to 3.5 times, 2 to 3.5 times, 2.1 to 3.5 times, 2.2 to 3. 5 times, 2.3 times to 3.5 times, 2.4 times to 3.5 times, 2.5 times to 3.5 times, 2.6 times to 3.5 times, 2.7 times to 3.5 times, 2.8 times to 3.5 times, 2.9 times to 3.5 times, 3 times to 3.5 times, 3.1 times to 3.5 times, 3.2 times to 3.5 times, 3.3 times to 3.5 times, 3.4 times to 3.5 times, 1 times to 3.4 times, 1.1 times to 3.4 times, 1.2 times to 3.4 times, 1.3 times to 3.4 times, 1.4 times to 3.4 times, 1.5 times to 3.4 times, 1.6 times to 3.4 times, 1.7 times to 3.4 times, 1.8 times to 3.4 times, 1.9 times to 3.4 times, 2 times to 3.4 times, 2.1 times to 3.4 times, 2.2 times to 3.4 times, 2.3 times to 3.4 times, 2.4 times to 3.4 times, 2.5 times to 3.4 times, 2.6 times to 3.4 times, 2.7 times to 3.4 times, 2.8 times to 3.4 times, 2.9 times to 3.4 times, 3 times to 3.4 times, 3.1 times to 3.4 times, 3.2 times to 3.4 times, 3.3 times to 3.4 times, 1 times to 3.3 times, 1.1 times to 3.3 times, 1. 2 to 3.3 times, 1.3 to 3.3 times, 1.4 to 3.3 times, 1.5 to 3.3 times, 1.6 to 3.3 times, 1.7 to 3.3 times, 1.8 to 3.3 times, 1.9 to 3.3 times, 2 to 3.3 times, 2.1 to 3.3 times, 2.2 to 3.3 times, 2.3 to 3.3 times, 2.4 to 3.3 times, 2.5 times to 3.3 times, 2.6 times to 3.3 times, 2.7 times to 3.3 times, 2.8 times to 3.3 times, 2.9 times to 3.3 times, 3 times to 3.3 times, 3.1 times to 3.3 times, 3.2 times to 3.3 times, 1 times to 3.2 times, 1.1 times to 3.2 times, 1.2 times to 3.2 times, 1.3 times to 3.2 times, 1.4 times to 3. 2 times, 1.5 times to 3.2 times, 1.6 times to 3.2 times, 1.7 times to 3.2 times, 1.8 times to 3.2 times, 1.9 times to 3.2 times, 2 times to 3.2 times, 2.1 times to 3.2 times, 2.2 times to 3.2 times, 2.3 times to 3.2 times, 2.4 times to 3.2 times, 2.5 times to 3.2 times, 2.6 times to 3.2 times, 2.7 times to 3.2 times, 2.8 times to 3.2 times, 2.9 times to 3.2 times, 3 times to 3.2 times, 3.1 times to 3.2 times, 1 times to 3.1 times, 1.1 times to 3.1 times, 1.2 times to 3.1 times, 1.3 times to 3.1 times, 1.4 times to 3.1 times, 1.5 times to 3.1 times, 1.6 times to 3.1 times, 1.7 times to 3.1 times, 1. 8 times to 3.1 times, 1.9 times to 3.1 times, 2 times to 3.1 times, 2.1 times to 3.1 times, 2.2 times to 3.1 times, 2.3 times to 3.1 times, 2.4 times to 3.1 times, 2.5 times to 3.1 times, 2.6 times to 3.1 times, 2.7 times to 3.1 times, 2.8 times to 3.1 times, 2.9 times to 3.1 times, 3 times to 3.1 times, 1 times to 3 times, 1.1 times to 3 times, 1.2 times to 3 times, 1.3 times to 3 times, 1.4 times to 3 times, 1.5 times to 3 times, 1.6 times to 3 times, 1.7 times to 3 times, 1.8 times to 3 times, 1.9 times to 3 times, 2 times to 3 times, 2.1 times to 3 times, 2.2 times to 3 times, 2.3 times to 3 times, 2.4 times to 3 times, 2.5 times to 3 times, 2.6 times to 3 times, 2.7 times to 3 times, 2.8 times to 3 times, 2.9 times to 3 times, 1 times to 2.9 times, 1.1 times to 2.9 times, 1.2 times to 2.9 times, 1.3 times to 2.9 times, 1.4 times to 2.9 times, 1.5 times to 2.9 times, 1.6 times to 2.9 times, 1.7 times to 2.9 times, 1.8 times to 2.9 times, 1.9 times to 2. 9 times, 2 times to 2.9 times, 2.1 times to 2.9 times, 2.2 times to 2.9 times, 2.3 times to 2.9 times, 2.4 times to 2.9 times, 2.5 times to 2.9 times, 2.6 times to 2.9 times, 2.7 times to 2.9 times, 2.8 times to 2.9 times, 1 times to 2.8 times, 1.1 times to 2.8 times, 1.2 times to 2.8 times, 1.3 times to 2 .8 times, 1.4 times to 2.8 times, 1.5 times to 2.8 times, 1.6 times to 2.8 times, 1.7 times to 2.8 times, 1.8 times to 2.8 times, 1.9 times to 2.8 times, 2 times to 2.8 times, 2.1 times to 2.8 times, 2.2 times to 2.8 times, 2.3 times to 2.8 times, 2.4 times to 2.8 times, 2.5 times to 2.8 times, 2.6 times to 2.8 times, 2.7 times to 2.8 times, 1 times to 2.7 times, 1.1 times to 2.7 times, 1.2 times to 2.7 times, 1.3 times to 2.7 times, 1.4 times to 2.7 times, 1.5 times to 2.7 times, 1.6 times to 2.7 times, 1.7 times to 2.7 times, 1.8 times to 2.7 times, 1.9 times to 2.7 times, 2 times to 2.7 times, 2. 1 to 2.7 times, 2.2 to 2.7 times, 2.3 to 2.7 times, 2.4 to 2.7 times, 2.5 to 2.7 times, 2.6 to 2.7 times, 1 to 2.6 times, 1.1 to 2.6 times, 1.2 to 2.6 times, 1.3 to 2.6 times, 1.4 to 2.6 times, 1.5 to 2.6 times, 1.6 to 2.6 times , 1.7 to 2.6 times, 1.8 to 2.6 times, 1.9 to 2.6 times, 2 to 2.6 times, 2.1 to 2.6 times, 2.2 to 2.6 times, 2.3 to 2.6 times, 2.4 to 2.6 times, 2.5 to 2.6 times, 1 to 2.5 times, 1.1 to 2.5 times, 1.2 to 2.5 times, 1.3 to 2.5 times, 1.4 times to 2.5 times, 1.5 times to 2.5 times, 1.6 times to 2.5 times, 1.7 times to 2.5 times, 1.8 times to 2.5 times, 1.9 times to 2.5 times, 2 times to 2.5 times, 2.1 times to 2.5 times, 2.2 times to 2.5 times, 2.3 times to 2.5 times, 2.4 times to 2.5 times, 1 times to 2.4 times, 1.1 times to 2. 4 times, 1.2 times to 2.4 times, 1.3 times to 2.4 times, 1.4 times to 2.4 times, 1.5 times to 2.4 times, 1.6 times to 2.4 times, 1.7 times to 2.4 times, 1.8 times to 2.4 times, 1.9 times to 2.4 times, 2 times to 2.4 times, 2.1 times to 2.4 times, 2.2 times to 2.4 times, 2.3 times to 2.4 times, 1 times to 2.3 times, 1.1 times to 2.3 times, 1.2 times to 2.3 times, 1.3 times to 2.3 times, 1.4 times to 2.3 times, 1.5 times to 2.3 times, 1.6 times to 2.3 times, 1.7 times to 2.3 times, 1.8 times to 2.3 times, 1.9 times to 2.3 times, 2 times to 2.3 times, 2.1 times to 2.3 times, 2.2 times to 2.3 times, 1 times to 2.2 times, 1.1 times to 2.2 times, 1.2 times to 2.2 times, 1.3 times to 2.2 times, 1.4 times to 2.2 times, 1.5 times to 2.2 times, 1.6 times to 2.2 times, 1.7 times to 2.2 times, 1.8 times to 2.2 times, 1.9 times to 2.2 times, 2 times to 2.2 times, 2.1 times to 2.2 times, 1 times to 2.1 times, 1.1 times to 2.1 times, 1.2 times to 2.1 times, 1.3 times to 2.1 times, 1.4 times to 2.1 times, 1.5 times to 2.1 times, 1.6 times to 2.1 times, 1.7 times to 2.1 times, 1.8 times to 2.1 times, 1.9 times to 2.1 times, 2 times to 2.1 times, 1 times to 2 times, 1.1 times to 2 times, 1.2 times to 2 times, 1.3 times to 2 times, 1.4 times to 2 times, 1.5 times to 2 times, 1.6 times to 2 times, 1.7 times to 2 times, 1.8 times to 2 times, 1.9 times to 2 times, 1 times to 1.9 times, 1.1 times to 1.9 times, 1.2 times to 1.9 times, 1.3 times to 1.9 times, 1.4 times to 1.9 times, 1.5 times to 1.9 times, 1.6 times to 1.9 times, 1.7 times to 1.9 times, 1.8 times to 1.9 times, 1 times to 1.8 times, 1.1 times to 1.8 times, 1.2 times to 1.8 times, 1.3 times to 1.8 times, 1.4 times to 1.8 times, 1.5 times to 1.8 times, 1.6 times to 1.8 times, 1.7 times to 1.8 times, 1 times to 1.7 times, 1.1 times to 1.7 times, 1.2 times to 1.7 times, 1.3 times to 1.7 times, 1.4 times to 1.7 times, 1.5 times to 1.7 times, 1.6 times to 1.7 times, 1 times to 1.6 times, 1.1 times to 1.6 times, 1.2 times to 1.6 times, 1.3 times to 1.6 times, 1.4 times to 1.6 times, 1.5 times to 1.6 times, 1 times to 1.5 times, 1.1 times to 1.5 times, 1.2 times to 1.5 times, 1.3 times to 1.5 times, 1.4 times to 1.5 times, 1 times to 1.4 times, 1.1 times to 1.4 times, 1.2 times to 1.4 times, 1.3 times to 1.4 times, 1 times to 1.3 times, 1.1 times to 1.3 times, 1.2 times to 1.3 times, 1 times to 1.2 times, 1.1 times to 1.3 times or 1 times to 1.1 times).

[0078] Also provided are embodiments of the above-described process for preparing a free radical functionalized PIBSA product, wherein the process comprises reacting polyisobutylene (such as high vinylidene polyisobutylene) with a free radical initiator and an ethylenically unsaturated acylating agent at a temperature of 150° C. to 225° C. to prepare a free radical functionalized PIBSA product, wherein the polyisobutylene is brought to the reaction temperature in the continuous reactor prior to commencing continuous addition of the free radical initiator to the polyisobutylene in the continuous reactor; and wherein the ethylenically unsaturated acylating agent is added to the continuous reactor: (i) as a mixture with the polyisobutylene; (ii) as a mixture with the free radical initiator; and / or (iii) continuously and separately from the polyisobutylene or the free radical initiator.

[0079] An illustrative, non-limiting embodiment of the method described herein for preparing a free radical functionalized PIBSA product may include feeding polyisobutylene to a two-stage or three-stage reactor system at 170° C., wherein each stage includes adding a maleic anhydride acylating agent and a di-tert-butyl peroxide initiator to the polyisobutylene flowing through the reactor system. With a half-life of about 6 minutes for di-tert-butyl peroxide, each stage is allowed to react for about 20 minutes to allow most of the initiator to be consumed before adding another dose. After two or three stages, within about 40 minutes to 60 minutes, the reaction is complete and the desired product has been obtained.

[0080] Nitrogen compounds

[0081] In certain embodiments, the nitrogen-containing compound has: (a) a nitrogen atom capable of reacting with a free radical functionalized PIBSA product to form an imide; and (b) at least one quaternizable amino group. In certain embodiments, the quaternizable amino group may be a primary amino group, a secondary amino group, or a tertiary amino group. The quaternizable amino group is any primary amino group, a secondary amino group, or a tertiary amino group on the nitrogen-containing compound that can react with a quaternizing agent to become a quaternary amino group. In certain embodiments, the quaternizing agent is suitable for converting the quaternizable amino group into a quaternary nitrogen group.

[0082] In certain embodiments, the nitrogen-containing compound may be represented by the formula:

[0083]

[0084] wherein X is an alkylene group containing 1 to 4 carbon atoms; R 2 is hydrogen or a hydrocarbyl group; and R 3 and R 4 A hydrocarbon group.

[0085] Suitable non-limiting examples of nitrogen-containing compounds include: N, N-dimethyl-aminopropylamine, N, N-diethyl-aminopropylamine, N, N-dimethyl-aminoethylamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, isomeric amines (including butanediamine, pentanediamine, hexanediamine and heptanediamine), diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine, N-methyl-3-amino-1-propylamine or mixtures thereof. Nitrogen-containing compounds capable of reacting with an acylating agent and further having an amino group that can be quaternized may also include aminoalkyl-substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine. In some embodiments, the nitrogen-containing compound does not include dimethylaminopropylamine.

[0086] In certain embodiments, the nitrogen-containing compound may be an imidazole, such as an imidazole of the formula:

[0087]

[0088] wherein R is an amine capable of reacting in the methods described herein and having 3 to 8 carbon atoms.

[0089] In certain embodiments, the nitrogen-containing compound may be represented by the formula:

[0090]

[0091] Wherein each X is individually a C1 to C6 alkylene group, and each R is individually hydrogen or a C1 to C6 alkyl group. In certain embodiments, X may be individually a C1, C2 or C3 alkylene group. In certain embodiments, each R may be individually H or a C1, C2 or C3 alkyl group.

[0092] Quaternizable compounds

[0093] In certain embodiments, the reaction to prepare the quaternizable compound may be carried out at a temperature of greater than 80° C., such as greater than 90° C. or greater than 100° C. In certain embodiments, the reaction to prepare the quaternizable compound may be carried out at a temperature of 80° C. to 200° C., such as 90° C. to 200° C., 100° C. to 200° C., 125° C. to 200° C., 80° C. to 175° C., 90° C. to 175° C., 100° C. to 175° C., 125° C. to 175° C., 80° C. to 150° C., 90° C. to 150° C., 100° C. to 150° C., or 125° C. to 150° C. In certain embodiments, water of reaction, such as water produced during the condensation reaction, may be removed.

[0094] The free radical functionalized PIBSA product and the nitrogen-containing compound may be reacted in a ratio of 3:1 to 1:1.2, or 1.5:1 to 1:1.1, or 2:1 to 1:1.05, such as in a 1:1 ratio.

[0095] Quaternizing Agents

[0096] In certain embodiments, the quaternizing agent comprises at least one of a dialkyl sulfate, an alkyl cyclopentane halide, a hydrocarbyl substituted carbonate, or a hydrocarbyl epoxide. In certain embodiments, the quaternizing agent comprises a hydrocarbyl epoxide in combination with an acid.

[0097] In certain embodiments, the quaternizing agent may include an alkyl halide, such as a chloride, iodide, or bromide; an alkyl sulfonate; a dialkyl sulfate, such as dimethyl sulfate and diethyl sulfate; a sultone; an alkyl phosphate; a C 1-12 Trialkyl phosphate; di-C 1-12 Alkyl phosphate; borate ester; boric acid C 1-12 Alkyl esters; alkyl nitrites; alkyl nitrates; dialkyl carbonates, such as dimethyl oxalate; alkyl alkanoates, such as methyl salicylate; O,O-di-C 1-12 Alkyl dithiophosphate; or a mixture thereof.

[0098] In certain embodiments, the quaternizing agent may be derived from dialkyl sulfates (such as dimethyl sulfate or diethyl sulfate), N-oxides, sultones (such as propane sultone and butane sultone); alkyl halides, acyl halides or aryl halides, such as methyl chloride and ethyl chloride, methyl bromide and ethyl bromide or methyl iodide and ethyl iodide or benzyl chloride, and hydrocarbon (or alkyl) substituted carbonates. If the alkyl halide is benzyl chloride, the aromatic ring is optionally further substituted by an alkyl or alkenyl group.

[0099] In certain embodiments, the alkyl group of the alkyl-substituted carbonate can contain 1 to 50,1 to 20,1 to 10 or 1 to 5 carbon atoms per group.In one embodiment, the alkyl-substituted carbonate contains two alkyl groups that can be identical or different.The example of suitable alkyl-substituted carbonate comprises dimethyl carbonate or diethyl carbonate.

[0100] In certain embodiments, the quaternizing agent may comprise a hydrocarbyl epoxide, such as a hydrocarbyl epoxide represented by the formula:

[0101]

[0102] Each R 1 , R 2 , R 3 and R 4is independently H or a hydrocarbyl group having 1 to 50 carbon atoms. Examples of hydrocarbyl epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and combinations thereof. In certain embodiments, the hydrocarbyl epoxide may be an alcohol functionalized epoxide, a C4 to C 14 Epoxides and mixtures thereof. Exemplary C4 to C 14 Epoxides are those in which each R 1 , R 2 , R 3 and R 4 are independently H or C2 to C 12 In certain embodiments, the epoxide may be C4 to C 14 Epoxides. Epoxides suitable as quaternizing agents in the present technology may include, for example, C4 to C 14 Epoxides such as 2-ethyloxirane, 2-propyloxirane, and the like, and C4 to C6 alkylene oxides having branched and cyclic or aromatic substituents. 14 Epoxides, such as styrene oxide. C4 to C 14 Epoxides may also include epoxidized triglycerides, fats or oils; epoxidized alkyl esters of fatty acids; and mixtures thereof. In certain embodiments, the hydrocarbon epoxide may be C4 to C 20 Epoxides. Exemplary alcohol-functionalized epoxides may include those in which each R 1 , R 2 , R 3 and R 4 Those independently H or a hydroxyl-containing hydrocarbyl group. In certain embodiments, the hydroxyl-containing hydrocarbyl group may contain 2 to 32, or 3 to 28, or even 3 to 24 carbon atoms. Exemplary alcohol-functionalized epoxide derivatives may include, for example, glycidol, etc.

[0103] In certain embodiments, the hydrocarbyl epoxide may be used in combination with an acid. The acid used with the hydrocarbyl epoxide may be a separate component, such as acetic acid. In certain embodiments, there may be a small amount of the acid component, but <0.2 moles or <0.1 moles of acid per mole of hydrocarbyl acylating agent. These acids may also be used with other quaternizing agents described herein. Suitable acids may also include, for example, carboxylic acids (such as acetic acid and / or tall oil fatty acids), propionic acid, 2-ethylhexanoic acid, and the like, and mixtures thereof.

[0104] In certain embodiments, the quaternizing agent may include an ester of a carboxylic acid, or an ester of a polycarboxylic acid, that is capable of reacting with a tertiary amine to form a quaternary ammonium salt. In certain embodiments, such materials may be described as compounds having the following structure: 19 -C(=O)-OR 20 ; where R19 is an (optionally substituted) alkyl, alkenyl, aryl or alkylaryl group, and R 20 is a hydrocarbon group containing 1 to 22 carbon atoms. Suitable compounds include, but are not limited to, esters of carboxylic acids having a pKa of 3.5 or less. In certain embodiments, the compound is an ester of a carboxylic acid comprising at least one of a substituted aromatic carboxylic acid, an α-hydroxycarboxylic acid, or a polycarboxylic acid. In certain embodiments, the compound is an ester of a substituted aromatic carboxylic acid, so R 19 is a substituted aryl group. 19 R may be a substituted aryl group, a phenyl group or a naphthyl group having 6 to 10 carbon atoms. 19 It may be suitably substituted with one or more groups selected from alkoxycarbonyl, nitro, cyano, hydroxyl, SR' or NR'R', wherein each of R' and R'' may independently be hydrogen or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. In certain embodiments, R' and R'' are each independently hydrogen or an (optionally substituted) alkyl group containing 1 to 22, 1 to 16, 1 to 10 or 1 to 4 carbon atoms. In certain embodiments, R 19 is an aryl group substituted by one or more groups selected from hydroxy, alkoxycarbonyl, nitro, cyano and NH2. 19 R may be a polysubstituted aryl radical, for example trihydroxyphenyl, but may also be a monosubstituted aryl radical, for example an ortho-substituted aryl radical. 19 R may be substituted by a group selected from OH, NH2, NO2 or COOMe. 19 It may be an aryl group substituted with a hydroxyl group. 19 is a 2-hydroxyphenyl group. 20 R may be an alkyl or alkylaryl group, for example an alkyl or alkylaryl group containing 1 to 16 carbon atoms, or 1 to 10, or 1 to 8 carbon atoms. 20 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl or isomers thereof. In certain embodiments, R 20 is benzyl or methyl. In certain embodiments, the quaternizing agent is methyl salicylate.

[0105] In certain embodiments, the quaternizing agent may include an ester of an alpha-hydroxycarboxylic acid. Examples of suitable compounds containing the residue of an α-hydroxycarboxylic acid include: (i) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxyisobutyric acid; (ii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-methylbutyric acid; (iii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-ethylbutyric acid; (iv) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of lactic acid; and (v) methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl and phenyl esters of glycolic acid. In certain embodiments, the quaternizing agent includes methyl 2-hydroxyisobutyrate.

[0106] In certain embodiments, the quaternizing agent includes an ester of a polycarboxylic acid. Included in this definition are dicarboxylic acids and carboxylic acids having more than 2 acidic moieties. In certain embodiments, the ester is an alkyl ester having an alkyl group containing 1 to 4 carbon atoms. Suitable examples include oxalic acid diesters, phthalic acid diesters, maleic acid diesters, malonic acid diesters, or citric acid diesters or triesters.

[0107] In certain embodiments, the quaternizing agent is an ester of a carboxylic acid having a pKa less than 3.5. In certain embodiments in which the compound includes more than one acid group, reference is made to the first dissociation constant. The quaternizing agent may be selected from esters of carboxylic acids selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, and 2,4,6-trihydroxybenzoic acid. In certain embodiments, the quaternizing agent may include dimethyl oxalate, terephthalate (such as dimethyl terephthalate), and methyl 2-nitrobenzoate.

[0108] For example, quaternizing agents capable of coupling more than one quaternizable compound may also be used. "Coupling" more than one quaternizable compound refers to a compound in which at least two quaternizable compounds react with the same quaternizing agent to form at least two quaternizable compounds connected by the quaternizing agent. In some cases, such quaternizing agents may also be referred to herein as coupled quaternizing agents, and may include, for example, polyepoxides, such as diepoxides, triepoxides, or higher epoxides; polyhalides; epoxyhalides; aromatic polyesters; and mixtures thereof.

[0109] In certain embodiments, the quaternizing agent may be a polyepoxide. The polyepoxide may include, for example, polyglycidyl groups, which may include, for example, diepoxyoctane; ethylene glycol diglycidyl ether; neopentyl glycol diglycidyl ether; 1,4-butanediol diglycidyl ether; 3-(bis(glycidyloxymethyl)methoxy)-1,2-propanediol; 1,4-cyclohexanedimethanol diglycidyl ether; diepoxycyclooctane; bisphenol A diglycidyl ether; 4-vinyl-1-cyclohexene diepoxide; N,N-diglycidyl-4,4-glycidyloxyaniline; 1,6-hexane diglycidyl ether; trimethylolpropane triglycidyl ether; polypropylene glycol diglycidyl ether; polyepoxidized triglycerides, fats or oils; and mixtures thereof.

[0110] In certain embodiments, the quaternizing agent may be derived from a polyhalide, such as a chloride, iodide, or bromide. Such polyhalides may include, but are not limited to: 1,5-dibromopentane; 1,4-diiodobutane; 1,5-dichloropentane; 1,12-dichlorododecane; 1,12-dibromododecane; 1,2-diiodoethane; 1,2-dibromoethane; and mixtures thereof.

[0111] In certain embodiments, the quaternizing agent may be an epoxy halide, such as epichlorohydrin and the like.

[0112] In certain embodiments, the quaternizing agent may be a polyaromatic ester. Examples of polyaromatic esters may include, but are not limited to: 4,4'-oxybis(methyl benzoate); dimethyl terephthalate; and mixtures thereof.

[0113] In certain embodiments, the molar ratio of the quaternizable compound to the quaternizing agent is from 1:0.1 to 2, or from 1:1 to 1.5, or from 1:1 to 1.3. In certain embodiments, such as when a coupled quaternizing agent is used, the ratio of the quaternizable compound to the quaternizing agent may be from 2:1 to 1:1.

[0114] In certain embodiments, the quaternizing agent can be used in the presence of a protic solvent (e.g., 2-ethylhexanol, water, and combinations thereof). In certain embodiments, the quaternizing agent can be used in the presence of an acid. In certain embodiments, the quaternizing agent can be used in the presence of an acid and a protic solvent.

[0115] Composition

[0116] Also provided is a composition comprising a reaction product, the reaction product comprising a quaternary ammonium salt. In certain embodiments, the composition may also comprise at least one other additive. In certain embodiments, the at least one other additive may be at least one of a detergent, a demulsifier, a lubricant, a cold flow improver, or an antioxidant, provided that the at least one other additive is not a reaction product comprising a quaternary ammonium salt.

[0117] In certain embodiments, at least one other additive includes at least one hydrocarbyl-substituted succinic acid and / or at least one hydrocarbyl-substituted quaternary ammonium salt (other than a reaction product comprising a quaternary ammonium salt). The hydrocarbyl substituent may be a polyisobutylene having a number average molecular weight in the range of 100 to 5000.

[0118] The number average molecular weight (M) n ) can be measured using gel permeation chromatography (GPC) using a Waters GPC 2000 equipped with a refractive index detector and Waters EmpowerTM data acquisition and analysis software. Samples were run against polystyrene calibration standards. The column was polystyrene (PLgel, 5 microns, purchased from Agilent / Polymer Laboratories, Inc.). For the mobile phase, individual samples were dissolved in tetrahydrofuran and filtered with a PTFE filter before they were injected into the GPC port. Waters GPC 2000 operating conditions: injector, column and pump / solvent chamber temperature, 40°C; autosampler control: run time, 40 minutes; injection volume: 300 microliters; pump, system pressure, about 90 bar (maximum pressure limit, 270 bar; minimum pressure limit, 0 psi); flow rate: 1.0 ml / min; differential refractometer, sensitivity, -16; scale factor: 6.

[0119] In certain embodiments, at least one other additive comprises at least one detergent / dispersant, which is an amphiphilic substance having at least one hydrophobic hydrocarbon group with a number average molecular weight of 100 to 10,000 and at least one polar moiety selected from the following: (i) a monoamino or polyamino group with up to 6 nitrogen atoms (at least one nitrogen atom has basic properties); (ii) a hydroxyl group combined with a monoamino or polyamino group (at least one nitrogen atom has basic properties); (iii) a polyoxy-C2 to C4 alkylene moiety terminated by a hydroxyl group, a monoamino or polyamino group (at least one nitrogen atom has basic properties) or by a carbamate group; (iv) a moiety derived from succinic anhydride and having a hydroxyl and / or amino and / or amide and / or imido group; and / or (v) a moiety obtained by the Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine. In certain embodiments, at least one other additive may comprise at least one Mannich compound.

[0120] In certain embodiments, the present technology provides a composition comprising a reaction product, the reaction product comprising a quaternary ammonium salt as described herein, and the use of the composition in a fuel composition to improve the dehydration of the fuel composition. In certain embodiments, the present technology provides a composition comprising a reaction product, the reaction product comprising a quaternary ammonium salt as described herein, and the use of the composition in a lubricating composition of an oil of lubricating viscosity. In certain embodiments, the fuel and / or lubricant composition may additionally comprise at least one additional additive. Depending on the desired results and / or the application in which the composition will be used, these additional additives may be added to any composition described herein. When the term "additional additive (additional additive / additional additives)" is used herein, it means (unless the context otherwise requires) at least one additive that is not (and / or does not contain) a reaction product comprising a quaternary ammonium salt as described herein.

[0121] While any of the additional additives described herein may be used in any of the fuel and / or lubricant compositions of the present invention (depending on the desired results and / or the application in which the composition will be used), the following additional additives are particularly useful in the fuel and / or lubricant compositions: antioxidants, corrosion inhibitors, detergents and / or dispersant additives other than the reactant product comprising the quaternary ammonium salt described herein, cold flow improvers, foam inhibitors, demulsifiers, lubricants, metal passivators, valve seat recession additives, biocides, antistatic agents, antifreeze agents, fluidizing agents, combustion improvers, seal swell agents, wax control polymers, antifouling agents, gas-hydrate inhibitors, or any combination thereof.

[0122] Demulsifiers suitable for use as additional additives may include, but are not limited to, aryl sulfonates and polyalkoxylated alcohols, such as polyethylene oxide and polypropylene oxide copolymers, and the like. Demulsifiers may also include nitrogen-containing compounds, such as oxazoline and imidazoline compounds and fatty amines, and Mannich compounds. Mannich compounds are reaction products of alkylphenols and aldehydes (such as formaldehyde) with amines (such as amine condensates and polyalkylene polyamines). The materials described in the following U.S. patents are exemplary: U.S. Patents 3,036,003; 3,236,770; 3,414,347; 3,448,047; 3,461,172; 3,539,633; 3,586,629; 3,591,598; 3,634,515; 3,725,480; 3,726,882; and 3,980,569. Other suitable demulsifiers are alkali metal or alkaline earth metal salts of phenols and naphthalene sulfonates substituted by alkyl and alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds, such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-amylphenol ethoxylates), fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO) (e.g., including in the form of EO / PO block copolymers), polyethyleneimine or other polysiloxanes. Any commercially available demulsifier in an amount sufficient to provide a treatment level of 5ppm to 50ppm in the fuel may be suitably employed. In certain embodiments, there is no demulsifier as an additional additive in the fuel and / or lubricant composition. Demulsifiers may be used alone or in combination.

[0123] Suitable antioxidants used as additional additives include, for example, hindered phenols or derivatives thereof and / or diarylamines or derivatives thereof. Suitable detergents / dispersants used as additional additives include, for example, polyetheramines or nitrogen-containing detergents, including but not limited to PIB amine detergents / dispersants, succinimide detergents / dispersants and other quaternary salt detergents / dispersants, including quaternized PIB / amines and / or amide dispersants / detergents derived from polyisobutylene succinimide. Suitable cold flow improvers used as additional additives include, for example, esterified copolymers of maleic anhydride and styrene and / or copolymers of ethylene and vinyl acetate. Suitable lubricity improvers or friction modifiers used as additional additives may be based on fatty acids or reaction products of fatty acids, including, for example, fatty acid esters. Examples include tall oil fatty acids, such as described in, for example, WO 98 / 004656, and monoolein. Reaction products of natural or synthetic oils, which are described in US Pat. No. 6,743,266 B2, such as triglycerides and alkanolamines are also suitable as such lubricity improvers. Additional examples include commercial tall oil fatty acids containing polycyclic hydrocarbons and / or rosin acids.

[0124] Suitable metal deactivators for use as additional additives include, for example, aromatic triazoles or derivatives thereof, including but not limited to benzotriazole. Other suitable metal deactivators include, for example, salicylic acid derivatives, such as N,N′-disalicylidene-1,2-propylenediamine. Suitable valve seat depression additives for use as additional additives include, for example, alkali metal sulfosuccinates. Suitable foam inhibitors and / or defoamers for use as additional additives include, for example, organosiloxanes (such as polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, trimethyl-trifluoro-propylmethylsiloxane), polyacrylates, polymethacrylates, polyacrylamides, fluoroacrylates, etc. Suitable fluidizers for use as additional additives include, for example, mineral oils and / or poly(α-olefins) and / or polyethers. Combustion improvers suitable for use as additional additives include, for example, octane and hexadecane improvers. Suitable cetane number improvers which are suitable as further additives are, for example, aliphatic nitrates, such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides, such as di-tert-butyl peroxide.

[0125] Additional additives may also include diester, diamide, ester-amide and ester-imide friction modifiers prepared by reacting alpha-hydroxy acids with amines and / or alcohols, optionally in the presence of known esterification catalysts. Examples of alpha-hydroxy acids include glycolic acid, lactic acid, alpha-hydroxy dicarboxylic acids (such as tartaric acid) and / or alpha-hydroxy tricarboxylic acids (such as citric acid), and amines and / or alcohols, optionally in the presence of known esterification catalysts. These friction modifiers, which are generally derived from tartaric acid, citric acid or their derivatives, may be derived from branched amines and / or alcohols, resulting in the friction modifiers themselves having a large number of branched hydrocarbon groups in their structure. Examples of suitable branched alcohols for preparing such friction modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohol, and mixtures thereof. The friction modifier may be present at 0 to 6 wt % or 0.001 to 4 wt %, or 0.01 to 2 wt % or 0.05 to 3 wt % or 0.1 to 2 wt % or 0.1 to 1 wt % or 0.001 to 0.01 wt %, based on the total weight of the composition.

[0126] Additional additives may include a detergent / dispersant comprising a hydrocarbyl-substituted acylating agent. The acylating agent may be, for example, a hydrocarbyl-substituted succinic acid, or a condensation product of a hydrocarbyl-substituted succinic acid with an amine or an alcohol; i.e., a hydrocarbyl-substituted succinimide or a hydrocarbyl-substituted succinate. In certain embodiments, the detergent / dispersant may be a polyisobutylene-substituted succinic acid, amide, or ester, wherein the polyisobutylene substituent has a number average molecular weight of 100 to 5000. In certain embodiments, the detergent may be a C6 to C 18Substituted succinic acids, amides or esters. A more comprehensive description of hydrocarbyl-substituted acylating agent detergents can be found in paragraphs

[0017] to

[0036] of US 2011 / 0219674 A1.

[0127] In certain embodiments, detergents / dispersants used as additional additives may be quaternary ammonium salts other than those found in the reaction products of the present technology. These various quaternary ammonium salts may be quaternary ammonium salts prepared from hydrocarbyl-substituted acylating agents, such as polyisobutyl succinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight greater than 1200, polyisobutyl succinic anhydride having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or polyisobutyl succinic acid or anhydride having a hydrocarbyl substituent with a number average molecular weight of 1000. In certain embodiments, such quaternary ammonium salts prepared from the reaction of a nitrogen-containing compound and a hydrocarbyl-substituted acylating agent having a number average molecular weight of 1300 to 3000 may be imides. In certain embodiments, such quaternary ammonium salts prepared by the reaction of a nitrogen-containing compound and an acyl substituted acylating agent having a number average molecular weight greater than 1200 or having a number average molecular weight of 300 to 750 can be an amide or an ester. In certain embodiments, the acyl substituted acylating agent can include a monocarboxylic acid, a dimer carboxylic acid, or a trimer carboxylic acid having 8 to 54 carbon atoms and react with a primary or secondary amine. Suitable acids include, but are not limited to, monocarboxylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, hexacosanoic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, translinoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and monocarboxylic acid, dimer acid, or trimer acid of docosahexaenoic acid. The hydrocarbyl-substituted acylating agent can also be a copolymer formed by copolymerizing at least one monomer, which is an ethylenically unsaturated hydrocarbon having 2 to 100 carbon atoms. The monomer can be linear, branched or cyclic. The monomer can have an oxygen or nitrogen substituent, but will not react with an amine or alcohol. The monomer can react with a second monomer, which is a carboxylic acid or a carboxylic acid derivative having 3 to 12 carbon atoms. The second monomer can have one or two carboxylic acid functional groups and react with an amine or alcohol. When prepared using this method, the hydrocarbyl-substituted acylating agent copolymer has a number average molecular weight of 500 to 20,000. Alternatively, the hydrocarbyl-substituted acylating agent can be a terpolymer, which is a reaction product of ethylene and at least one monomer with (i) one or more alkenyl esters of aliphatic monocarboxylic acids having 1 to 24 carbon atoms or (ii) an alkyl ester of acrylic acid or methacrylic acid, and the at least one monomer is an ethylenically unsaturated monomer having at least one tertiary nitrogen atom. In certain embodiments, the nitrogen-containing compound of the different quaternary ammonium salts may be an imidazole or a nitrogen-containing compound having any of the following formulas:

[0128]

[0129] Wherein R can be C1 to C6 alkylene group; each of R1 and R2 can be C1 to C6 alkylene group individually; and each of R3, R4, R5 and R6 can be hydrogen or C1 to C6 alkyl group individually. In certain embodiments, R1 or R2 can be, for example, C1, C2 or C3 alkylene group. In certain embodiments, each R3, R4, R5, R6 can be, for example, H or C1, C2 or C3 alkyl group. In certain embodiments, the quaternizing agent for preparing different quaternary ammonium salts can be dialkyl sulfate, alkyl halide, hydrocarbon-substituted carbonate, hydrocarbon epoxide, carboxylate, alkyl ester or mixtures thereof. In certain embodiments, the quaternizing agent can be hydrocarbon epoxide. In certain embodiments, the quaternizing agent can be hydrocarbon epoxide combined with acid. In certain embodiments, the quaternizing agent can be salicylate, oxalate or terephthalate. In certain embodiments, the hydrocarbyl epoxide may be an alcohol functionalized epoxide or a C4 to C 14 In certain embodiments, the hydrocarbyl epoxide may be an alcohol functionalized epoxide or a C4 to C 20 Epoxides. In certain embodiments, the quaternizing agent is multifunctional, resulting in the additional quaternary ammonium salt being a coupled quaternary ammonium salt. Different quaternary ammonium salts may include, but are not limited to, quaternary ammonium salts having a hydrophobic portion in the anion. Exemplary compounds include quaternary ammonium compounds having the formula:

[0130]

[0131] Where R 0 , R 1 , R 2 and R 3 Each is individually an optionally substituted alkyl, alkenyl or aryl group, and R comprises an optionally substituted hydrocarbyl moiety having at least 5 carbon atoms. The different quaternary ammonium salts may also include polyetheramines, which are the reaction products of a polyether-substituted amine comprising at least one tertiary quaternizable amino group and a quaternizing agent that converts the tertiary amino group into a quaternary ammonium group.

[0132] In certain embodiments, the dispersant may be post-treated by reacting with any of a variety of reagents. Among the various reagents are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References to such treatments are listed in detail in U.S. Patent No. 4,654,403.

[0133] The fuel and / or lubricant composition described herein may include a detergent as an additional additive. Many detergents used in the field of engine lubrication obtain most or all of their basicity or total base number ("TBN") from the presence of alkaline metal-containing compounds (metal hydroxides, oxides or carbonates, such as such metals based on calcium, magnesium or sodium). Such metal overbased detergents (also referred to as overbased or superbased salts) are generally single-phase homogeneous Newtonian systems, characterized in that the metal content exceeds the metal content that would be present for neutralization according to the stoichiometric amount of the metal and the specific acidic organic compound that reacts with the metal. Overbased materials can be prepared by reacting a mixture of an acidic material (such as an inorganic acid or a low-carbon carboxylic acid, such as carbon dioxide) with an acidic organic compound (also referred to as a substrate), a stoichiometric excess of a metal base (possibly in a reaction medium in an inert organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for an acidic organic substrate). In certain embodiments, there is a small amount of a promoter, such as a phenol or alcohol, and in some cases, there is a small amount of water. The acidic organic substrate may have a sufficient number of carbon atoms to provide solubility in oil. Such overbased materials and methods of preparing them are well known to those skilled in the art. Patents describing techniques for preparing basic metal salts of sulfonic acids, carboxylic acids, phenols, phosphonic acids, and mixtures of any two or more of these include U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109. Salixarate detergents are described in U.S. Patent 6,200,936. In certain embodiments, the detergent may contain a metal-containing salicylate detergent, such as an overbased hydrocarbyl-substituted calcium salicylate detergent, which is described in US Pat. Nos. 5,688,751 and 4,627,928.

[0134] Viscosity improvers (sometimes also referred to as viscosity index improvers or viscosity modifiers) can be used as additional additives in the compositions described herein. Viscosity improvers can be polymers, including polyisobutylene, polymethacrylates ("PMA") and polymethacrylic acid esters, hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenyl aromatics-conjugated diene copolymers and polyolefins. PMA is prepared from a mixture of methacrylate monomers having different alkyl groups. The alkyl group can be a straight or branched chain group containing 1 to 18 carbon atoms. Most PMAs are viscosity modifiers and pour point depressants.

[0135] Multifunctional viscosity improvers that also have dispersant and / or antioxidant properties are known and may optionally be used as additional additives in fuel and / or lubricant compositions. Dispersant viscosity modifiers ("DVMs") are an example of such multifunctional additives. DVMs may be prepared by copolymerizing small amounts of nitrogen-containing monomers with alkyl methacrylates to yield an additive having some combination of dispersancy, viscosity regulation, pour point depression, and / or dispersancy. Vinyl pyridine, N-vinyl pyrrolidone, and N,N'-dimethylaminoethyl methacrylate are examples of nitrogen-containing monomers. Polyacrylates obtained from the polymerization or copolymerization of one or more alkyl acrylates may also be used as such viscosity modifiers.

[0136] Antiwear agent can be used as other additive in fuel and / or lubricant composition as herein described. Antiwear agent can include phosphorus-containing antiwear agent / extreme pressure agent, such as metal thiophosphate, phosphoric acid ester and its salt, phosphorus-containing carboxylic acid, ester, ether and amide, and phosphite. In certain embodiments, phosphorus antiwear agent can deliver 0.01 wt % to 0.2 wt %, or 0.015 wt % to 0.15 wt %, or 0.02 wt % to 0.1 wt %, or 0.025 wt % to 0.08 wt % phosphorus amount to exist. Antiwear agent can be zinc dialkyl dithiophosphate (ZDP). For some ZDP that can contain 11% P, suitable amount can include 0.09 wt % to 0.82 wt %. Non-phosphorus-containing antiwear agent includes boric acid ester (including borated epoxide), dithiocarbamate compound, molybdenum-containing compound and sulfided olefin. In certain embodiments, fuel and / or lubricant composition of the present invention does not contain phosphorus-containing antiwear agent / extreme pressure agent.

[0137] Foam suppressors that can be used as additional additives in the fuel and / or lubricant compositions described herein include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers include fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers. In certain embodiments, the composition may include a C5-C 17 Silicone-containing defoamer in combination with alcohol.

[0138] Pour point depressants which may be used as further additives in the fuel and / or lubricant compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates and / or polyacrylamides.

[0139] The metal passivator may be selected from derivatives of benzotriazole (such as tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-amino-2-propanol, derivatives of dimercaptothiadiazole, octylamine octanoate, PIBSA or condensation products of dodecenylsuccinic anhydride and / or fatty acids such as oleic acid and polyamines. The metal passivator may also be described as a corrosion inhibitor.

[0140] Seal swell agents that may be used as additional additives in the compositions described herein may include sulfolene derivatives, which are available from Exxon under the trade name Necton-37 TM (FN 1380) and Mineral Seal Oil TM (FN 3200) was purchased commercially.

[0141] Fuel composition

[0142] Also provided is a fuel composition comprising a fuel and a reaction product and optionally also comprising at least one of the above-mentioned other additives, the reaction product comprising a quaternary ammonium salt. In certain embodiments, the fuel may be a diesel fuel. In certain embodiments, the fuel may include gasoline. In certain embodiments, the reaction product comprising the quaternary ammonium salt may be present in an amount of 5 ppm to 1,000 ppm by weight (such as 5 ppm to 750 ppm by weight, 5 ppm to 500 ppm by weight, 5 ppm to 250 ppm by weight, 5 ppm to 200 ppm by weight, 5 ppm to 150 ppm by weight, 5 ppm to 100 ppm by weight, 10 ppm to 1,000 ppm by weight, 10 ppm to 750 ppm by weight, 10 ppm to 500 ppm by weight, 10 ppm to 250 ppm by weight, 10 ppm to 200 ppm by weight, 10 ppm to 150 ppm by weight, 10 ppm to 100 ppm by weight, 15 ppm to 1,000 ppm by weight, 15 ppm to 750 ppm by weight, 15 ppm to 500 ppm by weight, ppm, 15 wt ppm to 250 wt ppm, 15 wt ppm to 200 wt ppm, 15 wt ppm to 150 wt ppm, 15 wt ppm to 100 wt ppm, 20 wt ppm to 1,000 wt ppm, 20 wt ppm to 750 wt ppm, 20 wt ppm to 500 wt ppm, 20 wt ppm to 250 wt ppm, 20 wt ppm to 200 wt ppm, 20 wt ppm to 150 wt ppm, 20 wt ppm to 100 wt ppm, 25 wt ppm to 1,000 wt ppm, 25 wt ppm to 750 wt ppm, 25 ...5 wt ppm to 250 wt ppm, 25 wt ppm to 200 wt ppm, 25 wt ppm to 150 wt ppm, or 25 wt ppm to 100 wt ppm).

[0143] Also provided is a method for improving the dehydration (i.e., demulsification) performance of a fuel composition, the method comprising incorporating the above composition into a fuel composition. Also provided is the use of the above composition for providing improved dehydration performance in a fuel (such as a fuel that is liquid at room temperature).

[0144] Also provided is a method of reducing and / or preventing injector deposits in an engine, the method comprising supplying a fuel composition as described herein to a fuel injector of the engine and operating the engine.

[0145] Also provided is the use of a fuel composition as described herein for reducing and / or preventing internal deposits in an engine operated with the fuel composition.

[0146] In certain embodiments, the fuel composition may include a fuel that is liquid at room temperature and can be used to fuel an engine. The fuel may be liquid at ambient conditions, such as room temperature (20° C. to 30° C.). The fuel may be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. The hydrocarbon fuel may be obtained by refining or optionally (hydrogenating) treating a crude oil source. It may be a single stream or a mixture of different fractions from a refinery stream.

[0147] In certain embodiments, the fuel is gasoline, and in other embodiments, the fuel is leaded gasoline or unleaded gasoline. In certain embodiments, the fuel is diesel fuel. The hydrocarbon fuel may be a hydrocarbon prepared by a method such as a Fischer-Tropsch process. Examples of such fuels include gas-to-liquid (GTL) processes, biomass-to-liquid (BTL) processes, and coal-to-liquid (CTL) processes. The hydrocarbon portion may alternatively be prepared by hydrocracking or hydrogenation of vegetable oils. These hydrocarbon fuels may be used alone or in combination with other hydrocarbons or non-hydrocarbon fuels. The hydrocarbon fuel may be a petroleum distillate, including gasoline as defined by EN228 or ASTM specification D4814, or diesel fuel as defined by EN590 or ASTM specification D975.

[0148] Non-hydrocarbon fuel can be oxygenated composition, it is generally referred to as oxygenate, comprises alcohol, ether, ketone, carboxylic acid ester, nitroalkane or their mixture.Non-hydrocarbon fuel can comprise for example methanol, ethanol, methyl tertiary butyl ether, methyl ethyl ketone, transesterified oil and / or fat from plant and animal, such as rapeseed methyl ester and soybean methyl ester, and nitromethane.The mixture of hydrocarbon and non-hydrocarbon fuel can comprise for example gasoline and methanol and / or ethanol, diesel fuel and ethanol and diesel fuel and transesterified vegetable oil (such as rapeseed methyl ester).

[0149] In certain embodiments, the liquid fuel is an aqueous emulsion in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. In certain embodiments, the fuel may have a sulfur content of 5000ppm or less, 1000ppm or less, 300ppm or less, 200ppm or less, 30ppm or less, or 10ppm or less by weight. In certain embodiments, the fuel may have a sulfur content of 1ppm to 100ppm by weight. In certain embodiments, the fuel comprises 0ppm to 1000ppm, or 0ppm to 500ppm, or 0ppm to 100ppm, or 0ppm to 50ppm, or 0ppm to 25ppm, or 0ppm to 10ppm, or 0ppm to 5ppm of alkali metals, alkaline earth metals, transition metals, or mixtures thereof. In certain embodiments, the fuel contains 1 ppm to 10 ppm by weight of alkali metals, alkaline earth metals, transition metals, or mixtures thereof. It is well known in the art that fuels containing alkali metals, alkaline earth metals, transition metals, or mixtures thereof may have a greater tendency to form deposits, thereby contaminating or clogging common rail injectors. The fuels of the present invention are present in the fuel composition in a major amount generally greater than 50 wt %, and in certain embodiments, greater than 90 wt %, greater than 95 wt %, greater than 99.5 wt %, or greater than 99.8 wt %.

[0150] Based on the gross weight of fuel composition, the reaction product that comprises quaternary ammonium salt can be in the scope of 5ppm to 750ppm, 5ppm to 1000ppm or 5ppm to 500ppm or 10ppm to 250ppm or 10ppm to 150ppm or 15ppm to 100ppm to the treatment rate of fuel composition.In certain embodiments, based on the gross weight of fuel composition, the treatment rate scope can be 250ppm to 1000ppm or 250ppm to 750ppm or 500ppm to 750ppm or 250ppm to 500ppm.

[0151] In certain embodiments, the fuel composition may also include at least one other additive as described above. In certain embodiments, at least one other additive may include at least one demulsifier. Suitable demulsifiers may include but are not limited to aryl sulfonates and polyalkoxylated alcohols, such as polyethylene oxide and polypropylene oxide copolymers, etc. Demulsifiers may also include nitrogenous compounds, such as oxazoline and imidazoline compounds and fatty amines, and Mannich compounds. Mannich compounds are the reaction products of alkylphenols and aldehydes (especially formaldehyde) and amines (especially amine condensates and polyalkylene polyamines). The materials described in the following U.S. patents are exemplary: U.S. Patents 3,036,003; 3,236,770; 3,414,347; 3,448,047; 3,461,172; 3,539,633; 3,586,629; 3,591,598; 3,634,515; 3,725,480; 3,726,882; and 3,980,569. Other suitable demulsifiers are, for example, alkali metal or alkaline earth metal salts of alkyl-substituted phenols and naphthalenesulfonates and alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-amylphenol ethoxylates), fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO) (e.g., including in the form of EO / PO block copolymers), polyethyleneimine or another polysiloxane. Suitable demulsifiers also include hydrocarbyl-substituted dicarboxylic acids in the form of free acids or in the form of anhydrides, which anhydrides may be intramolecular anhydrides, such as succinic acid, glutaric acid or phthalic anhydride, or intermolecular anhydrides that connect two dicarboxylic acid molecules together. The hydrocarbyl substituent may have 12 to 2000 carbon atoms and may contain polyisobutylene substituents having a number average molecular weight of 300 to 2800. The dicarboxylic acid that exemplary alkyl replaces includes but is not limited to the acid that the alkyl replaces derived from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dioic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid or terephthalic acid, maleic acid, fumaric acid or glutaconic acid.In one embodiment, fuel composition of the present invention does not include the demulsifier as other additive.In the gross weight of fuel, demulsifier can be 0ppm to 50ppm (such as for example 1ppm to 50ppm, 5ppm to 50ppm, 1ppm to 25ppm, 5ppm to 25ppm, 1ppm to 20ppm or 5ppm to 20ppm) to the suitable treatment rate of fuel.

[0152] In certain embodiments, the at least one additional additive may include at least one detergent / dispersant. Suitable detergents / dispersants may include amphiphilic substances having at least one hydrophobic hydrocarbon group having a number average molecular weight of from 100 to 10,000 and at least one of the following moieties: (i) mono- or polyamino groups having up to 6 nitrogen atoms, at least one of which has basic character; (ii) hydroxyl groups in combination with mono- or polyamino groups, at least one of which has basic character; (iii) carboxyl groups or alkali metal or alkaline earth metal salts thereof; (iv) sulfonic acid groups or alkali metal or alkaline earth metal salts thereof; (v) polyoxy-C2 to C4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one of which has basic character, or by carbamate groups; (vi) carboxylate groups; (vii) moieties derived from succinic anhydride and having hydroxyl and / or amino and / or amide and / or imide groups; and / or (viii) moieties obtained by the Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

[0153] In certain embodiments, the hydrophobic hydrocarbon groups in these detergents / dispersants (which ensure adequate solubility in the fuel) have a number average molecular weight of 85 to 20,000, 1113 to 10,000, or 300 to 5000. In certain embodiments, the detergents / dispersants have a number average molecular weight of 300 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. n In certain embodiments, the hydrophobic hydrocarbon group may be a polypropylene group, a polybutylene group, and / or a polyisobutylene group, and the number average molecular weight thereof is 300 to 5000, 300 to 3000, 500 to 2500, or 700 to 2500. In certain embodiments, the detergent / dispersant has a number average molecular weight of 800 to 1500.

[0154] In certain embodiments, at least one additional additive may include at least one high TBN nitrogen-containing detergent / dispersant, such as a succinimide, which is a condensation product of a hydrocarbyl-substituted succinic anhydride and a poly(alkyleneamine). Exemplary succinimide detergents / dispersants are more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892. Another class of ashless dispersants are high molecular weight esters prepared by the reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. U.S. Pat. No. 3,381,022 describes such materials in more detail.

[0155] The nitrogen-containing detergent / dispersant may be the reaction product of a carboxylic acid-derived acylating agent and an amine. The acylating agent may vary from formic acid and its acylated derivatives to acylating agents with high molecular weight aliphatic substituents of up to 5,000, 10,000 or 20,000 carbon atoms. The amino compound may vary from ammonia itself to an amine (typically having aliphatic substituents of up to 30 carbon atoms and up to 11 nitrogen atoms). Suitable acylated amino compounds may be those formed by reacting an acylating agent having a hydrocarbyl substituent of at least 8 carbon atoms with a compound containing at least one primary or secondary amine group. The acylating agent may be a monocarboxylic acid or a polycarboxylic acid (or their reactive equivalents), such as substituted succinic acid, phthalic acid or propionic acid, and the amino compound may be a polyamine or a mixture of polyamines, such as a mixture of ethylene polyamines. Alternatively, the amine may be a hydroxyalkyl-substituted polyamine. The hydrocarbyl substituent in such an acylating agent may contain at least 10 carbon atoms. In certain embodiments, the hydrocarbyl substituent may contain at least 12, such as 30 or 50 carbon atoms. In certain embodiments, it may contain up to 200 carbon atoms. The number average molecular weight (M) of the hydrocarbyl substituent of the acylating agent is n ) may be 170 to 2800, such as 250 to 1500. In certain embodiments, the M of the substituent group n M may be in the range of 500 to 1500, or alternatively 500 to 1100. In certain embodiments, the M of the substituent group n It may be in the range of 700 to 1300. In certain embodiments, the hydrocarbyl substituent may have a number average molecular weight of 700 to 1000, or 700 to 850, or for example 750.

[0156] Another class of ashless dispersants are the Mannich bases. These are materials formed from the condensation of higher molecular weight, alkyl-substituted phenols, alkylene polyamines and aldehydes such as formaldehyde, and are described in more detail in US Pat. No. 3,634,515.

[0157] Useful nitrogen-containing dispersants include the product of a Mannich reaction between (a) an aldehyde, (b) a polyamine and (c) an optionally substituted phenol. The phenol may be substituted so that the molecular weight of the Mannich product is less than 7500. Optionally, the molecular weight may be less than 2000, less than 1500, less than 1300 or, for example, less than 1200, less than 1100, less than 1000. In certain embodiments, the Mannich product has a molecular weight of less than 900, less than 850 or less than 800, less than 500 or less than 400. The substituted phenol may be substituted with up to 4 groups on the aromatic ring. For example, it may be a trisubstituted or disubstituted phenol. In certain embodiments, the phenol may be a monosubstituted phenol. The substitution may be at one or more ortho and / or meta and / or para positions. To form the Mannich product, the molar ratio of aldehyde to amine is 4:1 to 1:1 or 2:1 to 1:1. The molar ratio of aldehyde to phenol may be at least 0.75:1; such as 0.75:1 to 4:1, preferably 1:1 to 4:1, or 1:1 to 2:1. To form a Mannich product, the molar ratio of phenol to amine may be at least 1.5:1, such as at least 1.6:1, at least 1.7:1, at least 1.8:1, or at least 1.9:1. The molar ratio of phenol to amine may be at most 5:1; for example, it may be at most 4:1, or at most 3.5:1. In certain embodiments, it is at most 3.25:1, at most 3:1, at most 2.5:1, at most 2.3:1, or at most 2.1:1.

[0158] Other dispersants used as additional additives may include polymeric dispersant additives, which are typically hydrocarbon-based polymers containing polar functionality to impart dispersing properties to the polymer. Amines may be used to prepare high TBN nitrogen-containing dispersants. One or more poly(alkyleneamines) may be used, and these poly(alkyleneamines) may include one or more poly(ethyleneamines) having 3 to 5 ethylene units and 4 to 6 nitrogen units. Such materials include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). Such materials are commercially available in the form of mixtures containing various isomers of a certain range of numbers of ethylene units and nitrogen atoms and a variety of isomeric structures (including various cyclic structures). Poly(alkyleneamines) may also be included in relatively high molecular weight amines known in the industry as ethyleneamine kettle bottoms.

[0159] In certain embodiments, the fuel composition may additionally include a quaternary ammonium salt except the reaction product comprising a quaternary ammonium salt as described herein. These may include alkylamine quaternary ammonium salts. Other quaternary ammonium salts may include (a) a compound comprising (i) at least one tertiary amino group as described above, and (ii) a number-average molecular weight of 100 to 5000, or 250 to 4000, or 100 to 4000, or 100 to 2500 or 3000 hydrocarbyl substituents; and (b) a quaternizing agent suitable for converting the tertiary amino group of (a) (i) as described above into quaternary nitrogen. Other quaternary ammonium salts are more fully described in U.S. Pat. Nos. 7,951,211, issued May 31, 2011; and 8,083814, issued December 27, 2011; and U.S. Publication Nos. 2013 / 0118062, issued May 16, 2013; 2012 / 0010112, issued January 12, 2012; 2013 / 0133243, issued May 30, 2013; 2008 / 0113890, issued May 15, 2008; and 2011 / 0219674, issued September 15, 2011; U.S. Pat. 2012 / 0149617, published on May 14, 2012; US2013 / 0225463, published on August 29, 2013; US2011 / 0258917, published on October 27, 2011; US ​​2011 / 0315107, published on December 29, 2011; US2013 / 0074794, published on March 28, 2013; US2012 / 0255512, published on October 11, 2012; US 2013 / 0333649, published on December 19, 2013; US 2013 / 0118062, published on May 16, 2013, and international publications WO 2011 / 141731, published on November 17, 2011; 2011 / 095819, published on August 11, 2011; and 2013 / 017886, published on February 7, 2013; WO 2013 / 070503, published on May 16, 2013; WO 2011 / 110860, published on September 15, 2011; WO 2013 / 017889, published on February 7, 2013; WO 2013 / 017884, published on February 7, 2013.

[0160] The quaternary ammonium salt used as an additional additive may be a quaternary ammonium salt prepared from a hydrocarbyl-substituted acylating agent, such as polyisobutyl succinic acid or anhydride having a hydrocarbyl substituent having a number average molecular weight greater than 1200, polyisobutyl succinic acid or anhydride having a hydrocarbyl substituent having a number average molecular weight of 300 to 750, or polyisobutyl succinic acid or anhydride having a hydrocarbyl substituent having a number average molecular weight of 1000.

[0161] In certain embodiments, the fuel composition may also include additional quaternary ammonium salts as additional additives. These additional salts may be imides prepared by the reaction of a nitrogen-containing compound with a hydrocarbyl-substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight of 1300 to 3000. In certain embodiments, the quaternary ammonium salt prepared by the reaction of a nitrogen-containing compound with a hydrocarbyl substituent with a number average molecular weight greater than 1200 or a hydrocarbyl-substituted acylating agent with a number average molecular weight of 300 to 750 is an amide or an ester.

[0162] In certain embodiments, the nitrogen-containing compounds of these additional quaternary ammonium salts may be imidazoles or nitrogen-containing compounds having any of the following formulae:

[0163]

[0164] wherein R may be a C1 to C6 alkylene group; each of R1 and R2 may individually be a C1 to C6 hydrocarbylene group; and each of R3, R4, R5 and R6 may individually be hydrogen or a C1 to C6 hydrocarbyl group.

[0165] In certain embodiments, the quaternizing agent used to prepare these additional quaternary ammonium salts can be a dialkyl sulfate, an alkyl halide, a hydrocarbon-substituted carbonate, a hydrocarbon epoxide, a carboxylate, an alkyl ester, or a mixture thereof. In certain embodiments, the quaternizing agent can be a hydrocarbon epoxide. In certain embodiments, the quaternizing agent can be a hydrocarbon epoxide combined with an acid. In certain embodiments, the quaternizing agent can be a salicylate, an oxalate, or a terephthalate. In certain embodiments, the hydrocarbon epoxide is an alcohol functionalized epoxide or a C4 to C 14 Epoxide.

[0166] In certain embodiments, the quaternizing agent is multifunctional, resulting in the additional quaternary ammonium salt being a coupled quaternary ammonium salt.

[0167] Exemplary treat rates of additional detergent / dispersant to the fuel compositions described herein are from 0 ppm to 500 ppm, or from 0 ppm to 250 ppm, or from 0 ppm to 100 ppm, or from 5 ppm to 250 ppm, or from 5 ppm to 100 ppm, or from 10 ppm to 100 ppm.

[0168] In certain embodiments, the at least one additional additive may include at least one cold flow improver. The cold flow improver may be at least one of the following: (1) C2 to C 40- copolymers of olefins with at least one further ethylenically unsaturated monomer; (2) comb polymers; (3) polyoxyalkylenes; (4) polar nitrogen compounds; (5) sulfocarboxylic acids or sulfonic acids or their derivatives; or (6) poly(meth)acrylates. It is possible to use mixtures of different representatives from one of the specific classes (1) to (6) and / or mixtures of representatives from different classes (1) to (6).

[0169] Suitable C2 to C 40 Olefin monomers are, for example, monomers having 2 to 20, or 2 to 10 carbon atoms, or 1 to 3, or 1 or 2 carbon-carbon double bonds, such as those having one carbon-carbon double bond. In the latter case, the carbon-carbon double bond may be arranged at the terminal (α-olefin) or internally. Suitable olefin monomers include α-olefins, such as α-olefins having 2 to 6 carbon atoms, for example propylene, 1-butene, 1-pentene, 1-hexene and / or ethylene. At least one additional ethylenically unsaturated monomer of category (1) may be selected from carboxylic acid alkenyl esters; for example C2 to C3 of carboxylic acids having 2 to 21 carbon atoms; 14 Alkenyl esters, such as vinyl esters and propenyl esters, wherein the hydrocarbon radical of the carboxylic acid may be linear or branched, such as vinyl esters; examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl pivalate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, (meth)acrylates; for example, (meth)acrylic acid with C1 to C 20 Alkanols, especially C1 to C 10 Alkanols, such as esters with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and their structural isomers and additional olefins; such as esters with molecular weights higher than the above C2 to C 40 Olefin base monomers, for example ethylene or propylene, suitable additional olefins are in particular C 10 To C 40 -α-olefins.

[0170] Suitable exemplary copolymers of class (1) are also those copolymers which comprise in copolymerized form two or more different alkenyl carboxylates which differ in their alkenyl functional groups and / or carboxylic acid groups. Likewise suitable are copolymers which, as well as the alkenyl carboxylates, comprise in copolymerized form at least one olefin and / or at least one (meth)acrylate.

[0171] C2 to C 40 -a-olefin terpolymer, C1 to C2 ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms 20C2 to C4 alkyl esters and saturated monocarboxylic acids having 2 to 21 carbon atoms 14 Alkenyl esters are also suitable as copolymers of class (1). Terpolymers of this type are described in WO 2005 / 054314. An exemplary terpolymer of this type is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.

[0172] In certain embodiments, at least one or additional ethylenically unsaturated monomer is copolymerized in the copolymer of category (1) in an amount of 1% to 50% by weight, such as 10% to 45% by weight or 20% to 40% by weight, based on the total copolymer. Thus, in terms of the weight of the monomer units in the copolymer of category (1), the major proportion may be derived from C2 to C 40 Base olefin. The copolymers of category (1) may have a number average molecular weight of from 1000 to 20,000, or from 1000 to 10,000, or from 1000 to 8000.

[0173] Exemplary comb polymers of component (2) can be obtained, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, followed by esterification of the anhydride or acid functions with an alcohol having at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins with esterified comonomers, for example esterified copolymers of styrene with maleic anhydride or esterified copolymers of styrene with fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleates. Homopolymers and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (2) are also those described, for example, in WO 2004 / 035715 and in “Comb-Like Polymers. Structure and Properties”, NA Phate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117 to 253 (1974). Mixtures of comb polymers are also suitable.

[0174] Polyoxyalkylenes suitable as components of category (3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene esters / ethers and mixtures thereof. These polyoxyalkylene compounds may contain at least one linear alkyl group, such as at least two linear alkyl groups, each of which has 10 to 30 carbon atoms; and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and U.S. Pat. No. 4,491,455. Suitable polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. In addition, suitable are polyoxyalkylene monoesters and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.

[0175] Polar nitrogen compounds suitable for use as components of class (4) may be ionic or nonionic and may have at least one substituent, or at least two substituents, which are in the form of a compound having the general formula >NR 7 The tertiary nitrogen atom form, where R 7 C8 to C 40 Hydrocarbyl. The nitrogen substituents may also be quaternized, i.e. in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides, which can be obtained by reacting at least one amine substituted by at least one hydrocarbyl with a carboxylic acid having 1 to 4 carboxyl groups or with suitable derivatives thereof. The amine may comprise at least one linear C8 to C 40 Suitable primary amines for the preparation of the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular amine mixtures which are available on an industrial scale, such as fatty amines or hydrogenated tallow amine, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acid substituted with long-chain hydrocarbon radicals.

[0176] Suitable sulfocarboxylic acids, sulfonic acids or their derivatives as cold flow improvers of class (5) are, for example, the oil-soluble carboxamides and carboxylates of o-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with an alkyl-substituted ammonium cation, as described in EP-A 261 957.

[0177] Poly(meth)acrylates suitable as cold flow improvers of class (6) are homopolymers or copolymers of acrylates and methacrylates. Also suitable are copolymers of at least two different (meth)acrylates which differ with respect to the esterifying alcohol. The copolymers optionally contain another different ethylenically unsaturated monomer in copolymerized form. The weight average molecular weight of the polymer is preferably from 50,000 to 500,000. The polymer may be methacrylic acid and a saturated C 14 and C 15 Copolymers of methacrylic esters of alcohols, the acid groups of which have been neutralized with hydrogenated tallow amine. Suitable poly(meth)acrylates are described, for example, in WO 00 / 44857.

[0178] Additional additives comprising at least one cold flow improver may be added to the fuel composition in an amount of 0 wt ppm to 5000 wt ppm, or 10 wt ppm to 5000 wt ppm, or 20 wt ppm to 2000 wt ppm, or 50 wt ppm to 1000 wt ppm, or 100 wt ppm to 700 wt ppm, or 200 wt ppm to 500 wt ppm, based on the total weight of the fuel composition.

[0179] Lubricating composition

[0180] Also provided is a lubricating composition comprising an oil of lubricating viscosity and the above composition. The reaction product comprising the quaternary ammonium salt may be present in the lubricating composition in an amount of 1 wt % to 5 wt % based on the total weight of the lubricating composition. In certain embodiments, the oil of lubricating viscosity may have a total sulfated ash level of less than 1 wt % based on the total weight of the lubricating composition. In certain embodiments, the oil of lubricating viscosity may have a total phosphorus content of less than 0.11 wt % based on the total weight of the lubricating composition.

[0181] Also provided is a method of lubricating a crankcase of an engine, the method comprising supplying the lubricating composition described herein to the engine and operating the engine.

[0182] Also provided is the use of the lubricating composition described herein for lubricating the crankcase of an engine.

[0183] The oil of lubricating viscosity can include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and / or hydrofining, unrefined oils, refined oils, re-refined oils or mixtures thereof. A more detailed description of unrefined oils, refined oils and re-refined oils is provided in WO 2008 / 147704, in paragraphs

[0054] to

[0056] . A more detailed description of natural and synthetic lubricating oils is provided in paragraphs

[0058] to

[0059] of WO2008 / 147704. Synthetic oils can also be produced by Fischer-Tropsch reaction, and can be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In certain embodiments, oil can be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures and other gas-to-liquid oils.

[0184] The oil of lubricating viscosity may also be selected from any of the base oils in Group IV as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guide. The five base oils are classified as follows; Group I, >0.03% sulfur or <90% saturates, and a viscosity index of 80-120; Group II, <0.03% sulfur and ≥90% saturates, and a viscosity index of 80-120; Group III, <0.03% sulfur and ≥90% saturates, and a viscosity index of ≥120; Group IV, all polyalphaolefins; Group V, all other base oils. Groups I, II, and III may be referred to as mineral oil base stocks.

[0185] Exemplary treat rates of the reaction product comprising the quaternary ammonium salt to the lubricating oil are from 0.1 wt % to 10 wt %, or from 0.5 wt % to 5 wt %, or from 0.5 wt % to 2.5 wt %, or from 0.5 wt % to 1 wt %, or from 0.1 wt % to 0.5 wt %, or from 1 wt % to 2 wt %, based on the total weight of the lubricating oil.

[0186] The amount of oil of lubricating viscosity present in the lubricating compositions described herein is the balance remaining after subtracting the total amount of all additives (including the reaction product comprising the quaternary ammonium salt described herein) and any additional additives as described herein.

[0187] The lubricating compositions described herein may be in the form of a concentrate or a fully formulated lubricant. If the lubricating composition is in the form of a concentrate (which may be combined with additional oils to form a finished lubricant in whole or in part), the ratio of these additives to the oil of lubricating viscosity and / or diluent oil includes a range of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.

[0188] In certain embodiments, the lubricating compositions described herein can be used in an internal combustion engine. The internal combustion engine can be a spark ignition type or a compression ignition type. The internal combustion engine can be a 2-stroke or 4-stroke engine. The internal combustion engine can be a passenger car engine, a light diesel engine, a heavy diesel engine, a motorcycle engine, or a 2-stroke or 4-stroke marine diesel engine. The internal combustion engine can be a passenger car engine or a heavy diesel internal combustion engine.

[0189] In certain embodiments, the lubricating composition as described herein may include a high-based metal-containing detergent as an additional additive. High-based detergents are known in the art. High-based materials (otherwise referred to as high-based or super-based salts) are generally single-phase homogeneous systems characterized in that the metal content exceeds the metal content that would be present for neutralization according to the stoichiometry of the metal and the specific acidic organic compound that reacts with the metal. High-based materials are prepared by reacting an acidic material (such as an inorganic acid or a lower carboxylic acid, such as carbon dioxide) with a reaction medium comprising an acidic organic compound, a reaction medium comprising at least one organic solvent (mineral oil, naphtha, toluene, xylene, etc.) that is inert to the acidic organic material, a stoichiometric excess of a metal base, and a promoter (such as calcium chloride, acetic acid, phenol or alcohol). The acidic organic material may have a sufficient number of carbon atoms to provide solubility in the oil. The amount (stoichiometry) of the "excess" metal is generally expressed in terms of a metal ratio. The term "metal ratio" is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound. The metal ratio of a neutral metal salt is one. A salt with 4.5 times as much metal as is present in a normal salt would have an excess of metal of 3.5 equivalents or a ratio of 4.5. The term "metal ratio" is also explained in "Chemistry and Technology of Lubricants", 3rd edition, edited by RM Mortier and ST Orszulik, copyright 2010, page 219, subheading 7.25.

[0190] The overbased metal containing detergent may be selected from non-sulfur containing phenates, sulfur containing phenates, sulfonates, salicyclics, salicylates, carboxylates and mixtures thereof or their borated equivalents.The overbased detergent may be borated with a borated agent such as boric acid.

[0191] The overbased detergent may be a non-sulfur-containing phenate, a sulfur-containing phenate, a sulfonate, or a mixture thereof.

[0192] In certain embodiments, the overbased sulfonate detergent may be present in the lubricating composition in an amount of 0.01 wt % to 0.9 wt %, or 0.05 wt % to 0.8 wt %, or 0.1 wt % to 0.7 wt %, or 0.2 wt % to 0.6 wt %, based on the total weight of the lubricating composition.

[0193] In certain embodiments, the overbased sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.

[0194] The high-based sulfonate may have a total base number of 250 to 600, or 300 to 500 (based on oil-free). High-based detergents are known in the art. In certain embodiments, the sulfonate detergent may be a primary linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of U.S. Patent Application 2005065045. The linear alkylbenzene may have a benzene ring attached to any position on the linear chain, such as at the 2nd, 3rd or 4th position, or a mixture thereof. The primary linear alkylbenzene sulfonate detergent may be useful for assisting in improving fuel economy. In certain embodiments, the sulfonate detergent may be a metal salt of one or more oil-soluble alkyltoluene sulfonate compounds as disclosed in paragraphs

[0046] to

[0053] of U.S. Patent Application 2008 / 0119378.

[0195] In certain embodiments, the overbased sulfonate detergent comprises overbased calcium sulfonate.The calcium sulfonate detergent may have a metal ratio of 18 to 40 and a TBN of 300 to 500 or 325 to 425.

[0196] Other detergents may also include "hybrid" detergents formed from mixed surfactant systems including phenate and / or sulfonate components as described, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate; for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where, for example, a hybrid sulfonate / phenate detergent is employed, the hybrid detergent would be considered equivalent to the introduction of similar amounts of phenate and sulfonate detergents, respectively, into the various phenate and sulfonate detergents.

[0197] Other detergents may have alkali metal, alkaline earth metal or zinc counter ions. In certain embodiments, the metal may be sodium, calcium, barium or magnesium. Other detergents may be sodium, calcium or magnesium containing detergents.

[0198] Other detergents may be overbased detergents of phenates, sulphur-containing phenates, sodium, calcium or magnesium salts of salicyclics and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN (on an oil-free basis).

[0199] Phenate detergents may be derived from para-hydrocarbylphenols. Alkylphenols of this type may be coupled with sulfur and overbased, coupled with aldehydes and overbased, or carboxylated to form salicylate detergents. Suitable alkylphenols include alkylphenols alkylated with oligomers of propylene, such as tetrapropenylphenol (e.g., p-dodecylphenol or PDDP) and pentapropenylphenol. Other suitable alkylphenols include alkylphenols alkylated with alpha-olefins, isomerized alpha-olefins, and polyolefins such as polyisobutylene. In certain embodiments, the lubricating composition comprises less than 0.2 wt%, or less than 0.1 wt%, or less than 0.05 wt% of a phenate detergent derived from PDDP. In certain embodiments, the lubricating composition comprises a phenate detergent not derived from PDDP.

[0200] Based on the gross weight of the lubricating composition, the overbased detergent may be present in the lubricating composition in an amount of 0 wt % to 10 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %. For example, in a heavy-duty diesel engine lubricating composition, the detergent may be present in an amount of 2 wt % to 3 wt % of the lubricating composition. For a passenger car engine, the detergent may be present in the lubricating composition in an amount of 0.2 wt % to 1 wt %, based on the gross weight of the lubricating composition. In certain embodiments, the lubricating composition comprises at least one overbased detergent having a metal ratio of at least 3, or at least 8, or at least 15.

[0201] In certain embodiments, the lubricating composition comprises at least one dispersant as a further additive. The dispersant may be selected from succinimide dispersants, Mannich dispersants, succinamide dispersants, polyolefin succinates, amides, or ester-amides, or mixtures thereof.

[0202] The succinimide dispersant can be derived from an aliphatic polyamine. The aliphatic polyamine can be ethylene polyamine, propylene polyamine, butylene polyamine or a mixture thereof. In certain embodiments, the aliphatic polyamine can be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine bottoms, and mixtures thereof.

[0203] In certain embodiments, the dispersant may be a polyolefin succinate, amide, or ester-amide. For example, the polyolefin succinate may be a polyisobutylene succinate of pentaerythritol or a mixture thereof. The polyolefin succinate-amide may be polyisobutylene succinic acid reacted with an alcohol such as pentaerythritol and an amine such as a diamine or diethylamine.

[0204] The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide. The polyisobutylene from which the polyisobutylene succinic anhydride may be derived may have a number average molecular weight of 350 to 5000, or 550 to 3000, or 750 to 2500. Succinimide dispersants and methods for their preparation are disclosed in, for example, U.S. Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433 and 6,165,235, 7,238,650 and EP Patent Application 0 355 895A.

[0205] Dispersants can also be post-processed by conventional methods by reacting with any of various reagents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes and ketones, carboxylic acids (such as terephthalic acid), hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxides and phosphorus compounds. In certain embodiments, the post-processed dispersant is borated. In certain embodiments, the post-processed dispersant can react with dimercaptothiadiazoles. In certain embodiments, the post-processed dispersant can react with phosphoric acid or phosphorous acid. In certain embodiments, the post-processed dispersant can react with terephthalic acid and boric acid (as described in U.S. Patent Application US2009 / 0054278).

[0206] In certain embodiments, the dispersant may be borated or non-borated. The borated dispersant may be a succinimide dispersant. In certain embodiments, the ashless dispersant may be boron-containing, i.e., boron has been incorporated and delivered to the lubricant composition. The boron-containing dispersant may be present in an amount that delivers at least 25 ppm of boron, at least 50 ppm of boron, or at least 100 ppm of boron to the lubricating composition. In certain embodiments, the lubricating composition may be free of a boron-containing dispersant. In certain embodiments, the lubricating composition has no more than 10 ppm of boron.

[0207] Dispersants used in the lubricating compositions described herein, which may be used as additional additives, may be prepared / obtained / obtainable from the reaction of succinic anhydride by an "ene" reaction or a "thermal" reaction, by what may be referred to as a "direct alkylation process". The "ene" reaction mechanism and general reaction conditions are summarized in "Maleic Anhydride", pages 147-149, edited by B. C Trivedi and B C Culbertson, and published by Plenum Press in 1982. Dispersants prepared by processes including an "ene" reaction may be polyisobutylene succinimide having carbocyclic rings present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the dispersant molecules. The "ene" reaction may have a reaction temperature of 180°C to less than 300°C, or 200°C to 250°C, or 200°C to 220°C.

[0208] Dispersants may also be obtained / obtainable from chlorine-assisted processes, typically involving Diels-Alder chemistry resulting in the formation of carbocyclic bonds. The dispersants produced by the chlorine-assisted process may be polyisobutylene succinimide having carbocyclic rings present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules. Thermal and chlorine-assisted processes are described in more detail in U.S. Pat. No. 7,615,521, columns 4 to 5, and Preparation Example A and Preparation Example B.

[0209] The dispersant may have a carbonyl to nitrogen ratio (CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2. In certain embodiments, the dispersant may have a CO:N ratio of 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2, or 1:1.4 to 1:0.6.

[0210] In certain embodiments, the dispersant may be a succinimide dispersant and may include polyisobutylene succinimide, wherein the polyisobutylene from which the polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000 or 750 to 2500. The dispersant may be present in the lubricating composition in an amount of 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.5 wt % to 9 wt %, or 1 wt % to 8.5 wt %, or 1.5 wt % to 5 wt %, based on the total weight of the lubricating composition.

[0211] In certain embodiments, the lubricating composition may include a molybdenum compound as an additional additive. The molybdenum compound may be an antiwear agent or an antioxidant. The molybdenum compound may be selected from molybdenum dialkyl dithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide 0 ppm to 1000 ppm, 5 ppm to 1000 ppm, 10 ppm to 750 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum to the lubricating composition.

[0212] In certain embodiments, the lubricating composition may also include an antioxidant as an additional additive. The antioxidant includes sulfided olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as platinum dithiocarbamates), hydroxy thioethers, or mixtures thereof. Based on the gross weight of the lubricating composition, the antioxidant may be present in the lubricating composition in an amount of 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt %, or 0.3 wt % to 1.5 wt %.

[0213] In certain embodiments, the lubricating composition may further comprise a phenolic or aminic antioxidant or a mixture thereof as an additional additive, and optionally, the antioxidant may be present in an amount of 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt % or 1 wt % to 2.5 wt %, based on the total weight of the lubricating composition.

[0214] Diarylamine or alkylated diarylamine can be phenyl-α-naphthylamine (PANA), alkylated diphenylamine or alkylated phenylnaphthylamine or their mixture.Alkylated diphenylamine can include dinonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctylated diphenylamine, didecyl diphenylamine, decyl diphenylamine and their mixture.In certain embodiments, diphenylamine can include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine or their mixture.In certain embodiments, alkylated diphenylamine can include nonyl diphenylamine or dinonyl diphenylamine.Alkylated diarylamine can include octyl, dioctyl, nonyl, dinonyl, decyl or didecyl phenyl naphthylamine.

[0215] Hindered phenol antioxidants may contain sec-butyl and / or t-butyl groups as hindering groups. The phenol group may typically be further substituted with a hydrocarbyl group (typically a straight or branched alkyl group) and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol or 4-dodecyl-2,6-di-tert-butylphenol. In certain embodiments, the hindered phenol antioxidant may be an ester and may include, for example, Irganox® from Ciba. TM L-135. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry can be found in US Patent 6,559,105.

[0216] Examples of molybdenum dithiocarbamates that can be used as antioxidants include commercially available materials sold under the following trade names: such as Molybdenum Dithiocarbamate from RT Vanderbilt Co., Ltd. and and Adeka Sakura-Lube TM S-100, S-165, S-600 and 525, or mixtures thereof.

[0217] In certain embodiments, the lubricating composition may also include a viscosity modifier as an additional additive. Viscosity modifiers are known in the art and may include hydrogenated styrene-butadiene rubber, ethylene-propylene copolymers, copolymers of ethylene and propylene and higher olefins, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkylstyrenes, polyolefins, esters of maleic anhydride-olefin copolymers (such as esters described in International Application WO2010 / 014655), esters of maleic anhydride-styrene copolymers, or mixtures thereof. Viscosity modifiers may include block copolymers (such as hydrogenated styrene-butadiene copolymers or hydrogenated styrene-isoprene copolymers) comprising (i) vinyl aromatic monomer blocks and (ii) conjugated diene olefin monomer blocks, polymethacrylates, ethylene-alpha olefin copolymers, hydrogenated star polymers comprising conjugated diene monomers (such as butadiene or isoprene) or star polymers of polymethacrylates, or mixtures thereof.

[0218] In certain embodiments, the viscosity modifier may be a dispersant viscosity modifier.The dispersant viscosity modifier may include a functionalized polyolefin, for example, an ethylene-propylene copolymer that has been functionalized with an acylating agent such as maleic anhydride and amines.

[0219] In certain embodiments, the dispersant viscosity modifier comprises an olefin copolymer further functionalized with a dispersant amine group. The olefin copolymer may be an ethylene-propylene copolymer. The olefin copolymer may have a number average molecular weight of 5000 to 20,000, or 6000 to 18,000, or 7000 to 15,000. The olefin copolymer may have a shear stability index of 0 to 20, or 0 to 10, or 0 to 5 measured by an Orbahn shear test (ASTM D6278).

[0220] The formation of dispersant viscosity modifiers is well known in the art. Dispersant viscosity modifiers may include, for example, those described in US 7,790,661 at column 2, line 48 to column 10, line 38.

[0221] In certain embodiments, the dispersant viscosity modifier may be prepared by grafting an olefinic carboxylic acid acylating agent to 15 mol % to 80 mol % of ethylene, 20 mol % to 85 mol % of C 3-10 The grafted polymer is prepared by grafting a polymer of an α-monoolefin and 0 to 15 mol % of a non-conjugated diene or triene (the polymer) and further reacting the grafted polymer with an amine (usually an aromatic amine).

[0222] Dispersant viscosity modifiers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with acylating agents such as maleic anhydride and amines; polymethacrylates functionalized with amines, or styrene-maleic anhydride copolymers reacted with amines. Suitable amines may be aliphatic or aromatic amines and polyamines. Examples of suitable aromatic amines include nitroaniline, aminodiphenylamine (ADPA), alkylene-coupled polyaromatic amines, and mixtures thereof. A more detailed description of dispersant viscosity modifiers is provided in the following documents: International Publication WO2006 / 015130 or U.S. Patents 4,863,623; 6,107,257; 6,107,258; 6,117,825; and US 7,790,661.

[0223] In certain embodiments, dispersant viscosity modifiers may include those described in U.S. Patent No. 4,863,623 (see column 2, line 15 to column 3, line 52) or International Publication No. WO 2006 / 015130 (see page 2, paragraphs

[0008] and paragraphs

[0065] to

[0073] ).

[0224] In certain embodiments, the lubricating compositions disclosed herein may further include a dispersant viscosity modifier, which may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.2 wt % to 1.2 wt %, based on the total weight of the lubricating composition.

[0225] In certain embodiments, the lubricating composition may further comprise at least one friction modifier as an additional additive. In certain embodiments, the friction modifier may be selected from derivatives of long-chain fatty acid derivatives of amines, long-chain fatty esters, or long-chain fatty epoxides; fatty imidazolines; amine salts of alkyl phosphoric acids; fatty alkyl tartaric acid esters; fatty alkyl tartar imides; fatty alkyl tartaric amides; fatty maleates and imides, fatty (poly) glycolates; and fatty hydroxyacetamides. Based on the total weight of the lubricating composition, the friction modifier may be present in the lubricating composition in an amount of 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt %. In certain embodiments, as used herein, the term "fatty alkyl" or "fat" with respect to the friction modifier means a carbon chain having 10 to 22 carbon atoms, such as a straight carbon chain.

[0226] Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty acid esters or fatty epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene polyamines; amine salts of alkyl phosphoric acids; fatty alkyl tartaric acid esters; fatty alkyl tartarimides; fatty alkyl tartaramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerides, such as glycerol monooleate; borated glycerides; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxy and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and their salts.

[0227] Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyl dithiophosphates, molybdenum dithiocarbamates, sunflower or soybean oil monoesters of polyols, and aliphatic carboxylic acids.

[0228] In certain embodiments, the friction modifier may be a long chain fatty acid ester. In certain embodiments, the long chain fatty acid ester may be a monoester and / or a triglyceride.

[0229] In certain embodiments, the lubricating composition may also include at least one antiwear agent as an additional additive. Examples of suitable antiwear agents include titanium compounds, tartaric acid derivatives (such as tartaric acid esters, amides or tartarimides), malic acid derivatives, citric acid derivatives, glycolic acid derivatives, oil-soluble amine salts different from the phosphorus compounds of the present invention, sulphurized olefins, metal dihydrocarbyl dithiophosphates (such as dialkyl zinc dithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates and bis (S-alkyl dithiocarbamoyl) disulfides).

[0230] The antiwear agent may include a tartrate or tartrimide as disclosed in International Publication No. WO 2006 / 044411 or Canadian Patent No. CA 1 183125. The tartrate or tartrimide may contain an alkyl ester group, wherein the total carbon atoms on the alkyl group is at least 8. The antiwear agent may include a citrate as disclosed in U.S. Patent Application No. 20050198894.

[0231] Another class of additives includes oil-soluble titanium compounds, such as disclosed in US 7,727,943 and US2006 / 0014651. The oil-soluble titanium compound can be used as an anti-wear agent, a friction modifier, an antioxidant, a deposition control additive, or more than one of these functions. The oil-soluble titanium compound can be a titanium (IV) alkoxide. The titanium alkoxide is formed by a monohydric alcohol, a polyhydric alcohol, or a mixture thereof. The monohydric alkoxide can have 2 to 16 carbon atoms or 3 to 10 carbon atoms. The titanium alkoxide can be titanium (IV) isopropoxide. The titanium alkoxide can be 2-ethylhexyl titanium (IV). The titanium compound can include an alkoxide of an adjacent 1,2-diol or a polyhydric alcohol. The 1,2-adjacent diol can contain a fatty acid monoester of glycerol, such as when the fatty acid is oleic acid. The oil-soluble titanium compound can be a titanium carboxylate. The titanium (IV) carboxylate can be titanium neodecanoate.

[0232] In certain embodiments, the lubricating composition may also include at least one phosphorus-containing antiwear agent as an additional additive. The phosphorus-containing antiwear agent may be a zinc dialkyl dithiophosphate, a phosphite, a phosphate, a phosphonate, and an ammonium phosphate, or a mixture thereof. Examples of zinc dithiophosphates include isopropyl methyl amyl zinc dithiophosphate, isopropyl isooctyl zinc dithiophosphate, di(cyclohexyl) zinc dithiophosphate, isobutyl 2-ethylhexyl zinc dithiophosphate, isopropyl 2-ethylhexyl zinc dithiophosphate, isobutyl isopentyl zinc dithiophosphate, isopropyl n-butyl zinc dithiophosphate, and combinations thereof. The zinc dialkyl dithiophosphate may provide 0.01 wt % to 0.1 wt % of phosphorus to the lubricating composition, or provide 0.015 wt % to 0.075 wt % of phosphorus to the lubricating composition, or 0.02 wt % to 0.05 wt % of phosphorus in an amount present in the lubricating composition. In certain embodiments, the lubricating composition does not contain or is substantially free of zinc dialkyl dithiophosphate. The antiwear agent may be present in the lubricating composition in an amount of 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt %, based on the total weight of the lubricating composition.

[0233] In certain embodiments, the lubricating composition may further include at least one ashless antiwear agent (e.g., present in an amount of 0.01 wt % to 5 wt % or 0.1 wt % to 2 wt %, based on the total weight of the lubricating composition), such as an ashless antiwear agent represented by the formula:

[0234]

[0235] in

[0236] Y and Y' are independently -O-, >NH, >NR 3 or by combining the Y and Y' groups and forming R between the two >C=O groups 1 -N< group to form an imide group;

[0237] X is independently -ZO-Z'-, >CH2, >CHR 4 、>CR 4 R 5 、>C(OH)(CO2R 2 )、>C(CO2R 2 )2 or>CHOR 6 ;

[0238] Z and Z' are independently >CH2, >CHR 4 、>CR 4 R 5 、>C(OH)(CO2R 2 ) or>CHOR 6 ;

[0239] n is 0 to 10, provided that when n=1, X is not >CH2, and when n=2, both X are not >CH2;

[0240] m is 0 or 1;

[0241] R 1 are independently hydrogen or a hydrocarbyl group typically containing 1 to 150 carbon atoms, provided that when R 1 When it is hydrogen, m is 0, and n is greater than or equal to 1;

[0242] R 2 is a hydrocarbyl group generally containing 1 to 150 carbon atoms;

[0243] R 3 , R 4 and R 5 are independently a hydrocarbyl group; and

[0244] R 6 is hydrogen or a hydrocarbyl group generally containing 1 to 150 carbon atoms.

[0245] In certain embodiments, the ashless antiwear agent may be a compound obtained / obtainable by a process comprising reacting glycolic acid, 2-haloacetic acid or lactic acid or an alkali metal salt thereof or an alkali metal salt thereof (such as glycolic acid or 2-haloacetic acid) with at least one member selected from the group consisting of amines, alcohols and amino alcohols. For example, the compound may be represented by at least one of the following formulae:

[0246]

[0247] in

[0248] Y is independently oxygen or >NH or >NR 1 ;

[0249] R 1 are independently hydrocarbyl groups typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms;

[0250] Z is hydrogen or methyl;

[0251] Q is a residue of a diol, triol or higher polyol, a diamine, triamine or higher polyamine, or an amino alcohol (e.g., Q is a diol, a diamine or an amino alcohol)

[0252] g is 2 to 6, or 2 to 3, or 2;

[0253] q is 1 to 4, or 1 to 3, or 1 to 2;

[0254] n is 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3; and

[0255] Ak1 is an alkylene group (such as ethylene) containing 1 to 5, or 2 to 4, or 2 to 3 carbon atoms; and

[0256] b is 1 to 10, or 2 to 8, or 4 to 6, or 4.

[0257] Exemplary Industrial Applications

[0258] The compositions described herein may be used as / for a liquid fuel composition, for an oil of lubricating viscosity (e.g., a lubricating composition), and / or as a lubricating composition, such as for use in an internal combustion engine. The internal combustion engine may be a gasoline or diesel engine. Exemplary internal combustion engines include, but are not limited to, spark ignition and compression ignition engines; 2-stroke or 4-stroke cycles; liquid fuels supplied via direct injection, indirect injection, port injection, and carburetors; homogeneous charge compression ignition engines; common rail and unit injector systems; light (e.g., passenger cars) and heavy (e.g., commercial truck) engines; and engines fueled with hydrocarbon and non-hydrocarbon fuels and mixtures thereof. The engine may be part of an integrated emission system that incorporates the following elements: an EGR system; aftertreatment, including a three-way catalyst, an oxidation catalyst, NO x absorbers and catalysts, catalyzed and non-catalyzed particulate traps, optionally with fuel-borne catalysts; variable valve timing; and injection timing and rate shaping.

[0259] In certain embodiments, the subject matter disclosed herein may be used with a diesel engine having a direct fuel injection system (in which the fuel is injected directly into the combustion chamber of the engine). The ignition pressure may be greater than 1000 bar, and in one embodiment, the ignition pressure may be greater than 1350 bar. Therefore, the direct fuel injection system may be a high-pressure direct fuel injection system with an ignition pressure greater than 1350 bar. Exemplary types of high-pressure direct fuel injection systems include, but are not limited to, unit direct injection (or "pump and nozzle") systems and common rail systems. In a unit direct injection system, a high-pressure fuel pump, a fuel metering system, and a fuel injector are combined into one device. A common rail system has a series of injectors connected to the same accumulator or rail. The rail is then connected to the high-pressure fuel pump. A unit direct injection or common rail system may also include an optional turbocharged or supercharged direct injection system.

[0260] In certain embodiments, the subject matter disclosed herein can be used to provide at least comparable, if not improved, detergency (deposit reduction and / or prevention) performance in conventional and modern diesel engines compared to conventional additives. In addition, the technology can provide similar or improved dehydration (or demulsification) performance compared to conventional compounds in conventional and modern diesel engines.

[0261] In another embodiment, a lubricating composition comprising a reaction product comprising a quaternary ammonium salt can be used to lubricate an internal combustion engine (eg, for crankcase lubrication).

[0262] Embodiments of the present technology may provide at least one of antiwear performance, friction regulation (particularly for improving fuel economy), detergent performance (particularly deposit control or varnish control), or dispersancy (particularly soot control, sludge control, or corrosion control). Example

[0263] The subject matter disclosed herein can be better understood with reference to the following examples, which are only used to further illustrate the subject matter disclosed herein. The exemplary embodiments should not be interpreted as limiting the subject matter in any way.

[0264] Preparation Material A

[0265] 550M will be used by using the free radical functionalization method described herein (which produces a free radical functionalized PIBSA product) n Polyisobutylene succinic anhydride (1113.6 g: 1.74 mol) prepared by reacting high vinylidene polyisobutylene with maleic anhydride was heated to 70°C and charged to a 2L round bottom flange flask equipped with a stirrer, a condenser with a Dean-Stark trap, a nitrogen inlet, a subline addition pipe, and a thermocouple / temperature control system. N,N-dimethylaminopropylamine (179.3 g: 1.74 mol) was then charged via the subline addition line over 90 minutes, maintaining the batch temperature below 120°C. The batch was then heated to 150°C and maintained at that temperature for 3 hours, collecting about 30 mL of water. The resulting product comprising a non-quaternized free radical functionalized succinimide detergent was cooled and collected.

[0266] Preparation of material B

[0267] 1000 M will be converted to PIBSA by using the free radical functionalization method described herein, which produces a free radical functionalized PIBSA product. nPolyisobutylene succinic anhydride (1899.7 g: 1.72 mol) prepared by reacting high vinylidene polyisobutylene with maleic anhydride was heated to 70°C and charged to a 3 L round bottom flange flask equipped with a stirrer, a condenser with a Dean-Stark trap, a nitrogen inlet, a split line addition line, and a thermocouple / temperature control system. N,N-dimethylaminopropylamine (176.0 g: 1.72 mol) was then charged via the split line addition line over 60 minutes, maintaining the batch temperature below 120°C. The batch was then heated to 150°C and maintained at that temperature for 3 hours, collecting about 30 mL of water. The resulting product comprising a non-quaternized free radical functionalized succinimide detergent was cooled and collected.

[0268] Preparation of Materials C

[0269] 550M will be made by using the conventional "ene" reaction n Polyisobutylene succinic anhydride (700.3 g: 1.10 mol) prepared by reacting high vinylidene polyisobutylene with maleic anhydride was heated to 70°C and charged to a 2L round bottom flask equipped with a stirrer, a condenser with a Dean-Stark trap, a nitrogen inlet, a split-line addition line, and a thermocouple / temperature control system. N,N-dimethylaminopropylamine (112.3 g: 1.10 mol) was then charged via the split-line addition line over 90 minutes, maintaining the batch temperature below 120°C. The batch was then heated to 150°C and maintained at that temperature for 3 hours, collecting about 30 mL of water. The resulting product containing a non-quaternized succinimide detergent was cooled and collected.

[0270] Preparation of Materials D

[0271] By using the conventional "ene" reaction, 1000M n Polyisobutylene succinic anhydride (2000 g: 1.81 mol) prepared by reacting high vinylidene polyisobutylene with maleic anhydride was heated to 70°C and charged to a 3 liter round bottom flask equipped with a stirrer, a condenser with a Dean-Stark trap, a nitrogen inlet, a split-line addition line, and a thermocouple / temperature control system. NN-dimethylaminopropylamine (185.2 g: 1.81 mol) was then charged via the split-line addition line over 60 minutes, maintaining the batch temperature below 120°C. The batch was then heated to 150°C and maintained at that temperature for 3 hours, collecting about 30 mL of water. The resulting product containing a non-quaternized succinimide detergent was cooled and collected.

[0272] Example 1

[0273] Prepared material A (848.8 g: 1.13 mol) was charged into a 2 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (255.6 g: 1.96 mol), acetic acid (68.1 g: 1.13 mol), and water (26.6 g: 1.46 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (139.7 g: 2.41 mol) was then added subsurface via a PTFE head peristaltic pump over a period of about 2 hours. The batch was maintained at 70°C for 4 hours. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product containing a free radical functionalized quaternized succinimide detergent having an acetate counterion was cooled and collected.

[0274] Example 2

[0275] Prepared material A (321.2 g: 0.44 mol) was charged into a 1 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (116.4 g: 0.90 mol), tall oil fatty acid (TOFA, 113.8 g: 0.44 mol), and water (8.7 g: 0.48 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (54.1 g: 0.93 mol) was then added subsurface via a PTFE head peristaltic pump over a period of about 60 minutes. The batch was maintained at 70°C for 4 hours. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product comprising a free radical functionalized quaternized succinimide detergent with a TOFA counterion was cooled and collected.

[0276] Example 3

[0277] Prepared material B (399.5 g: 0.34 mol) was charged into a 1 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (153.6 g: 1.18 mol), acetic acid (21.0 g: 0.35 mol), and water (4.0 g: 0.22 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (36.4 g: 0.63 mol) was then added subsurface via a syringe pump over a period of about 2 hours. The batch was maintained at 70°C for 4 hours. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product comprising a free radical functionalized quaternized succinimide detergent having an acetate counterion was cooled and collected.

[0278] Example 4

[0279] Prepared material C (952.6 g: 1.32 mol) was charged into a 2 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (305.9 g: 2.35 mol), acetic acid (83.8 g: 1.39 mol), and water (28.7 g: 1.58 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (154 g: 2.65 mol) was then added subsurface via a PTFE head peristaltic pump over a period of about 2 hours. The batch was maintained at 70°C for 90 minutes. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product comprising a quaternized succinimide detergent having an acetate counterion was cooled and collected.

[0280] Example 5

[0281] Prepared material C (337.1 g: 0.45 mol) was charged into a 1 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (122.8 g: mol), TOFA (112 g: 0.45 mol), and water (10.1 g: 0.56 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (56.8 g: 0.98 mol) was then added subsurface via a PTFE head peristaltic pump over a period of about 60 minutes. The batch was maintained at 70°C for 4 hours. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product comprising a quaternized succinimide detergent with a TOFA counterion was cooled and collected.

[0282] Example 6

[0283] Preparation material D (726.2 g: 0.70 mol) was charged into a 2 L round bottom flange flask equipped with a stirrer, a condenser with a dry ice / acetone trap, a nitrogen inlet, and a thermocouple / temperature control system. 2-Ethylhexanol (306.3 g: 2.35 mol), acetic acid (42.6 g: 0.71 mol), and water (12.8 g: 0.71 mol) were added to the flask, and the mixture was stirred with an overhead stirrer and heated to 70°C. Propylene oxide (89.7 g: 1.54 mol) was then added subsurface via a PTFE head peristaltic pump over a period of about 2 hours. The batch was maintained at 70°C for 90 minutes. The heating was then turned off, and the batch was purged for 60 minutes via a subsurface dip-leg to remove residual propylene oxide. The resulting product comprising a quaternized succinimide detergent having an acetate counterion was cooled and collected.

[0284] Solubility test

[0285] The following test method can be used to test the solubility of the examples in fuel: 0.1 wt% of the example compound can be added to the reference fuel RF79-07 (referred to as RF79) and mixed gently. This solution can then be further diluted with the reference fuel RF-79 to prepare a 15 ppm (by weight) solution. If the sample shows precipitation, the example compound being tested may not be suitable for use in fuel.

[0286] Demulsification test

[0287] Demulsification testing (ASTM D1094-07, "Standard Test Method for Water Reactivity of Aviation Fuels") was performed to measure the ability of the examples to demulsify fuel and water mixtures. Example compounds were added to room temperature fuel at various ppm by weight based on the total weight of the fuel.

[0288] Then the fuel (80mL, RF79) comprising the embodiment compound is added to a clean 100mL graduated cylinder. Then the phosphate buffer solution (20mL) with a pH of 7.0 is added to the graduated cylinder and the graduated cylinder is plugged. The graduated cylinder is shaken for 2 minutes with 2 to 3 strokes per second, and is placed on a flat surface. Then at several time points, such as at intervals of 3 minutes, 5 minutes, 7 minutes, 10 minutes, 15 minutes and 30 minutes, the volume or water recovery of the water layer is measured. The results are reported as the mean value of 2 measurements.

[0289] Examples 1 through 6 were tested according to the Demulsification Test at the amounts (ppm by weight) shown in Table 1, and the amount of water recovered at each time interval is reported in mL as shown in Table 1.

[0290] Table 1

[0291]

[0292] Embodiments based on free radical functionalized PIBSA products generally demulsify water / fuel mixtures more quickly than embodiments based on conventionally prepared PIBSA.

[0293] Packaging Testing

[0294] A series of 4 packages were prepared as shown in Table 2, with the amounts shown as the number of parts of each additive added to the package.

[0295] Table 2

[0296] Components Packaging 1 Packaging 2 Packaging 3 Packaging 4 Example 4 27.26 ----- ----- ----- Example 1 ----- 27.26 ----- ----- Example 5 ----- ----- 27.26 ----- Example 2 ----- ----- ----- 27.26 Demulsifier 1.60 1.60 1.60 1.60 Solvents 71.14 71.14 71.14 71.14

[0297] Each of Packages 1 through 4 was added to RF79 at a treat rate (reported in ppm by weight) to deliver the quaternary ammonium salt level (“Quat Level,” reported in ppm by weight) in each fuel as shown in Table 3.

[0298] Table 3

[0299]

[0300]

[0301] The fuels of Examples A through L were tested according to the Demulsification Test and the amount of water recovered at each time interval is reported in mL as shown in Table 4.

[0302] Table 4

[0303]

[0304] Unless otherwise expressly indicated or required by the background in the examples or otherwise, all numerical values ​​of the amount of substance, reaction conditions, molecular weight, number of carbon atoms, etc. specified in this specification should be understood to be modified by the word "about". As used herein, the term "about" means that the value of a given amount is within ± 20% of the specified value. In other embodiments, the value is within ± 15% of the specified value. In other embodiments, the value is within ± 10% of the specified value. In other embodiments, the value is within ± 5% of the specified value. In other embodiments, the value is within ± 2.5% of the specified value. In other embodiments, the value is within ± 1% of the specified value. In other embodiments, the value is within the range of the clearly described values ​​that will be understood by those of ordinary skill in the art based on the disclosure provided herein, with a composition substantially similar to the literal amount described herein.

[0305] It should be understood that the upper and lower limits of the amounts, ranges, and ratios described herein can be independently combined, and any amount within the disclosed range is considered to provide a minimum or maximum value of a narrower range in an alternative embodiment (of course, provided that the minimum amount of the range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts of each element of the subject matter disclosed herein can be used together with the ranges or amounts of any other element.

[0306] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the subject matter. In this regard, the scope of the present invention is limited solely by the following claims.

Claims

1. A method for preparing a reaction product, the method comprising: reacting the free radical functionalized PIBSA product with a nitrogen-containing compound to form a quaternizable compound; and reacting the quaternizable compound with a quaternizing agent to form the reaction product; wherein the reaction product comprises a quaternary ammonium salt.

2. The method of claim 1, wherein the nitrogen-containing compound has: (a) a nitrogen atom capable of reacting with the free radical functionalized PIBSA product to form an imide; and (b) at least one quaternizable amino group.

3. A process according to claim 1 or claim 2, wherein the quaternizing agent is suitable for converting the quaternizable amino groups into quaternary nitrogen groups.

4. The method of any one of claims 1 to 3, wherein the quaternizing agent comprises at least one of an alkyl sulfonate, a dialkyl sulfate, an alkyl halide, a sultone, an alkyl phosphate, a borate, an alkyl nitrite, an alkyl nitrate, a dialkyl carbonate, an alkyl alkanoate, a hydrocarbyl-substituted carbonate, or a hydrocarbyl epoxide.

5. The method of any one of claims 1 to 4, wherein the quaternizing agent comprises a hydrocarbyl epoxide in combination with an acid.

6. The method of any one of claims 1 to 5, wherein the free radical functionalized PIBSA product is the product of a process comprising the steps of: reacting polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150° C. to 225° C. to produce the product; wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

7. The process of claim 6 wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the process.

8. The method of claim 6, combining the ethylenically unsaturated acylating agent with the free radical initiator for addition to the polyisobutylene after bringing the polyisobutylene to the reaction temperature.

9. The method of any one of claims 6 to 8, wherein the free radical functionalized PIBSA product comprises less than 15 wt% of material comprising two or more polyisobutylene units linked by one or more acylating agent units.

10. The process according to any one of claims 6 to 9, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

11. The method of any one of claims 6 to 10, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

12. The method according to claim 11, wherein the organic peroxide initiator comprises diglutaryl, dilauroyl peroxide, benzoyl peroxide, dicumyl peroxide, di(tert-butyl) peroxide, tert-butyl hydroperoxide, 3,4-dimethyl-3,4-diphenyl-hexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxy-3,5,5-trimethyl-hexanoate, di(2,4-dichlorobenzoyl) peroxide, di(2-methylbenzoyl) peroxide, or di(4-tert-butylcyclohexyl) peroxydicarbonate.

13. The method of any one of claims 6 to 12, wherein the ethylenically unsaturated acylating agent comprises maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride or methylenemalonic anhydride.

14. The method according to any one of claims 6 to 13, wherein the free radical functionalized PIBSA product comprises at least one compound of the following general formula I: in: Each R 1 independently represents: –(CH2)–(C(CH2))–(CH3); H; or absent; wherein when R 1 When not present, a dotted double bond represents a double bond, and when R 1 When present, dashed double bonds represent single bonds; Each m is independently an integer from 1 to 52; and Each n is independently 0, 1 or 2.

15. The process according to any one of claims 6 to 14, wherein the free radical functionalized PIBSA product comprises at least 30 mol% of the at least one compound of formula I.

16. The method of any one of claims 6 to 15, wherein the free radical functionalized PIBSA product comprises less than 40 wt% unreacted polyisobutylene.

17. A composition comprising the reaction product of the method of any one of claims 1 to 16.

18. A fuel composition comprising a fuel and the composition according to claim 17.

19. A lubricating composition comprising an oil of lubricating viscosity and the composition of claim 17.

20. A method of improving the dehydration properties of a fuel composition, the method comprising incorporating the composition of claim 17 into the fuel composition.

21. A method of reducing and / or preventing injector deposits in an engine, the method comprising supplying a fuel composition according to claim 18 to a fuel injector of the engine and operating the engine.

22. A method of lubricating a crankcase of an engine, the method comprising supplying the lubricating composition of claim 19 to the engine and operating the engine.

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