Methods for producing free radical functionalized derivatives of PIBSA products and compositions comprising same

Abstract

There is provided a lubricant composition comprising: (a) an oil of lubricating viscosity; and (b) a succinimide, succinimide or succinate obtained by reacting (i) an amine or an alcohol; and (ii) a reaction product obtained by a process comprising the steps of: (A) reacting a polyisobutylene with a free radical initiator and an ethylenically unsaturated acylating agent at a reaction temperature of 150 DEG C to 225 DEG C to produce the reaction product; (B) wherein the polyisobutylene is brought to the reaction temperature prior to addition of the free radical initiator; and (C) wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the radical initiator. Also provided are methods for producing reaction products comprising such succinimides, succinimides, or succinate esters; methods of using such reaction products in lubricant compositions; the use of such a lubricant composition; and methods of using such lubricant compositions.

Description

[0001] The disclosed technology relates to methods for producing reaction products of polyisobutylene with an initiator and an acylating agent, derivatives of acylated polyisobutylene contained in such reaction products, and the use of these derivatives in lubricant compositions.

[0002] Acylated polyisobutylenes such as polyisobutylene succinic anhydride / acid ("PIBSA") are used as chemical intermediates in the production of a large number of chemical compositions. 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. Known methods for producing PIBSA may require hazardous chemicals, high temperatures, long reaction times, and / or high energy requirements, and may result in by-products and / or impurities (resulting in poor color and / or black specks / resins, which may require filtering the product), which reduces the potential market for the product and / or requires undesirable maintenance of reaction equipment.

[0003] For example, polyisobutylene containing high levels of tri- and tetra-substituted olefin end groups can be reacted with maleic anhydride in the presence of chlorine to form the desired PIBSA product. Disadvantages of this process include the need to use chlorine as a promoter, which generally results in some chlorine incorporation into the final PIBSA product, and the formation of insoluble colored impurities in the product. The formation of these insoluble impurities affects manufacturing yields because these solids can agglomerate within the reaction tank, which results in increased maintenance downtime for cleaning the reaction tank to remove these insoluble solids.

[0004] As another example, polyisobutylene containing high levels of terminal vinylidene olefin end groups can be reacted with maleic anhydride in the presence of heat to form the desired PIBSA product. In commercial manufacturing facilities, this conversion has several disadvantages, including the high reaction temperatures required to form the desired product, long reaction times, and the potential for promoting decomposition of the acylating agent before the desired reaction occurs. An undesirable side effect of these processing conditions is that the product may become visibly colored (usually orange / light brown).

[0005] An alternative to these exemplary methods includes reacting high vinylidene polyisobutylene with maleic anhydride at a relatively low reaction temperature in the presence of a free radical initiator. US 5,112,507 teaches that high vinylidene polyisobutylene reacted with maleic anhydride in the presence of a free radical initiator and a reaction solvent forms a PIBSA product that is structurally different from both PIBSA formed by a thermal process and PIBSA prepared by a chlorination process. Under certain reaction conditions, highly reactive polyisobutylene and maleic anhydride form alternating copolymers in which the monomer units are represented by the following general formula:

[0006]

[0007] The degree of polymerization is represented by n and indicates the number of repeating units present in the copolymer. The reaction temperature is affected by the choice of solvent, as most reactions are run at the reflux temperature of the solvent indicated. The reactions were run between 40°C and 140°C.

[0008] US 5,565,528 and US 5,616,668 teach that the desired reaction products can be formed in the absence of solvent at reaction temperatures slightly higher than those taught in US 5,112,507. However, long reaction times can promote color formation in the product and reduce manufacturing yields on a commercial production scale.

[0009] Thus, in certain embodiments, the disclosed technology provides a method for producing PIBSA that provides an improvement over at least one of the above-mentioned disadvantages of known methods and can provide more desirable PIBSA reaction products, potentially leading to higher quality reaction products and / or reduced maintenance of reaction equipment. For example, the subject matter described herein can allow for the preparation of PIBSA products in significantly reduced time cycles and / or can minimize undesirable maleic anhydride decomposition that can lead to the formation of colored impurities.

[0010] In addition, the disclosed technology provides methods of utilizing the improved PIBSA reaction products to produce derivatives thereof, uses of such derivatives in lubricating compositions, methods of using such derivatives in lubricating compositions, lubricating compositions comprising the derivatives, and lubrication methods utilizing the lubricating compositions.

[0011] The subject matter disclosed herein provides a lubricant composition comprising: (a) an oil of lubricating viscosity; and (b) a succinimide, succinamide, or succinate obtained by reacting: (i) an amine or an alcohol; and (ii) a free radical functionalized PIBSA product obtained by a process comprising the steps of: (A) 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 reaction product; (B) wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and (C) wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

[0012] The subject matter disclosed herein also provides a method for producing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with an amine or an alcohol to form a reaction product; wherein the reaction product comprises at least one of a succinimide, a succinamide, or a succinate.

[0013] The following implementations of the present subject matter are contemplated:

[0014] 1. A lubricant composition comprising: (a) an oil of lubricating viscosity; and (b) a succinimide, succinamide or succinate obtained by reacting: (i) an amine or alcohol; and (ii) a free radical functionalized PIBSA product obtained by a process comprising the steps of: (A) 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 reaction product; (B) wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and (C) wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

[0015] 2. The lubricant composition of embodiment 1, wherein the amine is a polyamine.

[0016] 3. A lubricant composition according to embodiment 2, wherein the polyamine contains at least one >N—H group per molecule.

[0017] 4. The lubricant composition of embodiment 2 or embodiment 3, wherein the polyamine is an aliphatic polyamine.

[0018] 5. The lubricant composition of embodiment 4, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

[0019] 6. The lubricant composition of embodiment 5, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or a polyamine still bottom.

[0020] 7. The lubricant composition of any one of embodiments 1 to 6, wherein the alcohol is a polyhydroxy aliphatic alcohol.

[0021] 8. The lubricant composition according to embodiment 7, wherein the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

[0022] 9. The lubricant composition according to any one of embodiments 1 to 8, wherein the succinic acid ester obtained is further reacted with an amine.

[0023] 10. The lubricant composition of embodiment 9, wherein the amine is an aliphatic amine.

[0024] 11. The lubricant composition of embodiment 10, wherein the aliphatic amine is an aliphatic polyamine.

[0025] 12. The lubricant composition of embodiment 11, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

[0026] 13. The lubricant composition of embodiment 12, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

[0027] 14. The lubricant composition of any one of embodiments 1 to 13, wherein the succinimide, succinamide, or succinic acid ester is post-treated with a post-treating agent to produce a post-treated succinimide, a post-treated succinimide, or a post-treated succinic acid ester.

[0028] 15. The lubricant composition according to embodiment 14, wherein the post-treatment agent comprises at least one of urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, 2,5-dimercaptothiadiazole, or an aromatic diacid having an acid group at the 1,3 or 1,4 position on the benzene ring.

[0029] 16. The lubricant composition according to embodiment 15, wherein the phosphorus compound is phosphoric acid or anhydride.

[0030] 17. The lubricant composition of embodiment 15 or embodiment 16, wherein the aromatic diacid having acid groups at the 1,3 or 1,4 position on the benzene ring is terephthalic acid.

[0031] 18. The lubricant composition of any one of embodiments 14 to 17, wherein the post-treated succinimide or post-treated succinamide is a borated succinimide or a borated succinamide.

[0032] 19. The lubricant composition according to any one of embodiments 1 to 18, further comprising at least one additional additive, the additional additive comprising at least one of a detergent, a dispersant, a friction modifier, an antiwear agent, an extreme pressure agent, a corrosion inhibitor, a viscosity modifier, a defoamer, a demulsifier, or a seal swell agent.

[0033] 20. A method of lubricating a mechanical device, the method comprising supplying the lubricant composition according to any one of embodiments 1 to 19 to the mechanical device.

[0034] 21. The method of embodiment 20, wherein the mechanical device is a crankcase, a gear, a gearbox, a shaft gear or a transmission of an internal combustion engine.

[0035] 22. A method according to embodiment 21, wherein the internal combustion engine is a spark ignition engine or a compression ignition engine.

[0036] 23. The method of embodiment 21, wherein the gear, the gearbox or the axle gear comprises a differential or a limited slip differential.

[0037] 24. The method of embodiment 21, wherein the transmission is an automatic transmission.

[0038] 25. The method of embodiment 24, wherein the automatic transmission comprises a continuously variable transmission, an infinitely variable transmission, a toroidal transmission, a continuously slipping torque converter clutch, a stepped automatic transmission, or a dual clutch transmission.

[0039] 26. The method of embodiment 21, wherein the transmission is a manual transmission.

[0040] 27. The method of embodiment 26, wherein the manual transmission is an agricultural tractor transmission.

[0041] 28. A method for producing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with an amine or an alcohol to form the reaction product; wherein the reaction product comprises at least one of a succinimide, a succinamide, or a succinate.

[0042] 29. The method of embodiment 28, wherein the amine is a polyamine.

[0043] 30. A method according to embodiment 29, wherein the polyamine contains at least one >N—H group per molecule.

[0044] 31. The method of embodiment 28 or embodiment 29, wherein the polyamine is an aliphatic polyamine.

[0045] 32. The method of embodiment 31, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

[0046] 33. The method of embodiment 32, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

[0047] 34. The method of any one of embodiments 28 to 33, wherein the alcohol is a polyhydroxy aliphatic alcohol.

[0048] 35. The method according to embodiment 34, wherein the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

[0049] 36. The process according to any one of embodiments 28 to 35, wherein the succinic acid ester obtained is further reacted with an amine.

[0050] 37. The method of embodiment 36, wherein the amine is an aliphatic amine.

[0051] 38. The method of embodiment 37, wherein the aliphatic amine is an aliphatic polyamine.

[0052] 39. The method of embodiment 38, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

[0053] 40. The method of embodiment 39, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

[0054] 41. The method of any one of embodiments 28 to 40, wherein the succinimide, succinamide, or succinic acid ester is post-treated with a post-treating agent to produce a post-treated succinimide, a post-treated succinimide, or a post-treated succinic acid ester.

[0055] 42. A method according to embodiment 41, wherein the post-treatment agent includes at least one of urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, 2,5-dimercaptothiadiazole, or an aromatic diacid having an acid group at the 1,3 or 1,4 position on the benzene ring.

[0056] 43. The method of embodiment 42, wherein the phosphorus compound is phosphoric acid or anhydride.

[0057] 44. The method according to embodiment 42 or embodiment 43, wherein the aromatic diacid having acid groups at the 1,3 or 1,4 position on the benzene ring is terephthalic acid.

[0058] 45. The method of any one of embodiments 41 to 44, wherein the post-treated succinimide or post-treated succinamide is a borated succinimide or a borated succinamide.

[0059] 46. ​​The method of any one of embodiments 28 to 45, 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.

[0060] 47. The method of embodiment 46, wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the method.

[0061] 48. The method of embodiment 46, 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.

[0062] 49. The method of any one of embodiments 46 to 48, 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.

[0063] 50. The method according to any one of embodiments 46 to 49, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

[0064] 51. The method of any one of embodiments 46 to 50, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

[0065] 52. The method of embodiment 51, wherein the organic peroxide initiator comprises diglutaroyl, dilauroyl peroxide, benzoyl peroxide, diisopropylbenzene 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.

[0066] 53. The method of any one of embodiments 46 to 52, 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.

[0067] 54. The method according to any one of embodiments 46 to 53, wherein the free radical functionalized PIBSA product comprises at least one compound of the following general formula I:

[0068]

[0069] 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.

[0070] 55. The method of embodiment 54, wherein the free radical functionalized PIBSA product comprises at least 30 mol% of the at least one compound of formula I.

[0071] 56. The method of any one of embodiments 46 to 55, wherein the free radical functionalized PIBSA product comprises less than 40 wt% unreacted polyisobutylene.

[0072] 57. A composition comprising the reaction product of the method according to any one of embodiments 28 to 57.

[0073] 58. A lubricant composition comprising an oil of lubricating viscosity and the composition of embodiment 57.

[0074] 59. According to the lubricant composition described in embodiment 58, the lubricant composition also contains at least one additional additive, and the additional additive includes at least one of a detergent, a dispersant, a friction modifier, an anti-wear agent, an extreme pressure agent, a corrosion inhibitor, a viscosity modifier, a defoamer, a demulsifier or a seal swelling agent.

[0075] 60. A method of lubricating a mechanical device, the method comprising supplying the lubricant composition according to embodiment 58 or embodiment 59 to the mechanical device.

[0076] 61. The method of embodiment 60, wherein the mechanical device is a crankcase, gear, gearbox, shaft gear or transmission of an internal combustion engine.

[0077] 62. A method according to embodiment 61, wherein the internal combustion engine is a spark ignition engine or a compression ignition engine.

[0078] 63. A method according to embodiment 61, wherein the gear, the gearbox or the shaft gear includes a differential or a limited slip differential.

[0079] 64. A method according to embodiment 61, wherein the transmission is an automatic transmission.

[0080] 65. A method according to embodiment 64, wherein the automatic transmission includes a continuously variable transmission, an infinitely variable transmission, a toroidal transmission, a continuously slipping torque converter clutch, a stepped automatic transmission or a dual clutch transmission.

[0081] 66. A method according to embodiment 61, wherein the transmission is a manual transmission.

[0082] 67. A method according to embodiment 66, wherein the manual transmission is an agricultural tractor transmission.

[0083] Various features and embodiments of the present subject matter are described below by way of non-limiting illustration.

[0084] As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other such materials that can be prepared by the condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, whether or not the condensation reaction is actually carried out to produce the product directly. Thus, for example, a particular ester can be prepared by an ester exchange reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0085] 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.

[0086] 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 can connect 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 will also be apparent to those skilled in the art, and include, for example, halo, hydroxyl, alkoxy, sulfhydryl, alkylthiol, nitro, nitroso and sulfinyl.

[0087] Therefore, 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 selected from the group consisting of: halo, hydroxyl, alkoxy, mercapto, alkylthiol, nitro, nitroso and sulfinyl; and / or (iii) hydrocarbon groups containing heteroatoms 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. The 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 connected to the rest of the molecule, wherein the group is composed of carbon atoms and hydrogen atoms.

[0088] It is known that some of the substances 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 thus formed, 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.

[0089] 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.

[0090] As used herein, the term "substantially" means that the value of a given amount 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.

[0091] 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.

[0092] 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 statement of "comprising" herein, the term is also intended to encompass the phrases "consisting essentially of" and "consisting of" as alternative embodiments, wherein "consisting of" excludes any elements or steps not specified and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

[0093] 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.

[0094] Reaction products comprising succinimide, succinamide and / or succinate

[0095] A lubricant composition is provided, the lubricant composition comprising: (a) an oil of lubricating viscosity; and (b) a succinimide, succinamide or succinate obtained by reacting: (i) an amine or an alcohol; and (ii) a free radical functionalized PIBSA product (as defined herein) obtained by a process comprising the steps of: (A) 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 reaction product; (B) wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and (C) wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

[0096] In certain embodiments, amine is a polyamine. In certain embodiments, polyamine per molecule contains at least one> NH group. In certain embodiments, polyamine is an aliphatic polyamine. In certain embodiments, aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine or butylene polyamine. In certain embodiments, ethylene polyamine includes at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyamine bottom residue.

[0097] In certain embodiments, the alcohol is a polyhydroxy aliphatic alcohol. In certain embodiments, the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

[0098] In certain embodiments, the succinate obtained is further reacted with an amine. In certain embodiments, the amine is an aliphatic amine. In certain embodiments, the aliphatic amine is an aliphatic polyamine. In certain embodiments, the aliphatic polyamine is at least one of ethylenepolyamine, propylenepolyamine or butylenepolyamine. In certain embodiments, the ethylenepolyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyamine bottom residues.

[0099] In certain embodiments, succinimide, succinamide or succinate are post-treated with a post-treatment agent to produce post-treated succinimide, post-treated succinimide or post-treated succinate. In certain embodiments, the post-treatment agent includes urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compound, phosphorus compound, 2,5-dimercaptothiadiazole or at least one of aromatic diacids with acid groups at positions 1,3 or 1,4 on the benzene ring. In certain embodiments, the phosphorus compound is phosphoric acid or anhydride. In certain embodiments, the aromatic diacid with acid groups at positions 1,3 or 1,4 on the benzene ring is terephthalic acid. In certain embodiments, the post-treated succinimide or post-treated succinamide is borated succinimide or borated succinamide.

[0100] Also provided is a method for producing a reaction product, the method comprising: reacting a free radical functionalized PIBSA product with an amine or an alcohol to form a reaction product; wherein the reaction product comprises at least one of succinimide, succinamide, or succinate. In certain embodiments, a composition comprising the reaction product of such a method is provided.

[0101] In certain embodiments, amine is a polyamine. In certain embodiments, polyamine per molecule contains at least one> NH group. In certain embodiments, polyamine is an aliphatic polyamine. In certain embodiments, aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine or butylene polyamine. In certain embodiments, ethylene polyamine includes at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyamine bottom residue.

[0102] In certain embodiments, the alcohol is a polyhydroxy aliphatic alcohol. In certain embodiments, the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

[0103] In certain embodiments, the succinate obtained is further reacted with an amine. In certain embodiments, the amine is an aliphatic amine. In certain embodiments, the aliphatic amine is an aliphatic polyamine. In certain embodiments, the aliphatic polyamine is at least one of ethylenepolyamine, propylenepolyamine or butylenepolyamine. In certain embodiments, the ethylenepolyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyamine bottom residues.

[0104] In certain embodiments, succinimide, succinamide or succinate are post-treated with a post-treatment agent to produce post-treated succinimide, post-treated succinimide or post-treated succinate. In certain embodiments, the post-treatment agent includes urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compound, phosphorus compound, 2,5-dimercaptothiadiazole or at least one of aromatic diacids with acid groups at positions 1,3 or 1,4 on the benzene ring. In certain embodiments, the phosphorus compound is phosphoric acid or anhydride. In certain embodiments, the aromatic diacid with acid groups at positions 1,3 or 1,4 on the benzene ring is terephthalic acid. In certain embodiments, the post-treated succinimide or post-treated succinamide is borated succinimide or borated succinamide.

[0105] Free radical functionalized PIBSA products

[0106] 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 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. Thus, the term "free radical functionalized PIBSA product" as used herein refers to the product of this 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.

[0107] 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 producing 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 produce 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.

[0108] 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.

[0109] In certain embodiments, a method for producing 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 produce a free radical functionalized PIBSA product.

[0110] In certain embodiments, a method for producing a free radical functionalized PIBSA product may comprise 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 produce 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.

[0111] In certain embodiments, a method for producing a free radical functionalized PIBSA product may comprise 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 produce 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.

[0112] In certain embodiments, a method for producing 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 produce 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; and 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.

[0113] In certain embodiments, a method for producing 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 produce 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.

[0114] Compared to known methods for producing PIBSA, the above-described methods for producing 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 following detailed description and examples. 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.

[0115] In certain embodiments, the reaction temperature for producing the free radical functionalized PIBSA product in the methods described herein can be from 155°C to 225°C, 160°C to 225°C, 165°C to 225°C, 166°C to 225°C, 167°C to 225°C, 168°C to 225°C, 169°C to 225°C, 170°C to 225°C, 171°C to 225°C, 172°C to 225°C, 173°C to 225°C, 174°C to 225°C, 175°C to 225°C, 150°C to 220°C, 155°C to 220°C, 160°C to 220°C, 165°C to 220°C, 166°C to 220°C, 167°C to 220°C, 168°C to 220°C, 169°C to 225°C to 220°C, 170°C to 220°C, 171°C to 220°C, 172°C to 220°C, 173°C to 220°C, 174°C to 220°C, 175°C to 220°C, 150°C to 215°C, 155°C to 215°C, 160°C to 215°C, 165°C to 215°C, 166°C to 215°C, 167°C to 215°C ℃、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℃、166 ℃ 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 20 5℃、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.

[0116] In certain embodiments, the total amount of free radical initiator added during the process of producing a free radical functionalized PIBSA product described herein 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. , 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 , 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, 0.02 0.02 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, 0.02 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 0.3 5 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 0.14 equivalents Equivalent, 0.03 equivalent to 0.13 equivalent, 0.03 equivalent to 0.12 equivalent, 0.03 equivalent to 0.11 equivalent, 0.03 equivalent to 0.1 equivalent, 0.04 equivalent to 0.9 equivalent, 0.04 equivalent to 0.8 equivalent, 0.04 equivalent to 0.7 equivalent, 0.04 equivalent to 0.6 equivalent, 0.04 equivalent to 0.5 equivalent, 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).

[0117] In certain embodiments, the total amount of ethylenically unsaturated acylating agent added during the process of producing a free radical functionalized PIBSA product described herein 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 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 equivalents, 0.5 equivalents to 2.6 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 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 equivalents , 0.7 equivalents to 2 equivalents, 0.7 equivalents to 1.9 equivalents, 0.7 equivalents to 1.8 equivalents, 0.7 equivalents to 1.7 equivalents, 0.7 equivalents to 1.6 equivalents, 0.7 equivalents to 1.5 equivalents, 0.7 equivalents to 1.4 equivalents, 0.7 equivalents to 1.3 equivalents, 0.7 equivalents to 1.2 equivalents, 0.7 equivalents to 1.1 equivalents, 0.7 equivalents 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).

[0118] 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.

[0119] 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, the polyisobutylene comprises an average of 3 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 3 to 9 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 4 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 4 to 16 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 5 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 5 to 22 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 7 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 26 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 7 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 10 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 7 to 9 isobutylene monomer units per molecule. In certain embodiments, the 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, polyisobutylene comprises an average of 8 to 14 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 12 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 10 isobutylene monomer units per molecule. In certain embodiments, polyisobutylene comprises an average of 8 to 9 isobutylene monomer units per molecule. In certain embodiments, 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, the polyisobutylene comprises an average of 9 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 9 to 26 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 10 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 42 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 10 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 16 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 14 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 10 to 12 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 54 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 12 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 12 to 22 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 14 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 14 to 34 isobutylene monomer units per molecule. In certain embodiments, the 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, the 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, the polyisobutylene comprises an average of 16 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 16 to 18 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 50 isobutylene monomer units per molecule.In certain embodiments, the 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, the polyisobutylene comprises an average of 18 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 24 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 22 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 18 to 20 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 20 to 40 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 22 to 55 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 22 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 22 to 24 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 24 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 55 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 24 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 28 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 24 to 26 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 46 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 26 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 26 to 40 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 28 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 28 to 30 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 56 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 30 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 30 to 32 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 32 to 54 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 32 to 36 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 32 to 34 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 38 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 34 to 36 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 36 to 38 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 38 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 38 to 40 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 48 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 46 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 44 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 40 to 42 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 42 to 55 isobutylene monomer units per molecule. In certain embodiments, the 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, the polyisobutylene comprises an average of 48 to 51 isobutylene monomer units per molecule.In certain embodiments, the polyisobutylene comprises an average of 48 to 50 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 56 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 55 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 54 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 53 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 52 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 50 to 51 isobutylene monomer units per molecule. In certain embodiments, the polyisobutylene comprises an average of 51 to 56 isobutylene monomer units per molecule. In certain embodiments, the 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.

[0120] 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.

[0121] In certain embodiments, organic peroxide initiators include 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.

[0122] 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.

[0123] In certain embodiments, the ethylenically unsaturated acylating agent may comprise one or more compounds falling within the following general formula:

[0124]

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] In certain embodiments, the free radical functionalized PIBSA product comprises at least one compound of the following Formula I:

[0130]

[0131] 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.

[0132] 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.

[0133] 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. 、

[0134] 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.

[0135] Also provided are embodiments of the above-described method of producing 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 produce 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.

[0136] 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.

[0137] In certain embodiments, at least two of the two or more additions are separated in time by at least the 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).

[0138] Also provided are embodiments of the above-described method for producing a free radical functionalized PIBSA product, wherein the method 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 produce 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.

[0139] An illustrative, non-limiting embodiment of the method for producing a free radical functionalized PIBSA product described herein 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.

[0140] Amine reactants

[0141] The free radical functionalized PIBSA product can be further reacted with an amine-containing compound capable of reacting with the acylating group of PIBSA to form a succinimide or succinamide, which can be used as a dispersant in various compositions, including lubricant compositions.

[0142] Succinimide and succinamide dispersants can be derived from aliphatic polyamines or mixtures thereof. The aliphatic polyamine can be an aliphatic polyamine such as ethylene polyamine, propylene polyamine, butylene polyamine or mixtures thereof. In certain embodiments, the aliphatic polyamine can be an ethylene polyamine. In certain embodiments, the aliphatic polyamine can be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottom residues and mixtures thereof.

[0143] The amine reactants may be those described in the art as "polyamine bottoms". Polyamine bottoms are polyamine mixtures obtained as residues from stripping of complex mixtures of alkylene (usually ethylene) polyamines, including cyclic condensation products such as piperazine. These complex alkylene polyamine mixtures are typically those produced by the reaction of alkylene chlorides (usually alkylene dichlorides) with ammonia or the reaction of ethyleneimine with a ring-opening agent (such as water or ammonia). In general, alkylene polyamine bottoms may be characterized as having less than 2 wt%, typically less than 1 wt%, of materials having a boiling point below 200°C.

[0144] Suitable ethylene polyamine bottoms are those designated "E-100", available from Dow Chemical Co., Freeport Tex., USA. This material has a nominal specific gravity specification of 1.0168 at 15.6°C; N% = 33.15, and a kinematic viscosity at 40°C = 121 mm 2 / s (centistokes, cSt). Gas chromatography showed it to contain about 0.93% light ends (most likely diethylenetriamine), 0.72% triethylenetetramine, tetraethylenepentamine, and 76.61% pentaethylenehexamine and higher levels (all by weight). Another example of polyethylene bottoms is the product sold by Union Carbide Chemicals as HPA-X, which has an equivalent weight (per N) = 40.5.

[0145] The polyamines contain at least one >NH group per molecule. These polyamine bottoms may be reacted with the acylating agent alone, or they may be used with other amines, polyamines, or mixtures thereof, provided that the major amount is the alkylene polyamine bottoms based on equivalent NH.

[0146] The acylated amine may contain at least one member of the group consisting of amides, imides and salts. The acylated amine is typically a mixture of two or more of these. The acylated amine may have a base value resulting from the presence of the amine.

[0147] Typically the total base number based on the pure chemical (i.e. correcting for the presence of any diluent oil) is from 17 or 20 to 35, more typically from 20 or 24 to 30. In certain embodiments it may be from 17 to 20. When the acylated amine is prepared from a low chlorine containing acylating agent, the chlorine content of the acylated amine is correspondingly low. Based on the pure chemical, the chlorine content may be up to 0.6%, for example from 0.01% to 0.6% or to 0.4% or to 0.2%.

[0148] The reaction of preparing the hydrocarbyl-substituted acylating agent is usually carried out in the substantial absence of a diluent, although a substantially inert, generally liquid diluent such as mineral oil or a hydrocarbon solvent may be used. The reaction of the hydrocarbyl-substituted acylating agent with the amine may also be carried out in the pure state or in the presence of a substantially inert, generally liquid diluent. Typically, if a diluent is used, it comprises mineral oil which is retained in the product. If a volatile diluent is used, it is generally necessary to remove the diluent by techniques such as distillation so that the resulting product has an acceptable flash point, i.e., is not unacceptably flammable. When the diluent is present in the acylated amine, it is generally present in an amount of 30 to 70 parts per 100 parts of the acylated amine. As described above, the remaining unreacted polyolefin from the reaction to form the hydrocarbyl-substituted acylating agent is considered to be part of the diluent. The following examples illustrate the hydrocarbyl-substituted carboxylic acid acylating agents and acylated amines described herein. All temperatures are in degrees Celsius, parts and percentages are by weight, and filtration is performed with a diatomaceous earth filter aid.

[0149] Alcohol reactant

[0150] Another class of dispersants that can be prepared from free radical functionalized PIBSA products are succinates. These materials are similar to one or more of the above-mentioned succinimides, except that they can be considered to be prepared by the reaction of a free radical functionalized PIBSA product with a polyhydroxy aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Aromatic succinates can also be prepared. In some cases, these ester-type dispersants can be post-treated with amines such as poly(ethyleneamine).

[0151] Post-processing

[0152] The above-mentioned succinimide, succinamide and succinate can be post-treated. The post-treated dispersant is usually obtained by reacting succinimide, succinamide or succinate with a reagent such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds such as boric acid, phosphorus compounds such as phosphoric acid or anhydrides, 2,5-dimercaptothiadiazole (DMTD) or aromatic diacids having acid groups in the 1,3 or 1,4 positions on the benzene ring (such as terephthalic acid).

[0153] Borated dispersants are typically obtained by reacting succinimide, succinamide or succinate with a boron compound reagent such as boric acid (to obtain a "borated dispersant"). The borated dispersant may be additionally functionalized with a sulfur or phosphorus moiety. The dispersant component in the borated dispersant may be a mixture of multiple dispersants, which may be of different types; optionally, at least one may be a succinimide dispersant. In certain embodiments, the borated dispersant may be a borated polyisobutylene succinimide dispersant, wherein the polyisobutylene portion thereof may have a number average molecular weight of 750 to 2200, or 750 to 1350, or 750 to 1150. The one or more borated dispersants may be prepared in a manner having an N:CO ratio of 0.9:1 to 1.6:1, or 0.95:1 to 1.5:1, or 1:1 to 1.4:1. The amount of the borated dispersant in the composition may be, for example, 0.05 to 2.0 wt%. In other embodiments, the amount is 0.1 to 1.0%, or 0.15 to 0.75% of the final blended fluid formulation. In concentrates, the amount will be proportionally higher.

[0154] In certain embodiments, the succinimide or succinamide of the present technology can be a borated succinimide or succinamide prepared by heating together: (i) a dispersant base; (ii) 2,5-dimercapto-l,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-l,3,4-thiadiazole, or an oligomer thereof; (iii) a boronating agent; and (iv) a dicarboxylic acid optionally selected from the following aromatic compounds: 1,3 diacids and 1,4 diacids; and / or (v) optionally a phosphoric acid compound, wherein the heating is sufficient to provide a product of (i), (ii), (iii) and optionally (iv) or (v) that is soluble in an oil of lubricating viscosity.

[0155] Lubricant composition

[0156] The above reaction products can be used in various compositions, such as lubricant compositions. In certain embodiments, the lubricant composition may include an oil having a lubricating viscosity and a reaction product comprising at least one of succinimide, succinamide, or succinate. In certain embodiments, the lubricant composition may include at least one additional additive. In certain embodiments, at least one additional additive may include at least one of a detergent, a dispersant, a friction modifier, an antiwear agent, an extreme pressure agent, a corrosion inhibitor, a viscosity modifier, a defoamer, a demulsifier, or a seal swell agent.

[0157] In certain embodiments, a method for lubricating a mechanical device is provided, the method comprising supplying a lubricant composition to the mechanical device. In certain embodiments, the mechanical device is a crankcase, gear, gearbox, axle gear or transmission of an internal combustion engine. In certain embodiments, the internal combustion engine is a spark ignition engine or a compression ignition engine. In certain embodiments, the gear, gearbox or axle gear comprises a differential or a limited slip differential. In certain embodiments, the transmission is an automatic transmission. In certain embodiments, the automatic transmission comprises a continuously variable transmission (continuouslyvariable transmission), a continuously variable transmission (infinitely variable transmission), a toroidal transmission, a continuous slip torque conversion clutch, a stepped automatic transmission or a dual clutch transmission. In certain embodiments, the transmission is a manual transmission. In certain embodiments, the manual transmission is an agricultural tractor transmission.

[0158] In certain embodiments, the technology provides lubricating compositions that can be used in internal combustion engines. The internal combustion engine can be a spark ignition type or a compression ignition type. The internal combustion engine can be a 2-stroke engine or a 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. Typically, the internal combustion engine can be a passenger car engine or a heavy diesel internal combustion engine.

[0159] In certain embodiments, a lubricant composition is provided, comprising: an oil of lubricating viscosity; 0.01 wt % to 12 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 6 wt %, or 0.1 wt % to 2 wt % of the succinimide, succinamide, and / or succinate of the present technology; 0.01 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 % of a high base detergent; and a phosphorus-containing antiwear agent selected from (i) a nonionic phosphorus compound, which may be a hydrocarbyl phosphite; (ii) an amine salt of a phosphorus compound, (iii) a zinc dialkyl dithiophosphate, or (iv) a plurality of zinc dialkyl dithiophosphates.

[0160] In certain embodiments, a method for lubricating a crankcase of an internal combustion engine is provided, the method comprising supplying a lubricant composition to the crankcase of the internal combustion engine, the lubricant composition comprising: an oil of lubricating viscosity; 0.01 wt % to 12 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 6 wt %, or 1 wt % to 5 wt % of the succinimide, succinamide, and / or succinate of the present technology; 0.01 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 % of a high base detergent; and a phosphorus-containing antiwear agent selected from (i) a nonionic phosphorus compound, which may be a hydrocarbyl phosphite; (ii) an amine salt of a phosphorus compound, (iii) a zinc dialkyl dithiophosphate, or (iv) a plurality of zinc dialkyl dithiophosphates.

[0161] In certain embodiments, a lubricating composition is provided that can be employed in a gear, a gearbox, or an axle gear. The gearbox can have a differential or a limited slip differential.

[0162] In certain embodiments, a lubricant composition is provided, comprising: 0.01 wt % to 12 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 6 wt %, or 0.1 wt % to 2 wt % of a succinimide, succinamide and / or succinate of the present technology; an olefin sulfide (e.g., present at 0.1 wt % to 7 wt %, or 0.2 wt % to 6 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 5 wt %); and a thiadiazole (e.g., present at 0.1 wt % to 0.5 wt %, or 0.15 wt % to 0.4 wt %, or 0.15 wt % to 0.35 wt %).

[0163] In certain embodiments, a method is provided for lubricating a gear or gearbox including a differential, a limited slip differential, or an axle gear by supplying a lubricant composition to the gear or gearbox, the lubricant composition comprising: 0.01 wt % to 12 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 6 wt %, or 0.1 wt % to 2 wt % of a succinimide, succinamide, and / or succinate of the present technology; an olefin sulfide (e.g., present at 0.1 wt % to 7 wt %, or 0.2 wt % to 6 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 5 wt %); and a thiadiazole (e.g., present at 0.1 wt % to 0.5 wt %, or 0.15 wt % to 0.4 wt %, or 0.15 wt % to 0.35 wt %).

[0164] In certain embodiments, a lubricating composition is provided that can be used in an automatic transmission. Automatic transmissions include continuously variable transmissions (CVTs), infinitely variable transmissions (IVTs), toroidal transmissions, continuously slipping torque converter clutches (CSTCCs), stepped automatic transmissions, and dual clutch transmissions (DCTs).

[0165] In certain embodiments, a lubricant composition is provided, the lubricant composition comprising: an oil of lubricating viscosity; 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 3 wt %, or 0.1 wt % to 2 wt % of the present technology of succinimide, succinamide, and / or succinate; a phosphorus-containing antiwear agent selected from (i) a nonionic phosphorus compound, which may be a hydrocarbyl phosphite, or (ii) an amine salt of a phosphorus compound; a calcium-containing detergent, for example, present in an amount of 110 ppm-700 ppm, 130 ppm-600 ppm, 150 ppm-500 ppm, or 160 ppm-400 ppm calcium; and optionally a friction modifier, for example, present in an amount of 0 wt % to 4 wt %, or 0.1 wt % to 4 wt %, 0.2 wt % to 3 wt %, 0.3 wt % to 3 wt %, 0.25 wt % to 2.5 wt %. In certain embodiments, a friction modifier is present. In certain embodiments, friction modifiers are absent.

[0166] In certain embodiments, a method for lubricating an automatic transmission is provided, the method comprising supplying a lubricant composition to the automatic transmission, the lubricant composition comprising: an oil having a lubricating viscosity; 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 3 wt %, or 0.1 wt % to 2 wt % of a succinimide, succinamide, and / or succinate ester of the present technology; a phosphorus-containing antiwear agent selected from (i) a nonionic phosphorus compound, which may be a hydrocarbyl phosphite, or (ii) an amine salt of a phosphorus compound; and a calcium-containing detergent, for example present in an amount to deliver 110 ppm-700 ppm, 130 ppm-600 ppm, 150 ppm-500 ppm, or 160 ppm-400 ppm calcium.

[0167] In certain embodiments, a lubricant composition is provided, comprising: an oil of lubricating viscosity; 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 3 wt %, or 0.1 wt % to 2 wt % of the succinimide, succinamide, and / or succinate of the present technology; 0.05 wt % to 1 wt % of thiadiazole; 0.1 wt % to 5 wt % of a dispersant other than the succinimide, succinamide or succinate of the present technology; and 0.1 wt % to 4 wt % of a detergent.

[0168] In certain embodiments, a method for lubricating a manual transmission by supplying a lubricant composition to the manual transmission is provided, the lubricant composition comprising: oil of lubricating viscosity; 0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 3 wt %, or 0.1 wt % to 2 wt % of the succinimide, succinamide, and / or succinate of the present technology; 0.05 wt % to 1 wt % of thiadiazole; 0.1 wt % to 5 wt % of a dispersant other than the succinimide, succinamide or succinate of the present technology; and 0.1 wt % to 4 wt % of a detergent.

[0169] Oil of lubricating viscosity

[0170] The above-mentioned succinimides, succinamides and succinates can be further used in lubricating oils to provide at least one of antiwear properties, friction regulation (especially for improving fuel economy), detergent properties (especially deposit control or varnish control), dispersancy (especially soot control or sludge control) or corrosion control.

[0171] Lubricant composition also comprises the oil with lubricating viscosity.Such oil comprises natural oil and synthetic oil, derived from hydrocracking, hydrogenation and hydrofining oil, unrefined oil, refined oil, re-refined oil or their mixture.The more detailed description of unrefined oil, refined oil and re-refined oil is provided in the

[0054] paragraph to the

[0056] paragraph of International Publication WO2008 / 147704 (similar disclosure is provided in U.S. Patent Application 2010 / 197536, referring to

[0072] to

[0073] ).The more detailed description of natural lubricating oil and synthetic lubricating oil is described in the

[0058] paragraph to the

[0059] paragraph of WO2008 / 147704 respectively (similar disclosure is provided in U.S. Patent Application 2010 / 197536, referring to

[0075] to

[0076] ). Synthetic oils may also be produced by the Fischer-Tropsch reaction and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In certain embodiments, oils may be produced by the Fischer-Tropsch gas-to-liquid synthesis process and other gas-to-liquid oils.

[0172] Oils of lubricating viscosity may also be defined in accordance with the provisions of "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", April 2008 edition, Section 1.3, Subheading 1.3 "Base Stock Categories". API guidelines are also summarized in U.S. Patent No. 7,285,516 (see Column 11, Line 64 to Column 12, Line 10). In certain embodiments, the oil of lubricating viscosity may be an API Group II, Group III, Group IV oil, or a mixture thereof.

[0173] The amount of oil of lubricating viscosity present is typically the balance remaining after subtracting the sum of the amounts of the compound and other performance additives from 100 weight percent.

[0174] The lubricant composition may be in the form of a concentrate and / or a fully formulated lubricant. If the lubricant 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.

[0175] Detergent

[0176]

[00136] In certain embodiments, the lubricant composition comprises, in addition to the succinimides, succinamides, and succinate esters of the present technology, an overbased metal-containing detergent or mixtures thereof.

[0177] Overbased detergents are known in the art. Overbased materials (also referred to as overbased or superbased 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. Overbased materials are prepared by reacting an acidic material (usually an inorganic acid or a lower carboxylic acid, typically carbon dioxide) with a reaction medium comprising an acidic organic compound, 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 metallic base, and a promoter, such as a mixture of calcium chloride, acetic acid, phenol or alcohol. The acidic organic material will generally have a sufficient number of carbon atoms to provide solubility in 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 will have an excess of metal of 3.5 equivalents or a ratio of 4.5. The term "metal ratio" is also explained in the standard textbook entitled "Chemistry and Technology of Lubricants", 3rd edition, edited by RM Mortier and ST Orszulik, copyright 2010, page 219, subheading 7.25.

[0178] The overbased metal containing detergent may be selected from non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, carboxylates and mixtures thereof or their borated equivalents.The overbased detergent may be borated with a borated agent such as boric acid.

[0179] The overbased detergent may be a non-sulfur-containing phenate, a sulfur-containing phenate, a sulfonate, or a mixture thereof.

[0180] In a specific embodiment, the lubricant composition comprises a high-based sulfonate. High-based sulfonates generally have a total base number (by oil-free) of 250 to 600 or 300 to 500. High-based detergents are known in the art. In certain embodiments, the sulfonate detergent may be mainly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in U.S. Patent Application 2005065045 (and granting U.S. Patent No. 7,407,919)

[0026] to

[0037] paragraphs. Linear alkylbenzene may have a benzene ring attached to any position on the straight chain, typically at the 2nd, 3rd or 4th positions, or a mixture thereof. Mainly linear alkylbenzene sulfonate detergents may be particularly 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 disclosed in

[0046] to

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

[0181] In certain embodiments, the overbased metal detergent comprises overbased calcium sulfonate.The overbased sulfonate detergent may have a metal ratio of 18 to less than 40 and a TBN of 300 to 500 or 325 to 425.

[0182] Overbased detergents may also include "hybrid" detergents formed from mixed surfactant systems containing phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, as described, 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 used, the mixed detergent would be considered equivalent to the amounts of different phenate and sulfonate detergents incorporating similar amounts of phenate and sulfonate soaps, respectively.

[0183] Overbased detergents may have alkali metal, alkaline earth metal or zinc counter ions. In certain embodiments, the metal may be sodium, calcium, barium or magnesium. Typically, other detergents may be sodium, calcium or magnesium containing detergents (typically, calcium or magnesium containing detergents).

[0184] Overbased detergents may typically be overbased detergents of sodium, calcium or magnesium salts of phenates, sulphur-containing phenates, salicylates and salicylates. Overbased phenates and salicylates typically have a total base number (TBN) of 180 to 450 TBN (on an oil-free basis).

[0185] Phenolate detergents are typically derived from para-alkylphenols. Alkylphenols of this type may be combined with sulfur and be highly basic, combined with aldehydes and be highly basic or carboxylated to form salicylate detergents. Suitable alkylphenols include alkylphenols alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e. p-dodecylphenol or PDDP) and pentapropenylphenol. Other suitable alkylphenols include alkylphenols alkylated with alpha-olefins, isomerized alpha-olefins and polyolefins like polyisobutylene. In certain embodiments, the lubricating composition includes less than 0.2 wt %, or less than 0.1 wt % or even less than 0.05 wt % of a phenate detergent derived from PDDP. In certain embodiments, the lubricant composition includes a phenate detergent not derived from PDDP.

[0186] The high alkaline detergent can be present in an amount of 0% to 10% by weight, or 0.1% to 10% by weight, or 0.2% to 8% by weight, or 0.2% to 3% by weight. For example, in a heavy-duty diesel engine, the detergent can be present in an amount of 2% to 3% by weight of the lubricant composition. For a passenger car engine, the detergent can be present in an amount of 0.2% to 1% by weight of the lubricant composition. In certain embodiments, the engine oil lubricant composition further comprises at least one high alkaline detergent having a metal ratio of at least 3, or at least 8, or at least 15.

[0187] In certain embodiments, the overbased detergent may comprise a calcium-containing detergent. The calcium-containing detergent may be an overbased detergent, a non-overbased detergent, or a mixture thereof. Typically, the detergent may be overbased.

[0188] The preparation of calcium-containing detergents is known in the art. Patents describing the preparation of overbased calcium-containing detergents include U.S. Patent Nos. 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.

[0189] The calcium-containing detergent can be a non-high alkalinity detergent (also referred to as a neutral detergent). The TBN of non-high alkalinity can be 20 mg KOH / g to less than 200 mg KOH / g or 30 mg KOH / g to 100 mg KOH / g or 35 mg KOH / g to 50 mg KOH / g. The TBN of non-high alkalinity calcium-containing detergent can also be 20 mg KOH / g to 175 mg KOH / g or 30 mg KOH / g to 100 mg KOH / g. When non-high alkalinity calcium-containing detergent is prepared by strong acid (such as alkyl-substituted sulfonic acid), TBN can be lower (e.g., 0 mg KOH / g to 50 mg KOH / g or 10 mg KOH / g to 20 mg KOH / g).

[0190] The calcium containing detergent may be an overbased detergent which may have a TBN greater than 200 mg KOH / g (typically 250 to 600 mg KOH / g or 300 to 500 mg KOH / g).

[0191] The calcium-containing detergent can be formed by the reaction of an alkaline calcium compound and an acidic detergent base. The acidic detergent base may include alkylphenols, aldehyde-coupled alkylphenols, sulphurized alkylphenols, alkylaromatic sulfonic acids (such as alkylnaphthalenesulfonic acids, alkyltoluenesulfonic acids or alkylbenzenesulfonic acids), aliphatic carboxylic acids, calixarene, salixarene, alkylsalicylic acid or mixtures thereof.

[0192] Metallic alkaline compounds are used to provide alkalinity to detergents. Alkaline calcium compounds are compounds of hydroxides or oxides of metals.

[0193] The oxides and / or hydroxides may be used alone or in combination. The oxides or hydroxides may be hydrated or dehydrated, although hydrated is typical. In certain embodiments, the basic calcium compound may be calcium hydroxide, which may be used alone or in combination with other metal basic compounds. Calcium hydroxide is commonly referred to as lime. In certain embodiments, the metal basic compound may be calcium oxide, which may be used alone or in combination with other metal basic compounds.

[0194] In summary, when alkylphenol, aldehyde-coupled alkylphenol and sulphurized alkylphenol are used to prepare calcium-containing detergents, the detergents can be referred to as calcium phenate. The calcium phenate can be alkyl phenate, aldehyde-coupled alkyl phenate, sulphurized alkyl phenate or a mixture thereof.

[0195] The TBN of the calcium phenate can vary from less than 200 mg KOH / g or 30 mg KOH / g to 175 mg KOH / g (typically 150 mg KOH / g to 175 mg KOH / g) mg KOH / g for neutral phenates to 200 mg KOH / g or more to 500 mg KOH / g or 210 mg KOH / g to 400 mg KOH / g (typically 230 mg KOH / g to 270 mg KOH / g) mg KOH / g for overbased phenates.

[0196] The alkyl group of the phenate (ie, alkyl phenate) may contain 4 to 80, or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.

[0197] In certain embodiments, the calcium-containing detergent may be a sulfonate or a mixture thereof. Sulfonates may be prepared from mono- or di-hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl or dicyclopentadienyl) sulfonic acids, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35, or 9 to 30 carbon atoms.

[0198] The hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms. Examples of suitable alkyl groups include branched and / or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl or mixtures thereof.

[0199] In certain embodiments, the hydrocarbyl-substituted sulfonic acid may include polypropylene benzene sulfonic acid and / or C16-C24 alkyl benzene sulfonic acid or mixtures thereof.

[0200] In certain embodiments, the calcium sulfonate detergent may be primarily a 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 (and issued U.S. Patent No. 7,407,919). In some embodiments, the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3, or 4 positions of the linear chain, and in some cases primarily in the 2 position.

[0201] When neutral or weakly alkaline, the TBN of the calcium sulfonate detergent may be less than 100 mg KOH / g, or less than 75 mg KOH / g, typically 20 to 50 mg KOH / g, or 0 to 20 mg KOH / g.

[0202] When overbased, the calcium sulfonate detergent may have a TBN greater than 200 mg KOH / g, or from 300 mg KOH / g to 550 mg KOH / g, or from 350 mg KOH / g to 450 mg KOH / g.

[0203] The detergent may be borated or non-borated.

[0204] The chemical structures of sulfonate and phenate detergents are known to those skilled in the art. The standard textbook entitled "Chemistry and Technology of Lubricants", 3rd edition, edited by RM Mortier and ST Orszulik, copyright 2010, pages 220 to 223, provides a general disclosure of such detergents and their structures under subheading 7.2.6.

[0205] In certain embodiments, the calcium-containing detergent may be an overbased calcium sulfonate, an overbased calcium phenate, or a mixture thereof. Typically, the detergent may be an overbased calcium sulfonate.

[0206] In certain embodiments, calcium-containing detergents can be mixed with zinc-containing, barium-containing, sodium-containing or magnesium-containing detergents. Zinc-containing, barium-containing, sodium-containing or magnesium-containing detergents are also well known in the art and are described in the same references describing calcium-containing detergents. However, TBN and metal ratios may be slightly different. Zinc-containing, barium-containing, sodium-containing or magnesium-containing detergents may be phenates, sulfur-containing phenates, sulfonates, salicylic acid alcohol salts or salicylates. Usually, zinc-containing, barium-containing, sodium-containing or magnesium-containing detergents may be magnesium phenate, magnesium-sulfur-containing phenates or magnesium sulfonates.

[0207] Dispersants

[0208] In certain embodiments, the engine oil lubricant composition comprising the succinimide, succinamide or succinate of the present technology may also include a dispersant or a mixture thereof. The dispersant may be selected from a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinate, an amide or an ester-amide, or a mixture thereof.

[0209] In certain embodiments, the engine oil lubricant composition comprises a dispersant or a mixture thereof. The dispersant may exist as a single dispersant. The dispersant may exist as a mixture of two or more (usually two or three) different dispersants, at least one of which may be a succinimide dispersant.

[0210] The succinimide dispersant may be derived from an aliphatic polyamine or a mixture thereof. The aliphatic polyamine may be an aliphatic polyamine such as ethylene polyamine, propylene polyamine, butylene polyamine or a mixture thereof. In certain embodiments, the aliphatic polyamine may be an ethylene polyamine. In certain embodiments, the aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottom residues and mixtures thereof.

[0211] 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, typically diethylamine.

[0212] The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide. Typically, the number average molecular weight of the polyisobutylene from which the polyisobutylene succinic anhydride is derived may be 350 to 5000, or 550 to 3000, or 750 to 2500. Succinimide dispersants and methods of making them are disclosed, for example, in U.S. Pat. Nos. 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.

[0213] Dispersant can also utilize conventional methods to carry out post-treatment by reacting with any one of various reagents.These reagents 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, epoxide and phosphorus compounds.In certain embodiments, the dispersant of post-treatment is borated.In certain embodiments, the dispersant of post-treatment can react with dimercaptothiadiazoles.In certain embodiments, the dispersant of post-treatment can react with phosphoric acid or phosphorous acid.In certain embodiments, the dispersant of post-treatment is to react with terephthalic acid and boric acid (as described in U.S. Patent Application US2009 / 0054278).

[0214] In certain embodiments, the dispersant may be borated or non-borated. Typically, 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 lubricant composition. In certain embodiments, the lubricant composition may be free of a boron-containing dispersant, i.e., no more than 10 ppm of boron is delivered to the final formulation.

[0215] The dispersant may be prepared / obtained / obtainable from the reaction of succinic anhydride by an "ene" reaction or a "thermal" reaction, by what may be called a "direct alkylation process". The "ene" reaction mechanism and general reaction conditions are summarized in "Maleic Anhydride", pages 147 to 149, edited by BC Trivedi and BC Culbertson, and published by Plenum Press in 1982. The dispersant prepared by a process including an "ene" reaction may be a polyisobutylene succinimide having a carbon ring present on less than 50 mol %, or 0 to less than 30 mol %, or 0 to less than 20 mol %, or 0 mol % 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.

[0216] Dispersants may also be obtained / obtainable by a chlorine-assisted process, typically involving a Diels-Alder chemical reaction resulting in the formation of a carbocyclic bond. This process is known to those skilled in the art. The dispersant produced by the chlorine-assisted process may be a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules. Both thermal and chlorine-assisted processes are described in more detail in U.S. Patent No. 7,615,521, columns 4 to 5 and Preparation Examples A and B.

[0217] 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.

[0218] In certain embodiments, the dispersant may be polyisobutylene succinimide, wherein the number average molecular weight of the polyisobutylene from which the polyisobutylene succinimide is derived is from 350 to 5000 or from 750 to 2500. The dispersant may be present at 0 wt % to 20 wt %, or 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 % of the lubricant composition.

[0219] In certain embodiments, the engine oil lubricant composition comprising the succinimide, succinamide or succinate of the present technology can be a lubricant composition further comprising a molybdenum compound. The molybdenum compound can be an antiwear agent or an antioxidant. The molybdenum compound can be selected from dialkyl dithiophosphate molybdenum, dithiocarbamate molybdenum, amine salts of molybdenum compounds and mixtures thereof. The molybdenum compound can provide 0ppm to 1000ppm, or 5ppm to 1000ppm, or 10ppm to 750ppm, 5ppm to 300ppm, or 20ppm to 250ppm of molybdenum to the lubricant composition.

[0220] In certain embodiments, the engine oil lubricant composition comprising succinimide, succinamide and succinate of the present technology may also include an antioxidant.Antioxidant includes sulfided olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as dithiocarbamate platinum), hydroxy thioethers or their mixtures.In certain embodiments, lubricant composition includes antioxidant or their mixture.Antioxidant can exist in 0 weight % to 15 weight % or 0.1 weight % to 10 weight % or 0.5 weight % to 5 weight % or 0.5 weight % to 3 weight % or 0.3 weight % to 1.5 weight % of lubricant composition.

[0221] In certain embodiments, the dispersant can be a mixture comprising: (i) a non-borated dispersant comprising polyisobutylene succinimide, wherein the polyisobutylene used to prepare the non-borated dispersant has a number average molecular weight of 550 to 1150, or 750 to 1150, or 900 to 1000 (typically commercially available at a number average molecular weight of about 950); and (ii) a borated dispersant comprising polyisobutylene succinimide, wherein the polyisobutylene used to prepare the non-borated dispersant has a number average molecular weight of 550 to 1150, or 750 to 1150, or 900 to 1000 (typically commercially available at a number average molecular weight of about 950).

[0222] In certain embodiments, the dispersant may be a mixture comprising: (a) a non-borated dispersant comprising polyisobutylene succinimide, wherein the polyisobutylene used to prepare the non-borated dispersant has a number average molecular weight of 550 to 1150, or 750 to 1150, or 900 to 1000 (typically commercially available at a number average molecular weight of about 950); and (b) a borated dispersant which may also be a product prepared by heating together: (i) a dispersant base; (ii) 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or an oligomer thereof; (iii) a boronating agent; and (iv) a dicarboxylic acid optionally selected from an aromatic compound selected from the group consisting of a 1,3 diacid and a 1,4 diacid; or (v) optionally a phosphoric acid compound, wherein the heating is sufficient to provide a product of (i), (ii), (iii) and optionally (iv) or (v) which is soluble in an oil of lubricating viscosity.

[0223] Antioxidants

[0224] In certain embodiments, the engine oil lubricant composition comprises the succinimides, succinamides and succinates of the present technology, and further comprises a phenolic or amino acid antioxidant or a mixture thereof, and wherein the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt %. In another embodiment, when present, the antioxidant may be present at 0.2 wt % to 1.2 wt %, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt %, or 0.5 wt % to 0.8 wt % of the lubricant.

[0225] Diarylamine or alkylated diarylamine can be phenyl-a-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.

[0226] Hindered phenol antioxidants typically contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenol group can 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 can be an ester and can include, for example, Irganox from Ciba TM L-135. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in U.S. Pat. No. 6,559,105. If present, the phenolic oxidant may be present at 0.1 wt % to 2 wt %, or 0.2 wt % to 1.5 wt %, or 0.1 wt % to 1 wt %, or 0.4 wt % to 1.0 wt % of the lubricant composition.

[0227] Examples of molybdenum dithiocarbamates useful as antioxidants include commercially available materials sold under trade names such as: Molyvan A and 855 (from Vanderbilt Co., Ltd.) and Adeka Saknra-Lube TM S-100, S-165, S-600 and 525 or mixtures thereof.

[0228] Viscosity modifier

[0229] In certain embodiments, the engine oil lubricant composition comprising the succinimide, succinamide and succinate of the present technology also includes a viscosity modifier.Viscosity modifiers are known in the art and can 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, polyalkylstyrene, polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in International Application WO 2010 / 014655), esters of maleic anhydride-styrene copolymers or mixtures thereof.Viscosity modifiers may include block copolymers comprising: (i) vinyl aromatic monomer blocks and (ii) conjugated diene olefin monomer blocks (such as hydrogenated styrene-butadiene copolymers or hydrogenated styrene-isoprene copolymers), 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.

[0230] Dispersant Viscosity Modifier

[0231] In certain embodiments, the viscosity modifier may be a dispersant viscosity modifier.The dispersant viscosity modifier may include a functionalized polyolefin, such as an ethylene-propylene copolymer that has been functionalized with an acylating agent such as maleic anhydride and amines.

[0232] In certain embodiments, the dispersant viscosity modifier comprises an olefin copolymer further functionalized with a dispersant amine group. Typically, the olefin copolymer is an ethylene-propylene copolymer. The olefin copolymer has a number average molecular weight of 5000 to 20,000, or 6000 to 18,000, or 7000 to 15,000. The olefin copolymer can have a shear stability index of 0 to 20, or 0 to 10, or 0 to 5, as measured by Orbahn shear test (ASTM D6278) as described above.

[0233] The formation of dispersant viscosity modifiers is well known in the art. Dispersant viscosity modifiers may include, for example, those described in US Pat. No. 7,790,661 at column 2, line 48 to column 10, line 38.

[0234] In certain embodiments, the dispersant viscosity modifier may be prepared by grafting an olefinic carboxylic acid acylating agent to 15 mol % to 80 mol % ethylene, 20 mol % to 85 mol % C 3-10 The invention is prepared by grafting a polymer of an α-monoolefin and 0 to 15 mol % of a non-conjugated diene or triene, the polymer having an average molecular weight of 5000 to 20,000, and further reacting the grafted polymer with an amine (usually an aromatic amine).

[0235] Dispersant viscosity modifiers may include functionalized polyolefins, such as 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 disclosed in the following documents: International Publication WO2006 / 015130 or U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; 6,117,825; and U.S. Pat. No. 7,790,661.

[0236] In certain embodiments, the dispersant viscosity modifier may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or International Publication WO 2006 / 015130 (see page 2, paragraph

[0008] , and the preparation examples are described in paragraphs

[0065] to

[0073] ). In certain embodiments, the dispersant viscosity modifier may include those described in U.S. Pat. No. 7,790,661, column 2, line 48 to column 10, line 38.

[0237] In certain embodiments, the engine oil lubricant composition comprising the succinimides, succinamides and succinates of the present technology further comprises a dispersant viscosity modifier. The dispersant viscosity modifier may be present in an amount of 0% to 5% by weight, or 0% to 4% by weight, or 0.05% to 2% by weight, or 0.2% to 1.2% by weight of the lubricant composition.

[0238] Friction modifier

[0239] In certain embodiments, in addition to the succinimide, succinamide and succinate of the present technology, the engine oil lubricant composition also includes a friction modifier. In certain embodiments, the friction modifier can 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; tartaric acid fatty alkyl esters; fatty alkyl tartar imides; fatty alkyl tartar amides; fatty maleates and imides, fatty (poly) glycolates; and fatty hydroxyacetamides. The friction modifier can be present in 0% to 6% by weight of the lubricant composition, or 0.01% to 4% by weight, or 0.05% to 2% by weight, or 0.1% to 2% by weight. As used herein, the term "fatty alkyl" or "fat" with respect to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.

[0240] 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; hydroxyalkyl amides; 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 of fatty carboxylic acids with guanidine, aminoguanidine, urea or thiourea and their salts.

[0241] 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.

[0242] In certain embodiments, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a monoester, and in another embodiment the long chain fatty acid ester may be a triglyceride.

[0243] Antiwear Agents

[0244] In certain embodiments, the lubricant composition comprising the succinimide, succinamide and / or succinate of the present technology may also include at least one antiwear agent. 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 of phosphorus compounds, sulphurized olefins, metal dialkyl dithiophosphates (such as dialkyl zinc dithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, compounds containing thiocarbamates (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates and bis (S-alkyl dithiocarbamoyl) disulfides).

[0245] In certain embodiments, the antiwear agent may include a tartrate or tartrimide as disclosed in International Publication No. WO 2006 / 044411 or Canadian Patent No. CA1 183 125. The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms on the alkyl group is at least 8. In certain embodiments, the antiwear agent may include a citrate, as disclosed in U.S. Patent Application No. 20050198894.

[0246] Another class of additives includes oil-soluble titanium compounds, such as those disclosed in U.S. Pat. No. 7,727,943 and US2006 / 0014651. Oil-soluble titanium compounds can be used as anti-wear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In certain embodiments, the oil-soluble titanium compound is a titanium (IV) alkoxide. Titanium alkoxides are formed from the following substances: monohydric alcohols, polyhydric alcohols, or mixtures thereof. Monohydric alcohol salts can have 2 to 16 carbon atoms or 3 to 10 carbon atoms. In certain embodiments, the titanium alkoxide is titanium (IV) isopropoxide. In certain embodiments, the titanium alkoxide is 2-ethylhexyl titanium (IV). In certain embodiments, the titanium compound includes an alcohol salt of an adjacent 1,2-diol or polyhydric alcohol. In certain embodiments, the 1,2-adjacent diol includes a fatty acid monoester of glycerol, typically the fatty acid being oleic acid.

[0247] In certain embodiments, the oil-soluble titanium compound is a titanium carboxylate. In certain embodiments, the titanium (IV) carboxylate is titanium neodecanoate.

[0248] In certain embodiments, the antiwear agent may be a phosphorus-containing antiwear agent, which may be zinc dialkyl dithiophosphates, phosphites, phosphates, phosphonates, and ammonium phosphates, or mixtures thereof.

[0249] In certain embodiments, the lubricant composition may also include a phosphorus-containing antiwear agent, typically a zinc dialkyl dithiophosphate. Zinc dialkyl dithiophosphates are known in the art. 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. Zinc dialkyl dithiophosphates may provide 0.01 wt % to 0.1 wt % phosphorus to the lubricating composition or provide 0.015 wt % to 0.075 wt % phosphorus or 0.02 wt % to 0.05 wt % phosphorus to the lubricating composition.

[0250] In certain embodiments, the lubricant composition further comprises one or more zinc dialkyl dithiophosphates such that the amine (thio)phosphate additive provides at least 50% of the total phosphorus present in the lubricating composition, or at least 70% of the total phosphorus in the lubricating composition, or at least 90% of the total phosphorus. In certain embodiments, the lubricant composition is free or substantially free of zinc dialkyl dithiophosphates.

[0251] The antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricant composition.

[0252] In certain embodiments, in addition to the succinimides, succinamides, and succinates of the present technology, the lubricant composition further comprises 0.01 wt % to 5 wt % or 0.1 wt % to 2 wt % of an ashless antiwear agent represented by the formula:

[0253]

[0254] Wherein Y and Y' are independently -O-, >NH, >NR 3 or by bringing the Y and Y' groups together and forming R between the two >C=O groups 1 -N< group and the imide group formed; X is independently -ZO-Z'-, >CH2, >CHR 4 、>CR 4 R 5 、>C(OH)(CO2R 2)、>C(CO2R 2 )2 or>CHOR 6 ; Z and Z' are independently>CH2,>CHR 4 、>CR 4 R 5 、>C(OH)(CO2R 2 ) or>CHOR 6 ; n is 0 to 10, provided that when n=1, X is not>CH2, and when n=2, both X are not>CH2; m is 0 or 1; R 1 are independently hydrogen or a hydrocarbyl group typically containing from 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; R 2 is a hydrocarbon group usually containing 1 to 150 carbon atoms; R 3 , R 4 and R 5 are independently a hydrocarbon group; and R 6 is hydrogen or a hydrocarbyl group generally containing 1 to 150 carbon atoms.

[0255] In certain embodiments, the engine oil lubricant composition containing the succinimides, succinamides and succinates of the present technology further contains 0.01 wt % to 5 wt % or 0.1 wt % to 2 wt % of an ashless antiwear agent, the ashless antiwear agent being obtained / obtainable by a method comprising reacting glycolic acid, 2-halo-acetic acid or lactic acid or an alkali metal salt thereof or an alkali metal salt (typically glycolic acid or 2-halo-acetic acid) with at least one member selected from the group consisting of amines, alcohols and amino alcohols. For example, the compound can be represented by the following formula:

[0256]

[0257] Wherein Y is independently oxygen or >NH or >NR 1 ; R 1 is independently a hydrocarbon group typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms; Z is hydrogen or methyl; Q is the residue of a diol, triol or higher polyol, a diamine, a triamine or higher polyamine or an amino alcohol (typically, Q is a diol, a diamine or an amino alcohol), g is 2 to 6, or 2 to 3, or 2; q is 1 to 4, or 1 to 3, or 1 to 2; n is 0 to 10, 0 to 6, 0 to 5, 1 to 4 or 1 to 3; and Ak:1 is an alkylene group containing 1 to 5, or 2 to 4 or 2 to 3 (typically ethylene) carbon atoms; and b is 1 to 10, or 2 to 8, or 4 to 6, or 4.

[0258] This compound is known and described in International Publication No. WO 2011 / 022317 and issued US Pat. Nos. 8,404,625, 8,530,395 and 8,557,755.

[0259] In certain embodiments, the lubricant compositions disclosed herein are free of zinc dialkyldithiophosphates.

[0260] In certain embodiments, the lubricant compositions disclosed herein contain zinc dialkyl dithiophosphates.

[0261] In certain embodiments, the antiwear agent is a phosphorus-containing compound. In certain embodiments, the phosphorus-containing compound may be a nonionic phosphorus compound.

[0262] In certain embodiments, the phosphorus-containing compound comprises two or more (possibly up to four) nonionic phosphorus compounds. Typically, the nonionic phosphorus compounds may have an oxidation of +3 or +5. Various embodiments comprise phosphites, phosphates, or mixtures thereof.

[0263] In certain embodiments, the phosphorus-containing compound comprises a nonionic phosphorus compound (phosphite C 4-6 alkyl esters) and amine salts of phosphoric acid or esters.

[0264] The phosphorus-containing compound includes a nonionic phosphorus compound (which is phosphorous acid C 4-6 Hydrocarbon ester) or a mixture thereof. Phosphorous acid C 4-6 Hydrocarbyl esters include those represented by the formula:

[0265]

[0266] wherein each R"' may independently be hydrogen or a hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon atoms, provided that at least one R"' group is a hydrocarbyl group. Typically, phosphorous acid C 4-6 The hydrocarbyl ester comprises dibutyl phosphite.

[0267] Phosphorous acid C 4-6 The hydrocarbyl ester may deliver at least 175 ppm or at least 200 ppm of the total amount of phosphorus delivered by the phosphorus-containing compound.

[0268] Phosphorous acid C 4-6 The hydrocarbyl ester may deliver at least 45 weight percent, or from 50 weight percent to 100 weight percent, or from 50 weight percent to 90 weight percent, or from 60 weight percent to 80 weight percent of the total amount of phosphorus from the phosphorus-containing compound.

[0269] The phosphorus-containing compound may comprise a second phosphite having a formula similar to that disclosed above, except that R'' may comprise 2 to 40, 8 to 24, or 11 to 20 carbon atoms, provided that the second phosphite is not phosphorous acid C4-6 Hydrocarbyl Esters. Examples of suitable hydrocarbyl groups include propyl, dodecyl, tetradecyl, hexadecyl, octadecyl, propenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl groups.

[0270] As used herein, the term "alk(en)yl" is intended to include moieties having alkyl and / or alkenyl groups.

[0271] In certain embodiments, the phosphorus-containing compound comprises phosphorous acid C 4-6 Hydrocarbon ester (usually dibutyl phosphite) and phosphorous acid C 12-18 A mixture of alk(en)yl hydrogen esters and optionally phosphoric acid. In various embodiments, phosphoric acid is present or absent.

[0272] In certain embodiments, the phosphorus-containing compound comprises phosphorous acid C 4-6 Hydrocarbon ester (usually dibutyl phosphite) and phosphorous acid C 16-18 The phosphite alkyl (alkenyl) hydrogen ester can be a mixture of phosphite alkyl hydrogen ester and phosphite alkenyl hydrogen ester or phosphite alkenyl hydrogen ester and phosphite alkyl hydrogen ester. In certain embodiments, the phosphite alkyl (alkenyl) hydrogen ester can be a mixture of phosphite alkenyl hydrogen ester and phosphite alkyl hydrogen ester and optionally phosphoric acid. Phosphoric acid may be present or absent.

[0273] In certain embodiments, the phosphorus-containing compound comprises phosphorous acid C 4-6 Hydrocarbon ester (usually dibutyl phosphite) and phosphorous acid C 11-14 The mixture of alkyl (alkenyl) hydrogen esters. The alkyl (alkenyl) hydrogen phosphite can be a mixture of alkyl hydrogen phosphite and alkenyl hydrogen phosphite or alkenyl hydrogen phosphite and alkyl hydrogen phosphite. In certain embodiments, the alkyl (alkenyl) hydrogen phosphite can be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optional phosphoric acid.

[0274] In certain embodiments, the phosphorus-containing compound comprises phosphorous acid C 4-6 A mixture of a hydrocarbyl ester (usually dibutyl phosphite) and phosphoric acid.

[0275] In certain embodiments, the lubricant composition comprises a package comprising a phosphorus-containing compound and a nonionic phosphorus compound that is a hydrocarbyl phosphite.

[0276] In certain embodiments, the lubricant composition further comprises phosphorous acid C 8-20 Hydrocarbon ester, or phosphorous acid C 12-18 Hydrocarbon ester, or phosphorous acid C 16-18 Hydrocarbon esters.

[0277] In certain embodiments, an amine salt of phosphoric acid. In certain embodiments, an amine salt of phosphoric acid can be derived from an amine salt of phosphate. An amine salt of phosphoric acid can be represented by the following formula:

[0278]

[0279] Where R 3 and R 4 may independently be hydrogen or a hydrocarbon typically containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms, provided that at least one is a hydrocarbyl group; and R 5 , R 6 , R 7 and R 8 R may independently be hydrogen or a hydrocarbyl group, provided that at least one is a hydrocarbyl group. 3 and / or R 4 The hydrocarbon group may be straight chain, branched chain or cyclic. 3 and / or R 4 Examples of the hydrocarbon group include straight or branched chain alkyl groups including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. 3 and / or R 4 Examples of the cyclic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl.

[0280] In certain embodiments, the phosphate can be an amine salt of a mixture of monoalkyl and dialkyl phosphates. The monoalkyl and dialkyl groups can be straight chain or branched.

[0281] The amine salt of phosphoric acid can be derived from an amine, such as a primary amine, a secondary amine, a tertiary amine, or a mixture thereof. The amine can be aliphatic, or cyclic, aromatic or non-aromatic, typically aliphatic. In certain embodiments, the amine includes an aliphatic amine, such as an aliphatic tertiary amine-primary amine.

[0282] Examples of suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine and dodecylamine, and fatty amines such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other useful fatty amines include commercially available fatty amines such as Amines (commercially available from Akzo Chemicals, Chicago, Ill.) such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, where the letter designation is associated with a fatty group such as cocoyl, oleyl, tallow or stearyl.

[0283] Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, N-methyl-1-amino-cyclohexane, 2C and ethylpentylamine. The secondary amine may be a cyclic amine such as piperidine, piperazine and morpholine.

[0284] Examples of tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine ( DMOD).

[0285] In certain embodiments, the amine is in the form of a mixture. Examples of suitable amine mixtures include (i) tertiary alkyl primary amines having 11 to 14 carbon atoms, (ii) tertiary alkyl primary amines having 14 to 18 carbon atoms, or (iii) tertiary alkyl primary amine carbon atoms having 18 to 22 carbon atoms. Other examples of tertiary alkyl primary amines include tertiary butylamine, tertiary hexylamine, tertiary octylamine (such as 1,1-dimethylhexylamine), tertiary decylamine (such as 1,1-dimethyloctylamine), tertiary dodecylamine, tertiary tetradecylamine, tertiary hexadecylamine, tertiary octadecylamine, tertiary tetracosylamine, and tertiary octadecylamine.

[0286] In certain embodiments, useful amine mixtures are " 81R" or " JMT”. 81R and JMT (both produced and sold by Rohm & Haas) is a mixture of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines.

[0287] Amine salts of phosphoric acid can be prepared as described in U.S. Pat. No. 6,468,946. Column 10, lines 15 to 63 describe the formation of phosphoric acid esters by reaction of phosphorus compounds, followed by reaction with amines to form amine salts of phosphoric acid hydrocarbon esters. Column 10, lines 64 to column 12, lines 23 describe the preparation of examples of the reaction between phosphorus pentoxide and alcohols (having 4 to 13 carbon atoms), followed by reaction with amines (typically 81-R) to form an amine salt of a phosphate ester.

[0288] Sulfur-containing extreme pressure agent

[0289] The sulfur-containing extreme pressure agent may be an olefin sulfide or a mixture thereof. The olefin sulfide may include polysulfide or a sulfided olefin, such as sulfided isobutylene, or a mixture thereof.

[0290] In certain embodiments, the olefin sulfide comprises a polysulfide.

[0291] In certain embodiments, the olefin sulfide comprises sulfided isobutylene.

[0292] In certain embodiments, the olefin sulfide comprises a mixture of sulfided isobutylene and polysulfides.

[0293] In certain embodiments, at least 50% by weight of the polysulfide molecules are a mixture of trisulfides or tetrasulfides. In certain embodiments, at least 55% by weight or at least 60% by weight of the polysulfide molecules are a mixture of trisulfides or tetrasulfides.

[0294] Polysulfides include sulfurized organic polysulfides derived from oils, fatty acids or esters, olefins or polyolefins.

[0295] Oils that may be sulfurized include natural or synthetic oils such as mineral oil, lard, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (eg, myristoleate and oleyloleate), and synthetic unsaturated esters or glycerides.

[0296] Fatty acids include those containing 8 to 30 or 12 to 24 carbon atoms. Examples of fatty acids include oleic acid, linoleic acid, linolenic acid and tall oil. Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters such as those obtained from animal fats and vegetable oils including tall oil, linseed oil, soybean oil, rapeseed oil and fish oil.

[0297] Polysulfide comprises the olefin derived from multiple olefinic hydrocarbons.Olefinic hydrocarbons have one or more double bonds conventionally.In certain embodiments, olefin contains 3 to 30 carbon atoms.In other embodiments, olefin contains 3 to 16 or 3 to 9 carbon atoms.In certain embodiments, sulfurized olefin comprises the olefin derived from propylene, isobutylene, amylene or their mixture.

[0298] In certain embodiments, the polysulfide comprises a polyolefin derived from polymerizing an olefin as described above by known techniques.

[0299] In certain embodiments, polysulfides include dibutyl tetrasulfide, methyl sulfide of oleic acid, alkyl phenol sulfides, dipentene sulfides, dicyclopentadiene sulfides, terpenes sulfides, and Diels-Alder adduct sulfides.

[0300] Other additives

[0301] The lubricant composition may also include a sulfur-containing corrosion inhibitor. The sulfur-containing corrosion inhibitor may be a thiadiazole compound or a mixture thereof. The thiadiazole compound may include a 2,5-dimercapto-1,3,4-thiadiazole compound substituted with a single or dihydrocarbyl group. Examples of thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole or oligomers thereof, 2,5-dimercapto-1,3-4-thiadiazole substituted with a hydrocarbyl group, 2,5-dimercapto-1,3-4-thiadiazole substituted with hydrocarbylsulfur, or oligomers thereof. Hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole oligomers are generally formed by forming sulfur-sulfur bonds between 2,5-dimercapto-1,3,4-thiadiazole units to form oligomers of two or more of the thiadiazole units. These thiadiazole compounds may also be used in the post-treatment of dispersants as mentioned below, for forming dimercaptothiadiazole derivatives of polyisobutylene succinimide.

[0302] Examples of suitable thiadiazole compounds include at least one of dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole or 4-5-dimercapto-[1,2,3]-thiadiazole. Generally, readily available materials such as 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbylsulfide-substituted 2,5-dimercapto-1,3,4-thiadiazole are generally utilized.

[0303] Foam suppressors that may be used in the 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 oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers.

[0304] Pour point depressants that may be used in the compositions disclosed herein include poly-alpha-olefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates, or polyacrylamides.

[0305] Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.

[0306] The metal deactivator may be selected from derivatives of benzotriazole (typically tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-amino-2-propanol, derivatives of dimercaptothiadiazole, octylamine octanoate, condensation products of dodecenylsuccinic acid or anhydride and / or fatty acids such as oleic acid with polyamines. Metal deactivators may also be described as corrosion inhibitors.

[0307] Seal swell agents include the sulfolene derivative Exxon Necton-37 TM (FN 1380) and Exxon MineralSeal Oil TM (FN 3200). Example

[0308] 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.

[0309] The following examples are generally prepared according to the following representative preparation scheme for preparing succinimide or succinamide derivatives from PIBSA products (free radical functionalized PIBSA products, referred to as "RF", or conventional PIBSA products prepared by conventional thermal methods, referred to as "thermal"): PIBSA and diluent oil are loaded into a round-bottom flask equipped with a Dean-Stark water trap, an addition funnel, a temperature probe, and an overhead stirrer. The mixture is heated to about 110°C-120°C, and the amine is added dropwise over 30 to 60 minutes. After the amine is added, the reaction mixture is heated to about 150°C-160°C, and maintained at 150°C-160°C for about 4 hours-6 hours while removing the reaction water. Once the removal of the reaction water is complete, the reaction mixture is cooled and poured into a wide-mouth bottle. In some cases, the derived succinamide or succinimide is post-treated with a post-treatment agent (such as boric acid, phosphoric acid, dimethylthiothiadiazole or an aromatic diacid).

[0310] The dispersants described in Table 1 were prepared according to the method described in the previous paragraph.

[0311] Table 1

[0312]

[0313] A 60:40 mixture of 2300Mn high vinylidene PIB and 1000Mn high vinylidene PIB

[0314] B 85:15 mixture of 2300Mn high vinylidene PIB and 550Mn high vinylidene PIB

[0315] C Polyvinylamine bottom residue

[0316] D Tetraethylenetriamine

[0317] E85:15 mixture of polyethyleneamine bottoms and diethylenetriamine

[0318] Inventive Examples INV D1 and INV D2 were evaluated in commercial engine oil lubricants for piston deposit control in the EA888 piston cleanliness test and the VW TDi3 piston deposit test. Both tests evaluate the ability of the additive package to minimize the amount of deposits on the piston during engine operation. The data shown in Table 2 indicate that at equal active material treat rates, the inventive examples prepared from free radical functionalized polyisobutylene succinic anhydride have comparable piston deposition performance to the comparative dispersant COMP D1 prepared from polyisobutylene succinic anhydride prepared by a known thermal process in the absence of a free radical initiator.

[0319] Table 2

[0320]

[0321] The heat resistance of the inventive examples INV D5 and INV D6 was evaluated by the ASTM dropping point (D2256) test in commercial greases. The dropping point of a grease is an indicator of the heat resistance of a grease and is the temperature at which the grease changes from a semi-solid to a liquid state under specific test conditions. It depends on the type of thickener used and the cohesiveness of the oil and the thickener of the grease. The data shown in Table 2 indicate that at equal active material treatment rates, the inventive examples INV D5 and INV D6 prepared from free radical functionalized polyisobutylene succinic anhydride have comparable dropping point performance to the comparative dispersant COMP D1 prepared from polyisobutylene succinic anhydride, which was prepared by a known thermal method in the absence of a free radical initiator.

[0322] Table 3

[0323] INV D5 INV D6 COMP D4 D2265(Drop point) Dropping point 259℃ 259℃ 262 259℃

[0324] Inventive Examples INV D3 and INV D4 were evaluated in commercial transmission fluids to assess the shift quality of automatic transmissions, the ability of the fluids to prevent automatic transmission shudder, and the frictional properties of the fluids to prevent catastrophic transmission damage in continuously variable transmissions. The data shown in Table 4 indicate that at equal active material treatment rates, the inventive examples prepared from free radical functionalized polyisobutylene succinic anhydride have equivalent friction and anti-shudder performance in automatic transmissions when compared to comparative dispersants COMP D2 and COMP D3 prepared from polyisobutylene succinic anhydride, which were prepared by a known thermal process in the absence of a free radical initiator. The data shown in Table 5 indicate that inventive examples INV D3 and INV D4 prepared from free radical functionalized polyisobutylene succinic anhydride have equivalent frictional performance in continuously variable transmissions when compared to comparative dispersants COMP D2 and COMP D3 prepared from polyisobutylene succinic anhydride, which were prepared by a known thermal process in the absence of a free radical initiator.

[0325] Inventive Examples INV D5 and INV D6 were evaluated in commercial gear fluids for assessment in the L-60-1 oxidation test. The data shown in Table 7 indicate that at equivalent active material treat rates, the inventive examples prepared from free radical functionalized polyisobutylene succinic anhydride have comparable oxidative stability in gear oil fluids to comparative dispersants COMP D4 and COMP D5 prepared from polyisobutylene succinic anhydride prepared by a known thermal process in the absence of a free radical initiator.

[0326] Table 4

[0327]

[0328] Table 5

[0329]

[0330] Table 6

[0331]

[0332]

[0333] Table 7

[0334]

[0335] 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.

[0336] 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.

[0337] 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 lubricant composition, comprising: a. oil of lubricating viscosity; and b. a succinimide, succinamide or succinate ester obtained by reacting: i. amine or alcohol; and ii. A free radical functionalized PIBSA product obtained by a process comprising the steps of: A. 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 reaction product; B. wherein the polyisobutylene is brought to the reaction temperature prior to adding the free radical initiator; and C. wherein the ethylenically unsaturated acylating agent is added at any time before or during the addition of the free radical initiator.

2. The lubricant composition of claim 1, wherein the amine is a polyamine.

3. The lubricant composition of claim 2, wherein the polyamine contains at least one >N—H group per molecule.

4. A lubricant composition according to claim 2 or claim 3, wherein the polyamine is an aliphatic polyamine.

5. The lubricant composition according to claim 4, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine or butylene polyamine.

6. The lubricant composition of claim 5, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

7. The lubricant composition according to any one of claims 1 to 6, wherein the alcohol is a polyhydroxy aliphatic alcohol.

8. The lubricant composition according to claim 7, wherein the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

9. The lubricant composition according to any one of claims 1 to 8, wherein the succinic acid ester obtained is further reacted with an amine.

10. The lubricant composition of claim 9, wherein the amine is an aliphatic amine.

11. The lubricant composition of claim 10, wherein the aliphatic amine is an aliphatic polyamine.

12. The lubricant composition according to claim 11, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine or butylene polyamine.

13. The lubricant composition of claim 12, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

14. The lubricant composition according to any one of claims 1 to 13, wherein the succinimide, succinamide or succinic acid ester is post-treated with a post-treating agent to produce a post-treated succinimide, a post-treated succinimide or a post-treated succinic acid ester.

15. The lubricant composition of claim 14, wherein the post-treatment agent comprises at least one of urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, 2,5-dimercaptothiadiazole, or aromatic diacids having acid groups at the 1,3 or 1,4 positions on the benzene ring.

16. The lubricant composition according to claim 15, wherein the phosphorus compound is phosphoric acid or anhydride.

17. A lubricant composition according to claim 15 or claim 16, wherein the aromatic diacid having acid groups at the 1,3 or 1,4 positions on the benzene ring is terephthalic acid.

18. The lubricant composition according to any one of claims 14 to 17, wherein the post-treated succinimide or post-treated succinamide is a borated succinimide or a borated succinamide.

19. The lubricant composition according to any one of claims 1 to 18, further comprising at least one additional additive, the additional additive comprising at least one of a detergent, a dispersant, a friction modifier, an antiwear agent, an extreme pressure agent, a corrosion inhibitor, a viscosity modifier, a defoamer, a demulsifier or a seal swell agent.

20. A method of lubricating a mechanical device, the method comprising supplying the mechanical device with a lubricant composition according to any one of claims 1 to 19.

21. A method for producing a reaction product, the method comprising: reacting the free radical functionalized PIBSA product with an amine or an alcohol to form the reaction product; The reaction product comprises at least one of succinimide, succinamide or succinate.

22. The method of claim 21, wherein the amine is a polyamine.

23. The method of claim 22, wherein the polyamine contains at least one >N—H group per molecule.

24. A method according to claim 21 or claim 22, wherein the polyamine is an aliphatic polyamine.

25. The method of claim 24, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

26. The method of claim 25, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

27. The method of any one of claims 21 to 26, wherein the alcohol is a polyhydroxy aliphatic alcohol.

28. The method of claim 27, wherein the polyhydroxy aliphatic alcohol is selected from glycerol, pentaerythritol or sorbitol.

29. The process according to any one of claims 21 to 28, wherein the succinic ester obtained is further reacted with an amine.

30. The method of claim 29, wherein the amine is an aliphatic amine.

31. The method of claim 30, wherein the aliphatic amine is an aliphatic polyamine.

32. The method of claim 31, wherein the aliphatic polyamine is at least one of ethylene polyamine, propylene polyamine, or butylene polyamine.

33. The process of claim 32, wherein the ethylene polyamine comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyamine bottoms.

34. The method of any one of claims 21 to 33, wherein the succinimide, succinamide or succinic acid ester is post-treated with a post-treating agent to produce a post-treated succinimide, a post-treated succinimide or a post-treated succinic acid ester.

35. The method of claim 34, wherein the post-treatment agent comprises at least one of urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, 2,5-dimercaptothiadiazoles, or aromatic diacids having acid groups at the 1,3 or 1,4 positions on the benzene ring.

36. The method of claim 35, wherein the phosphorus compound is phosphoric acid or anhydride.

37. A process according to claim 35 or claim 36 wherein the aromatic diacid having acid groups at the 1,3 or 1,4 positions on the benzene ring is terephthalic acid.

38. The method of any one of claims 34 to 37, wherein the post-treated succinimide or post-treated succinamide is a borated succinimide or a borated succinamide.

39. The method of any one of claims 21 to 38, wherein the free radical functionalized PIBSA product is the product of a process comprising: 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.

40. The process of claim 39, wherein the ethylenically unsaturated acylating agent is combined with the polyisobutylene at the beginning of the process.

41. The method of claim 39, 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.

42. The method of any one of claims 39 to 41, wherein the free radical functionalized PIBSA product comprises less than 15 weight percent of material comprising two or more polyisobutylene units linked by one or more acylating agent units.

43. The method of any one of claims 39 to 42, wherein the polyisobutylene comprises an average of 3 to 56 isobutylene monomer units per molecule.

44. The method of any one of claims 39 to 43, wherein the free radical initiator comprises an organic peroxide initiator or a peracid initiator.

45. The method of claim 44, 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.

46. ​​The method of any one of claims 39 to 45, 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.

47. The method of any one of claims 39 to 46, 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.

48. The method of claim 47, wherein the free radical functionalized PIBSA product comprises at least 30 mol% of the at least one compound of Formula I.

49. The method of any one of claims 39 to 48, wherein the free radical functionalized PIBSA product comprises less than 40 wt% unreacted polyisobutylene.

50. A composition comprising the reaction product of the method of any one of claims 21 to 49.

51. A lubricant composition comprising an oil of lubricating viscosity and the composition of claim 50.

52. The lubricant composition of claim 51, further comprising at least one additional additive, the additional additive comprising at least one of a detergent, a dispersant, a friction modifier, an antiwear agent, an extreme pressure agent, a corrosion inhibitor, a viscosity modifier, a defoamer, a demulsifier, or a seal swell agent.

53. A method of lubricating a mechanical device, the method comprising supplying a lubricant composition according to claim 51 or claim 52 to the mechanical device.

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