Compounds, their manufacture and use

Abstract

The present invention is also directed to a new process for making bis-polyisobutenyl amine by reacting polyisobutylene epoxide with a polyamine, optionally in the presence of a catalyst, protic solvent initiator, and / or diluent. In addition, the present invention is also directed to a number of uses of bis-polyisobutenyl amine, including but not limited to the use of bis-polyisobutenyl amine in lubricants, surfactants, emulsifiers, resins, and the like.

Description

[0001] Priority Claim This application is based on U.S. Non-Provisional Application No. 18 / 509,797, filed on November 15, 2023, with the same title, and claims priority to U.S. Non-Provisional Application No. 18 / 509,797, the disclosure of which is incorporated herein by reference. Technical Field

[0002] This invention relates to a novel compound, its preparation, and its uses. In particular, the novel compound is a novel polyisobutylene compound, especially bis-polyisobutylenolamine and its derivatives. The invention also relates to a novel process for preparing said bis-polyisobutylenolamine, its derivatives, and compositions, and its numerous uses in lubricants, surfactants, emulsifiers, resins, etc. Background Technology

[0003] Polyisobutylene (PIB) is well known in the field and is typically produced by polymerizing isobutylene in the presence of a catalyst. PIB is a long-chain molecule composed of isobutylene molecules of various lengths and has different number-average molecular weights (Mn) and polydispersity indices (PDI), thus providing selective properties such as viscosity.

[0004] Conventional PIB compounds and compositions, primarily composed of internally unsaturated (double bonds), tend to have lower reactivity and are mainly made from isobutylene and typically aluminum-based catalysts. More reactive PIB compounds and compositions also exist, with a higher percentage of unsaturated (double bonds) at the ends of the PIB molecule, and are mainly made from more selective fluorinated catalysts (e.g., BF3).

[0005] As is well known, variations in PIB compounds and compositions, differences in unsaturation, and more particularly, the α-vinylene content depend on process conditions such as the concentration of isobutylene used, temperature, catalyst, and solvent.

[0006] In most cases, the reactivity of PIB determines its application and ultimately the performance of the final product using PIB. Conventional PIB is used in applications such as sealants, caulks, adhesives, packaging, and greases. More reactive PIB is primarily used in lubricants and fuel additives; however, conventional PIB can also be used. Other applications include sizing, ethylene oxide derivatives, and use in rubber compositions.

[0007] PIB (preferably, more reactive PIB) is primarily used in the preparation of well-known lubricants such as polyisobutylene succinic imide or polyisobutylene succinic amide (PIBSI). PIBSI is formed by reacting polyisobutylene succinic anhydride (PIBSA) or polyisobutylene succinic acid, an intermediate of PIBSI, with a monoamine or polyamine (especially a primary amine). Most nonpolar PIBs require reaction with, for example, maleic anhydride to form polar groups, which enable the linking group (i.e., succinic anhydride) to react to form PIBSA. This technique is well known in the art and described in numerous patents and publications, including U.S. Patent Nos. 7,339,007 and 9,315,761, which are incorporated herein by reference in their entirety.

[0008] Most commercial PIBSIs are prepared using a thermal process starting with PIBs having a relatively high proportion of terminal vinyl bonds (referred to in the industry as "reactive or highly reactive" PIBs). PIBs with high or moderate reactivity are well known in the art and further described in U.S. Patent Nos. 6,562,913 and 9,309,339, which are incorporated herein by reference in their entirety. Conventional PIBs typically have a relatively low content of terminal vinyl bonds and generally require halogen-containing catalysts (e.g., aluminum chloride) in combination with polyisobutylene, see, for example, U.S. Patent No. 5,326,921.

[0009] The aforementioned thermal and halogen-assisted reactions often produce significant amounts of turbidity and highly colored deposits, which must be filtered out from the final product PIBSI before use. During the reaction, the thermal process often generates tar that coats the reactor walls, necessitating frequent, time-consuming, and therefore costly reactor vessel cleaning. The formation of deposits and tar is believed to be at least in part due to the decomposition and / or polymerization of unsaturated enophiles, typically maleic anhydride. Efforts have been made to eliminate the resulting turbidity and deposits, as illustrated in U.S. Patents 7,339,007, 4,958,034, 5,021,169, and 5,241,003.

[0010] Below is a structure of PIBSI, where the polyisobutylene moiety retains the unsaturated double bond. Due to the retained unsaturation, PIBSI contains highly reactive allyl hydrogens, which is an undesirable source of reactivity.

[0011]

[0012] In the PIBSI structure shown above, PIB represents the remaining portion of the polyisobutylene polymer, and y is related to the specific polyamine used.

[0013] Therefore, it would be beneficial if PIBSI or PIBSI-type compounds could be prepared without the need for maleic anhydride and without retaining the unsaturation that produces reactive allyl hydrogens, both of which lead to undesirable side reactions such as color, turbidity, and deposition.

[0014] US Patent Publication US2014 / 0087983A1, published on March 27, 2014, relates to a lubricant and fuel dispersant containing an amination product of an epoxide-terminated vinyl macromonomer (VTM) and an amino compound (e.g., a polyalkylene polyamine, such as ethyleneamine), and excluding vinylene-terminated monomers (e.g., PIB).

[0015] US Patent Publication US2006 / 0063844A1, issued to Nagy et al. (“Nagy”) on March 23, 2006, discloses a method for preparing amine-functionalized polyisobutylene, a mixture of mono-polyisobutyl monoamine and bis-polyisobutyl monoamine, primarily for use in microemulsion coatings.

[0016] A second known chemical method for preparing additives for use in applications similar to PIBSI using PIB (which does not use maleic anhydride as a linker for the amine) involves producing polyisobutylene epoxides using polyisobutylene. Monoamines or polyamines (especially primary amines) can then react directly with a tensioned three-membered epoxy ring to form an alcoholamine, more specifically a polyisobutylene alcoholamine.

[0017] U.S. Patent No. 3,794,586 relates to a lubricating oil composition comprising a reaction between a polyolefin epoxide and an amine compound (including a polyisobutylene epoxide) to form a reaction product of a mono-polyisobutylene hydroxyalkyl-substituted polyamine. U.S. Patents Nos. 6,497,736 and 6,346,129 disclose fuel compositions containing mono-polyisobutylene hydroxyalkyl-substituted amines for use as automotive fuel detergents. Furthermore, Canadian Patent Application CA 2,856,684A1 describes an amine mixture of mono-polyisobutylene amine and aliphatic amine for use in cleaning intake valves and nozzles in an engine.

[0018] While these mono-polyisobutylene alcohol amines are useful, in various applications, particularly as fuel and oil lubricants or additives, there is a need to improve their solubility, reduce their reactivity to side reactions, and meet other performance criteria. Therefore, there is a need in the field for a modified compound or composition that provides improved chemical and physical properties. Summary of the Invention

[0019] This invention relates to a novel compound or composition, its preparation, and its use. The novel product, bis-polyisobutylene alcoholamine (referred to herein as bPIBAA), is represented by the following general formula: , and / or , Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100, and R is from C1 to C2. 10 Branched, cyclic, or linear alkylene groups (or combinations thereof), and y is an integer from 1 to about 20, preferably from about 1 to 15, and most preferably from 1 to 10. In one embodiment of the above general formula, x is 100 and y is an integer from 1 to 10, while in another embodiment, x is 50 and y is 2 to 10. In yet another embodiment of the above general formula, x is an integer in the range of 90 to 110 and y is an integer from 1 to 10, while in another embodiment, x is an integer in the range of 40 to 60 and y is an integer from 2 to 10. In the most preferred embodiment, R is ethylene.

[0020] The above-mentioned bPIBAA compound is typically prepared by reacting polyisobutylene epoxide with a polyamine, and is represented by the following formula:

[0021] Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100, and R is from C1 to C2. 10 Branched, cyclic, or linear alkylene groups (or combinations thereof), and y is an integer from 1 to about 20, preferably from about 1 to 15, and most preferably from 1 to 10. In one embodiment of the above general formula, x is 100 and y is an integer from 1 to 10, while in another embodiment, x is 50 and y is 2 to 10. In yet another embodiment of the above general formula, x is an integer in the range of 90 to 110 and y is an integer from 1 to 10, while in another embodiment, x is an integer in the range of 40 to 60 and y is an integer from 2 to 10.

[0022] The process for preparing the bPIBAA of the present invention comprises reacting (a) polyisobutylene epoxide (PIBEP) with a polyamine in the presence of a diluent and optionally a Lewis acid or Bronsted acid catalyst. In a preferred embodiment, the polyisobutylene epoxide is selected from one or more type I, type II, or type III polyisobutylene epoxides represented by the following formula:

[0023] Where x is an integer between 1 and about 200, preferably between 1 and about 150, and most preferably between 1 and 100.

[0024] In a preferred embodiment, the amount of type 1, type 2, and / or type 3 polyisobutylene epoxide is at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol%, and most preferably greater than 70 mol%. In another embodiment, the molar percentage of type 3 polyisobutylene epoxide is at least 50 mol% to about 60 mol%, preferably about 65 mol% to about 70 mol%, and most preferably greater than about 70 mol%. In another embodiment, the molar percentage of type 3 polyisobutylene epoxide is at least 70 mol% to about 80 mol%, preferably from about 80 mol% to 85 mol% to about 90 mol% to 95 mol%. In another embodiment, the molar percentage of type 1 and type 3 polyisobutylene epoxide is at least 85 mol% or higher up to about 98 mol%, and most preferably greater than about 90 mol% to 95 mol.

[0025] In one embodiment, a combination of type I, type II, and type III polyisobutylene epoxides is used in the process for preparing bPIBAA according to the present invention. In a preferred embodiment, type III polyisobutylene epoxide is used at a concentration greater than 70 mol%, preferably greater than 80 mol%, or even 90 mol%.

[0026] The polyamine used in the reaction with polyisobutylene epoxide can be any amine, preferably a monoamine or polyamine, more preferably a polyamine. In one embodiment, the polyamine is represented by the following formula:

[0027] Where R is C1 to C 10Branched, cyclic, or linear alkylene groups (or combinations thereof), where y is an integer from 1 to about 20, preferably from about 1 to 15, and most preferably from 1 to 10 (inclusive). In one embodiment, preferred polyamines include, but are not limited to, methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc., aromatic polyamines, cyclic polyamines such as piperazines and N-aminoalkyl-substituted piperazines, etc. Specific, non-limiting representative examples of such polyamines also include ethylenediamine, diethylenetriamine, triethylenetetramine, tri-(2-aminoethyl)-amine, propylenediamine, triethylenediamine, tripropylaminetetramine, tetraethylenepentamine, and heptaethylenehexamine. The amine may be pure or a mixture, such a mixture being exemplified by commercially available ethyleneamine E-100 manufactured by Huntsman Corporation, The Woodlands, TX. Other amine compounds used in this invention may be ethoxylated amines, such as ethanolamines, etc.

[0028] In a preferred embodiment, at least one diluent may be used in the reaction between polyisobutylene epoxide and polyamine to improve solubility and mixability in the process. In one embodiment, the at least one diluent is selected from one or more of the following: benzene, toluene, xylene; saturated aliphatic hydrocarbons, such as pentane, hexane, heptane; paraffinic, cycloalkanes, aromatic base oils, such as well-known Group I, II, III, IV, or V base oils, including poly-α-olefins or any other compound that affects the viscosity of the reaction.

[0029] In another embodiment, optionally, a Lewis acid or Brønsted acid catalyst may be used and selected from one or more of the following: aluminum trichlorotrifluoro, boron trifluoro, titanium tetrachloro, ferric chloride; BF3: ether, BF3: alcohol; or a solid catalyst containing portions of Lewis acid and Brønsted acid, such as silica, silica-alumina, or organic acid and water.

[0030] In another preferred embodiment, at least one proton solvent initiator is used in the reaction between polyisobutylene epoxide, polyamine, and proton solvent initiator in the absence of a catalyst or without a catalyst. In one embodiment, the at least one initiator is preferably at least one organic hydroxy compound, preferably an alcohol or water, and most preferably an alcohol (e.g., methanol or ethanol).

[0031] The temperatures used in the above processes are typically below the depolymerization temperature of polyisobutylene epoxide. These non-limiting reaction temperatures are typically from about 60°C to about 260°C, more typically from about 100°C to about 240°C, preferably from about 150°C to about 230°C, and most preferably from about 180°C to about 225°C. Depending on the process, the temperature may be even lower, depending on the catalyst used and the reaction process.

[0032] The process reaction can be carried out under atmospheric conditions in an open container, or under moderate pressure in a closed container, wherein the non-limiting pressure is up to about 300 psi, preferably from about 10 psi to about 70 psi, and most preferably from about 35 psi to about 55 psi. The reaction pressure will be a function of the partial pressure of each reactant at the reaction temperature.

[0033] The reaction that produces bPIBAA often forms a bPIBAA composition in which the (dominant) percentage of more than 50 mol%, preferably more than 60 mol%, more preferably more than 70 mol%, and even more preferably more than 80 mol%, and most preferably more than 90 mol%, is bPIBAA. The small amounts of components present in the composition may include isomers from polyamines, a mixture of unreacted polyisobutylene epoxides and byproducts of the initial epoxidation of isobutylene (e.g., primarily alcohols, aldehydes, and unreacted polyisobutylene), and very small amounts (if detectable) of monosubstituted poly-isobutanolamines (in amounts less than 2 mol% of the bPIBAA composition, typically less than 1 mol% to 0 (undetectable)).

[0034] Surprisingly, among other findings, it has been discovered that by controlling the molar ratio of polyisobutylene to polyamine, the percentage of trace components can be reduced or virtually eliminated. The reaction of the polyisobutylene epoxide with the polyamine that produces bPIBAA was found to use a molar ratio of polyamine to isobutylene epoxide of less than 1:1, preferably less than 0.9:1, more preferably 0.8:1, even more preferably 0.7:1, even more preferably less than 0.6:1, or 0.5:1 or less than 0.5:1. In another preferred embodiment, the molar ratio between the polyamine and isobutylene epoxide is in the range of less than 1:1 to 0.2:1, more preferably 0.9:1 to 0.2:1, even more preferably 0.8:1 to 0.2:1, even more preferably 0.7:1 to 0.2:1, even more preferably 0.6:1 to 0.3:1, and most preferably 0.5:1 to 0.2:1.

[0035] In another embodiment, the molar ratio of polyamine to polyisobutylene epoxide is such that a slightly excess to a slightly excess amount of polyisobutylene epoxide is used. In another embodiment, the preferred molar ratio of polyamine to polyisobutylene epoxide is such that for every mole of polyamine used, at least two moles of polyisobutylene epoxide are used.

[0036] In a preferred embodiment, the present invention relates to a process for preparing a bPIBAA composition, the process comprising the following steps: (a) In a reactor, polyisobutylene epoxide is contacted with a polyamine, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.9:1; (b) Optionally, a diluent may be introduced; (c) Optionally, a catalyst may be added to the reactor; and (d) Optionally, a proton solvent initiator may be added to the reactor; wherein the bPIBAA composition contains more than 50 mole percent (50 mol%) of bPIBAA.

[0037] In another embodiment of the above process, when the polyamine to polyisobutylene epoxide ratio is less than 0.6:1, the bPIBAA composition contains more than 70 mol%, preferably more than 80 mol%, of bPIBAA. In yet another embodiment, when the polyamine to polyisobutylene epoxide ratio is less than 0.5:1, the bPIBAA composition contains more than 90 mol%, preferably more than 95 mol%, of bPIBAA.

[0038] In the above process, the preferred polyisobutylene epoxide is preferably type 3 polyisobutylene epoxide, and the polyamine is tetraethylenepentamine or heptaethylenehexamine or a mixture thereof. Such a mixture is exemplified by commercially available ethyleneamine E-100 produced by Huntsman Corporation in Woodlands, Texas. The molar ratio between the polyamine and the polyisobutylene epoxide is less than 1:1, preferably less than 0.8:1, more preferably less than 0.6:1, and most preferably less than 0.5:1.

[0039] The bPIBAA of the present invention exhibits many advantageous effects superior to mono-polyisobutyl alcoholamines and, regarding the advantages of PIBSI, includes color improvement, minimal turbidity / deposits generated during the reaction, and a final product free of or largely free of unsaturation, thereby eliminating the allyl hydrogen present in PIBSI. It has also been found that, in some cases, the bPIBAA of the present invention has a significantly lower viscosity (KV100) compared to similar PIBSI. Furthermore, by measuring the increase in viscosity (KV40), it was surprisingly found that, based on equal weight percentages, lubricants containing the bPIBAA of the present invention, used as a dispersant or in a dispersant configuration, exhibit significantly better oxidation resistance in some cases compared to the same lubricant containing PIBSI as a dispersant. Given the higher oxidative stability of the bPIBAA of the present invention compared to conventional PIBSA or PIBSI, the bPIBAA of the present invention can also be used as an emulsifier for use in oil / water emulsions, such as in paints or coatings, and even in explosive emulsion compositions. Attached Figure Description

[0040] This disclosure is illustrated by way of example and not limitation with reference to the accompanying drawings, in which the same reference characters always refer to the same parts, and in the accompanying drawings: Figure 1 This shows the GPC representation of bPIBAA on a logarithmic scale; Figure 2 A visual comparison of the colors of bPIBAA and PIBSI is shown; Figure 3 The kinematic viscosity (KV100) of PIBSI and bPIBAA at 100°C is shown using ASTM D-445; and Figure 4 The results of the oxidation test using CEC-L48 are shown, which compares the kinematic viscosity (KV40) of PIBSI and bPIBAA at 40°C.

[0041] While the disclosed processes and compositions are readily modified and substituted, the accompanying drawings illustrate specific embodiments described in detail herein by way of example. However, it should be understood that the description of specific embodiments herein is not intended to limit the invention to the particular forms disclosed, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. Detailed Implementation

[0042] This article discloses a novel compound (i.e., bis-polyisobutylene alcohol amine (bPIBAA)), its reaction for preparing bPIBAA from polyisobutylene epoxide (PIBEP) with a polyfunctional amine, and many uses of bPIBAA.

[0043] Polyisobutylene and preparation of polyisobutylene epoxide. The currently used bPIBAA reaction product, polyisobutylene epoxide, is obtained by oxidizing the polyolefin with an oxidant to obtain an alkylene oxide or epoxide, wherein the ethylene oxide ring originates from the oxidation of the double bond in the polyolefin. The preferred polyolefin is polyisobutylene.

[0044] Polyisobutylene. Polyisobutylene (PIB) is a long-chain molecule synthesized by polymerizing or linking isobutylene molecules. Numerous well-known processes exist in the art for the preparation of PIB, including but not limited to those described in U.S. Patent Nos. 9,598,655, 9,617,363, 9,309,339, 6,562,913, 8,524,843, 8,946,361, 11,326,004, 9,074,026, and 9,809,665, and EP1381637B2, all of which are fully incorporated herein by reference.

[0045] Polyisobutylene (PIB) exists in various forms with a wide range of molecular weights, from several hundred to several million. Typically, a number-average molecular weight (Mn) is preferred, ranging from 100 to 5000, preferably 400 to 4000, and most preferably from about 500 to about 3500 or lower. Furthermore, due to varying chain lengths, PIBs also exhibit a wide range of polydispersity indices (PDIs), measured by GPC using polyisobutylene standards. These PDIs are typically in the range of about 1.3 to less than 5, more preferably from about 1.4 to less than 4, and most preferably from about 1.5 to less than 3. Both Mn and PDI are key properties for determining the useful viscosity and flash point of PIBs for a particular application.

[0046] PIBs are available from numerous commercial manufacturers, such as TPC Group, INEOS Oligomers, Infineum, Lubrizol, and BASF, each supplying various combinations of low-reactivity, medium-reactivity, and high-reactivity PIBs. Examples include GLISSOPAL® and OPPANOL® from BASF Corporation, Ludwigshafen, Germany; Indopol® products from INEOS Oligomers, London, UK; and LUBRIZOL 3108 from Lubrizol, Wickliffe, Ohio.

[0047] Various types of PIBs are available from the TPC Group in Houston, Texas, including: highly reactive PIBs (HR-PIBs), such as HR 545, HR595, and HR 5230; medium reactive PIBs (MR-PIBs), such as TPC 175 and TPC 1160; as well as di-isobutylene (DIB) and triisobutylene (TIB).

[0048] The determining factor for distinguishing between medium and high reactive PIBs is the degree of polymerization based on the concentration of various double bond end group types (i.e., α, β, tetrasubstituted, trisubstituted, and substituted α, etc.). Differences between PIBs can be determined by measuring the α-vinylene content. Conventional or low to medium PIBs have an α-vinylene isobutylene isomer content between 0 and 10%, while high reactive PIBs have an α-vinylene isobutylene isomer content between 60% and 90% or higher.

[0049] Surprisingly, it was also found that the bPIBAA of the present invention can be prepared using conventional or highly reactive PIBs as starting monomers for the preparation of polyisobutylene epoxides. In one embodiment, highly reactive PIBs are preferably used in the process for preparing polyisobutylene epoxide starting monomers that react with polyamines in the process of the present invention.

[0050] Epoxidation of olefins and other polymers Epoxidation of various olefins, including polymers with double bonds, is generally known in the field. Representative prior art illustrating various procedures for epoxidation of various types of unsaturated materials includes: Hafren et al., *Macromol. Rapid Commun.*, Vol. 26, pp. 82-86 (2005); Song et al., *J. Polym. Sci. Polym. Chem.*, Vol. 40, pp. 1484-1497 (2002); Shigenobu et al., *Maruzen Petrochemical*; Japanese Patent Application No. JP2001 031716A (published February 26, 2001); Suzuki et al., *Journal of Applied Polymer*. Science, Vol. 72, pp. 103-108 (1999); and Li et al., Macromolecules, Vol. 38, pp. 6767-6769 (2005). Epoxidation of nonpolymeric materials using catalysts or solvents of a chosen reaction medium is also commonly known in the field. Representative prior art references illustrating these types of epoxidation include: Hellmann et al., Angewandte Chemie International Edition, Vol. 30, No. 12, pp. 1638-1641 (1991); Van Vliet et al., Chem. Commun., pp. 821-822 (1999); and Neimann et al., Organic Letters, Vol. 2, No. 18, pp. 2861-2863 (2000).

[0051] Examples of different types of intermediate polyisobutylene epoxides produced according to the present invention are illustrated by the following reactions, which are referred to throughout as type 1, type 2, or type 3 polybutene epoxides:

[0052] Where x is from 1 to about 200, preferably from 1 to about 100, and most preferably from 1 to 50, and the content of the polyisobutylene epoxide material containing type I, type II, and / or type III polyisobutylene epoxides is at least 50 mol%, more preferably 60 mol%, and most preferably 80 mol% or greater than 80 mol%. In one embodiment of the above general formula, x is 100, while in another embodiment, x is 50. In yet another embodiment, x in the above general formula is an integer in the range of 90 to 110, and in another embodiment, x is an integer in the range of 40 to 60. Type III epoxides are generally considered to be highly reactive to amination, and these polyisobutylene epoxides are preferred. However, it has been surprisingly found that type I and type II epoxides also exhibit reactivity to amination. Therefore, polyisobutylene epoxides containing higher amounts of type I and type II epoxy groups are also suitable for use in this invention. In any case, if a type III epoxide is required, it can be produced starting from polyisobutylene containing a high concentration of type III double bonds.

[0053] In another embodiment, the polyisobutylene epoxide (PIBEP) has a number average molecular weight (Mn) in the range of 400 to 5000 and an ethylene oxide oxygen value of 2% to 0.15%, and preferably has an Mn in the range of 400 to 3500 and an ethylene oxide oxygen value of 2% to 0.22%, and more preferably has an Mn in the range of 400 to 3000 and an ethylene oxide oxygen value of 2% to 0.25%.

[0054] Examples of commercially available polyisobutylenes containing high concentrations of type 3 double bonds include TPC 5230, TPC 545, and TPC 595, manufactured and available from the TPC Group in Houston, Texas. Non-limiting examples of polyisobutylenes containing small amounts of type 3 double bonds but with increased content of type 1 and type 2 double bonds include Indopol H-100, H-300, H-1200, H-1500, H-1900, H-2100, H-6000, and H-18000, manufactured by INEOS Oligomers Ltd. in London, UK.

[0055] The presence of type 4 tetra-polyisobutylene epoxide is a consequence of the processes used to prepare polyisobutylene epoxides, and it exists in various amounts alongside all other types 1, 2, and 3. For example, type 4 is present in highly reactive polyisobutylene epoxides (type 3) in amounts ranging from about 1 mol% to less than 5 mol%, more likely from 1 mol% to less than 3 mol%, while in low to medium reactive polyisobutylene epoxides (types 1 and 2), type 4 is believed to exist in amounts between 25 mol% and 40 mol%, or higher, more likely from about 30 mol% to about 40 mol%.

[0056] polyamine In subsequent steps of the process, the epoxy ring of one or more of the above-described polyisobutylene epoxides is opened by an amine compound to form a direct bPIBAA compound or composition. It is believed that the amine compound (polyamine) can be a primary or secondary amine compound, but preferably not a tertiary amine compound. Specifically, it is preferred in the process to react with the primary amine group of a diamine or polyamine. Amine compounds having two or more amine groups in the process for preparing the bPIBAA compound or composition of the present invention include various diamines, polyamines, cyclic diamines, cyclic polyamines, alkylene diamines, and alkylene polyamines having the following general formula:

[0057] R is C1 to C 10 Branched, cyclic, or straight-chain alkylene groups (or combinations thereof), where y is an integer between 1 and 20, preferably between 1 and 15, and most preferably between 1 and 10. Examples of amine compounds include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc., aromatic polyamines, cyclic polyamines such as piperazines, and N-aminoalkyl-substituted piperazines such as aminoethylpiperazine (AEP) and aminoethanolamine (AEEA). Specific, non-limiting, representative examples of such amine compounds include ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tri-(2-aminoethyl)amine, propylene diamine, trimethylene diamine, tripropylamine tetramine, tetraethylene pentamine, and heptaethylene hexamine; and other specific, non-limiting, representative examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tri-(2-aminoethyl)amine, propylene diamine, trimethylene diamine, tripropylamine tetramine, tetraethylene pentamine, and heptaethylene hexamine.

[0058] The amine compound may be pure or a mixture, such a mixture being exemplified by commercially available amineethyleneamine E-100 (E-100) manufactured by Huntsman Corporation in Woodlands, Texas. Other amine compounds that may be used in this invention may be ethoxylated amines, such as ethanolamine.

[0059] Other amine compounds that can be used in this invention are polyetheramines, including JEFFAMINE® D-230 and JEFFAMINE® D-400, which are available as non-limiting examples from Huntsman Corporation in Woodlands, Texas. These polyetheramines are represented by the following general formula:

[0060] For the D-230, x is 2.5, while for the D-400, x is 6.1.

[0061] According to the present invention, other exemplary amine compounds include polyetheramines, and may be amine-terminated polyethers, such as combinations of polyethylene oxide (PEO), polypropylene oxide (PPO), or PEO / PPO copolymers. For example, some commercially available polyethers include: poly(ethylene glycol) bis(3-aminopropyl ether), poly(propylene glycol) bis(2-aminopropyl ether), poly(propylene glycol) bis(2-aminopropyl ether), poly(propylene glycol) bis(2-aminopropyl ether), poly(propylene glycol)-block-poly(ethylene glycol)-block poly(propylene glycol) bis(2-aminopropyl ether) (3.5:8.5, PO: EO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (3.5:15.5, PO:EO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (3.5:40.5, PO:EO), glycerol tris(poly(propylene glycol)), amine-terminated ether poly(tetrahydrofuran), bis(3-aminopropyl) terminal, etc.

[0062] In one embodiment, the molar ratio of the polyamine to the polyisobutylene epoxide is less than 1:1, preferably less than 0.9:1, more preferably 0.8:1, even more preferably 0.7:1, and even more preferably less than 0.6:1, or 0.5:1 or less. In another preferred embodiment, the molar ratio between the polyamine and the isobutylene epoxide is in the range of less than 1:1 to 0.2:1, more preferably 0.9:1 to 0.2:1, even more preferably from 0.8:1 to 0.2:1, even more preferably from 0.7:1 to 0.2:1, even more preferably from 0.6:1 to 0.3:1, and most preferably from 0.5:1 to 0.2:1.

[0063] In another embodiment, the molar ratio of polyamine to polyisobutylene epoxide is such that a slight excess to a slight excess of polyisobutylene epoxide is used. In another embodiment, the preferred molar ratio of polyamine to polyisobutylene epoxide is such that for every mole of polyamine used, at least two moles of polyisobutylene epoxide are used.

[0064] diluent Due to the high viscosity of polyisobutylene epoxide, it is desirable to carry out the amination reaction in the presence of at least one hydrocarbon diluent. It is believed that when the viscosity is too high, the reactive sites are less accessible, and the desired reactants are difficult to diffuse to the reactive sites.

[0065] The desired diluent should be stable and non-reactive to the reactants and the resulting final product bPIBAA. In one embodiment, at least one diluent is selected from one or more of the following: benzene, toluene, xylene; saturated aliphatic hydrocarbons, such as pentane, hexane, heptane; paraffinic, cycloalkanes, aromatic base oils, such as well-known Group I, II, III, IV, or V base oils, including poly-α-olefins or any other compound that can be used to affect the viscosity of the reaction.

[0066] The preferred diluent is one that is easily removed from the final product (toluene, heptane, etc.) or one that can remain in the final mixture (i.e., base oil or PAO).

[0067] catalyst Optionally (though preferred), a catalyst may be used in the process of the present invention to accelerate the reaction rate and increase the overall conversion to the bPIBAA product and composition. Such catalysts are well known in the art and are used depending on the process, reactor configuration, reaction conditions, monomers, etc. Non-limiting examples of suitable catalysts include Lewis acids used alone (e.g., aluminum trichloroethylene, boron trifluoroethylene, titanium tetrachloroethylene, ferric chloride) or their base adducts (e.g., BF3:ether, BF3:alcohol, etc.), or solid catalysts containing portions of Lewis acids and Brønsted acids (e.g., silica, silica-alumina), and organic acids and water, such as acetic acid and water, may also be used.

[0068] The amount of catalyst is typically from about 0.05% by weight to about 10% by weight, and preferably from about 0.1% by weight to about 10% by weight, based on the total weight of the polyolefin epoxide. The most preferred catalyst is a Lewis acid, such as boron trifluoride.

[0069] Initiator In practice, catalysts are used in combination with or alone with proton solvent initiators. In another embodiment, at least one proton solvent initiator is used in the reaction between polyisobutylene epoxide, polyamine, and diluent, with or without a catalyst. In one embodiment, the at least one initiator is preferably at least one organic hydroxy compound, preferably an alcohol or water, and most preferably an alcohol, such as methanol or ethanol. The typical amount of proton solvent initiator used is less than 1 wt% of the weight of the polyisobutylene epoxide.

[0070] Reactors and conditions Depending on the reactor type and configuration, reaction conditions can be varied, as is well known to those skilled in the art. In one embodiment, a batch process for producing bPIBAA involves introducing PIBEP into the reactor (preferably in a jacketed, heated, and stirred reactor to a specified temperature and pressure) in the presence of a diluent, followed by the introduction of the polyamine along with a catalyst (if used) or separately from the proton solvent initiator. In one embodiment, one or more of the following steps may be required: removing the diluent, neutralizing and removing the catalyst, and filtering or washing the reaction product synthesized in the reactor. In another embodiment, the diluent is a base oil, and therefore the reaction product can be used as is. In one embodiment, the polyamine is introduced into the reactor in stages during the reaction process.

[0071] The temperature of the reactor and its contents must be below the depolymerization temperature of the epoxidized polyolefin and polyisobutylene epoxide. Such reaction temperatures are typically from about 60°C to about 260°C, more typically from about 100°C to about 240°C, preferably from about 150°C to about 230°C, and most preferably from about 180°C to about 225°C.

[0072] The reaction can be carried out in an open container under atmospheric conditions, or in a closed container under moderate pressure (e.g., up to about 300 psi, preferably from about 10 psi to about 70 psi, and most preferably from about 35 psi to about 55 psi). The reaction pressure will be a function of the partial pressure of the individual reactants at the reaction temperature.

[0073] Bis-polyisobutylene alcohol amine compounds and compositions The novel product (bis-polyisobutylene alcoholamine (referred to herein as bPIBAA)) produced by the process described above is represented by the following general formula: , and / or , Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100, and R is C1 to C2. 10Branched, cyclic, or straight-chain alkylene groups (or combinations thereof), where y is an integer from 1 to about 20, preferably from about 1 to 15, and most preferably from 1 to 10. In one embodiment of the above general formula, x is 100 and y is an integer from 1 to 10, while in another embodiment, x is 50 and y is 2 to 10. In yet another embodiment of the above general formula, x is an integer in the range of 90 to 110 and y is an integer from 1 to 10, while in another embodiment, x is an integer in the range of 40 to 60 and y is an integer from 2 to 10. Such compounds of the present invention have at least two amino groups.

[0074] In another embodiment, the bPIBAA composition comprises a bPIBAA compound in percentages of more than 50 mol%, more preferably more than 60 mol%, even more preferably more than 70 mol%, and most preferably more than 80 mol%.

[0075] In another embodiment, the reaction used to produce bPIBAA often produces a bPIBAA composition in which more than 55 mol%, preferably more than 65 mol%, more preferably more than 75 mol%, and even more preferably more than 85 mol%, and even more preferably more than 95 mol%, of the composition is bPIBAA. The small amounts of components present in the composition may include isomers from polyamines, a mixture of unreacted polyisobutylene epoxides and byproducts of the initial epoxidation reaction of isobutylene (e.g., primarily alcohols, aldehydes, and unreacted polyisobutylene), and very small amounts (if detectable) of mono-isobutanolamine (in amounts less than 2 mol% of the bPIBAA composition, typically less than 1 mol% to 0 (undetectable)).

[0076] In one embodiment, the bPIBAA composition of the present invention does not contain monosubstituted poly-isobutanolamine.

[0077] In one embodiment, the bPIBAA composition comprises: (i) 5 mol% to 98 mol% of one or more bis-polyisobutylene alcohol amine compounds; (ii) up to 15 mol% of unreacted polyisobutylene; and (iii) up to 15 mol% of one or more unreacted polyisobutylene epoxides, wherein the sum of the mol% of i, ii and iii is between 98 mol% and 100 mol%.

[0078] In one embodiment, the bPIBAA composition comprises: (i) 5 mol% to 98 mol% of bPIBAA, preferably greater than 60 mol%, even more preferably greater than 70 mol%, even more preferably greater than 80 mol%, and especially greater than 85 mol% or greater than 90 mol%; (ii) up to 15 mol% of unreacted polyisobutylene, preferably less than 10 mol%, more preferably less than 5 mol%; (iii) up to 15 mol% of unreacted polyisobutylene epoxide and / or byproducts, such as polyisobutylene alcohol, preferably less than 10 mol%, more preferably less than 5 mol%; and (iv) preferably less than 2 mol% of mono-PIB, more preferably less than 1 mol%, wherein the sum of the mol% from i, ii, iii and iv is 100 mol.

[0079] In one embodiment, the bPIBAA composition has a number-average molecular weight (Mn) in the range of 800 to 10,000, preferably from 800 to 8000, more preferably from 800 to 7000, and most preferably from 800 to 6000. In an alternative embodiment, the bPIBAA composition has an Mn in the range of 820 to 10,000, preferably from 850 to 10,000, and most preferably from 900 to 10,000.

[0080] In another embodiment, the bPIBAA composition has a polydispersity index (PDI) in the range of 1.2 to 5, preferably from 1.2 to 4, more preferably from 1.2 to 3.5, and most preferably from 1.2 to 3.

[0081] In another aspect, the viscosity of the bPIBAA composition at 100°C, using ASTM D-445, is in the range of 10 cSt to 10,000 cSt, preferably from 15 cSt to 8,000 cSt, more preferably from 20 cSt to 6,000 cSt, and most preferably from 25 cSt to 5,000 cSt.

[0082] The bPIBAA composition has one or more of the above-described embodiments or aspects in any combination of Mn, PDI and / or viscosity.

[0083] In another embodiment, the bPIBAA compound or composition has Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and viscosity in the range of 25 cSt to 5000 cSt.

[0084] In another embodiment, for the bPIBAA composition of the present invention, particularly when type 1 and / or type 2 is the main polyisobutylene epoxide used to form the bPIBAA compound, the amount of fluorine or chlorine contained in the bPIBAA composition is no more than 10 ppm, preferably less than 5 ppm, more preferably less than 2 ppm, and most preferably less than 1 ppm up to 0.

[0085] Uses of bPIBAA bPIBAA compositions can be used as emulsifiers, stabilizers, corrosion inhibitors, and dispersants in formulations of various lubricants, fuels, and aqueous fluids.

[0086] Specifically, bPIBAA compositions can be used as dispersant additives in engine oil lubricant formulations and as fuel additive formulations. bPIBAA compositions can also be used to improve the strength and durability of products such as adhesives, sealants, oils, and greases.

[0087] When used in lubricating oils, the bPIBAA composition can be used as a dispersant additive. Lubricating oils used with the bPIBAA compositions of the present invention can be mineral oils or synthetic oils with lubricating viscosity, and are preferably suitable for use in the crankcase of internal combustion engines. The lubricating oils can be derived from synthetic or natural sources. Mineral oils used as base oils in the present invention include paraffinic oils, naphthenic oils, and other oils commonly used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of α-olefins with suitable viscosity.

[0088] Lubricating oil concentrates used for the disclosed bPIBAA are also included within the scope of this invention. The concentrates of this invention typically comprise about 90% to 50% by weight of an oil having a lubricating viscosity, and about 10% to 50% by weight of the bPIBAA of this invention. Generally, the concentrate contains sufficient diluent to make it easy to handle during transport and storage. Suitable diluents for the concentrate include any inert diluent (preferably an oil having a lubricating viscosity) to allow the concentrate to be readily mixed with a lubricating oil to prepare a lubricating oil composition.

[0089] Other additives that may be present in formulations include rust inhibitors, foam inhibitors, corrosion inhibitors, metal passivators, pour point depressants, antioxidants, and various other well-known additives, as well as other uses, including in adhesives, sealants, greases, emulsifiers, paints and coatings, and polymer formulations.

[0090] In one embodiment, using the percentage change in viscosity measured by KV40 (ASTM D-445, at 40°C), the oxidative stability of the bPIBAA (only) composition in the base oil, measured in CEC–L48-00, is less than 1000%, more preferably less than 800%, even more preferably less than 600%, and most preferably less than 400%. The base oil typically constitutes a greater than 40%, preferably greater than 50%, more preferably greater percentage of Group I, II, III, IV, and V oils as defined by the American Petroleum Institute (including their current standards for passenger car and standard gasoline engine oils, diesel engine oils, and marine oils), which are fully incorporated herein by reference. The bPIBAA composition is combined with Group I to V base oils, wherein the bPIBAA composition has a Mn of 800 to 8000, preferably 800 to 6000, more preferably 800 to 5000.

[0091] In one aspect, the present invention is directed to the use of lubricating compositions in gasoline or diesel engines for improving fuel economy and / or wear protection, wherein the lubricating composition comprises from 1 wt% to 20 wt% of a bPIBAA compound or composition having a Mn of from 800 to 10000.

[0092] The lubricating composition may also contain ashless dispersants, borate-treated ashless dispersants, non-borrate-treated ashless dispersants, detergents (i.e., calcium salicylate, calcium sulfonate, magnesium phenolate, and calcium phenolate) or other typical components well known in the relevant fields.

[0093] In one embodiment, based on KV40 (1) using the CEC L-48-00 test method, the preferred KV40 of the bPIBAA oil formulation is an increase of less than 500%, preferably less than 300%, and most preferably less than 200% in KV40 (1) compared to KV40 (2). The bPIBAA compound or composition in the oil formulation comprises from 1 wt% to 30 wt% of base oil, preferably from 2 wt% to 25 wt%, more preferably from 2 wt% to 20 wt%, and most preferably from 3 wt% to 15 wt%.

[0094] Formulations used in dispersants, lubricants, greases, corrosion inhibitors, gear oils, and base stocks are described in the following U.S. patents and publications: US11,629,308, US10,808,196, US9,926,509, US7,851,418, US8,691,738, US8,399,390, US3,850,822, US11,788,027, US11,773,343, US9,228,152, and US9,282,730. 6. US6,844,300, US9,783,630, US7,998,340, US7,820,600, US8,163,682, US6,551,967, US6,00 1,780, US6,686,321, US5,942,476, US5,360,564, US4,402,841, US3,873,455 and US3,850,822, US 10,494,584, US11,732,208, US2023 / 0323234AA, US10,793,802, 10,781,411, US10,611,981, US10, 358,616, US11,685,872, 11,059,924, US10,829,712, 11,136,523, US10,781,393, US10,640,724, US US11,346,643, US11,680,782, US11,034,912, US11,427,515, US11,788,027, US11,788,026 and US11,608,477, which are incorporated herein by reference in their entirety, such that a person skilled in the art would consider replacing one or more components in the above formulations, particularly those components that function similarly to PIBSI or have other polymers used in lubricating oil formulations.

[0095] Another aspect of the invention is a lubricant composition comprising a bPIBAA compound or composition and PIBSI or other useful polymers (e.g., α-olefin oligomers, including ethylene oligomers or propylene oligomers), as described in U.S. Patent No. 9,315,761, which is incorporated herein by reference in its entirety.

[0096] In one embodiment, the invention relates to a lubricating composition for automotive gears, shafts, and / or bearings, comprising an oil having a lubricating viscosity, the oil comprising a bPIBAA compound or composition, optionally comprising a detergent and / or a borate dispersant.

[0097] In one embodiment, the present invention is directed to a low, medium, and high viscosity lubricating composition comprising: (a) an oil and one or more detergents having a viscosity KV (100°C) ranging from 2 cSt to 100 cSt, from 2 cSt to 50 cSt, from 2 cSt to 30 cSt, or from 2 cSt to 10 cSt; 1% to 30% of a bPIBAA composition or compound; and / or said lubricating composition having a dynamic viscosity, typically in the range of 1.8 cP to 90 cP, from 1.8 cP to 45 cP, from 1.8 cP to 27 cP, or from 1.8 cP to 9 cP, as measured using ASTM D-455, wherein the KV (100°C) value is divided by the density of the lubricating composition.

[0098] One aspect of the invention is a combustible composition for use in clean fuel delivery systems, intake systems, and combustion chambers, wherein the combustible composition comprises one or more bPIBAA compounds or compositions in an amount of up to 40% by weight, based on the total weight of the combustible composition.

[0099] Another aspect of the present invention relates to a lubricating composition comprising a bPIBAA compound or composition, and two or more base oils, an ashless dispersant, an antioxidant, a detergent, and an anti-wear agent. In another embodiment of the above-described lubricating composition, in addition to the bPIBAA compound or composition, the lubricating composition further comprises one or more metal detergents, friction modifiers, viscosity modifiers, antioxidants, etc., including amination products of epoxide-terminated vinyl macromonomers and amino compounds.

[0100] In another aspect of the invention, bPIBAA compounds or compositions can be used as emulsifiers, including their use not only as emulsions in the paint and coatings industry, but also in emulsion form in explosive applications.

[0101] Non-limiting examples of potential uses of bPIBAA compounds or compositions are found in U.S. Patent Nos. US4,933,028, US5,026,442, US5,160,387, US5,670,739, US5,470,407, US6,514,361, US6,165,297, US8,603,959, US7,972,454, US5,920,031, US7,044,988, U The explosive emulsion formulations discussed in US5,936,194, US6,929,707, US6,939,420, US6,800,154, US6,951,589, US5527,491, and US4,844,756 are all incorporated herein by reference in their entirety, wherein bPIBAA generally replaces, or is used in combination with, PIBSA or PIBSI in various explosive compositions; and furthermore,). In another respect, the explosive composition is prepared according to any of the methods described in the foregoing US patents.

[0102] In one embodiment, the bPIBAA compound or composition is used for explosive, downhole oil applications (e.g., hydraulic fracturing). In another aspect, the present invention relates to an aerated emulsion explosive composition comprising a gas-generating agent solution containing an inorganic nitrate (i.e., alkaline earth metal nitrite, alkali metal nitrite, etc., or combinations thereof) and / or an ammonium substance (i.e., ammonium chloride, ammonium nitrate, ammonium chlorate, ammonium perchlorate, etc., or combinations thereof) in combination with the bPIBAA compound (or composition), and optionally an accelerator (i.e., thiourea, thiocyanate, iodide, cyanate, acetate, etc.), wherein the pH of the gas-generating agent solution is between 5 and 9 and / or the molar ratio of inorganic nitrite to ammonium substance is 10:1 to 1:10.

[0103] In another aspect, the present invention relates to a water-in-oil emulsion comprising a continuous oil phase and a discontinuous aqueous phase, the oil phase comprising a bPIBAA compound or composition, and the aqueous phase comprising a hydroxylamine. In this respect, the oil-in-oil emulsion is as follows: wherein the hydroxylamine is diethylethanolamine or any other similar polyamine, including cyclic or aromatic polyamines, the aqueous phase further comprises an oxidizing salt (e.g., ammonium nitrate), and optionally also comprises a sensitizer (i.e., microspheres).

[0104] In another aspect, the present invention is directed to an explosive composition comprising a discontinuous oxidizing phase containing at least one oxygen-supplying component (i.e., an oxygen-supplying salt, such as ammonium nitrate, ammonium chlorate, etc.), a continuous organic phase containing at least one immiscible organic liquid (i.e., an organic liquid immiscible with water, such as natural oil, oil derived from coal or shale, or synthetic oil including silicone base oil), an emulsified amount of bPIBAA compound or composition, and optionally a stabilizer (i.e., phospholipids or aliphatic glycols, etc.), and a sensitizer (i.e., resin microspheres or other gas-containing particulate materials, such as hollow glass particles).

[0105] The present invention also relates to a method for reducing friction between contact surfaces of a mechanical device, the method further comprising lubricating the surfaces with a lubricating composition as described above. In one aspect, the aforementioned mechanical device is a spark-ignition or compression-ignition internal combustion engine, including mechanical devices used in any application employing lubricants, such as automobiles, trucks, tractors, boats, bicycles, trains, windmills, airplanes, and even lawn equipment.

[0106] Example The following examples illustrate preferred embodiments of the invention. Those skilled in the art will understand that the techniques disclosed in the following examples represent techniques that the inventors have found to work well in the practice of the invention, and therefore can be considered as constituting preferred modes for their practice. However, based on this disclosure, those skilled in the art will understand that many changes can be made to the specific embodiments disclosed without departing from the spirit and scope of the invention, and still obtaining the same or similar results.

[0107] Test Analysis and Specifications The ethylene oxide value of polyisobutylene epoxide (PIB epoxide) was determined using ASTM test method D 1652. The quantitative determination of bis-polyisobutylene alcoholamine (bPIBAA) was based on the stoichiometry of the reagents used. 1 H and 13 Both C-cell nuclear magnetic resonance (NMR) and C-cell nuclear magnetic resonance (NMR) are relevant. 1 Accurate quantitative analysis of bis-polyisobutylenolamine products by ¹H NMR may be unreliable due to strong intramolecular and intermolecular interactions induced by hydrogen bonding between secondary amine protons and alcohols in the product molecules. However, by… 1 ¹H NMR, in addition to any additional "free" unsubstituted PIB moiety, determines the amount of unreacted polyisobutylene epoxide. This method can also quantify the rearrangement of unreacted polyisobutylene epoxide to polyisobutylene vinyl alcohol. The presence of any unreacted primary amine can be attributed to the CH₂ group adjacent to the primary amine. 13The presence of 1 / 2 C NMR peaks is used to determine this. Any unreacted primary amine indicates the presence of mono-polyisobutylenolamine or an unreacted amine. The increase in molecular weight associated with the formation of bis-polyisobutylenolamine is reflected in the product viscosity and gel permeation chromatography (GPC) chromatograms, as provided in Table 1.

[0108] The product passes through 1 H NMR and 13 C10 NMR characterization was performed as follows: NMR spectra were recorded at ambient temperature using a Bruker 600 MHz Neo Digital NMR Spectrometer. All chemical shifts were referenced to tetramethylsilane (TMS) as an external standard, and C10 NMR was performed with reference to CDCl3 solvent. δ H 7.24 ppm and δ C Residual proton and carbon signals at 77.0 ppm. Samples ranging from 60 mg to 100 mg were prepared in 0.5 mL CDCl3 (Sigma Aldrich). Spectra were analyzed by Fourier transform, with phase and baseline corrections performed using the Bruker TopSpin (version 4.0.7) automated procedure. Manual integration and selected peak normalization by integrating with the desired peaks were applied to all spectra. The integration region was distributed over a range of at least 25 times the linewidth (Hz) of the peaks in both directions, and the data obtained from peak integration were averaged from three separate manual measurements to minimize experimental uncertainty.

[0109] Comparative Example A–PIBSI In a 300 ml stainless steel stirred pressure vessel, 7.08 g of ethyleneamine E-100 and 300 g of PIBSA (0.061 mol) with a number-average molecular weight (Mn) of 2300 were mixed with 102.4 g of toluene. This yielded 0.024 mol of ethyleneamine E-100 (Huntsman, The Woodlands, TX), resulting in a molar ratio of 0.43:1 (amine:PIBSA). The reactants were heated to 190 °C for 42 hours under a nitrogen atmosphere to form a PIBSI product with a Mn of 4861 and a viscosity of 9216 cSt at 100 °C. Toluene was removed from the product by vacuum.

[0110] Comparative Example 1 Polyisobutylene epoxide (PIBEP) was synthesized from PIB 545, available from TPC Group in Houston, Texas. In a 300 ml stainless steel stirred pressure vessel, 60 g of PIBEP with a number-average molecular weight (Mn) of 450 and an ethylene oxide oxygen value of 1.56% was mixed with 0.147 mol of triethylenetetramine (TETA) at a molar ratio of 2:1 (amine:PIBEP) and heated to 190 °C for 12 hours under a nitrogen atmosphere. The mixture was then cooled to 150 °C. An additional 60 g of the same PIBEP was added to the reaction mixture. The final amine:PIBEP ratio of the reaction mixture was 1:1. The reactor was then heated to 250 °C for an additional 12 hours under a nitrogen atmosphere. The reaction pressure started at atmospheric pressure and generated autogenous pressure as the reaction was heated. The mass of the constituent components used is as follows: TETA (amine) = 21.45 g and PIBEP = 60 g.

[0111] PIBEP is almost completely converted (in) 1 (No epoxide was detected in ¹H NMR), however, PIBEP was the limiting reagent for the reaction. Approximately 54% of TETA remained unreacted, and the reaction primarily produced mono-polyisobutylene alcohol amine products, such as... 13 The large CH2 peak (adjacent to the primary amine) in the C NMR is shown. Based on the polystyrene standard, the Mn of the mono-polyisobutylene alcohol amine product was found to be 657.

[0112] Comparative Example 2 Comparative Example 1 was reproduced, with the following exceptions: the mass of the amine was 14.62 g and PIBEP was 100 g. The temperature was raised and maintained at 250°C throughout the reaction. The catalyst used was 0.10 g BF3 and 0.61 g methanol. The TETA:PIBEP molar ratio was 0.8:1, and the Mn of the final monoamine product obtained was 704 based on the polystyrene standard.

[0113] In a 300 ml stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) from Comparative Example 1 was mixed with 0.100 moles of triethylenetetramine (TETA) at a molar ratio of 0.8:1 (amine:PIBEP), using a methanol solution of 0.1 g of 14% boron trifluoride catalyst as a proton solvent initiator. The reactants were heated to 250 °C for 12 hours under a nitrogen atmosphere.

[0114] PIBEP is almost completely converted (in) 1(No epoxide was detected in ¹H NMR), however, PIBEP was the limiting reagent for the reaction. Compared to Comparative Example 1, approximately 2 mol% of TETA remained unreacted due to its lower molar concentration. The reaction produced primarily a mixture of mono-polyisobutylene alcohol amine product and bPIBAA, such as... 13 The large CH2 peak (adjacent to the primary amine) is shown in the C NMR.

[0115] Example 3 Comparative Example 1 was reproduced, with the following exceptions: the mass of the amine was 8.20 g, and the mass of PIBEP was 100 g. The temperature was raised and maintained at 250°C throughout the reaction. The catalyst used was 0.10 g of BF3 and 0.61 g of methanol. 13.8 g of toluene was used as a diluent. The amine:PIBEP molar ratio was 0.45:1, wherein the Mn of the final bis-polyisobutylenolamine product obtained (bPIBAA of the present invention) was 729 based on the polystyrene standard.

[0116] In a 300 ml stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 450 and an ethylene oxide oxygen value of 1.56% was mixed with 0.056 mol of triethylenetetramine (TETA) (molar ratio 0.45:1 (amine:PIBEP)), 0.1 g of a methanol solution containing 14% boron trifluoride catalyst, and 13.8 g of toluene. The reactants were heated to 250 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product by vacuum.

[0117] PIBEP is almost completely converted (in) 1 (No epoxide was detected in 1H NMR), however, TETA was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. The reaction produced mainly bis-polyisobutylene alcoholamine products (bPIBAA of the present invention), as shown by... 13 The absence of a CH2 peak (adjacent to the primary amine) in the C NMR and the significant increase in viscosity compared to the initial PIBEP are shown. Table 1 below shows the viscosity and GPC Mn behavior of this reaction product.

[0118] Example 4 Comparative Example 1 was reproduced, with the following exceptions: PIBEP 595 from TPC Group in Houston, Texas, was used to prepare the epoxide; the mass of the amine was 3.44 g, and the mass of PIBEP was 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.10 g of BF3 and 0.61 g of methanol. 18.4 g of toluene was used as a diluent. The amine:PIBEP molar ratio was 0.45:1, wherein the Mn of the final bis-polyisobutylenolamine product obtained (bPIBAA of the present invention) was 1517 based on the polystyrene standard.

[0119] In a 300 ml stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 950 and an ethylene oxide oxygen value of 0.82% was mixed with 0.023 mol of triethylenetetramine (TETA) (molar ratio 0.45:1 (amine:PIBEP)), 0.1 g of a 14% boron trifluoride methanol solution, and 18.4 g of toluene. The reactants were heated to 220 °C for 42 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum. The viscosity behavior of the reaction product is shown below.

[0120] PIBEP, with a high number-average molecular weight of 950, was almost completely converted (in... 1 (No epoxide was detected in 1H NMR), however, TETA was the limiting agent for the slightly excess reaction of the PIBEP. Toluene was added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. The reaction produced a product mainly consisting of bis-polyisobutylene alcoholamine (bPIBAA of the present invention), as described by... 13 The absence of a CH2 peak (adjacent to the primary amine) in the CNMR and the significant increase in viscosity compared to the initial PIBEP are shown. The following table illustrates the viscosity of the reaction product and the GPC Mn behavior.

[0121] Example 5 Comparative Example 1 was reproduced, with the following exceptions: PIBEP 595 from TPC Group in Houston, Texas, was used to prepare the epoxide; the mass of the amine was 3.44 g and the PIBEP was 100 g. The temperature was raised and maintained at 220°C throughout the reaction. No catalyst was used in this Example 6a. 18.4 g of toluene was used as a diluent. The amine:PIBEP ratio was 0.19:1, and the Mn of the final bis-polyisobutylenolamine product (bPIBAA of the present invention) was 712 based on the polystyrene standard.

[0122] In a 300 ml stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 450 and an ethylene oxide oxygen value of 1.56% was mixed with 0.023 mol of triethylenetetramine (TETA) (molar ratio 0.2:1 (amine:PIBEP)) and 18.4 g of toluene. The reactants were heated to 220 °C for 42 hours under a nitrogen atmosphere. Toluene was removed from the product by vacuum. The viscosity behavior of the reaction product is shown below.

[0123] The conversion rate of PIBEP to the bis-polyisobutylene alcohol amine product bPIBAA of this invention is approximately 20% (e.g., by means of...). 1 (Determined by ¹H NMR). TETA, a polyamine, is the limiting agent for the large excess reaction of the PIBEP. Toluene is added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. This reaction was not carried out using a BF3•methanol catalyst, indicating that the reaction can be carried out without a catalyst. The reaction produces mainly bis-polyisobutylene alcoholamine products (bPIBAA of the present invention), as determined by… 13 The absence of a CH2 peak (adjacent to the primary amine) in the C NMR and the increased viscosity compared to the initial PIBEP are shown. The following table illustrates the viscosity of the reaction product and the GPC Mn behavior.

[0124] This example 5 illustrates that even in the absence of a catalyst, polyamines are quantitatively consumed based on substoichiometric amounts because the reaction produces the desired bPIBAA product in the mixture, which also contains excess unreacted PIBEP.

[0125] Example 6 Comparative Example 1 was reproduced, with the following exceptions: PIBEP 595 from TPC Group in Houston, Texas, was used to prepare the epoxide; the mass of ethyleneamine E-100 amine was 6.37 g, and PIBEP was 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.10 g BF3 and 0.61 g methanol. 18.4 g toluene was used as a diluent. The amine:PIBEP molar ratio was 0.45:1, wherein the Mn of the final bis-polyisobutylenolamine product obtained (bPIBAA of the present invention) was 1507 based on the polystyrene standard.

[0126] In a 300 ml stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 950 and an ethylene oxide oxygen value of 0.82% was mixed with 0.024 moles of ethyleneamine E-100 (available from Huntsman Corporation, Woodlands, Texas) (molar ratio 0.45:1 (amine:PIBEP)), 0.1 g of a 14% boron trifluoride methanol solution catalyst, and 18.4 g of toluene. The reactants were heated to 220 °C for 42 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum. The viscosity behavior of the reaction product is shown below.

[0127] PIBEP is almost completely converted (in) 1 (No epoxide was detected in 1H NMR), however, ethyleneamine E-100 was the limiting agent for the very slight excess reaction of the PIBEP. Toluene was added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. The reaction produced a product mainly consisting of bis-polyisobutylene alcoholamine (bPIBAA of the present invention), as described by... 13 The absence of a CH2 peak (adjacent to the primary amine) in the C NMR and the significant increase in viscosity compared to the initial PIBEP are shown. The following table illustrates the viscosity and GPCMn behavior of this reaction product.

[0128] Examples 7 and 8 In a 600 ml stainless steel stirred pressure vessel, 300 g of polyisobutylene epoxide (PIBEP) (originating from PIB 5230 obtained from TPC Group in Houston, Texas, with a number-average molecular weight Mn of 2300 and an ethylene oxide oxygen value of 0.32%) was mixed with 0.028 mol of ethyleneamine E-100 (Huntsman, The Woodlands, TX) (molar ratio (amine:PIBEP) 0.43:1), 0.3 g of a 14% boron trifluoride methanol solution catalyst, and 103 g of toluene. The reactants were heated to 220 °C for 42 hours under a nitrogen atmosphere. Toluene was removed from the products by vacuum. The viscosity behavior of these reaction products is shown below.

[0129] For these examples, the conversion rate of PIBEP to the bis-polyisobutylene alcoholamine product of the present invention (the bPIBAA product of the present invention in Example 8) is greater than 80% (e.g., by means of...). 1 (Determined by H NMR). However, in Example 7, it is believed that less polyamine was used in this case than the target value, as based on 13 The presence of unreacted epoxides in the C NMR spectrum is the determining factor. Ethyleneamine E-100 amine is the limiting agent for the excess reaction of the PIBEP. Toluene is added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. The reaction produces a product primarily of bPIBAA, as shown by...13 The absence of a CH2 peak (adjacent to the primary amine) in the C NMR and the increased viscosity compared to the initial PIBEP are shown. The following table illustrates the viscosity of the reaction product and the Mn behavior of GPC. The formation of PIB vinyl alcohol increases due to ring-opening of the epoxide (possibly due to excess epoxide). The Mn of the desired bis-polyisobutylene alcohol amine product obtained is based on polystyrene standards 3016 and 3030.

[0130] Example 9 In a 600 ml stainless steel stirred pressure vessel, 300 g of polyisobutylene epoxide (PIBEP) (originating from PIB 595 obtained from TPC Group in Houston, Texas, with a number-average molecular weight Mn of 950 and an ethylene oxide oxygen value of 0.82%) was mixed with 0.071 mol of ethyleneamine E-100 (Huntsman, The Woodlands, TX) (molar ratio (amine:PIBEP) 0.43:1), 0.3 g of a 14% boron trifluoride methanol solution catalyst, and 56.7 g of toluene. The reactants were heated to 220 °C for 42 hours under a nitrogen atmosphere. Toluene was removed from the product by vacuum. The viscosity behavior of this reaction product is shown below.

[0131] PIBEP is almost completely converted (in) 1 (No epoxide was detected in 1H NMR), however, ethyleneamine E-100 was the limiting agent for the very slight excess reaction of the PIBEP. Toluene was added to reduce the viscosity of the reaction mixture, thereby promoting the reaction. The reaction produced a product mainly consisting of bis-polyisobutylene alcoholamine (bPIBAA of the present invention), as described by... 13 The absence of a CH2 peak (adjacent to the primary amine) in the C NMR and the significant increase in viscosity compared to the initial PIBEP are shown. The viscosity and GPCMn behavior of this reaction product are illustrated below. This Example 9 was carried out on a scale approximately three times larger than that used in Example 6. The desired bis-polyisobutylenolamine product (bPIBAA of the present invention) obtained had a Mn of 1513 based on the polystyrene standard and exhibited good reproducibility compared to the bPIBAA product of Example 7 with a Mn of 1507.

[0132] Table 1: Viscosity of reaction products and GPC Mn behavior.

[0133] It was found that when the molar ratio of primary amine to PIBEP is less than or equal to 1, preferably when used with toluene (or other suitable diluent) as a diluent and the reaction temperature does not exceed 260°C, the reaction to form the desired bPIBAA product is driven on the basis of the primary amine.

[0134] In Example 3, it was observed that the desired bPIBAA product reaction was driven to completion by using stoichiometric amounts of amine. Example 6 illustrates the use of ethyleneamine E-100, where this polyamine is a mixture with relatively long chains.

[0135] Figure 1 Figure 1 This is the GPC characterization of bPIBAA on a logarithmic scale. The GPC is determined as follows: the GPC is calibrated relative to the polyisobutylene standard.

[0136] GPC illustrates a comparison between polyisobutylene 5230 in Example 7 of the present invention and bPIBAA made using the polyisobutylene epoxide. The GPC shows a desired shift towards higher molecular weights, indicating the formation of bPIBAA.

[0137] Figure 2 Figure 2 This is a visual comparison of the color of bPIBAA from Example 7 with that of a typical PIBSI from Comparative Example A, made from a base PIB having the same Mn (nominal value 2300). Compared to PIBSI, the bPIBAA composition of the present invention has an improved color, produces very little turbidity / deposition during the reaction, and the final product has little or no unsaturation, which eliminates the allyl hydrogen present in PIBSI.

[0138] Based on the ASTM D-1500 ASTM (ASTM Color Scale) for color petroleum products (values ​​less than 0.5 indicate a light color, while 8 indicates a very dark color), such as... Figure 2 The bPIBAA compound or composition of Example 7 shown has a color in units of 1.5 (pure) ASTM color units and a turbidity of 7.78 NTU (NTU is a turbidity unit for turbidometers ranging from 0 to 500, where 0 represents clear oil and 500 represents extremely turbid oil) based on ASTM D-6181 Standard Test Method for Measurement of Turbidity in Mineral Insulating Oil of Petroleum Origin. For the comparative PIBSI compound or composition of Comparative Example A, as shown... Figure 2 As shown, it has a color of 3 (diluted) ASTM color units and a turbidity of 20.4 NTU. For reference, standard polyisobutylene has a color of less than 0.5 ASTM color units (virtually colorless) and a turbidity of less than 4 NTU.

[0139] The improvement in color is significant and will have an advantage in quality, which is considered a result of the absence of residual maleic anhydride in the formation of PIBSA. In one embodiment, as measured by ASTM D-6181, the turbidity of the bPIBAA composition or compound of the present invention is less than 20 NTU, preferably less than 15 NTU, more preferably less than 10 NTU, or in the range of 0.5 NTU to 15 NTU, preferably in the range of 2 NTU to 8 NTU. In another embodiment, alone or in combination with the above-mentioned turbidity values, the color of the bPIBAA composition or compound, as measured by ASTM-1500, is less than 3.5 ASTM color units, preferably less than 3 ASTM color units, and more preferably less than 2 ASTM color units, in the range of 1 ASTM color unit to 3 ASTM color units, preferably in the range of 1 ASTM color unit to 2 ASTM color units.

[0140] Figure 3 Figure 3 This is a graph showing the kinematic viscosity (KV100) measured at 100°C according to ASTM D-445. The graph shows a comparison between the polyisobutylene used to prepare the bPIBAA of Example 7 and the polyisobutylene of Comparative Example A. Lower viscosity oils result in lower fuel consumption and thus reduced CO2 emissions; therefore, dispersant additives with low initial viscosity and higher oxidative stability are highly desirable to minimize viscosity changes during use.

[0141] The process of this invention produces novel bPIBAA compounds or compositions that avoid the undesirable reactivity that typically leads to dimerization in the production and use of PIBSI. It has been surprisingly found that the bPIBAA compositions of this invention have significantly lower viscosity (KV100) compared to similar PIBSI components. The figures further illustrate another indication of the formation of bPIBAA due to the near doubling of viscosity.

[0142] Figure 4 Surprisingly, using test protocol CEC L-48-00 (a well-known standard test in the field), lubricant compositions containing bPIBAA exhibited significantly better oxidation resistance than similar compositions containing PIBSA. This was accomplished by testing two lubricant formulations, one containing 20 wt% bPIBAA (from Example 7) and the second containing 20 wt% PIBSI (from Comparative Example A), using RB PAO 4 (from RB Products, Inc., Scottsville, TX) as the base oil to form the oil formulation.

[0143] exist Figure 4 The results of these oxidation tests are provided, where KV1 (40) is the kinematic viscosity of the fresh, unoxidized oil formulation at 40°C. KV2 (40) is the kinematic viscosity of the oil formulation as an oxidized oil at 40°C, wherein the formulation was heated to 17°C and aerated for 192 hours. DKV is the difference or increase in viscosity of the oxidized oil formulation relative to the fresh oil formulation at 40°C. Finally, RKV (%) is the percentage increase in kinematic viscosity of the oxidized oil formulation compared to the kinematic viscosity of the fresh oil formulation.

[0144] Figure 4 The results show that the antioxidant properties of oils containing bPIBAA are significantly improved compared to PIBSI in the same oil formulation. After rigorous testing of the bPIBAA and PIBSI oil formulations of the present invention according to the scheme described in CEC L-48-00, the KV (40) of the bPIBAA oil formulation increased by only 127 cSt compared to 2041 cSt of the PIBSI oil formulation. This represents an unexpected order-of-magnitude improvement in viscosity change of the bPIBAA oil formulation relative to the PIBSI oil formulation of 180% vs. 2209%. The KV1 (40) of 20% solutions of bPIBAA and PIBSI are 70 cSt and 92 cSt, respectively.

[0145] Additional embodiments of the present invention include: 1. A bis-polyisobutylenolamine compound comprising the following general formula: , and / or , Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

[0146] 2. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein x is 100 and y is an integer from 1 to 10.

[0147] 3. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein x is 50 and y is an integer from 2 to 10.

[0148] 4. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein x is an integer from 1 to about 150 and y is an integer from 1 to about 20.

[0149] 5. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein x is 100, R is ethylene, and y is an integer from 1 to 10.

[0150] 6. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein x is 50, R is ethylene, and y is an integer from 2 to 10.

[0151] 7. The bis-polyisobutylenolamine compound as described in Example 1, wherein the bis-polyisobutylenolamine compound contains Mn in the range of 800 to 10,000.

[0152] 8. The bis-polyisobutylenolamine compound as described in Example 1, wherein the bis-polyisobutylenolamine compound comprises PDI in the range of 1.2 to 5.

[0153] 9. The bis-polyisobutylene alcohol amine compound as described in Example 1, wherein the bis-polyisobutylene alcohol amine compound has a viscosity in the range of 10 cSt to 10,000 cSt.

[0154] 10. The bis-polyisobutylenolamine compound as described in Example 1, wherein the bis-polyisobutylenolamine compound comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

[0155] 11. A bis-polyisobutylenolamine composition, said composition further comprising a bis-polyisobutylenolamine compound of the following general formula: , and / or , Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

[0156] 12. The bis-polyisobutylene alcohol amine composition as described in Example 11, wherein x is 90 to 110 and y is an integer from 1 to 10.

[0157] 13. The bis-polyisobutylenolamine composition as described in Example 11, wherein x is 40 to 60 and y is an integer from 2 to 10.

[0158] 14. The bis-polyisobutylene alcohol amine composition as described in Example 11, wherein x is 100, R is ethylene, and y is an integer from 1 to 10.

[0159] 15. The bis-polyisobutylene alcohol amine composition as described in Example 11, wherein x is 50, R is ethylene, and y is an integer from 2 to 10.

[0160] 16. The bis-polyisobutylene alcohol amine composition as described in Example 11, wherein the composition comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and viscosity in the range of 25 cSt to 5000 cSt.

[0161] 17. The bis-polyisobutylenolamine composition as described in Example 11, wherein the composition comprises more than 50 mol% of one or more of the bis-polyisobutylenolamine compounds.

[0162] 18. The bis-polyisobutylenolamine composition as described in Example 11, wherein the composition comprises more than 70 mol% of one or more of the bis-polyisobutylenolamine compounds.

[0163] 19. The bis-polyisobutylenolamine composition as described in Example 11, wherein the composition comprises more than 80 mol% of one or more of the bis-polyisobutylenolamine compounds.

[0164] 20. The bis-polyisobutylenolamine composition as described in Example 11, wherein the composition comprises more than 90 mol% of one or more of the bis-polyisobutylenolamine compounds.

[0165] 21. A bis-polyisobutylene alcohol amine composition comprising: (i) 5 mol% to 98 mol% of one or more bis-polyisobutylene alcohol amine compounds, (ii) up to 15 mol% of unreacted polyisobutylene, and (iii) up to 15 mol% of one or more unreacted polyisobutylene epoxides, wherein the sum of the mol% of i, ii and iii is between 98 mol% and 100 mol%.

[0166] 22. The bis-polyisobutylenolamine composition as described in Example 21, wherein the one or more bis-polyisobutylenolamine compounds comprise the following general formula: , and / or , Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

[0167] 23. The bis-polyisobutylene alcohol amine composition as described in Example 21, wherein the one or more of the unreacted polyisobutylene epoxides comprise one or more of the following formulas:

[0168] Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100.

[0169] 24. The bis-polyisobutylene alcohol amine composition as described in Example 21, wherein the composition comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and viscosity in the range of 25 cSt to 5000 cSt.

[0170] 25. The bis-polyisobutylenolamine composition as described in Example 22, wherein the composition comprises more than 80% of one or more of the bis-polyisobutylenolamine compounds.

[0171] 26. The bis-polyisobutylenolamine composition as described in Example 22, wherein the composition comprises more than 90 mol% of one or more of the bis-polyisobutylenolamine compounds.

[0172] 27. The bis-polyisobutylene alcohol amine composition as described in Example 21, wherein the composition further comprises (iv) less than 1 mol% of monoisobutylene alcohol amine, wherein the sum of the mol% of i, ii, iii and iv is 100 mol.

[0173] 28. The bis-polyisobutylene alcohol amine composition as described in Example 21, wherein the composition comprises PDI in the range of 1.2 to 5.

[0174] 29. The bis-polyisobutylenolamine composition as described in Example 21, wherein the bis-polyisobutylenolamine compound comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

[0175] 30. A bis-polyisobutylene alcohol amine compound.

[0176] 31. A bis-polyisobutylene alcohol amine compound produced by a process comprising the following steps: in a reactor, under reaction conditions, contacting a polyisobutylene epoxide with a polyamine, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.9:1.

[0177] 32. The bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.7:1.

[0178] 33. The bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.5:1.

[0179] 34. A bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the polyamine comprises the following general formula:

[0180] R is C1 to C 10 Branched, cyclic, or straight-chain alkylene groups (or combinations thereof), and y is an integer between 1 and 20.

[0181] 35. A bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the polyisobutylene epoxide is a mixture of type I, type II, and / or type III polyisobutylene epoxides as shown below:

[0182] 36. The bis-polyisobutylene alcohol amine compound produced by the process described in Example 35, wherein the polyisobutylene epoxide mainly comprises type 3 polyisobutylene epoxide.

[0183] 37. The bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the process further comprises the following steps: The diluent is introduced into the reactor.

[0184] 38. A bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the method further comprises the step of introducing a diluent, a catalyst and a proton solvent initiator into the reactor.

[0185] 39. The bis-polyisobutylene alcohol amine compound produced by the process described in Example 31, wherein the temperature is from about 60°C to about 260°C.

[0186] 40. A process for preparing a bis-polyisobutylene alcohol amine composition, the process comprising the steps of: (I) contacting a polyisobutylene epoxide with a polyamine in the presence of a diluent to form a reaction mixture; and (ii) introducing a catalyst and a proton solvent initiator into the reaction mixture, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.7:1.

[0187] 41. The process as described in Example 40, wherein the molar ratio of polyamine to polyisobutylene epoxide is less than 0.6:1.

[0188] 42. The process as described in Example 40, wherein the polyisobutylene epoxide is a type I, type II, and / or type III polyisobutylene epoxide as shown below:

[0189] 43. The process as described in Example 42, wherein the polyisobutylene epoxide is primarily type 3.

[0190] 44. The process as described in Example 40, wherein the polyisobutylene epoxide comprises Mn from 400 to 5000 and ethylene oxide oxygen value from 2% to 0.15%.

[0191] 45. The process as described in Example 40, wherein the polyisobutylene epoxide comprises Mn from 400 to 3000 and ethylene oxide oxygen value from 2% to 0.25%.

[0192] 46. ​​The process as described in Example 40, wherein the polyisobutylene epoxide comprises epoxidized highly reactive polyisobutylene having an α-vinyl isobutylene isomer content between 60 mol% and 90 mol%.

[0193] 47. The process as described in Example 46, wherein the highly reactive polyisobutylene contains Mn in the range of 400 to 5000.

[0194] 48. The process as described in Example 47, wherein the bis-polyisobutylene alcohol amine composition comprises Mn in the range of 800 to 10,000.

[0195] 49. The process as described in Example 40, wherein the polyamine comprises the following general formula:

[0196] Where R is C1 to C 10 Branched, cyclic, or straight-chain alkylene groups (or combinations thereof), and y is an integer between 1 and 20.

[0197] 50. A lubricating composition comprising a bis-polyisobutylene alcohol amine compound and / or a composition thereof.

[0198] 51. A lubricating composition comprising a base oil and a bis-polyisobutylene alcohol amine composition.

[0199] 52. The lubricating composition as described in Example 51, wherein the bis-polyisobutylene alcohol amine composition comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

[0200] 53. A method for lubricating an internal combustion engine, comprising supplying the internal combustion engine with a lubricating composition as described in Example 51.

[0201] 54. A method for improving the oxidative stability of a crankcase lubricant, wherein the method comprises: lubricating the crankcase using a lubricating composition as described in Example 51.

[0202] 55. The lubricating composition as described in Example 51, wherein the lubricating composition contains an increase of less than 500% between KV40(1) and KV40(2) of the lubricating composition, using the measurement standard according to CEC L-48-00.

[0203] 56. The lubricating composition as described in Example 51, wherein the lubricating composition comprises 1% to 30% by weight of one or more base oils selected from Group I, II, III, IV or V as defined by the American Petroleum Institute in 2023.

[0204] 57. The lubricating composition as described in Example 51, wherein the lubricating composition further comprises two or more of a base oil, an ashless dispersant, an antioxidant, a detergent, an oxidation inhibitor, and an anti-wear agent.

[0205] 58. A method for reducing friction between contact surfaces of a mechanical device, the method further comprising lubricating the surfaces using a lubricating composition as described in Example 51.

[0206] 59. The method as described in Example 58, wherein the mechanical device is a spark-ignition or compression-ignition internal combustion engine.

[0207] 60. A combustible composition for cleaning a fuel delivery system, an intake system, and a combustion chamber, wherein the combustible composition comprises, by weight up to 40% of the total weight of the combustible composition, the compound as described in Example 50.

[0208] 61. The composition as described in Example 51 is intended for use in adhesives, sealants, greases, emulsifiers, paints and coatings, and polymer formulations.

[0209] 62. An aerated emulsion explosive composition comprising a bis-polyisobutylene alcohol amine compound and / or composition as described in Example 50, and a gas-generating agent solution comprising an inorganic nitrate and an ammonium substance.

[0210] 63. The gas-filled emulsion explosion composition as described in Example 62 further comprises an accelerator and / or a sensitizer.

[0211] 64. A water-in-oil emulsion comprising a continuous oil phase and a discontinuous aqueous phase, wherein the continuous oil phase comprises a bis-polyisobutylene alcohol amine compound and / or composition as described in Example 50, and the aqueous phase comprises a hydroxylamine.

[0212] 65. An emulsion explosion composition comprising: a discontinuous oxidant phase containing at least one oxygen-supplying component, a continuous organic phase containing at least one immiscible organic compound, an emulsified amount of a bis-polyisobutylene alcohol amine compound, and / or the composition as described in Example 50.

[0213] 66. The emulsion explosion composition as described in Example 65 further comprises a stabilizer and a sensitizer.

[0214] The invention has been described herein with reference to specific embodiments for particular applications. While selected embodiments have been illustrated and described in detail, it will be understood that various substitutions and modifications can be made. The process can be extended to other chemical reactions, such as the direct reaction of polyisobutylene epoxide with alcohols or polyols (e.g., polyethylene oxide). Those skilled in the art who understand the teachings will recognize that various additional substitutions and modifications can be made without departing from the spirit and scope of the invention and as defined in the appended claims.

Claims

1. A bis-polyisobutylene alcohol amine compound.

2. A bis-polyisobutylene alcoholamine compound comprising the following general formula: ， and / or ， Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

3. The bis-polyisobutylene alcohol amine compound of claim 1, wherein x is 150 and y is an integer from 1 to 20, preferably x is 50 and y is an integer from 2 to 10, and most preferably.

4. The bis-polyisobutylene alcohol amine compound of claim 1, wherein x is 100, R is ethylene, and y is an integer from 1 to 10, preferably x is 50, R is ethylene, and y is an integer from 2 to 10.

5. The bis-polyisobutylenolamine compound of claim 1, wherein the bis-polyisobutylenolamine compound comprises Mn in the range of 800 to 10,000.

6. The bis-polyisobutylene alcohol amine compound of claim 1, wherein the bis-polyisobutylene alcohol amine compound comprises PDI in the range of 1.2 to 5.

7. The bis-polyisobutylene alcohol amine compound of claim 1, wherein the bis-polyisobutylene alcohol amine compound comprises a viscosity in the range of 10 cSt to 10,000 cSt.

8. The bis-polyisobutylenolamine compound according to at least one of claims 1 to 7, wherein the bis-polyisobutylenolamine compound comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

9. A bis-polyisobutylenolamine composition, said composition comprising, further comprising, a bis-polyisobutylenolamine compound of the following general formula: ， and / or ， Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

10. The bis-polyisobutylene alcohol amine composition of claim 9, wherein x is 90 to 110 and y is an integer from 1 to 10, preferably x is 40 to 60 and y is an integer from 2 to 10.

11. The bis-polyisobutylene alcohol amine composition of claim 9, wherein x is 100, R is ethylene and y is an integer from 1 to 10, preferably x is 50, R is ethylene and y is an integer from 2 to 10.

12. The bis-polyisobutylene alcohol amine composition according to at least one of claims 9 to 11, wherein the composition comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

13. The bis-polyisobutylenolamine composition of claim 12, wherein the composition comprises more than 50 mol% of one or more of the bis-polyisobutylenolamine compounds.

14. The bis-polyisobutylenolamine composition according to at least one of claims 9 to 13, wherein the composition comprises more than 70 mol%, preferably more than 80%, and most preferably more than 90% of one or more of the bis-polyisobutylenolamine compounds.

15. A bis-polyisobutylene alcohol amine composition comprising: (i) 5 mol% to 98 mol% of one or more bis-polyisobutylene alcohol amine compounds, (ii) up to 15 mol% of unreacted polyisobutylene, and (iii) up to 15 mol% of one or more unreacted polyisobutylene epoxides, wherein the sum of the mol% of i, ii and iii is between 98 mol% and 100 mol%.

16. The bis-polyisobutylenolamine composition of claim 15, wherein the one or more bis-polyisobutylenolamine compounds comprise the following general formula: ， and / or ， Where x is an integer from 1 to approximately 200, and R is a series of integers from C1 to C2. 10 Branched, cyclic, or straight-chain alkylene groups, and y is an integer between 1 and about 20.

17. The bis-polyisobutylene alcohol amine composition according to at least one of claims 15 to 16, wherein the one or more unreacted polyisobutylene epoxides comprise one or more of the following formulas: ， Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably an integer between 1 and 100.

18. The bis-polyisobutylene alcohol amine composition according to at least one of claims 15 to 17, wherein the composition comprises Mn in the range of 800 to 6000, PDI in the range of 1.2 to 3, and a viscosity in the range of 25 cSt to 5000 cSt.

19. The bis-polyisobutylenolamine composition according to at least one of claims 15 to 18, wherein the composition comprises more than 80%, preferably more than 90%, of one or more of the bis-polyisobutylenolamine compounds.

20. The bis-polyisobutylene alcohol amine composition according to at least one of claims 15 to 19, wherein the composition further comprises (iv) less than 1 mol% of monoisobutylene alcohol amine, wherein the sum of mol% of i, ii, iii and iv is 100 mol.

21. A bis-polyisobutylene alcohol amine compound produced by a process comprising the following steps: in a reactor, under reaction conditions, contacting a polyisobutylene epoxide with a polyamine, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.9:1, preferably less than 0.7:1, and most preferably less than 0.5:

1.

22. A process for preparing a bis-polyisobutylene alcohol amine composition, the process comprising the following steps: (i) In the presence of a diluent, contact the polyisobutylene epoxide with the polyamine to form a reaction mixture; and (ii) introduce a catalyst and a proton solvent initiator into the reaction mixture, wherein the molar ratio of the polyamine to the polyisobutylene epoxide is less than 0.7:1, preferably less than 0.6:

1.

23. The process according to at least one of claims 21 to 22, wherein the polyisobutylene epoxide comprises 400 to 5000 Mn and 2% to 0.15% ethylene oxide oxygen value.

24. The process according to at least one of claims 21 to 23, wherein the polyisobutylene epoxide comprises epoxidized highly reactive polyisobutylene having an α-vinylisobutylene isomer content between 60 mol% and 90 mol%.

25. The process of claim 24, wherein the highly reactive polyisobutylene comprises Mn in the range of 400 to 5000.

26. The process according to at least one of claims 21 to 25, wherein the bis-polyisobutylene amine composition comprises Mn in the range of 800 to 10,000.

27. The process of claim 22, wherein the polyamine comprises the following general formula: ， Where R is C1 to C 10 Branched, cyclic, or straight-chain alkylene groups or combinations thereof, and y is an integer between 1 and 20.

28. A lubricating composition comprising a bis-polyisobutylene alcohol amine compound and / or a composition thereof.

29. A lubricating composition comprising a base oil and a bis-polyisobutylene alcohol amine composition.

30. Use of the compound of claim 1 in a lubricating composition for reducing friction between contact surfaces of a mechanical device, and for use in a combustible composition for cleaning a fuel delivery system.

31. Use of the compound as claimed in claim 1 in an emulsion explosive composition as a water-in-oil emulsion. The present invention relates to bis-polyisobutylenolamine compounds, preferably having at least two amino groups, and compositions thereof.

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