Compounds, their manufacture and use

Abstract

The present invention relates to a polyisobutylene polyether alcohol amine compound and compositions thereof. The present invention is also directed to a novel process for producing a polyisobutylene polyether alcohol amine compound by reacting a polyisobutylene epoxide with a specific polyether amine, a protic solvent, a diluent, and optionally a catalyst. Furthermore, the present invention is further directed to a number of uses of the polyisobutylene polyether alcohol amine compound and compositions, including but not limited to its use in lubricants, interfacial active agents, emulsifiers, adhesives, resins, and the like.

Description

[0001] Priority Claim This application is based on and asserts priority to U.S. non-provisional application No. 18 / 931,902, filed on October 30, 2024, as a partial continuation, which is based on parent application No. 18 / 904,859 with the same title, filed on October 2, 2024, the disclosure of which is incorporated herein by reference. Invention Field

[0002] This invention relates to novel compounds, their preparation, and uses. In particular, the novel compounds are novel polyisobutylene compounds, more particularly, polyisobutylene polyether alcohol amines, and more specifically, mono-polyisobutylene polyether alcohol amines, bis-polyisobutylene polyether alcohol amines, tris-polyisobutylene polyether alcohol amines, and tetrakis-polyisobutylene polyether alcohol amines, and mixtures thereof. This invention also relates to novel processes for generating these mono-, bis-, tris-, and tetra-polyisobutylene polyether alcohol amine compositions, and their uses in lubricants, surfactants, emulsifiers, resins, adhesives, and many similar applications. Background of the Invention

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

[0004] Traditional PIB compounds and compositions, primarily characterized by internal unsaturation (double bonds), tend to have low reactivity and are mainly derived from isobutylene and typical aluminum-based catalysts. More reactive PIB compounds and compositions, however, exhibit a higher percentage of unsaturation at the ends of the PIB molecule and are primarily generated from more selective fluorinated catalysts such as BF3.

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

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

[0007] PIB, preferably more reactive, is primarily used to generate well-known lubricants such as polyisobutylene succinimide or polyisobutylene succinamide (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). PIB, being mostly nonpolar, requires reaction with, for example, maleic anhydride to form a polar group, enabling the linking group (i.e., succinic anhydride) to react and 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 produced using a thermal process that begins with PIBs having a relatively high proportion of terminal vinyl bonds (referred to in the industry as "reactive" or "highly reactive" PIBs). Highly or moderately reactive PIBs are well known in the art and are 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 amount of terminal vinyl bonds, see, for example, U.S. Patent No. 3,272,746.

[0009] The aforementioned thermal and halogen-assisted reactions often produce significant amounts of haze and highly colored deposits, which must be filtered off before use in the final product (PIBSI). Tar is often generated during thermal processes, which coats the reactor walls, necessitating frequent, time-consuming, and therefore costly cleaning of the reaction vessel. The formation of deposits and tar is believed to be at least partly due to the decomposition and / or polymerization of unsaturated enophiles (typically maleic anhydride). Efforts have been made to eliminate the resulting haze and deposits, as documented in U.S. Patent Nos. 7,339,007, 4,958,034, 5,021,169, and 5,241,003.

[0010] U.S. Patent No. 3,794,586 relates to a lubricating oil composition comprising a reaction of a polyolefin epoxide and an amine compound (including polyisobutylene epoxide) to form a reaction product of a mono-polyisobutylene hydroxyalkyl-substituted polyether amine. U.S. Patent Nos. 6,497,736 and 6,346,129 disclose fuel compositions containing mono-polyisobutylene hydroxyalkyl-substituted amines for use as automotive fuel cleaners. Furthermore, Canadian Patent Application CA 2,856,684A1 describes an amine mixture of mono-polyisobutylene amine and aliphatic amines for use in cleaning engine intake valves and nozzles.

[0011] Based on both ether and amine groups, polyetheramines are well-known aliphatic organic species in the industry. Polyetheramines are typically produced by reacting ethylene oxide or propylene oxide with a polyol followed by amination. Commercially available polyetheramines are available in various molecular weights, including monofunctional, difunctional, and trifunctional forms. The main uses of polyetheramines are as epoxy resin curing agents and as fuel additives or cleaners to prevent sludge and other deposits in gasoline engines. For example, see U.S. Patent Nos. 4,975,096, 5,489,630, 7,550,550, and 9,315,761; U.S. Patent Publications 2013 / 00234451A1 and 2018 / 0023020A1; and European Patent EP128715B1.

[0012] U.S. Patent Nos. 7,820,604, 7,928,044, and 7,816,309 and European Patent EP2,797,970B1 discuss the reaction of copolymers and terpolymers of polyisobutylene and maleic anhydride, as well as polyisobutylene / maleic anhydride / hexadecene compositions, with polyetheramines to produce oil additives. U.S. Patent No. 9,315,761 addresses the use of metallocene-made vinyl-terminated polypropylene copolymers and vinyl-terminated atactic polypropylene epoxides and the reaction of these polymers with polyetheramines. U.S. Patent Publication No. US2018 / 002320A1 discloses the typical reaction of PIBSI with polyetheramines to produce polyisobutylene polyetherimides. These compounds have properties very similar to PIBSI, maintaining unsaturation in the final product and are not alcoholic amines.

[0013] The US Patent Publication No. US2014 / 0087983A1, published on March 27, 2014, is for lubricants and fuel dispersants containing amination products of epoxide-terminated macromonomers and amine compounds such as polyalkylene polyamines and ethylenediamines, but does not refer to polyetheramines.

[0014] US Patent Publication No. US2006 / 0063844A1, published on March 23, 2006, discloses a method for generating amine-functionalized polyisobutylene primarily for microemulsion coating applications from a mixture of mono- and bis-polyisobutylene, which is mainly functionalized with monoamine, and mono- and bis-polyisobutylamine.

[0015] While the generation of specific polyisobutylene alcohol amines from polyisobutylene epoxides is known, there is a need to modify the chemical properties of head groups derived from fuel and engine oil lubricant additives, adhesives and sealants, epoxy and polyurea coatings, composites, emulsion stabilizers, paraffin inhibitors, and the like, affecting the solubility, reactivity, and performance standards of the final compounds in a variety of applications. Furthermore, there is a persistent need in the field for highly efficient one-pot synthesis of these compounds with minimal byproducts, thereby improving compounds or compositions that offer enhanced multifunctional chemical and physical properties. Summary of the Invention

[0016] This invention relates to novel compounds or compositions, their preparation, and their uses. These novel compounds and compositions are selected from the general group consisting of polyisobutylene polyether alcoholamines (PIB-PEAA), more specifically mono-polyisobutylene polyether alcoholamines (mPIB-PEAA), bis-polyisobutylene polyether alcoholamines (bPIB-PEAA), tri-polyisobutylene polyether alcoholamines (tPIB-PEAA), and tetra-polyisobutylene polyether alcoholamines (tkPIB-PEAA). This invention also relates to mixtures of two or more of mPIB-PEAA, bPIB-PEAA, tPIB-PEAA, and tkPIB-PEAA.

[0017] In one embodiment, the novel compound or composition is a mono-polyisobutylene polyether alcoholamine (referred to herein as mPIB-PEAA), represented by the following general formula (1): Equation (1) Wherein, x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100; R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is CH3; z is an integer from 1 to about 100, preferably from about 1 to 75, and most preferably from 2 to 50; and Y' is an alkyl group having 1 to 10 carbon atoms, preferably CH3 or an amino group, such as (-NH2), preferably in all embodiments of formula (1) above, Y' is an amino group (-NH2). In one embodiment of the above general formula (1), x is an integer from 75 to 125, preferably x is 100, z is an integer from 2 to 35, and Y' is an amino group (-NH2). In another embodiment of the above general formula (1), x is an integer from 35 to 75, preferably x is 50, z is an integer from 2 to 10, and Y' is an amino group (-NH2). In yet another embodiment of the above general formula (1), x is an integer from 90 to 110, z is an integer from 2 to 35, and Y' is an amino group (-NH2). In yet another embodiment of the above general formula (1), x is an integer from 40 to 60, z is an integer from 2 to 10, and Y' is an amino group (-NH2).

[0018] In another embodiment, the novel compound or composition is mPIB-PEAA, represented by the following general formula (2): Equation (2) Wherein, x is an integer from 1 to 200, preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is an ethyl group, n is an integer from 1 to 20, and z, z', z'' are the same or different, preferably the same, and are independent integers from 5 to 100, preferably from a lower limit of 5 to 6 to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0019] In another embodiment, the novel compound or composition is mPIB-PEAA, which is represented by the following general formula (3): Equation (3) Wherein R and R' are independently hydrogen, methyl or ethyl, or C1-C5 alkyl groups, and x is an integer from 1 to 200, preferably from 1 to about 150, and most preferably from 1 to 100, and z, z', z'' and z''' are the same or different, preferably the same, and are independently integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6, to 85.

[0020] In one embodiment, the novel compound or composition is a bis-polyisobutylene polyether alcoholamine (referred to herein as bPIB-PEAA), represented by the following general formula (4): Equation (4) Where x and x' are the same or different, preferably the same, and are independent integers from 1 to 200, preferably from 1 to about 150 and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is CH3, and z is an integer from 1 to about 100, preferably from 1 to 75 and most preferably from 2 to 50. In one embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 75 and 125, preferably x and x' is 100, and z is an integer from 2 to 35. In another embodiment of the above general formula (4), x and x' is 50, and z is an integer from 2 to 10. In yet another embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 90 to 110, and z is an integer from 2 to 35. In yet another embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 40 to 60, and z is an integer from 2 to 10.

[0021] In another embodiment, the novel compound or composition is bPIB-PEAA, represented by the following general formula (5): Equation (5) Wherein x and x' are the same or different, preferably the same, and are independent integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is an ethyl group, and z, z' and z'' are the same or different, preferably the same, and are independent integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0022] In another embodiment, the novel compound or composition is bPIB-PEAA, represented by the following general formula (6): Equation (6) Each R is independently hydrogen, methyl, or ethyl, R' is a C1-C5 alkyl group, and x and x' are the same or different, preferably the same, and are independently integers from 1 to 200, preferably from 1 to about 150, and most preferably from 1 to 100, and z, z', z'' and z''' are the same or different, preferably the same, and are independently integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0023] In one embodiment, the novel compound or composition is a tri-polyisobutylene polyether alcoholamine (referred to herein as tPIB-PEAA), represented by the following general formula (7): Equation (7) Wherein x, x' and x'' are the same or different, preferably the same, and are independent integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is an ethyl group, n is an integer from 1 to 20, and z, z' and z'' are the same or different, preferably the same, and are independent integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0024] In another embodiment, the novel compound or composition is tPIB-PEAA, represented by the following general formula (8): Equation (8) Each R is independently hydrogen, methyl, or ethyl, R' is a C1-C5 alkyl group, and x, x', and x'' are the same or different, preferably the same, and are independently integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, and z, z', z'', and z''' are the same or different, preferably the same, and are independently integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0025] In one embodiment, the novel compound or composition is a tetra-polyisobutylene polyether alcoholamine (referred to herein as tkPIB-PEAA), represented by the following general formula (9): Equation (9) Each R is independently hydrogen, methyl, or ethyl, R' is a C1-C5 alkyl group, and x, x', x'' and x''' are the same or different, preferably the same, and are independently integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, and z, z', z'' and z''' are the same or different, preferably the same, and are independently integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0026] The process for generating the polyisobutylene polyether alcoholamine (PIB-PEAA) compound of the present invention comprises reacting (a) a polyisobutylene epoxide (PIBEP) and a polyetheramine (PEA) in the presence of a diluent and optionally a Lewis acid or a Bronsted acid catalyst. In a preferred embodiment, the polyisobutylene epoxide is selected from one or more of type I, type II, or type III polyisobutylene epoxides represented by formulas 10, 11, and 12, respectively: , Type 1 Equation (10) , Type 2 Equation (11) , Type 3 Equation (12) Where x is an integer from 1 to about 200, preferably from 1 to about 150, and ideally between 1 and 100.

[0027] In one embodiment, the hydrophilic polyetheramine can be a mono-, di-, tri-, tetra-, or polyfunctional polyetheramine. Methods for preparing hydrophilic polyetheramines are well known and can be found, for example, in U.S. Patent Nos. 3,654,370, 3,832,402, 4,990,476, and 2017 / 0362164A1, the contents of which are incorporated herein by reference. Generally, these hydrophilic polyetheramines can be produced by alkylating a mono-, di-, tri-, tetra-, or polyfunctional alcohol or alkylphenol with an alkylene oxide (such as ethylene oxide, propylene oxide, butane oxide, or mixtures thereof) to form an alkylene oxide adduct, followed by catalytic amination of the alkylene oxide adduct in the presence of hydrogen and ammonia to form a polyetheramine. In some embodiments, the hydrophilic polyetheramine can be initiated by an amine, which is alkylated and then amination.

[0028] According to one embodiment, the polyetheramine, preferably a hydrophilic polyetheramine, is a polyether monoamine having formula (13) or formula (14): Equation (13) Where R is hydrogen or methyl, and a and b are independent integers from about 1 to about 150; or Equation (14) Where Y is hydrogen or methyl, Z is an alkyl group from 1 to 40 carbon atoms, or an alkylphenol group from 1 to 40 carbon atoms, and w is an integer from about 1 to about 100.

[0029] In another embodiment, the hydrophilic polyetheramine is a polyether monoamine having one of formulas (15) or (16): Equation (15) Equation (16) Commercially available polyether monoamines include the JEFFAMINE® M-series and XTJ-series amines, including but not limited to JEFFAMINE® M-600, M-1000, M-2005, M-2070, XTJ-435 and XTJ-436 amines available from Hustman.

[0030] In another embodiment, the hydrophilic polyetheramine is a polyether diamine having one or more of formulas (17), (18), and (19): Equation (17) Where c is an integer from approximately 2 to approximately 100, and preferably c is an integer from approximately 2 to approximately 40; or Equation (18) Where e is an integer from 2 to approximately 40, and d and f are independent integers from approximately 1 to approximately 10; or Equation (19) Where g is an integer from approximately 2 to approximately 3.

[0031] Commercially available polyether diamines include JEFFAMINE® D, ED and EDR amines, including but not limited to JEFFAMINE® D-200, D-400, D-2000, D-4000, ED-600, ED-900, ED-20003, EDR-148 and EDR-176 amines available from Hustman Company.

[0032] In yet another embodiment, the hydrophilic polyetheramine is a polyethertriamine having formula (20): Equation (20) Where R1 is hydrogen, methyl or ethyl, n is an integer of 0 or 1, and h, i and j are independent integers from about 1 to about 100.

[0033] Commercially available triamines include the JEFFAMINE® T-series amines, including but not limited to JEFFAMINE® T-403, T-3000 and T-5000 amines available from Hustman Company.

[0034] In another embodiment, the hydrophilic polyetheramine is a polyethertetraamine having formula (21): Equation (21) Each R2 is independently hydrogen, methyl, or ethyl, R3 is a C1-C10 alkyl group, and each M is independently an integer from about 2 to about 50.

[0035] Generally, the process for generating the polyisobutylene polyether amine compound of the present invention involves contacting a polyisobutylene epoxide, a hydrophilic polyether amine, a diluent, an optional geological solvent, and an optional catalyst in a reaction vessel at pressures, temperatures, and reaction times sufficient to form the compound of the present invention.

[0036] In one embodiment, the polyisobutylene polyether amine compound of the present invention is produced via a process comprising the following steps: (i) mixing polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less (amine: epoxide); (ii) optionally introducing a diluent into the reaction vessel with or without a catalyst; (iii) optionally adding a protic solvent to the reaction vessel; (iv) heating the reaction vessel under pressure for a period of time; (v) optionally removing the diluent; and (vi) recovering the polyisobutylene polyether amine compound.

[0037] In another embodiment, the process of the present invention is directed to a process for generating a polyisobutylene polyether amine compound, the process comprising the steps of: (i) mixing a polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less (amine: epoxide); (ii) optionally introducing a diluent into the reaction vessel with or without a catalyst; (iii) optionally adding a protic solvent; (iv) heating the reaction vessel under pressure for a period of time; (v) optionally removing the diluent; and (vi) recovering the polyisobutylene polyether amine compound.

[0038] In a preferred embodiment, the present invention relates to a process for generating a PIB-PEAA composition, the process comprising the steps of: (i) contacting a polyisobutylene epoxide with a hydrophilic polyether amine in a reactor at a molar ratio of hydrophilic polyether amine to polyisobutylene epoxide of less than 0.9:1 (amine: epoxide); (ii) optionally introducing a proton solvent; (iii) optionally adding a catalyst to the reactor; and (iv) adding a diluent to the reactor; and (iv) removing the diluent to form a PIB-PEAA composition comprising more than 50 molar percentages (50 mol%) of PIB-PEAA.

[0039] A surprising finding, among other discoveries, is that controlling the molar ratio of polyetheramine (PEA) to polyisobutylene produces very pure compounds with reduced or almost eliminated percentages of minor components.

[0040] In a general embodiment, in the process for generating the PIB-PEAA compound and composition of the present invention, the molar ratio of polyetheramine to isobutylene epoxide is less than 1:1, preferably less than 0.9:1, more preferably 0.8:1, and 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 of polyetheramine to isobutylene epoxide is in the range from 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.

[0041] Polyetheramines are produced with a target amine content. That is, a polyether may contain one molar equivalent of a primary amine (monoamine) and / or two molar equivalents of a primary amine (diamine) and / or three molar equivalents of a primary amine (triamine) and / or four molar equivalents of a primary amine (tetraamine) and / or possibly more (polyamine). The choice of the amine content of any particular polyetheramine is determined by the specific end-use application or the desired end-use properties.

[0042] In one embodiment, mono-PIB-PEAA is produced using a molar ratio of polyetheramine (one or more mono-, di-, tri-, and tetra-amines) to polyisobutylene epoxide of less than 1.2:1, preferably less than 1.1:1, more preferably less than 1.05:1, and most preferably about 1:1.

[0043] In another embodiment, bis-PIB-PEAA is produced using a molar ratio of polyetheramine (one or more di-, tri-, and tetraamines) to polyisobutylene epoxide of less than 0.7:1, preferably less than 0.6:1, more preferably less than 0.55:1, and most preferably about 0.5:1.

[0044] In another embodiment, PIB-PEAA is produced using a molar ratio of less than 0.5:1 of polyetheramine (one or more tri- and tetramines) to polyisobutylene epoxide, preferably less than 0.45:1, more preferably less than 0.4:1, and most preferably about 0.3:1.

[0045] In another embodiment, 4-PIB-PEAA is produced using a molar ratio of polyetheramine (tetraamine or higher) to polyisobutylene epoxide of less than 0.4:1, preferably less than 0.35:1, more preferably less than 0.3:1, and most preferably about 0.25:1.

[0046] In another embodiment, the molar ratio of polyetheramine to polyisobutylene epoxide is such that the polyisobutylene epoxide used is in slight to slight excess. In another embodiment, the molar ratio of polyetheramine to polyisobutylene epoxide is such that the polyetheramine used is in slight to slight excess. A preferred molar ratio of polyetheramine to polyisobutylene epoxide is such that one, two, three, or four moles of polyisobutylene epoxide are used per mole of polyetheramine to produce mono-, bis-, para-, or tetra-PIE-PEAA, depending on the amount of primary amine contained in the PEA.

[0047] In another embodiment of the above process, when the hydrophilic polyetheramine and polyisobutylene epoxide are as described above, the particular PIB-PEAA composition contains more than 70 mol%, preferably more than 80 mol%, more preferably more than 90 mol%, and most preferably more than 95 mol% of PIB-PEAA.

[0048] Polyisobutylene polyether alcohol amine compounds are used in many applications, including friction modification, dispersant, fuel additive, emulsion stabilizer, surfactant, adhesive, battery, etc.

[0049] Diagram Explanation

[0050] This disclosure is illustrated by way of example and not limitation, accompanied by drawings in which the same reference numerals always refer to the same elements, and in the drawings: Figure 1 This invention describes the GPC characterization of mono-polyisobutylene alcohol amine on a logarithmic scale.

[0051] Figure 2 This invention describes the GPC characterization of bis-polyisobutylene alcohol amine on a logarithmic scale.

[0052] Figure 3 This invention describes the GPC characterization of para-polyisobutylene alcohol amine on a logarithmic scale.

[0053] While the disclosed processes and compositions are readily modified and substituted, the drawings illustrate specific embodiments described 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 specific forms disclosed, but rather, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

[0054] Detailed description of the invention

[0055] This document discloses novel polyisobutylene polyether alcoholamines (PIB-PEAA), namely mono-polyisobutylene polyether alcoholamines (mPIB-PEAA), di-polyisobutylene polyether alcoholamines (bPIB-PEAA), tri-polyisobutylene polyether alcoholamines (tPIB-PEAA), and tetra-polyisobutylene polyether alcoholamines (tkPIB-PEAA), as well as processes for generating PIB-PEAA from polyisobutylene epoxides (PIBEP) and mono- or polyfunctional polyether alcoholamines, and numerous uses of PIB-PEAA. For the purposes of this patent specification and the appended claims, the term polyisobutylene polyether alcoholamine (PIB-PEAA) refers independently to each of the mPIB-PEAA, bPIB-PEAA, tPIB-PEAA, and tkPIB-PEAA compounds.

[0056] Polyisobutylene and the formation of polyisobutylene epoxide The polyisobutylene epoxide produced by the PIB-PEAA reaction currently used is obtained by oxidizing the polyolefin with an oxidizing agent to provide an epoxide or epoxide, wherein the ethylene oxide ring is oxidized from the double bond in the polyolefin. Polyisobutylene is a preferred polyolefin.

[0057] Polyisobutylene (PIB) is a long-chain molecule synthesized by polymerizing or linking isobutylene molecules. Many well-known processes for producing PIB exist in the field, including, but not limited to, 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, which are incorporated herein by reference in their entirety.

[0058] Polyisobutylene (PIB) exists in many forms with a wide range of molecular weights, from several hundred to several million. Generally, the preferred number-average molecular weight (Mn) is in the range of 100 to 5000, more preferably 400 to 4000, and most preferably about 500 to about 3500 or less. Furthermore, due to varying chain lengths, PIB also exhibits a wide range of polydispersity indices (PDI) measured using GPC with polyisobutylene standards, 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. Mn, along with PDI, are key properties used to determine the useful viscosity and flash point of PIB for a particular application.

[0059] PIBs are available from many commercial manufacturers, such as the TPC Group, INEOS Oligomers, Infineum, Lubrizol, and BASF. Each company offers a variety of combinations of low, medium, and high reactive PIBs, such as GLISSOPAL® and OPPANOL® from BASF in Ludwigshafen, Germany; Indopol® from INEOS Oligomers in London, UK; and LUBRIZOL 3108 from Lubrizol in Wycliffe, Ohio.

[0060] A variety of PIB types are available from TPC Group in Houston, Texas, including highly reactive PIBs (HR-PIBs) such as HR545, HR595 and HR5230; moderately reactive PIBs (LM-PIBs) such as TPC 175 and TPC 1160; and di-isobutylene (DIB) and triisobutylene (TIB).

[0061] The decisive 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 reactive 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.

[0062] Surprisingly, it was further discovered that the PIB-PEAA of the present invention can be generated using conventional or highly reactive PIB as the starting monomer for the formation of polyisobutylene epoxide. In one embodiment, highly reactive PIB is preferred in the process for generating the polyisobutylene epoxide starting monomer to be reacted with polyetheramine in the process of the present invention.

[0063] Epoxidation of olefins and other polymers Epoxidation of a wide variety of olefins, including polymers with double bonds, is well known in the field. Representative prior art showing various procedures for epoxidizing some types of unsaturated materials has been found in: Song et al., *Journal of Polymer Science and Polymer Chemistry*, 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 selected reaction media solvents is also well known in the field. Representative prior art references showing these types of epoxides 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). Examples of different types of intermediate polyisobutylene epoxides produced according to the present invention are illustrated in the following description via the reactions described below, which are always referred to as type I, type II, or type III polybutenes represented by formulas 10, 11, and 12 respectively: , Type 1 Equation (10) , Type 2 Equation (11) , Type 3 Equation (12) Where x is from 1 to about 200, preferably from 1 to about 150, more preferably from 1 to about 100, and most preferably between 1 and 50, and the content of polyisobutylene epoxide species containing type I, type II, and / or type III polyisobutylene epoxides is at least 50 mol%, preferably 60 mol%, and most preferably 80 mol% or higher. In one embodiment of the above general formula, x is 100, and in another embodiment, x is 50. In yet another embodiment of the above general formula, x 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.

[0064] It is generally believed that type 3 epoxides are more reactive to amination than type 1 and type 2 epoxides, and these polyisobutylene epoxides are preferred. However, it has been surprisingly found that type 1 and type 2 epoxides also exhibit reactivity to amination. Therefore, polyisobutylene epoxides containing higher amounts of type 1 and type 2 epoxy groups are also used in this invention. In any case, if a type 3 epoxide is desired, it is produced starting from polyisobutylene containing a high concentration of type 3 double bonds (as shown above).

[0065] In a preferred embodiment, the molar percentage of type 1, type 2, and / or type 3 polyisobutylene epoxides used in the process of the present invention 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% to about 80 mol%, preferably from about 80 mol% to 85 mol% to about 90 mol% to 95 mol%, and most preferably greater than about 95 mol%. In another embodiment, the molar percentage of type 3 polyisobutylene epoxides used is at least 50 mol% to about 60 mol%, preferably from about 65 mol% to about 70 mol%, and most preferably greater than about 70 mol%. In yet another embodiment, the molar percentage of type 3 polyisobutylene epoxides used 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 epoxides used is at least 85 mol% or up to 98 mol%, and preferably greater than about 90 mol% to 95 mol%.

[0066] In one embodiment, a combination of type I, type II, and type III polyisobutylene epoxides is used in the process of the present invention to generate polyisobutylene polyether alcoholamine. In a preferred embodiment, more than 70 mol%, preferably more than 80 mol%, or even 90 mol%, of type III polyisobutylene epoxide is used.

[0067] In yet 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%, more preferably in the range of 400 to 3500 and an ethylene oxide oxygen value of 2% to 0.22%, and even more preferably in the range of 400 to 3000 and an ethylene oxide oxygen value of 2% to 0.25%.

[0068] Commercially available examples of polyisobutylene containing high concentrations of type III double bonds are TPC 5230, TPC 545, and TPC 595, produced and obtained by TPC Corporation in Houston, Texas. Non-limiting examples of polyisobutylene containing low amounts of type III double bonds but with increased amounts of type I and type II double bonds are Indopol® H-100, H-300, H-1200, H-1500, H-1900, H-2100, H-6000, and H-18000, produced by INEOS Oligomers in London, UK.

[0069] The presence of type 4 tetra-polyisobutylene epoxide is due to the processes used to produce polyisobutylene epoxides, and it exists in various amounts alongside all other types 1, 2, and 3. For example, type 4 exists in highly reactive polyisobutylene epoxides (type 3) in amounts from about 1 to less than 5 mol%, more likely from 1 mol% to less than 3 mol%, and in low to medium reactive polyisobutylene epoxides (types 1 and 2), type 4 is believed to exist in amounts from 25 mol% to 40 mol% or higher, more likely from about 30 mol% to about 40 mol%.

[0070] hydrophilic polyetheramine Generally, these hydrophilic polyetheramines can be produced by alkylation of mono-, di-, tri-, tetra-, or polyfunctional alcohols or alkylphenols with alkyl oxides (such as ethylene oxide, propylene oxide, butane oxide, or mixtures thereof) to form alkyl oxide adducts, followed by catalytic amination of the alkyl oxide adducts in the presence of hydrogen and ammonia to form polyetheramines.

[0071] The polyetheramines used for reacting with polyisobutylene epoxides are preferably hydrophilic polyetheramines, which are mono-, di-, tri-, tetra-, or polyfunctional polyetheramines. Methods for preparing hydrophilic polyetheramines are well known and can be found, for example, in U.S. Patent Nos. 3,654,370, 3,832,402, and 4,990,476, the contents of which are incorporated herein by reference.

[0072] Hydrophilic polyetheramines are mono-, di-, tri-, tetra-, or polyfunctional polyetheramines based on PPG (polypropylene glycol) and PEG (polyethylene glycol) polyether backbones, as well as polytetramethylene glycol (PTMEG)-based polyetheramines or mixtures thereof.

[0073] There are many commercially available hydrophilic polyetheramines that can be reacted with polyisobutylene epoxides to produce the polyisobutylene polyether alcoholamine compounds of this invention. Huntsman Corporation of Woodland, Texas manufactures polyetheramines under the trade name JEFFAMINE® with various molecular weights (MW) and average amine hydrogen equivalents (AHEW) measured in grams per equivalent. While not wishing to be bound by any particular theory, it is believed that selecting an appropriate polyetheramine for a better use or application when producing the polyisobutylene polyether alcoholamine compounds of this invention will improve the desired use or application. For example, it is believed that the use of the polyisobutylene polyether alcoholamine compounds of this invention in epoxy resins may produce epoxy resins with improved water resistance, adhesion, flexibility, and other improved properties.

[0074] Monoamine One type of polyetheramine is called a monoamine, which, for the purposes of this article, is based on a PPG or PEG / PPG backbone. Huntsman manufactures a series of propylene glycol-based monoamines under the trademark JEFFAMINE®, including, for example, JEFFAMINE® M-600 with a molecular weight (Mw) of 600 and an AHEW of 291 g / equivalent, and M-2005 with a MW of 2000 and an AHEW of 1045 g / equivalent, both of which are claimed to be suitable for use with polymers that can be blended with other polymers. JEFFAMINE® monoamines based on polyethylene glycol, reportedly used in the formulation of emulsifiers and corrosion inhibitors, include M-1000 (MW 1000 and AHEW 489 g / equivalent), M-2070 (MW 2000 and AHEW 1040 g / equivalent), M-2095 (MW 2000 and AHEW 1120 g / equivalent), and M-3085 (MW 3000 and AHEW 1520 g / equivalent). Some of these monoamines are reportedly used in epoxy resins, pressure-sensitive adhesives, and the like.

[0075] According to one embodiment, the hydrophilic polyetheramine is a polyether monoamine having one of formula (22) or formula (23): Equation (22) Where R is hydrogen or methyl, and a and b are independent integers from about 1 to about 150; or Equation (23) Where Y is hydrogen or methyl, Z is an alkyl group from 1 to 40 carbon atoms, or an alkylphenol group from 1 to 40 carbon atoms, and w is an integer from about 1 to about 100.

[0076] In another embodiment, the hydrophilic polyetheramine is a polyether monoamine having one of formulas (15) or (16): Equation (15) or, Equation (16) In one embodiment, the mono-polyetheramine of the present invention having a PPG backbone is represented by formula (24): Equation (24) Where x is an integer from 1 to 200, and Z is an integer from 1 to 85, or x+z is approximately 3.6.

[0077] Commercially available polyether monoamines include the JEFFAMINE® M-series and XTJ-series amines, including but not limited to JEFFAMINE® M-600, M-1000, M-2005, M-2070, XTJ-435 and XTJ-436 amines available from Huntsman Corporation.

[0078] In one embodiment, the polyether monoamine has a molecular weight (Mw) in the range of 100 to 5000, preferably from 150 to 3500, and most preferably from 170 to 3000.

[0079] diamine Another type of polyetheramine is called polyether diamine, which is supplied by Huntsman Corporation under the trademark JEFFAMINE® D-series diamines. These diamines have various backbones based on polypropylene glycol, polyethylene glycol and mixtures thereof, as well as highly reactive diamines.

[0080] Examples of JEFFAMINE® D-series diamines based on polypropylene glycol and exhibiting low color and miscibility with a wide range of solvents include JEFFAMINE® D-230 (MW 230 and AHEW 60 g / equivalent), D-400 (MW 430 and AHEW 115 g / equivalent), D-2000 (MW 200 and AHEW 514 g / equivalent), D2010 (MW 2000 and AHEW ~514 g / equivalent), and D-4000 (MW 4000 and AHEW 1000 g / equivalent). These polyether diamines are claimed to be used in anti-collision coatings, hot melt adhesives, blends with polyurethane, polyurea, and polyamide adhesives, and the like.

[0081] Examples of JEFFAMINE® ED-series diamines, primarily based on the polyethylene glycol backbone, are said to impart complete water solubility and miscibility with solvents, and are mainly used to impart hydrophilicity to polymers and additives. These include: JEFFAMINE® ED-600 (MW 600 and AHEW 132 g / equivalent), ED-900 (MW 900 and AHEW 250 g / equivalent), and ED-2003 (MW 2000 and AHEW 575 g / equivalent). These polyether diamines are claimed to be used in epoxy resins, polyamide blends, hydrogel preparation, coatings, as antistatic agents, for treating textiles, and the like.

[0082] One example of JEFFAMINE® EDR, a highly reactive diamine primarily used in fast-curing adhesives and polyamide-modified products, is JEFFAMINE® EDR-148 (MW 148 with AHEW 37 g / equivalent), also available from Huntsman. Huntsman also manufactures polyetheramines based on [poly(tetramethylene ether glycol)] / (propylene glycol) copolymers or primarily composed of a [poly(tetramethylene ether glycol)] (PTMEG) backbone. Another example of JEFFAMINE® EDR is JEFFAMINE® THF-100 (AHEW 260 g / equivalent), which is claimed to improve the flexibility and adhesive-peel strength of epoxy resin formulations, as well as improve flexibility and low-temperature properties when used with polyamides.

[0083] In another embodiment, the hydrophilic polyetheramine is a polyether diamine having one of formulas (17), (18), or (19): Equation (17) Where c is an integer from approximately 2 to approximately 100, and preferably c is an integer from approximately 2 to approximately 40; or Equation (18) Where e is an integer from 2 to approximately 40, and d and f are independent integers from approximately 1 to approximately 10; or Equation (19) Where g is an integer from approximately 2 to approximately 3.

[0084] In one embodiment, preferred and useful polyetheramine compounds are polyetheramines, including non-limiting examples of JEFFAMINE® D-230 and JEFFAMINE® D-400, available from Huntsman Corporation, Woodland, Texas. These polyetheramines based on the polypropylene glycol (PPG) backbone are represented by formula (25): Equation (25) For JEFFAMINE® D-230, x is 2.5, and for JEFFAMINE® D-400, x is 6.1.

[0085] In one implementation, the polyetheramine is based on the polypropylene glycol (PPG) backbone and is represented by formula (26): Equation (26) The specific polyetheramine available from Huntsman Petrochemicals LLC in Woodland, Texas is JEFFAMINE® ED-600, where y is 9 and x+z≈3.6.

[0086] Commercially available polyether diamines include JEFFAMINE® D, ED and EDR amines, including but not limited to JEFFAMINE® D-200, D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148 and EDR-176 amines available from Huntsman Corporation.

[0087] In one embodiment, the polyether diamine has a molecular weight (Mw) in the range of 100 to 5000, preferably from 150 to 3000, and most preferably from 170 to 2500.

[0088] Triamine Another type of polyetheramine is known as polyether triamine, supplied by Huntsman Corporation under the trademark JEFFAMINE®, based on the polypropylene glycol backbone, in the T-series. Examples of JEFFAMINE® T-series triamines include JEFFAMINE® T-403 (MW 440 and AHEW 81 g / equivalent) and T-5000 (MW 5000 and AHEW 952 g / equivalent), which are claimed to be used in epoxy resins, for miscibility in solvents, for improving the strength and flexibility of polymers, as surfactants or corrosion inhibitors, and the like.

[0089] In yet another embodiment, the hydrophilic polyetheramine is a polyethertriamine having formula (20): Equation (20) Where R1 is hydrogen, methyl or ethyl, n is an integer of 0 or 1, and h, i, and j are independent integers from about 1 to about 100.

[0090] In one embodiment, the polyetheramine is a triamine based on a trifunctional polypropylene glycol (PPG) backbone, represented by formula (28): Equation (28) The specific polyetheramine available from Huntsman Petrochemical LLC in Woodland, Texas is Jeffamine T-403, with x+y+z≈5 or 6.

[0091] Commercially available triamines include the JEFFAMINE® T-series amines, including but not limited to JEFFAMINE® T-403, T-3000 and T-5000 amines available from Hunterman.

[0092] In yet another embodiment, the hydrophilic polyetheramine is a polyethertetraamine having formula (21): Equation (21) Each R2 is independently hydrogen, methyl, or ethyl, each R3 is a C1-C5 alkyl group, and each M is independently an integer from about 2 to about 50.

[0093] In one embodiment, the polyether triamine has a molecular weight (Mw) ranging from 150 to 5000, preferably from 200 to 3500, and most preferably from 200 to 3000.

[0094] Other polyether amines available from Huntsman Corporation for generating the polyisobutylene polyether alcohol amine compounds of this invention include: JEFFAMINE® SD-2001 (a difunctional secondary amine derived from JEFFAMINE® D-2000) (AHEW 1000 g / equivalent), reportedly used in resins to provide better reaction control and curing speed in applications such as polyurea spray coatings; and D-205 (AHEW similar to JEFFAMINE® D-230, but a more hindered primary amine) (AHEW 58 g / equivalent) for slower-reacting epoxy resins. Additionally, Huntsman Corporation manufactures JEFFAMINE® RFD-270 amine (AHEW 67 g / equivalent) with both rigid (cycloaliphatic) and flexible (polyether amine) segments in the same molecule, reportedly used in coatings, adhesives, and composites.

[0095] In yet another embodiment, the hydrophilic polyetheramine is a multifunctional polyetheramine. The multifunctional polyetheramine disclosed herein may be a polyether, di-, tri-, or tetra-amine, such as those described herein and in U.S. Patent Publication No. US 2018 / 0023020A1, published January 25, 2018, to Huntsman Petrochemicals, LLC, Woodland, Texas, which is incorporated herein by reference in its entirety, and especially for the purpose of disclosing the hydrophilic polyetheramine described therein.

[0096] In addition, several other grades of polyetheramines are commercially available from Clariant International AG in Switzerland. For example, Genamine T01 / 5000 is a triamine based on propoxylated ethylene glycol, terminal with primary amine groups, and with an average molecular weight of 5000 to 6000 g / mol; Genamine M41 / 2000 is a random copolymer of ethylene oxide and propylene oxide terminal with primary amine groups; and Genamine D01 / 2000 is a high molecular weight macromonomer with two reactive amine groups. BASF Ludwigshafen in Germany also supplies commercial-grade polyetheramines, such as polyetheramine D 400, polyetheramine D-2000, Baxxodur EC310, Baxxodur EC 130, and Baxxodur EC303. Several Chinese commercial suppliers of polyetheramines exist, such as Yangzhou Chenhua New Materials Co., Ltd., Qingdao Airo Surfactants Co., Ltd., and Wuxi Acrylic Technology Co., Ltd.

[0097] According to the present invention, the non-exclusive, exemplary list of other amine compounds includes polyetheramines and may be amine-terminated polyethers, such as combinations of polyethylene oxide (PEO), polypropylene oxide (PPO), or PEO / PPO copolymers. For example, some commercial polyethers include: polyethylene glycol bis(3-aminopropyl ether), polyethylene glycol bis(2-aminopropyl ether), polyethylene glycol bis(2-aminopropyl ether), polyethylene glycol bis(2-aminopropyl ether), polyethylene glycol bis(2-aminopropyl ether), polyethylene glycol-block polyethylene glycol-block polyethylene glycol bis(2-aminopropyl ether) (3.5:8.5, PO:EO), polyethylene glycol-block polyethylene glycol-block polyethylene glycol bis(2-aminopropyl ether) (3.5:15.5, PO:EO), polyethylene glycol-block polyethylene glycol-block polyethylene glycol bis(2-aminopropyl ether) (3.5:40.5, PO:EO), glycerol bis(polypropylene glycol), amine-terminated ether poly(tetrahydrofuran), bis(3-aminopropyl) terminal, and the like.

[0098] In one embodiment, the molar ratio of polyetheramine to polyisobutylene epoxide is less than 1:1, preferably less than 0.9:1, more preferably 0.8:1, and 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 polyetheramine and isobutylene epoxide is in the range of less than 1:1 to 0.2:1, preferably from 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, and even more preferably from 0.6:1 to 0.3:1, and most preferably from 0.5:1 to 0.2:1.

[0099] In another embodiment, the molar ratio of polyetheramine to polyisobutylene epoxide is such that the polyisobutylene epoxide used is in slight to slight excess. In another embodiment, a preferred molar ratio of polyetheramine to polyisobutylene epoxide is such that at least two moles of polyisobutylene epoxide are used for every mole of polyetheramine used.

[0100] The process of production Generally, the process for generating the polyisobutylene polyether amine compound of the present invention is by contacting polyisobutylene epoxide, hydrophilic polyether amine, diluent, proton solvent mixture, and optionally catalyst in a reaction vessel at pressure and temperature sufficient to form the compound of the present invention.

[0101] In one embodiment, the polyisobutylene polyether amine compound of the present invention is produced via a process comprising the following steps: (i) mixing polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) optionally introducing a diluent into the reaction vessel with or without a catalyst; (iii) optionally adding a protic solvent to the reaction vessel; (iv) heating the reaction vessel under pressure for a period of time; (v) optionally removing the diluent; and (vi) recovering the polyisobutylene polyether amine compound.

[0102] In another embodiment, the process of the present invention is directed to a process for generating a polyisobutylene polyether amine compound, the process comprising the steps of: (i) mixing a polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) optionally introducing a diluent into the reaction vessel with or without a catalyst; (iii) optionally adding a protic solvent; (iv) heating the reaction vessel under pressure for a period of time; (v) optionally removing the diluent; and (vi) recovering the polyisobutylene polyether amine compound.

[0103] In another embodiment, the process of the present invention is aimed at generating a polyisobutylene polyetheramine compound by reacting a hydrophilic polyetheramine with a polyisobutylene epoxide, preferably in a molar ratio of about 1:1 to the hydrophilic polyetheramine and the polyisobutylene epoxide. In yet another embodiment, the hydrophilic polyetheramine is a product produced by alkylating a mono-, di-, tri-, tetra-, or polyfunctional alcohol or alkylphenol with an alkylene oxide to form an alkylene oxide adduct, followed by catalytic amination of the alkylene oxide adduct in the presence of hydrogen and ammonia to form a polyetheramine.

[0104] The reaction for producing PIB-PEAA often produces a PIB-PEAA composition, wherein the main component of the composition, i.e., more than 50 mol%, preferably more than 60 mol%, more preferably higher than 70 mol%, and even more preferably higher than 80 mol%, and most preferably more than 90 mol%, is PIB-PEAA. Minor components present in the composition may include isomers of polyetheramines, unreacted polyisobutylene epoxides, and byproducts from the isobutylene-initiated epoxidation reaction, such as mixtures of alcohols, aldehydes, and unreacted polyisobutylene, and very small amounts (if detectable) of monosubstituted polyisobutylamines, which constitute less than 2 mol% of the PIB-PEAA composition, typically less than 1 mol% to 0 or undetectable.

[0105] diluent Due to the high viscosity of polyisobutylene epoxide, it is desirable that the amination reaction be carried out in the presence of at least one hydrocarbon diluent. It is believed that when the viscosity is too high, reactive sites are difficult to access, and the desired reactants are difficult to diffuse to the reactive sites.

[0106] The desired diluent should be stable and non-reactive to the reactants and the resulting end product (PIB-PEAA). In one embodiment, at least one diluent is selected from benzene, toluene, xylene; saturated aliphatic hydrocarbons such as pentane, hexane, heptane; paraffinic, cycloalkanes, aromatic base oils, for example known from Group I, II, III, IV, or V, including polyalphaolefins or any other compound that affects the viscosity of the reaction.

[0107] In a preferred embodiment, at least one diluent may be used in the reaction between polyisobutylene epoxide and hydrophilic polyetheramine to improve (in addition to) the solubility and miscibility in the process. In one embodiment, the at least one diluent is selected from benzene, toluene, xylene; saturated aliphatic hydrocarbons such as pentane, hexane, heptane; paraffinic, cycloalkanes, aromatic base oils, for example known from Group I, II, III, IV or V, including polyalphaolefins or any other compound that affects the viscosity of the reaction.

[0108] The best diluents are those that are easily removed from the final products (toluene, heptane, etc.) or those that remain in the final mixture (i.e., base oil or PAO).

[0109] catalyst Optionally, a catalyst may be used in the process of the present invention to accelerate the reaction rate and improve the overall conversion rate of the PIB-PEAA product to the 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 such as aluminum trichloroethylene, boron trifluoroethylene, titanium tetrachloroethylene, and ferric chloride, used alone or as a base adduct such as BF3:ether, BF3:alcohol, or solid catalysts containing both Lewis acid and Brønsted acid moieties, such as silica, silica-alumina, and organic acids and water, such as acetic acid and water.

[0110] In another embodiment, optionally, a Lewis acid or Brønsted acid catalyst may be used, selected to form one or more of aluminum trichlorochloro, boron trifluoro, titanium tetrachloro, and ferric chloride; BF3: ether, BF3: alcohol; or a solid catalyst containing Lewis acid and Brønsted acid moieties, such as silica, silica-alumina, or organic acid and water.

[0111] Based on the total weight of the polyolefin epoxide, the amount of catalyst is typically from about 0.05 to about 10 wt%, preferably from about 0.1 to about 10 wt%. The optimal catalyst is a Lewis acid such as boron trifluoride.

[0112] proton solvent In practice, the catalyst is used in combination with or alone with a protic solvent. In another embodiment, at least one protic solvent is used in the reaction between polyisobutylene epoxide, polyetheramine, and diluent, with or without a catalyst. In one embodiment, the at least one protic solvent is preferably at least one organic hydroxyl compound, preferably an alcohol or water, with the most preferred alcohol being methanol or ethanol. The amount of protic solvent used is typically less than 1% by weight, based on the weight of the polyisobutylene epoxide.

[0113] In another preferred embodiment, at least one proton solvent is used in the reaction between polyisobutylene epoxide, polyetheramine, and a proton solvent, with or without a catalyst. In one embodiment, the at least one proton solvent is preferably at least one organic hydroxyl compound, preferably an alcohol or water, with the most preferred alcohol being methanol or ethanol. It is believed that when a catalyst is used in combination with a proton solvent, the proton solvent acts as an initiator of the reaction.

[0114] Reactor and conditions Reaction conditions may vary depending on the type and configuration of the reactor, as is known to those skilled in the art. In one embodiment, a batch or continuous process is used to produce PIB-PEAA, wherein in a reactor, preferably jacketed, the reactor is heated and stirred to a specific temperature and pressure, PIBEP is introduced into the reactor in the presence of a diluent (if used), followed by the introduction of a polyetheramine along with a catalyst and optionally a protic solvent. In one embodiment, one or more of the following steps may be required: removal of the diluent, neutralization, and removal of the catalyst, filtration, or optionally washing of 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 yet another embodiment, the polyetheramine is introduced into the reactor in stages during the reaction.

[0115] The temperatures described above are typically below the depolymerization temperature of polyisobutylene epoxide. This non-limiting reaction temperature generally ranges from about 60°C to about 260°C, more generally 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 catalyst used, and the reaction procedure, the temperature can be even lower.

[0116] 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 more 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.

[0117] Polyisobutylene polyether alcoholamine compounds and compositions In one embodiment, the novel compound or composition is a mono-polyisobutylene polyether alcoholamine (referred to herein as mPIB-PEAA), represented by the following general formula (1): Equation (1) Where x is an integer from 1 to about 200, preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is CH3, and z is an integer from 1 to about 100, preferably from about 1 to 75, and most preferably from 2 to 50, and Y' is an alkyl group having 1 to 10 carbon atoms, preferably CH3 or an amino group such as (-NH2), and most preferably in all embodiments of the above formula (1), Y' is an amino group (-NH2). In one embodiment of the above general formula (1), x is an integer from 75 to 125, preferably x is 100, and z is an integer from 2 to 35, and Y' is an amino group (-NH2). In another embodiment of the above general formula (1), x is an integer from 35 to 75, preferably x is 50, and z is an integer from 2 to 10, and Y' is an amino group (-NH2). In yet another embodiment of the above general formula (1), x is an integer from 90 to 110, z is an integer from 2 to 35, and Y' is an amino group (-NH2). In yet another embodiment of the above general formula (1), x is an integer from 40 to 60, z is an integer from 2 to 10, and Y' is an amino group (-NH2).

[0118] In one embodiment, the novel compound or composition is a bis-polyisobutylene polyether alcoholamine (referred to herein as bPIB-PEAA), represented by the following general formula (4): Equation (4) Where x and x' are the same or different, preferably the same, and are independent integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, most preferably R is CH3, and z is an integer from 1 to about 100, preferably from about 1 to 75, and most preferably from about 2 to 50. In one embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 75 to 125, more preferably x and x' is 100, and z is an integer from 2 to 35. In another embodiment of the above general formula (4), x and x' is 50, and z is an integer from 2 to 10. In yet another embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 90 to 110, and z is an integer from 2 to 35. In yet another embodiment of the above general formula (4), x and x' are the same or different, preferably the same, and are independent integers from 40 to 60, and z is an integer from 2 to 10.

[0119] In yet another embodiment, the bPIB-PEAA compound of the present invention, generated from a polyether diamine having a PPG backbone, is represented by formula (27): Equation (27) Where x and x' are integers from 1 to 200, and z is an integer from 1 to 85, or x+x'+z is 5 or 6.

[0120] In one embodiment, the novel compound or composition is a para-polyisobutylene polyether alcoholamine (referred to herein as tPIB-PEAA), represented by the following general formula (7): Equation (7) Wherein x, x' and x'' are the same or different, preferably the same, and are independent integers from 1 to 200, more preferably from 1 to about 150, and most preferably from 1 to 100, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is an ethyl group, n is an integer from 1 to 20, and z, z' and z'' are the same or different, preferably the same, and are independent integers from 5 to 100, more preferably from a lower limit of 5 to 6, to an upper limit of about 90, and most preferably from 5 to 6 to 85.

[0121] In another embodiment, the PIB-PEAA composition comprises the above-mentioned PIB-PEAA compound in a percentage of more than 50 mol% based on the PIB-PEAA composition, more preferably more than 60 mol%, even more preferably more than 70%, and most preferably more than 80 mol%.

[0122] In another embodiment, the reaction for producing PIB-PEAA typically produces a PIB-PEAA composition, wherein the main component of the composition, i.e., more than 55 mol%, preferably more than 65 mol%, more preferably more than 75 mol%, and even more preferably more than 85 mol%, but even more preferably more than 95 mol%, is PIB-PEAA.

[0123] The small amount of components present in the composition may include isomers of polyetheramines, unreacted polyisobutylene epoxides, and byproducts of the initiation epoxidation reaction of isobutylene, such as mixtures of alcohols, aldehydes, and unreacted polyisobutylene.

[0124] In one embodiment, the PIB-PEAA composition comprises: (i) 5 to 98 mol% of one or more polyisobutylene polyether 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%.

[0125] In one embodiment, the PIB-PEAA composition comprises: (i) 5 mol% to 98 mol% of PIB-PEAA, preferably more than 60 mol%, even more than 70 mol%, and even more than 80 mol%, particularly more 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% of i, ii, iii and iv is up to 100 mol.

[0126] In one embodiment, the PIB-PEAA 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.

[0127] In another embodiment, the PIB-PEAA 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.

[0128] In another aspect, the PIB-PEAA composition has a viscosity at 100°C using ASTM D-455 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.

[0129] The PIB-PEAA composition has one or more of the above embodiments or aspects in any combination of Mn, PDI and / or viscosity.

[0130] In another embodiment, the PIB-PEAA 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.

[0131] In another embodiment, the PIB-PEAA composition of the present invention, particularly when type 1 and / or type 2 is the main polyisobutylene epoxide used to form the PIB-PEAA compound, contains no more than 10 ppm of fluorine or chlorine, preferably less than 5 ppm, more preferably less than 2 ppm, and most preferably less than 1 ppm down to 0.

[0132] Uses of PIB-PEAA PIB-PEAA compounds and compositions can be used as emulsifiers, stabilizers, corrosion inhibitors and dispersants in various lubricant, fuel or aqueous fluid formulations.

[0133] In particular, PIB-PEAA compounds and compositions can be used as dispersant additives in fuels. They can also be used to improve the strength and durability of products such as adhesives, sealants, oils, and greases.

[0134] When used in lubricating oils, PIB-PEAA compounds and compositions can be used as dispersant additives. Lubricating oils used with the PIB-PEAA compounds and compositions of this 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 this 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.

[0135] Lubricating oil concentrates used in conjunction with the disclosed PIB-PEAA compounds and compositions are also included within the scope of this invention. The concentrates of this invention typically comprise from about 90 to 50 weight percent of an oil with lubricating viscosity and from about 10 to 50 weight percent of the PIB-PEAA compounds and compositions of this invention. The concentrates generally contain sufficient diluent to facilitate handling during transport and storage. Suitable diluents for the concentrates include any inert diluent, preferably an oil with lubricating viscosity, so that the concentrate can be easily mixed with a lubricating oil to prepare a lubricating oil composition.

[0136] Other additives that may be present in a formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal passivators, pour point inhibitors, antioxidants, and a variety of other well-known additives, as well as other uses including in adhesives, sealants, greases, emulsifiers, paints and coatings, and polymer formulations.

[0137] The above-mentioned lubricating composition may further include ashless dispersants, borated ashless dispersants, non-borated ashless dispersants, detergents, namely calcium salicylate, calcium sulfonate, magnesium phenolate, and calcium phenolate, or other typical components well known in the relevant art.

[0138] Formulations for use as dispersants, lubricants, greases, corrosion inhibitors, gear oils, and base oils have been found in US 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, US9,282,736, US6,844,300, US9,783,630, US7,998,340, US7,820,600, US8,163,682, US6,551,967, US6 US1001,780, US6,686,321, US5,942,476, US5,360,564, US4,402,841, US3,873,455 and US3,850,822, US10,494,584, US11,732,208, US2023 / 0323234AA, US10,793,802,1 US10,781,411, US10,611,981, US10,358,616, US11,685,872, 11,059,924, US10,829,712, 11,136,523, US10,781,393, US10,640,724, 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, especially those components that function similarly to PIBSI or other polymers that can be used in lubricant formulations.

[0139] Non-limiting examples of potential uses of PIB-PEAA 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, and US7,044,980. 8. The explosive emulsion formulations discussed in US 5,936,194, US 6,929,707, US 6,939,420, US 6,800,154, US 6,951,589, US 5527,491, and US 4,844,756 are all incorporated herein by reference in their entirety, wherein PIB-PEAA is generally used in place of or in combination with PIBSA or PIBSI in various explosive compositions. In another respect, the explosive composition is prepared according to any of the methods described in the aforementioned US patents.

[0140] In one embodiment, the PIB-PEAA compound and composition are used in explosives and downhole oil applications such as hydraulic fracturing. In another embodiment, the PIB-PEAA compound and composition, or mixtures thereof, can be used as friction modifiers for belts and the like.

[0141] In yet another embodiment, the PIB-PEAA compound and compositions and mixtures thereof can be used as a dispersing solvent or dispersant. Non-limiting examples of uses for dispersing solvents include: breaking up oil into smaller droplets in water to facilitate bacterial metabolism; adding paint liquid during pigment dispersion to reduce the particle size of pigments and fillers; stabilizing pigments, which typically contain pigments with an affinity for absorbing pigment particles and compatibilizers compatible with resin solvent matrices; and in cleaning agents, surface cleaners, paints and coatings, textiles, and personal care applications.

[0142] In yet another embodiment, the PIB-PEAA compound and composition are intended for use as fuel additives. Currently, polyetheramines are primarily used as fuel additives in their unmodified form; however, the PIB-modified PIB-PEAA of this invention provides improved solubility in fuels, and the ashless combustion of PIB-PEAA also improves performance. It is believed that the alcohol functionality of the PIB-PEAA of this invention leads to hydrogen bonding to water in the fuel, providing significant benefits.

[0143] In one aspect of the invention, the PIB-PEAA compound and composition can be used as an emulsion stabilizer, especially since the PIB-PEAA of the present invention is amphiphilic, possessing both hydrophilic and hydrophobic properties.

[0144] In another aspect of the invention, PIB-PEAA compounds and compositions can be used as surfactants for cleaning, wetting, dispersing, foaming and defoaming properties, for example in detergents, fabric softeners, machine oils, soaps, paints, adhesives, inks and similar applications.

[0145] In yet another embodiment, the PIB-PEAA compound and composition are used in adhesive mixtures and reactive adhesives. In mixtures, the PIB portion of the PIB-PEAA of the present invention is believed to provide adhesive properties and compatibility with polar polymers such as acrylates. In reactive adhesives, the primary and secondary amines in the PIB-PEAA of the present invention are believed to react into a matrix, such as an epoxy resin adhesive. Furthermore, the functionality of the PIB is believed to modify hardness or additional adhesion.

[0146] In yet another embodiment, the PIB-PEAA compound and composition are intended for use in lithium-ion batteries. In combination with ethylene oxide and / or propylene oxide, PIB-PEAA is believed to improve rigidity and hydrophobicity by altering surface properties, resulting in improved ion transport and increased specific capacity.

[0147] The present invention also relates to a method for reducing friction between contact surfaces of a mechanical device, the method further comprising lubricating the surface with the lubricating composition described above. In one aspect, the mechanical device described above is a spark-ignition or compression-ignition internal combustion engine, including mechanical devices used in any application in which a lubricant is used, such as automobiles, trucks, tractors, boats, vehicles, trains, windmills, airplanes, or even lawn equipment.

[0148] Example The examples below illustrate preferred embodiments of the invention. Those skilled in the art will understand that the techniques disclosed in the examples represent techniques that the inventors have found to function well in the implementation of the invention, and therefore can be considered as preferred modes of implementation. However, based on the present 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 similar or identical results can still be obtained.

[0149] Test Analysis and Solution The ethylene oxide number of polyisobutylene epoxide (PIB epoxide or PIBEP) is determined using ASTM Test Method D 1652. The quantitative determination of polyisobutylene polyetheramine is based on the stoichiometry of the reagents used, along with... 1 H and 13 Both C and NMR. (By means) 1H NMR is used to determine the amount of unreacted polyisobutylene epoxide, in addition to any additional "free" unsubstituted PIB moiety. This method also quantifies the rearrangement of polyisobutylene epoxide into polyisobutylene vinyl alcohol without reaction with the polyetheramine. The presence of any unreacted primary polyetheramine can be determined by the presence of the CH group and the nearest CH3 group adjacent to the primary polyetheramine. 13 The C NMR peaks determine this. Any unreacted primary polyetheramines may indicate the presence of monoisobutylene polyetheramines or amines that did not participate in the reaction.

[0150] The products are as follows: 1 H NMR and 13 C10 NMR characterization: NMR spectra were recorded at ambient temperature on a Bruker 600 MHz Neo Digital NMR Spectrometer. All chemical shifts were referenced to tetramethylsilane (TMS) as an external standard and CDCl3 as a reference solvent. δ H 7.24 ppm and δ C Residual proton and carbon atom signals of 77.0 ppm. Samples were prepared at 60–100 mg in 0.5 mL of CDCl3 (Sigma Aldrich). Spectra were analyzed by Fourier transform and phase and baseline corrections were performed using the Bruker TopSpin (version 4.0.7) automated program. All spectra were manually integrated and normalized to selected peaks for the desired peak integration. The integration region was at least 25 times the peak linewidth (Hz) in both directions, and the peak integration data were the average of three separate manual measurements to minimize experimental uncertainty.

[0151] 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, 100 g of PIBEP with a number-average molecular weight of 450 and an ethylene oxide oxygen value of 1.88% was mixed with 0.113 mol of Jeffamine D-400 (Huntsman, Woodland, Texas) (molar ratio 1:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride methanol solution, and 26.3 g of toluene, and heated to 220 °C for 24 hours under a nitrogen atmosphere. The reaction pressure was initially atmospheric pressure, and pressure was introduced from the product as the reaction was heated. Toluene was removed from the product under vacuum.

[0152] PIBEP is almost completely converted (in) 1 No epoxide was detected in the 1H NMR; however, PIBEP was the limiting reagent for the reaction. Approximately 45% of the primary amine remained unreacted, and the reaction produced mainly mono-polyisobutylene polyether alcohol amine products, such as those obtained from... 13 The peaks of CH and CH3 (adjacent to the primary amine) appearing at 46.8 / 46.5 and 19.7 ppm in the C NMR are explained. Based on the polystyrene standard, the Mn of the mono-polyisobutylene polyether alcohol amine product was found to be 1028.

[0153] Example 2 Repeat Example 1 above with the following exception: A methanol solution containing 14% boron trifluoride was not used. The temperature was increased and maintained at 220°C throughout the reaction. Based on polystyrene standards, the final mono-polyisobutylene polyetheramine product obtained had a Mn of 944.

[0154] 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 1.88% was mixed with 0.113 mol of Jeffamine D-400 (molar ratio 1:1 (polyetheramine:PIBEP)) and 26.2 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0155] PIBEP is almost completely converted (in) 1 No epoxide was detected in the 1H NMR; however, PIBEP was the limiting reagent for the reaction. Approximately 45% of the primary amine remained unreacted, and the reaction produced mainly mono-polyisobutylene polyetheramine products, such as those derived from... 13 The peaks of CH and CH3 (adjacent to the primary amine) appearing at 46.8 / 46.5 and 19.7 ppm in the C NMR are explained. Based on the polystyrene standard, the Mn of the mono-polyisobutylene polyetheramine product was found to be 944.

[0156] Example 3 Example 1 was repeated with the following exceptions: Polyetheramine mass = 24.99 g, PIBEP = 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.71 g of a 14% boron trifluoride methanol solution. 22.2 g of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 0.48:1, and based on polystyrene standards, the final bis-polyisobutylene polyetheramine product obtained had a Mn of 1087.

[0157] 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 1.88% was mixed with 0.058 mol of Jeffamine D-400 (molar ratio 0.48:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride catalyst methanol solution, and 22.2 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0158] Polyetheramine was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture and promote the reaction. The reaction produced mainly bis-polyisobutylene polyetheramine products, such as those derived from... 13 The absence of CH and CH3 (adjacent to the primary amine) peaks at 46.8 / 46.5 and 19.7 ppm in the C NMR indicates that the Mn of the bis-polyisobutylene polyetheramine product is 1087.

[0159] Example 4 Example 1 was repeated with the following exception: Jeffamine ED-600 polyether diamine, based primarily on a polyethylene oxide backbone, with a polyetheramine mass of 67.60 g and PIBEP of 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was a 0.71 g solution of 14% boron trifluoride in methanol. 29.7 g of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 1:1, and based on polystyrene standards, the final mono-polyisobutylene polyetheramine product obtained had a Mn of 1150.

[0160] 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 1.88% was mixed with 0.113 mol of Jeffamine D-600 (molar ratio 1:1 (polyetheramine:PIBEP)), 0.71 g of a methanol solution containing 14% boron trifluoride catalyst, and 29.7 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0161] PIBEP is almost completely converted (in) 1 No epoxide was detected in the 1H NMR; however, PIBEP was the limiting reagent for the reaction. Approximately 45% of the primary amine remained unreacted, and the reaction produced mainly mono-polyisobutylene polyetheramine products, such as those derived from... 13The peaks of CH and CH3 (adjacent to the primary amine) appearing at 46.8 / 46.5 and 19.7 ppm in the C NMR are explained. Based on the polystyrene standard, the Mn of the mono-polyisobutylene polyetheramine product was found to be 1150.

[0162] Examples 5 and 6 Example 4 was repeated with the following exceptions: the mass of polyetheramine was 32.45 g and PIBEP was 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.71 g of a 14% boron trifluoride methanol solution. 23.8 g of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 0.48:1. Based on polystyrene standards, the final bis-polyisobutylene polyetheramine products obtained in Examples 5 and 6 had Mn values ​​of 1139 and 1103, respectively.

[0163] 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 1.88% was mixed with 0.058 mol of Jeffamine D-600 (molar ratio 0.48:1 (polyetheramine:PIBEP)), 0.71 g of a methanol solution containing 14% boron trifluoride catalyst, and 23.8 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0164] Polyetheramine was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture and promote the reaction. The reaction produced mainly bis-polyisobutylene polyetheramine products, such as those derived from... 13 The absence of CH and CH3 (adjacent to the primary amine) peaks at 46.8 / 46.5 and 19.7 ppm in the C NMR indicates this. Based on the polystyrene standard, the Mn values ​​of the bis-polyisobutylene polyetheramine products in Examples 5 and 6 were found to be 1139 and 1103, respectively.

[0165] Example 7 Example 3 was repeated with the following exceptions: 100 grams of polyisobutylene epoxide (PIBEP) derived from PIB 595, such as that obtained from TPC Group in Houston, Texas, had a number average molecular weight (Mn) of 950 and an ethylene oxide oxygen value of 0.88%. The mass of the polyetheramine was 11.35 grams. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.71 grams of 14% boron trifluoride in a methanol solution. 37.5 grams of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 0.48:1, and based on polystyrene standards, the final bis-polyisobutylene polyetheramine product obtained had an Mn of 1930.

[0166] 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 0.88% was mixed with 0.058 mol of Jeffamine D-400 (molar ratio 0.48:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride catalyst methanol solution, and 37.5 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0167] Polyetheramine was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture and promote the reaction. The reaction produced mainly bis-polyisobutylene polyetheramine products, such as those derived from... 13 The absence of CH and CH3 (adjacent to the primary amine) peaks at 46.8 / 46.5 and 19.7 ppm in the C NMR indicates that the Mn of the bis-polyisobutylene polyetheramine product is 1930.

[0168] Example 8 Example 3 was repeated with the following exceptions: 100 grams of polyisobutylene epoxide (PIBEP) derived from PIB 5230, such as that obtained from TPC Group in Houston, Texas, had a number average molecular weight (Mn) of 2300 and an ethylene oxide oxygen value of 0.40%. The mass of the polyetheramine was 5.31 grams. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.71 grams of a 14% boron trifluoride methanol solution. 70.7 grams of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 0.48:1, and based on polystyrene standards, the final bis-polyisobutylene polyetheramine product obtained had an Mn of 3997.

[0169] In a 300 mL stainless steel stirred pressure vessel, 100 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 2300 and an ethylene oxide oxygen value of 0.40% was mixed with 0.058 mol of Jeffamine D-400 (molar ratio 0.48:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride catalyst methanol solution, and 70.7 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0170] Polyetheramine was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture and promote the reaction. The reaction produced mainly bis-polyisobutylene polyetheramine products, such as those derived from... 13The absence of CH and CH3 (adjacent to the primary amine) peaks at 46.8 / 46.5 and 19.7 ppm in the C NMR indicates this. Based on the polystyrene standard, the Mn of the bis-polyisobutylene polyetheramine product was found to be 3997.

[0171] Example 9 Example 1 was repeated with the following exception: Jeffamine T-403 polyoxypropylene triamine, a trifunctional primary amine, with a polyetheramine mass of 41.75 g and PIBEP of 80 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was a 0.71 g solution of 14% boron trifluoride in methanol. 40.8 g of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 1:1, and based on polystyrene standards, the final mono-polyisobutylene polyetheramine product obtained had a Mn of 863.

[0172] In a 300 mL stainless steel stirred pressure vessel, 80 g of polyisobutylene epoxide (PIBEP) with a number-average molecular weight (Mn) of 450 and an ethylene oxide oxygen value of 1.88% was mixed with 0.095 mol of Jeffamine T-403 (molar ratio 1:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride catalyst methanol solution, and 40.8 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0173] PIBEP is almost completely converted (in) 1 No epoxide was detected in the 1H NMR; however, PIBEP was the limiting reagent for the reaction. Approximately 60% of the primary amine remained unreacted, and the reaction produced mainly mono-polyisobutylene polyetheramine products, such as those derived from... 13 The presence of CH and CH3 peaks (adjacent to the primary amine) at 46.9 / 46.4 and 19.7 ppm in the C NMR indicates that the Mn of the mono-polyisobutylene polyetheramine product is 863.

[0174] Example 10 Example 9 was repeated with the following exceptions: the mass of polyetheramine was 16.7 g and PIBEP was 100 g. The temperature was raised and maintained at 220°C throughout the reaction. The catalyst used was 0.71 g of a 14% boron trifluoride methanol solution. 63.5 g of toluene was used as a diluent. The polyetheramine:PIBEP molar ratio was 0.32:1, and based on polystyrene standards, the final tri-polyisobutylene polyetheramine product obtained had a Mn of 1121.

[0175] 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 1.88% was mixed with 0.058 mol of Jeffamine T-403 (molar ratio 0.48:1 (polyetheramine:PIBEP)), 0.71 g of a 14% boron trifluoride catalyst methanol solution, and 40.8 g of toluene. The reactants were heated to 220 °C for 24 hours under a nitrogen atmosphere. Toluene was removed from the product under vacuum.

[0176] Polyetheramine was the limiting agent in this slightly excess PIBEP reaction. Toluene was added to reduce the viscosity of the reaction mixture and promote the reaction. The reaction produced mainly para-isobutylene polyetheramine products, such as those derived from... 13 The absence of CH and CH3 (adjacent to the primary amine) peaks at 46.9 / 46.4 and 19.7 ppm in the C NMR indicates that the Mn of the tri-polyisobutylene polyetheramine product is 1121.

[0177] Table 1

[0178] Therefore, Table 1 shows that the compositions of the present invention, mPIB-PEAA, bPIB-PEAA and tPIB-PEAA, are produced in high yield using the process of the present invention with a preferred molar ratio of polyether amine to polyisobutylene epoxide (amine:PIB molar ratio), resulting in compositions and compounds with a wide range of viscosities and molecular weights.

[0179] Additional implementation schemes The following are other embodiments of the present invention.

[0180] Implementation Scheme 1. A polyisobutylene polyether alcohol amine compound.

[0181] Implementation Scheme 2. A mono-polyisobutylene polyether alcohol amine compound.

[0182] Implementation Scheme 3. A bis-polyisobutylene polyether alcohol amine compound.

[0183] Implementation Scheme 4. A para-polyisobutylene polyether alcohol amine compound.

[0184] Implementation Scheme 5. A tetra-polyisobutylene polyether alcohol amine compound.

[0185] Implementation Scheme 6. A mono-polyisobutylene polyether alcoholamine compound, represented by the following general formula (1):

[0186] Where x is an integer from 1 to about 200, R is H or an alkyl group having 1 to 10 carbon atoms, z is an integer from 1 to about 100, and Y' is an alkyl or amino group having 1 to 10 carbon atoms.

[0187] Implementation Scheme 7. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is an integer from 1 to about 100, R is CH3, and z is an integer from 2 to about 50, and Y' is an amino group (-NH2).

[0188] Implementation Scheme 8. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is an integer from 75 to 125 and z is an integer from 2 to 35, and Y' is an amino group (-NH2).

[0189] Implementation Scheme 9. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is 100 and z is an integer from 2 to 10, and Y' is an amine group (-NH2).

[0190] Implementation Scheme 10. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is an integer from 35 to 75, z is an integer from 2 to 10, and Y' is an amine group (-NH2).

[0191] Implementation Scheme 11. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is 50, z is an integer from 2 to 10, and Y' is an amino group (-NH2).

[0192] Implementation Scheme 12. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is an integer from 90 to 110, z is an integer from 2 to 10, and Y' is an amino group (-NH2).

[0193] Implementation Scheme 13. The mono-polyisobutylene polyether amine compound of Implementation Scheme 6, wherein x is an integer from 40 to 60, z is an integer from 2 to 10, and Y' is an amine group (-NH2).

[0194] Implementation Scheme 14. A bis-polyisobutylene polyether alcoholamine compound, represented by the following general formula (4):

[0195] Where x or x' are the same or different and are independent integers from 1 to about 200, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 1 to 100.

[0196] Implementation Scheme 15. The bis-polyisobutylene polyether alcohol amine compound of Implementation Scheme 14, wherein x or x' is an integer from 1 to about 100, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 50.

[0197] Implementation Scheme 16. The bis-polyisobutylene polyether alcohol amine compound of Implementation Scheme 14, wherein x or x' are the same or different and are independent integers from 75 to about 125, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 35.

[0198] Implementation Scheme 17. The bis-polyisobutylene polyether alcohol amine compound of Implementation Scheme 14, wherein x or x' is 50, R is CH3, and z is an integer from 2 to about 10.

[0199] Implementation Scheme 18. The bis-polyisobutylene polyether alcoholamine compound of Implementation Scheme 14, wherein x or x' are the same or different and are independent integers from 90 to about 110, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 35.

[0200] Implementation Scheme 19. The bis-polyisobutylene polyether alcohol amine compound of Implementation Scheme 14, wherein x or x' are the same or different and are independent integers from 40 to about 60, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 10.

[0201] Implementation Scheme 20. A para-polyisobutylene polyether alcoholamine compound, represented by the following general formula (7):

[0202] Where x, x' and x'' are the same or different and are independent integers from 1 to 200, R is H or an alkyl group having 1 to 10 carbon atoms, and z, z' and z'' are the same or different and are independent integers from 5 to 100.

[0203] Implementation Scheme 21. The para-polyisobutylene polyether amine compound of Implementation Scheme 20, wherein z, z' and z'' are the same or different and are independent integers in the range from 5 to 6 to 100.

[0204] Implementation Scheme 22. The para-polyisobutylene polyether amine compound of Implementation Scheme 20, wherein z, z' and z'' are the same or different and are independent integers in the range from 5 to 6 to 85.

[0205] Implementation Scheme 23. A polyisobutylene polyether alcoholamine compound, produced via a process comprising the following steps: (i) mixing a polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) optionally introducing a protonated solvent into the reaction vessel with or without a catalyst; (iii) adding a diluent to the reaction vessel; (iv) heating the reaction vessel under pressure for a period of time; (v) removing the diluent, or the diluent and the protonated solvent; and (vi) recovering the polyisobutylene polyether alcoholamine compound, wherein the hydrophilic polyether amine is selected from the group consisting of one or more of polyether monoamines, polyether diamines, polyether triamines, and polyether tetraamines.

[0206] Implementation Scheme 24. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the molar ratio of the polyether amine to the polyisobutylene epoxide is in the range from less than 1:1 to about 0.2:1.

[0207] Implementation Scheme 25. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the polyisobutylene epoxide comprises one or more of general formulas 10, 11 and 12.

[0208] Implementation Scheme 26. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the polyisobutylene epoxide is a type 3 polyisobutylene epoxide.

[0209] Implementation Scheme 27. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the number average molecular weight (Mn) of the polyisobutylene epoxide is in the range of 150 to 3000.

[0210] Implementation Scheme 28. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the ethylene oxide value of the polyisobutylene epoxide is in the range of 2% to 0.15%.

[0211] Implementation Scheme 29. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the reaction vessel is heated to a temperature in the range of about 60°C to about 260°C.

[0212] Implementation Scheme 30. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the compound has a number average molecular weight in the range of 170 to 2700.

[0213] Implementation Scheme 31. The polyisobutylene polyether alcoholamine compound produced by the process of Implementation Scheme 23, wherein the process produces: (i) 5 mol% to 98 mol% of the polyisobutylene polyether alcoholamine compound; (ii) up to 10 mol% of unreacted hydrophilic polyether alcoholamine; and (iii) up to 5 mol% of unreacted polyisobutylene epoxide, wherein the sum of the mol% of i, ii and iii is between 98 mol% and 100 mol%.

[0214] Implementation Scheme 32. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the compound is a mono-polyisobutylene polyether alcohol amine compound.

[0215] Implementation Scheme 33. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the compound is a bis-polyisobutylene polyether alcohol amine compound.

[0216] Implementation Scheme 34. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the compound is a para-polyisobutylene polyether alcohol amine compound.

[0217] Implementation Scheme 35. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the compound is a tetra-polyisobutylene polyether alcohol amine compound.

[0218] Implementation Scheme 36. The polyisobutylene polyether alcoholamine compound produced by the process of Implementation Scheme 23, wherein the polyisobutylene polyether alcoholamine composition comprises two or more of mono-polyisobutylene polyether alcoholamine compounds, bis-polyisobutylene polyether alcoholamine compounds, tri-polyisobutylene polyether alcoholamine compounds and tetra-polyisobutylene polyether alcoholamine compounds.

[0219] Implementation Scheme 37. The polyisobutylene polyether alcohol amine compound produced by the process of Implementation Scheme 23, wherein the polyisobutylene polyether alcohol amine 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.

[0220] Implementation Scheme 38. A process for generating a polyisobutylene polyether alcoholamine compound, the process comprising the steps of: (i) mixing a polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) introducing a protonated solvent into the reaction vessel with or without a catalyst; (iii) adding a diluent; (iv) heating the reaction vessel under pressure for a period of time; (v) removing the diluent and optionally the protonated solvent; and (vi) recovering the polyisobutylene polyether alcoholamine compound, wherein the hydrophilic polyether amine is selected from one or more of the group consisting of polyether monoamines, polyether diamines, polyether triamines, and polyether tetraamines.

[0221] Implementation Scheme 39. The process of Implementation Scheme 38, wherein the molar ratio of the polyetheramine to the polyisobutylene epoxide is in the range from less than 1:1 to about 0.2:1.

[0222] Implementation Scheme 40. The process of Implementation Scheme 38, wherein the polyisobutylene epoxide comprises one or more of formulas 10, 11 and 12.

[0223] Implementation Scheme 41. The process of Implementation Scheme 38, wherein the polyisobutylene epoxide is mainly type 3.

[0224] Implementation Scheme 42. The process of Implementation Scheme 38, wherein the polyisobutylene epoxide contains Mn from 150 to 5000 and ethylene oxide oxygen value from 2% to 0.15%.

[0225] Implementation Scheme 43. The process of Implementation Scheme 38, wherein the polyisobutylene epoxide contains Mn from 400 to 3000 and ethylene oxide oxygen value from 2% to 0.25%.

[0226] Implementation Scheme 44. The process of Implementation Scheme 38, wherein the polyisobutylene epoxide comprises epoxidized highly reactive polyisobutylene having an α-vinyl isobutylene isomer content between 60 mol% and 90 mol%.

[0227] Implementation Scheme 45. A polyisobutylene polyether alcoholamine produced via the process of Implementation Scheme 21, wherein the polyisobutylene polyether alcoholamine compound is used in, or as, a lubricating composition, an adhesive composition, a sealant composition, a grease composition, an emulsifier composition, a coating composition, a polymer composition, or a resin composition.

[0228] Implementation Scheme 46. A process for producing polyisobutylene polyether alcoholamine, comprising reacting a hydrophilic polyetheramine with a polyisobutylene epoxide at a molar ratio of about 1:1, wherein the hydrophilic polyetheramine is produced by alkylation of a mono-, di-, tri-, tetra-, or polyfunctional alcohol or alkylphenol with an alkyl oxide to form an alkyl oxide adduct, and then catalytically amination of the alkyl oxide adduct in the presence of hydrogen and ammonia to form the polyetheramine product.

[0229] Implementation Scheme 47. The process of Implementation Scheme 46, wherein the epoxide is selected from one or more of the group consisting of ethylene oxide, propylene oxide, or butane oxide.

[0230] Implementation Scheme 48. The process of Implementation Scheme 46, wherein the polyisobutylene polyether alcoholamine is a mono-polyisobutylene polyether alcoholamine.

[0231] Implementation Scheme 49. The process of Implementation Scheme 46, wherein the polyisobutylene polyether alcoholamine is bis-polyisobutylene polyether alcoholamine.

[0232] Implementation Scheme 50. The process of Implementation Scheme 46, wherein the polyisobutylene polyether alcoholamine is a para-polyisobutylene polyether alcoholamine.

[0233] This invention has been described with reference to specific embodiments for particular applications. Although selected embodiments have been detailed and described, it will be understood that various substitutions and modifications are possible. The process can potentially be extended to other chemical reactions, such as the direct reaction of polyisobutylene epoxide with alcohols or polyols, such as polyethylene oxide. Those skilled in the art and familiar with the teachings will recognize that various additional substitutions and changes are possible without departing from the spirit and scope of the invention and as defined by the following embodiments.

Claims

1. A polyisobutylene polyether alcoholamine compound.

2. The polyisobutylene polyether alcoholamine compound of claim 1, selected from the group consisting of mono-polyisobutylene polyether alcoholamine compounds, di-polyisobutylene polyether alcoholamine compounds, tri-polyisobutylene polyether alcoholamine compounds, and tetra-polyisobutylene polyether alcoholamine compounds.

3. The polyisobutylene polyether alcoholamine compound according to claim 2, characterized in that, The mono-polyisobutylene polyether alcoholamine compound is represented by the following general formula (1): ， Where x is an integer from 1 to 200, preferably from 1 to 100, and more preferably from 75 to 125, R is H or an alkyl group having 1 to 10 carbon atoms, preferably R is CH3, and z is an integer from 1 to 100, preferably from 2 to 50, and most preferably from 2 to 35, and Y' is an alkyl group or an amino group having 1 to 10 carbon atoms, preferably an amino group (-NH2).

4. The polyisobutylene polyether alcoholamine compound according to claim 3, characterized in that, The mono-polyisobutylene polyether amine compound is selected from the group consisting of general formula (1), wherein: a) x is 100 and z is an integer from 2 to 10, and Y' is an amino group (-NH2); (b) x is an integer from 35 to 75, z is an integer from 2 to 10, and Y' is an amino group (-NH2); c) x is 50, z is an integer from 2 to 10, and Y' is an amino group (-NH2); d) x is an integer from 90 to 110, z is an integer from 2 to 10, and Y' is an amino group (-NH2); and e) x is an integer from 40 to 60, z is an integer from 2 to 10, and Y' is an amino group (-NH2).

5. The polyisobutylene polyether alcoholamine compound according to claim 2, characterized in that, The bis-polyisobutylene polyether alcoholamine compound is represented by the following general formula (4): ， Where x or x' are the same or different and are independent integers from 1 to 200, preferably from 1 to 100, and more preferably from 75 to 125, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 1 to 100, preferably from 2 to 50, and more preferably from 2 to 35.

6. The polyisobutylene polyether alcoholamine compound according to claim 5, characterized in that, The bis-polyisobutylene polyether alcoholamine compound is selected from the group consisting of general formula (4), wherein: a) x or x' is 50, R is CH3, and z is an integer from 2 to about 10; b) x or x' is the same or different and is an integer independently from 90 to about 110, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 35; c) x or x' is the same or different and is an integer independently from 40 to about 60, R is an alkyl group having 1 to 10 carbon atoms, and z is an integer from 2 to about 10.

7. The polyisobutylene polyether alcoholamine compound according to claim 2, characterized in that, The tri-polyisobutylene polyether alcoholamine compound is represented by the following general formula (7): ， Wherein x, x' and x'' are the same or different and are independent integers from 1 to 200, R is H or an alkyl group having 1 to 10 carbon atoms, and z, z' and z'' are the same or different and are independent integers from 5 to 100, preferably in the range of 5 to 6 to 100, and most preferably in the range of 5 to 6 to 85.

8. A polyisobutylene polyether alcoholamine compound is produced via a process comprising the following steps: (i) mixing a polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) introducing a diluent into the reaction vessel with or without a catalyst; (iii) optionally adding a protic solvent to the reaction vessel; (iv) heating the reaction vessel under pressure for a period of time; (v) removing the diluent; and (vi) recovering the polyisobutylene polyether alcoholamine compound, wherein the hydrophilic polyether amine is selected from one or more of the group consisting of polyether monoamines, polyether diamines, polyether triamines and polyether tetraamines.

9. The polyisobutylene polyether alcoholamine compound produced by the process according to claim 8, characterized in that, The molar ratio of the polyetheramine to the polyisobutylene epoxide is in the range from less than 1:1 to about 0.2:

1.

10. The polyisobutylene polyether alcoholamine compound produced by the process according to claim 8, characterized in that, The polyisobutylene epoxide is one or more of type I, type II or type III polyisobutylene epoxides, preferably type III polyisobutylene epoxide or a combination of type I, type II or type III polyisobutylene epoxides, preferably has an ethylene oxide value in the range of 2% to 0.15%, more preferably has a Mn of 150 to 5000 and an ethylene oxide oxygen value of 2% to 0.15%, and most preferably has a Mn of 400 to 3000 and an ethylene oxide oxygen value of 2% to 0.25%.

11. The polyisobutylene polyether alcoholamine compound produced via this process according to at least one of claims 8 to 10, characterized in that, The process results in: (i) 5 mol% to 98 mol% of polyisobutylene polyether amine compound; (ii) up to 10 mol% of unreacted hydrophilic polyether amine; and (iii) up to 5 mol% of unreacted polyisobutylene epoxide, wherein the sum of the mol% of i, ii and iii is between 98 mol% and 100 mol%.

12. The polyisobutylene polyether alcoholamine compound produced via this process according to at least one of claims 8 to 11, characterized in that, The compound is selected from one of the groups consisting of: mono-polyisobutylene polyether alcoholamine compounds, bis-polyisobutylene polyether alcoholamine compounds, tri-polyisobutylene polyether alcoholamine compounds, and tetra-polyisobutylene polyether alcoholamine compounds.

13. A polyisobutylene polyether alcoholamine composition, characterized in that, The composition comprises a polyisobutylene polyether alcoholamine compound produced by the process as described in at least one of claims 8 to 12, wherein the polyisobutylene polyether alcoholamine composition comprises two or more of a mono-polyisobutylene polyether alcoholamine compound, a di-polyisobutylene polyether alcoholamine compound, a tri-polyisobutylene polyether alcoholamine compound, and a tetra-polyisobutylene polyether alcoholamine compound.

14. The polyisobutylene polyether alcoholamine composition according to at least one of claims 8 to 13, characterized in that, The polyisobutylene polyether alcohol amine 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.

15. A process for generating the polyisobutylene polyether alcoholamine compound as described in claims 1 to 7, characterized in that, The process comprises the following steps: (i) mixing polyisobutylene epoxide with a hydrophilic polyether amine in a reaction vessel at a molar ratio of about 1:1 or less; (ii) optionally introducing a protonated solvent into the reaction vessel using a catalyst; (iii) adding a diluent; (iii) heating the reaction vessel under pressure for a period of time; (iv) removing the diluent; and (v) recovering the polyisobutylene polyether amine compound, wherein the hydrophilic polyether amine is selected from the group consisting of one or more of polyether monoamines, polyether diamines, polyether triamines and polyether tetraamines.

16. The process as described in claim 15, characterized in that, The polyisobutylene epoxide contains Mn from 150 to 5000 and ethylene oxide oxygen from 2% to 0.15%, preferably Mn from 400 to 3000 and ethylene oxide oxygen from 2% to 0.25%.

17. A process for producing polyisobutylene polyether alcoholamine, characterized in that, The product is obtained by reacting a hydrophilic polyetheramine with a polyisobutylene epoxide in a molar ratio of approximately 1:1, wherein the hydrophilic polyetheramine is formed by alkylation of a mono-, di-, tri-, tetra-, or polyfunctional alcohol or alkylphenol with an alkyl oxide to form an alkyl oxide adduct, and then catalytically amination of the alkyl oxide adduct in the presence of hydrogen and ammonia to form the polyetheramine.

18. The process as described in claim 17, characterized in that, The epoxide is selected from one or more of the group consisting of ethylene oxide, propylene oxide, and butane oxide.

19. The process as described in claim 17, characterized in that, The polyisobutylene polyether alcoholamine is selected from the group consisting of mono-polyisobutylene polyether alcoholamine, di-polyisobutylene polyether alcoholamine and tri-polyisobutylene polyether alcoholamine.

20. Use of a polyisobutylene polyether alcohol amine in, or as, a lubricating composition, adhesive composition, sealant composition, grease composition, emulsifier composition, coating composition, polymer composition or resin composition.

Images